Adhesive film composition, and semiconductor wafer surface-protecting adhesive film manufactured using same

Abstract

The present specification provides an adhesive film composition, which comprises: a thermosetting resin including an amide group-containing monomer and a hydroxyl group-containing monomer; a thermosetting agent; and a photoinitiator, the adhesive film composition comprising more than 100 parts by weight and less than 4,000 parts by weight of the photoinitiator on the basis of 100 parts by weight of the thermosetting agent.

Description

Composition for adhesive film and adhesive film for protecting semiconductor wafer surface manufactured using the same

[0001] This application claims the benefit of the filing dates of Korean Patent Application No. 10-2024-0044010, filed with the Korean Intellectual Property Office on April 1, 2024, and Korean Patent Application No. 10-2025-0042033, filed with the Korean Intellectual Property Office on April 1, 2025, the entire contents of which are incorporated herein by reference.

[0002] The present specification relates to a composition for an adhesive film and an adhesive film for protecting a semiconductor wafer surface manufactured using the same.

[0003] With the recent trend toward miniaturization, high functionality, and increased capacity in electronic devices, the need for higher density and integration in semiconductor packaging is rapidly increasing. This demand is driving increasing semiconductor chip size, thinner chip thickness, and higher circuit integration. However, the modulus of the semiconductor chips themselves is decreasing, posing challenges to the manufacturing process and the reliability of the final product.

[0004] In response to the growing demand for larger and thinner semiconductors, a back grinding process is essential, which involves grinding the back of a wafer with a grinding wheel made of fine diamond particles to thin the chip and facilitate assembly. However, during this grinding process, damage to the wafer, such as contamination and cracking due to large amounts of silicon residue (dust) and particles, frequently occurs. Accordingly, the role of adhesive tapes or back grinding tapes for semiconductor wafer processing is becoming increasingly important.

[0005] During the back grinding process, a wafer protection adhesive tape is attached to the surface of the wafer to protect the wafer, and then the back of the wafer is polished to prevent the wafer from flipping or warping. However, as the demand for ultra-thin wafers increases, the thickness of the semiconductor wafer itself is polished to a level of 10 to 100 ㎛, and the existing wafer protection adhesive tape causes the wafer to warp during the polishing process, and this warping is the main cause of various problems in subsequent processes.

[0006] In addition, wafers are formed with relatively large unevenness, such as bumps. Therefore, if the adhesive tape for semiconductor wafer protection does not sufficiently fill the unevenness, there is a high risk of damage to the semiconductor wafer during the semiconductor wafer polishing process. Therefore, an unevenness absorption capacity that can easily fill the unevenness is required.

[0007] Therefore, it is necessary to prevent damage to the wafer, such as wafer contamination and cracking, during the back grinding process, and to conduct research on an adhesive film for protecting the surface of a semiconductor wafer that has excellent irregularity absorption ability and uniform physical properties to ensure a smooth back grinding process and does not leave residue when peeled.

[0008] The present specification provides a composition for an adhesive film and an adhesive film for protecting a semiconductor wafer surface manufactured using the same.

[0009] One embodiment of the present specification provides a composition for an adhesive film comprising a thermosetting resin including an amide group-containing monomer and a hydroxyl group-containing monomer; a thermosetting agent; and a photoinitiator, wherein the composition for an adhesive film comprises more than 100 parts by weight and less than 4,000 parts by weight of the photoinitiator relative to 100 parts by weight of the thermosetting agent.

[0010] Another embodiment of the present specification provides an adhesive layer comprising the composition for the adhesive film or a cured product thereof.

[0011] Another embodiment of the present specification provides an adhesive film for protecting a semiconductor wafer surface, comprising a substrate layer; an intermediate layer; and the adhesive layer.

[0012] Another embodiment of the present specification provides a method for manufacturing an adhesive film for protecting a surface of a semiconductor wafer, comprising the step of forming an adhesive layer by applying a composition for an adhesive film on a substrate layer, wherein the composition for an adhesive film comprises a thermosetting resin including an amide group-containing monomer and a hydroxyl group-containing monomer, a thermosetting agent, and a photoinitiator, and wherein the composition for an adhesive film comprises the photoinitiator in an amount of more than 100 parts by weight and less than 4,000 parts by weight relative to 100 parts by weight of the thermosetting agent.

[0013] An adhesive film for protecting a semiconductor wafer surface according to some embodiments of the present specification does not generate residue on the wafer surface after peeling.

[0014] An adhesive film for protecting a semiconductor wafer surface according to some embodiments of the present specification does not cause a bump ball pressing phenomenon on the wafer surface after peeling.

[0015] Figure 1 is a cross-sectional view of an adhesive film for protecting a semiconductor wafer surface according to one embodiment of the present specification.

[0016] [Explanation of symbols]

[0017] 10: Substrate layer

[0018] 20: Middle layer

[0019] 30: Adhesive layer

[0020] Hereinafter, the present specification is described in detail.

[0021] In this specification, when a part is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0022] In this specification, when it is said that a member is located “on” another member, this includes not only cases where a member is in contact with another member, but also cases where another member exists between the two members.

[0023] In this specification, the unit “parts by weight” may mean the weight ratio between each component.

[0024] One embodiment of the present specification provides a composition for an adhesive film comprising a thermosetting resin including an amide group-containing monomer and a hydroxyl group-containing monomer; a thermosetting agent; and a photoinitiator, wherein the composition for an adhesive film comprises more than 100 parts by weight and less than 4,000 parts by weight of the photoinitiator relative to 100 parts by weight of the thermosetting agent.

[0025] In this specification, "monomer" may mean a unit compound that can be converted into a polymer compound by a polymerization reaction, and may mean that all or part of two or more substituents in the structure of the compound are removed and a radical for bonding with another unit of the polymer is positioned at that position, and may mean a state in which the compound is polymerized and bound within the polymer. For example, when it is said to include a monomer, it may be included as the compound itself, or the monomer may be included in a state in which it is polymerized in any order and bound within the polymer. In addition, structures derived from the monomer may be included as repeating units within the polymer or copolymer.

[0026] In the present specification, the thermosetting resin includes an amide group-containing monomer and a hydroxyl group-containing monomer. This also includes a case where the thermosetting resin includes a polymer of the amide group-containing monomer and the hydroxyl group-containing monomer in addition to each monomer.

[0027] In one embodiment of the present specification, the amide group-containing monomer is at least one selected from the group consisting of (meth)acrylamide, dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide. Specifically, the amide group-containing monomer may be dimethyl(meth)acrylamide, but is not limited thereto. More specifically, the amide group-containing monomer may be dimethylacrylamide, but is not limited thereto.

[0028] In one embodiment of the present specification, the hydroxyl group (-0H)-containing monomer is at least one selected from the group consisting of unsaturated alcohols, hydroxyalkyl (meth)acrylates, and polypropylene glycol mono (meth)acrylate.

[0029] In one embodiment of the present specification, the unsaturated alcohol may be at least one selected from vinyl alcohol and allyl alcohol, but is not limited thereto.

[0030] In one embodiment of the present specification, the hydroxyalkyl (meth)acrylates may be at least one selected from among hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, and hydroxydecyl (meth)acrylate, but are not limited thereto.

[0031] In one embodiment of the present specification, the hydroxyl group-containing monomer is a hydroxyalkyl (meth)acrylate. Specifically, the hydroxyl group-containing monomer is hydroxyethyl (meth)acrylate. More specifically, the hydroxyl group-containing monomer is hydroxyethyl acrylate.

[0032] In one embodiment of the present specification, the thermosetting resin further comprises an alkyl (meth)acrylate monomer. This includes a case where the thermosetting resin comprises not only an alkyl (meth)acrylate monomer but also a polymer of an amide group-containing monomer, a hydroxyl group-containing monomer, and an alkyl (meth)acrylate monomer.

[0033] In one embodiment of the present specification, the alkyl (meth)acrylate monomer is an acrylate compound having a straight-chain or branched alkyl group having 1 to 15 carbon atoms, and may be, for example, at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, and lauryl (meth)acrylate, tetradecyl (meth)acrylate, but only Not limited.

[0034] In one embodiment of the present specification, the alkyl (meth)acrylate monomer is ethylhexyl (meth)acrylate. Specifically, the alkyl (meth)acrylate monomer is ethylhexyl acrylate.

[0035] In one embodiment of the present specification, the thermosetting resin includes a composition for producing a thermosetting resin or a cured product thereof.

[0036] In one embodiment of the present specification, the composition for producing a thermosetting resin includes the above-described amide group-containing monomer and hydroxyl group-containing monomer.

[0037] In one embodiment of the present specification, the composition for producing a thermosetting resin further includes an alkyl (meth)acrylate monomer.

[0038] In one embodiment of the present specification, the composition for producing a thermosetting resin includes a radical initiator.

[0039] In one embodiment of the present specification, the radical initiator may be any material used in the art without limitation. For example, it may be AIBN (azobisisobutyronitrile), but is not limited thereto.

[0040] In one embodiment of the present specification, the composition for the adhesive film contains 25 to 35 parts by weight of the thermosetting resin based on 100 parts by weight of the composition for the adhesive film.

[0041] In one embodiment of the present specification, the thermosetting resin contains 5 to 25 parts by weight of the amide group-containing monomer relative to 100 parts by weight of the thermosetting resin.

[0042] In one embodiment of the present specification, the thermosetting resin contains 5 to 15 parts by weight of a hydroxyl group-containing monomer relative to 100 parts by weight of the thermosetting resin.

[0043] In one embodiment of the present specification, the thermosetting resin contains 70 to 95 parts by weight of alkyl (meth)acrylate monomer per 100 parts by weight of the thermosetting resin.

[0044] In one embodiment of the present specification, the thermosetting resin in the adhesive film composition is thermoset and / or photoset to form a main chain. Since the main chain is formed by polymerization or copolymerization of the aforementioned types of amide group-containing monomers and hydroxyl group-containing monomers, when considering the positional relationship and reactivity, it can easily form a chemical bond with a compound (e.g., an isocyanate compound) for forming a side chain, and since a main chain having an appropriate chain length is formed, the desired level of adhesiveness and peeling force reduction rate can be realized.

[0045] In the present specification, the composition for the adhesive film includes a thermosetting agent. The thermosetting agent performs a crosslinking reaction with a functional group of a monomer included in the composition so that the adhesive layer exhibits an appropriate peel strength.

[0046] In one embodiment of the present specification, the thermosetting agent may include a bifunctional to hexafunctional isocyanate compound.

[0047] In this specification, an isocyanate compound means a compound having an isocyanate functional group.

[0048] In one embodiment of the present specification, the isocyanate compound is used as a thermosetting agent, thereby obtaining the advantage of a fast curing speed.

[0049] In one embodiment of the present specification, the isocyanate compound has an isocyanate group (-NCO) included in the molecule that reacts with the hydroxyl group (-OH) of the above-mentioned monomer to form a side chain.

[0050] In one embodiment of the present specification, the isocyanate compound is acryloyloxyethyl isocyanate (AOI), methacryloyloxyethyl isocyanate (MOI), methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), meta-xylene diisocyanate (MXDI), tetramethylxylene diisocyanate (TMXDI), 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, It may be at least one selected from among dicyclohexyl methane diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, 1,3,5-triisopropylphenylene-2,4-diisocyanate, diisocyanate made into an alicyclic by adding hydrogen to the benzene ring of the above MDI (H12 MDI), and diisocyanate made into an alicyclic by adding hydrogen to the benzene ring of xylene diisocyanate (hydrogenated XDI), but is not limited thereto. At this time, the above-mentioned components may be used alone or in combination of two or more. Specifically, the isocyanate-based compound may be a diisocyanate-based compound (curing agent) having a NCO-R-NCO structure. Here, R can be any one of a C3~C40 alicyclic hydrocarbon, a C6~C40 aromatic hydrocarbon, and a C1~C40 aliphatic hydrocarbon.

[0051] In one embodiment of the present specification, the composition for the adhesive film contains 0.5 to 10 parts by weight of the thermosetting agent based on 100 parts by weight of the composition for the adhesive film. Specifically, it contains 0.5 to 8 parts by weight.

[0052] When the type and content of the above-mentioned thermosetting compound are satisfied, the adhesive film for protecting the surface of a semiconductor wafer can exhibit excellent tensile strength required, and the adhesive film can be removed without residue.

[0053] In the present specification, the composition for the adhesive film includes a photoinitiator.

[0054] In one embodiment of the present specification, the photoinitiator may serve to initiate a photocuring reaction of the composition.

[0055] In one embodiment of the present specification, the photoinitiator may be used without limitation as long as it is a material used in the art. For example, the photoinitiator may be commercially available from Ciba Geigy, such as Irgacure #184 (hydroxycyclohexyl phenylketone), Irgacure #907 (2-methyl-1[4-(methythio)phenyl]-2-morpholinopropan-1-one), Irgacure #500 (hydroxyketones and benzophenone), Irgacure #651 (benzildimethyl-ketone), It may be at least one selected from, but is not limited to, Irgacure TPO (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide), Darocure #1173 (2-hydroxy-2-methyl-1-phenyl-propan-1-one), Darocure #116, CGI #1800 (bisacylphosphineoxide), CGI #1700 (bisacylphosphine oxide and hydroxy ketone) and I-651 of BASF.

[0056] In one embodiment of the present specification, the composition for the adhesive film contains the photoinitiator in an amount of more than 100 parts by weight and less than 4,000 parts by weight relative to 100 parts by weight of the thermal curing agent. That is, the weight ratio of the photoinitiator and the thermal curing agent (photoinitiator / thermal curing agent) is more than 1 and less than 40.

[0057] The above adhesive composition can obtain an appropriate range of tensile strength after UV irradiation by containing a photoinitiator and a thermal curing agent in the ratios described above, and the adhesive film can be easily removed without residue and ball pressing.

[0058] In one embodiment of the present specification, the composition for the adhesive film further includes at least one of a delay agent and a solvent.

[0059] In one embodiment of the present specification, the retarder delays curing and serves to ensure stability after mixing the adhesive composition. For example, it may be acetylacetone, but is not limited thereto.

[0060] In one embodiment of the present specification, the solvent serves to dissolve the aforementioned components. For example, it may be one or more of ethyl acetate and methyl ethyl ketone, but is not limited thereto.

[0061] In one embodiment of the present specification, the composition for the adhesive film includes a gel state.

[0062] In one embodiment of the present specification, the gelation degree of the composition for the adhesive film before irradiation with 700 mJ of UV is not limited. For example, it may be 60% or more, 70% or more, 80% or more, or 89% or more, and less than 95%.

[0063] In one embodiment of the present specification, the gelation degree of the adhesive film composition after 700 mJ of UV irradiation is 97% or more. In one embodiment of the present specification, the upper limit of the gelation degree after UV irradiation is not limited, but may be, for example, 100% or less. By exhibiting such a gelation degree after UV irradiation, there is an effect of suppressing a decrease in adhesive strength and suppressing the generation of residue.

[0064] In one embodiment of the present specification, the gel degree refers to the proportion of gel included in the composition, and can be measured by the following method.

[0065] (1) Measurement of gelation degree before UV irradiation

[0066] Prepare a release PET film, coat the adhesive film composition on the release PET film, and cut it into 50 mm x 50 mm sizes. After removing the release PET film, measure the weight (A), and soak the object from which the release PET film has been removed in ethyl acetate for one day. Prepare a steel mesh and measure the weight (B). Pour the object soaked in ethyl acetate for one day onto the steel mesh to remove the solvent, and dry the filtered material in an oven at 100°C for 1 hour. Measure the weight (C) after drying.

[0067] (2) Measurement of gelation degree after UV irradiation

[0068] Prepare a release PET film and coat the adhesive film composition on the release PET film. Cover the release PET film on the surface where the adhesive film composition is exposed, and then irradiate with UV. Cut the irradiated material into a size of 50 mm x 50 mm. After removing both release PET films, measure the weight (A), and soak the object from which the release PET films have been removed in ethyl acetate for one day. Prepare a steel mesh and measure the weight (B). Pour the object soaked in ethyl acetate for one day onto the steel mesh to remove the solvent, and dry the filtered material in an oven at 100°C for 1 hour. Measure the weight (C) after drying.

[0069] The gelation degree before and after UV irradiation is measured using the following mathematical formula 1.

[0070] [Mathematical Formula 1] Gelation Degree = [(CB) / A] x 100

[0071] - A: Weight after removing the heteromorphic PET film

[0072] - B: Weight of iron mesh

[0073] - C: Weight after drying

[0074] In one embodiment of the present specification, the gelation degree after UV irradiation increases compared to the gelation degree before UV irradiation. This means that the composition has changed into a more gel-like state through UV irradiation, and from this, it can be confirmed that the decrease in adhesiveness and the generation of residue can be suppressed through UV irradiation.

[0075] In one embodiment of the present specification, the viscosity of the adhesive film composition may be from about 300 cps to about 3000 cps. The adhesive film composition, while containing the aforementioned components to achieve the desired effect in one embodiment, can also achieve excellent coating properties when applied by controlling its viscosity within the aforementioned range. The viscosity can be measured using a method used in the art.

[0076] In one embodiment of the present specification, the composition for an adhesive film is a composition for an adhesive film for protecting a semiconductor wafer surface.

[0077] One embodiment of the present specification provides an adhesive layer comprising the aforementioned composition for an adhesive film or a cured product thereof.

[0078] In one embodiment of the present specification, the adhesive film composition is curable by heat treatment or light treatment. When the adhesive film composition is cured, it can be expressed as a cured product of the adhesive film composition.

[0079] In one embodiment of the present specification, the thickness of the adhesive layer may be 5 μm or more and 100 μm or less. Specifically, the thickness of the adhesive layer may be 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more, or 30 μm or more, and 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, or 75 μm or less. When the thickness of the adhesive layer is within the above-mentioned range, an adhesive film for protecting the surface of a semiconductor wafer having excellent mechanical properties can be realized.

[0080] One embodiment of the present specification provides an adhesive film for protecting a semiconductor wafer surface, comprising a substrate layer; an intermediate layer; and the adhesive layer.

[0081] The adhesive film protecting the surface of the semiconductor wafer serves to prevent damage to circuit patterns on the surface during the precision machining process of the semiconductor wafer, or contamination of the wafer by foreign substances or chemicals generated during the process. The adhesive film must be removed after the precision machining of the semiconductor wafer is completed, and it is important that the adhesive film be removed without damaging the surface of the wafer and without leaving any residue when peeled.

[0082] An adhesive film for protecting a semiconductor wafer surface according to one embodiment of the present specification has an adhesive layer including the aforementioned composition for an adhesive film or a cured product thereof, so that no residue is generated on the wafer surface upon peeling and no bump ball pressing phenomenon occurs.

[0083] FIG. 1 schematically illustrates a cross-section of an adhesive film for protecting a semiconductor wafer surface according to one embodiment of the present invention.

[0084] Referring to FIG. 1, the adhesive film for protecting the surface of a semiconductor wafer includes a base layer (10), an intermediate layer (20), and an adhesive layer (30).

[0085] In one embodiment of the present specification, the gelation degree of the adhesive layer before irradiation with 700 mJ UV is not limited. For example, it may be 60% or more, 70% or more, 80% or more, or 89% or more, and less than 95%.

[0086] In one embodiment of the present specification, the adhesive layer has a gelation degree of 97% or more after 700 mJ of UV irradiation. In one embodiment of the present specification, the upper limit of the gelation degree after UV irradiation is not limited, but may be, for example, 100% or less. By exhibiting such a gelation degree after UV irradiation, there is an effect of suppressing a decrease in adhesive strength and suppressing the generation of residue.

[0087] In one embodiment of the present specification, the gelation degree of the adhesive layer is measured by the same method as described above in the composition for the adhesive film.

[0088] In one embodiment of the present specification, the substrate layer is a layer disposed at the outermost layer when the adhesive film is attached to a semiconductor wafer, and primarily serves to protect the surface of the wafer.

[0089] In one embodiment of the present specification, the substrate layer is at least one selected from the group consisting of polyethylene terephthalate (PET) resin, polyethylene (PE) resin, polypropylene (PP) resin, polyimide (PI) resin, polyether ether ketone (PEEK) resin, polyvinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) resin, polyamide resin, polystyrene resin, polycarbonate resin, fluorine-based resin, and cellulose-based resin.

[0090] In one embodiment of the present specification, the substrate layer may be surface-treated to have excellent bonding strength with other layers, and for example, the substrate layer may be primed on the surface in contact with the thermosetting intermediate layer.

[0091] In one embodiment of the present specification, the thickness of the substrate layer may be 30 ㎛ or more and 200 ㎛ or less. Specifically, the thickness of the substrate layer may be 40 ㎛ or more, 50 ㎛ or more, 60 ㎛ or more, 70 ㎛ or more, 80 ㎛ or more, 90 ㎛ or more, or 100 ㎛ or more, and the thickness of the substrate layer may be 190 ㎛ or less, 180 ㎛ or less, 170 ㎛ or less, 160 ㎛ or less, or 150 ㎛ or less. When the thickness of the substrate layer satisfies the above-described range, the adhesive film for protecting the surface of a semiconductor wafer having excellent mechanical properties can be implemented.

[0092] In one embodiment of the present specification, the intermediate layer is a layer disposed between the substrate layer and the adhesive layer, and when a structure having a step exists on the wafer surface, it serves to provide excellent step absorption performance.

[0093] In one embodiment of the present specification, the intermediate layer includes a composition for forming an intermediate layer including an amide group-containing monomer and a hydroxyl group-containing monomer, or a cured product thereof.

[0094] In one embodiment of the present specification, the amide group-containing monomer and the hydroxyl group-containing monomer included in the composition for forming the intermediate layer are the same as those described in the adhesive layer.

[0095] In one embodiment of the present specification, the composition for forming the intermediate layer further includes at least one of an acrylate monomer and an acrylic acid monomer.

[0096] In one embodiment of the present specification, the acrylate monomer is an alkyl acrylate or an alkyl methacrylate. Specifically, among methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butylacrylate, isobutylacrylate, n-amyl acrylate, isoamyl acrylate, n-ethylhexylacrylate, 2-ethylhexylacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, n-ethylhexyl methacrylate, 2-ethylhexyl methacrylate, lauryl acrylate, ceryl acrylate, stearyl acrylate, lauryl methacrylate, cetyl methacrylate and stearyl methacrylate There may be more than one type.

[0097] In one embodiment of the present specification, the acrylic acid monomer is acrylic acid or methacrylic acid.

[0098] In one embodiment of the present specification, the composition for forming an intermediate layer contains 1 to 10 parts by weight of the amide group-containing monomer based on 100 parts by weight of the composition for forming an intermediate layer.

[0099] In one embodiment of the present specification, the intermediate layer forming composition contains 1 to 10 parts by weight of the hydroxyl group-containing monomer relative to 100 parts by weight of the intermediate layer forming composition.

[0100] In one embodiment of the present specification, the composition for forming the intermediate layer contains 20 to 40 parts by weight of the acrylate monomer relative to 100 parts by weight of the composition for forming the intermediate layer.

[0101] In one embodiment of the present specification, the composition for forming the intermediate layer contains 5 to 15 parts by weight of the acrylic acid monomer based on 100 parts by weight of the composition for forming the intermediate layer.

[0102] By including monomers in the above-described amount, the intermediate layer can realize excellent step absorption performance and can be attached to the substrate layer and the adhesive layer with appropriate adhesive strength, thereby contributing to securing durability of the adhesive film itself.

[0103] In one embodiment of the present specification, the composition for forming the intermediate layer further includes at least one selected from the group consisting of a photoinitiator and a photocuring agent.

[0104] In one embodiment of the present specification, the photoinitiator is not limited as long as it can initiate a photocuring reaction of the composition. Specific examples of the photoinitiator are the same as those described in the adhesive layer.

[0105] In one embodiment of the present specification, the photocuring agent may be at least one selected from the group consisting of 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and 1,12-dodecanediol di(meth)acrylate, but is not limited thereto.

[0106] In one embodiment of the present specification, the thickness of the intermediate layer may be 90 ㎛ or more and 1,000 ㎛ or less. Specifically, the thickness of the intermediate layer may be 100 ㎛ or more, 120 ㎛ or more, 140 ㎛ or more, or 150 ㎛ or more, and may be 950 ㎛ or less, 900 ㎛ or less, 850 ㎛ or less, or 800 ㎛ or less. When the thickness of the intermediate layer is within the above-mentioned range, an adhesive film for protecting a semiconductor wafer surface with excellent mechanical properties can be realized.

[0107] In one embodiment of the present specification, the adhesive film has a tensile strength of 5.6 MPa or more after 700 mJ UV irradiation. Specifically, the adhesive film has a tensile strength of 5.6 MPa or more after 700 mJ UV irradiation and a modulus of 0.209 or more.

[0108] In one embodiment of the present specification, the adhesive film has a tensile strength of 6.2 MPa or more after 1000 mJ UV irradiation. Specifically, the adhesive film has a tensile strength of 6.2 MPa or more after 1000 mJ UV irradiation and a modulus of 0.235 or more.

[0109] The upper limits of the above tensile strength and modulus are not limited, but for example, the tensile strength may be 30 Mpa or less, and the modulus may be 0.5 or less.

[0110] In one embodiment of the present specification, the adhesive film exhibits a tensile strength within the aforementioned range, thereby having the effect of preventing residue and ball compression.

[0111] In one embodiment of the present specification, the tensile strength is measured using a method used in the art. Specifically, it can be measured using a UTM. More specifically, the tensile strength is measured by preparing an adhesive film in a dogbone shape corresponding to the tensile strength measurement range (10 mm x 40 mm), irradiating the adhesive film with UV light, and then measuring the tensile strength using a UTM at a measurement speed of 100 mm / min.

[0112] In one embodiment of the present specification, the adhesive film has a Tack ratio of 48 or more when irradiated with 0 mJ of UV and when irradiated with 1000 mJ of UV.

[0113] The upper limit of the above Tack ratio is not limited, but may be, for example, 200 or less.

[0114] In one embodiment of the present specification, the adhesive film exhibits a Tack ratio within the aforementioned range, thereby having the effect of preventing residue and ball-pressing.

[0115] In one embodiment of the present specification, the Tack ratio is measured by measuring and comparing the Tack value when the UV irradiation amount on the adhesive film is different using a SUS Ball probe. Specifically, the Tack value of the adhesive film is measured using a SUS Ball probe in a texture analyzer under the conditions of a measurement speed of 10 mm / sec, a force of 500 g, and a contact time of 10 seconds, and then the Tack ratio can be measured by comparing the Tack values ​​when the irradiation amount is different (0, 300, 700, and 1000 mJ, respectively).

[0116] One embodiment of the present specification is a method for manufacturing an adhesive film for protecting a semiconductor wafer surface, comprising the step of forming an adhesive layer by applying a composition for an adhesive film on a substrate layer,

[0117] The composition for the adhesive film comprises a thermosetting resin including an amide group-containing monomer and a hydroxyl group-containing monomer, a thermosetting agent, and a photoinitiator,

[0118] The present invention provides a method for manufacturing an adhesive film for protecting a semiconductor wafer surface, wherein the composition for the adhesive film comprises more than 100 parts by weight and less than 4,000 parts by weight of the photoinitiator relative to 100 parts by weight of the thermal curing agent.

[0119] In one embodiment of the present specification, a step of forming an intermediate layer is further included before the step of forming an adhesive layer on the substrate layer. Specifically, the step includes a step of forming an intermediate layer on the substrate layer; and a step of applying a composition for an adhesive film on the intermediate layer to form an adhesive layer.

[0120] In one embodiment of the present specification, the step of forming an intermediate layer on the substrate layer may include a step of applying an intermediate layer forming composition on top of a separate release film and then photocuring it to produce a laminate of the intermediate layer and the release film; and a step of laminating the intermediate layer of the laminate so that it is in contact with one surface of the substrate layer and then peeling off the release film.

[0121] In one embodiment of the present specification, the step of forming an adhesive layer using the composition for an adhesive film may include a step of applying the composition for an adhesive film to a separate release film and then heat-curing it to form an adhesive layer; and a step of laminating the adhesive layer so that it is in contact with one surface of the base layer or the intermediate layer.

[0122] In this way, by manufacturing an adhesive film by forming the intermediate layer and the adhesive layer separately on top of the release film and then sequentially laminating them, the interface and surface properties of each layer can be secured to be suitable for a semiconductor process.

[0123] In the method for manufacturing the above adhesive film, the details regarding the substrate layer, the intermediate layer, the adhesive layer, the composition for the adhesive film, and the composition for forming the intermediate layer are as described above.

[0124] Hereinafter, examples will be provided to specifically explain this specification. However, the embodiments described herein may be modified in various ways, and the scope of this specification is not limited to the embodiments described below. The embodiments described herein are provided to more fully explain this specification to those of ordinary skill in the art.

[0125] Manufacturing example 1.

[0126] A mixture was prepared by mixing 85 parts by weight of ethylhexyl acrylate, 10 parts by weight of dimethyl acrylamide, 5 parts by weight of hydroxyethyl acrylate, and 0.5 parts by weight of AIBN (azobisisobutyronitile). Ethyl acetate was placed in a nitrogen-purged flask, and the mixture was added thereto, followed by reaction at 80°C for 8 hours with stirring. After completion of the reaction, 10 parts by weight of ethyl acetate and methacryloyloxyethyl isocyanate were added, and the reaction was conducted at 85°C for 12 hours to obtain a thermosetting resin A having a carbon-carbon double bond introduced therein.

[0127] An adhesive coating solution was obtained by adding a thermosetting agent (MDI, Basf) and a photoinitiator (I-651, Basf) to the above thermosetting resin in the amounts shown in Table 1 below. The adhesive coating solution was coated on a PET film and then dried to produce an adhesive layer.

[0128] A sample was prepared by laminating the adhesive layer manufactured above onto the intermediate layer in a laminate including PET and an intermediate layer.

[0129] Manufacturing example 2.

[0130] A thermosetting resin B was manufactured in the same manner as in Manufacturing Example 1, except that isobornyl acrylate (IBOA) was used instead of dimethylacrylamide in Manufacturing Example 1.

[0131] Experimental Example 1. Measurement of gelation degree

[0132] (1) Measurement of gelation degree before UV irradiation

[0133] A release PET film was prepared, an adhesive coating was applied to the release PET film, and then cut to a size of 50 mm x 50 mm. After removing the release PET film, the weight (A) was measured, and the object from which the release PET film had been removed was immersed in ethyl acetate for one day. A steel mesh was prepared, and the weight (B) was measured. The object immersed in ethyl acetate for one day was poured onto the steel mesh, and the solvent was removed. The filtered material was dried in an oven at 100°C for 1 hour. The weight (C) after drying was measured.

[0134] (2) Measurement of gelation degree after UV irradiation

[0135] A release PET film was prepared, and an adhesive coating solution was coated on the release PET film. After covering the release PET film on the surface where the composition for the adhesive film was exposed, 700 mJ UV was irradiated. The irradiated material was cut into a size of 50 mm x 50 mm. After removing both release PET films, the weight (A) was measured, and the object from which the release PET films were removed was immersed in ethyl acetate for one day. An iron mesh was prepared, and the weight (B) was measured. The object immersed in ethyl acetate for one day was poured onto the iron mesh to remove the solvent, and the filtered material was dried in an oven at 100°C for 1 hour. The weight (C) after drying was measured.

[0136] The gelation degree before and after UV irradiation was measured using the following mathematical formula 1.

[0137] [Mathematical Formula 1] Gelation Degree = [(CB) / A] x 100

[0138] - A: Weight after removing the heteromorphic PET film

[0139] - B: Weight of iron mesh

[0140] - C: Weight after drying

[0141] The gelation degree before and after UV exposure was measured for adhesive coating solutions with changed thermosetting agent content using the same method as above, and is shown in Table 1 below.

[0142] Experimental Example 2. Measurement of tensile strength

[0143] The sample was prepared in a dogbone shape corresponding to the tensile strength measurement range (10 mm x 40 mm). After irradiating the sample with UV, the tensile strength was measured using a UTM at a measurement speed of 100 mm / min.

[0144] The tensile strength of samples with changed thermosetting agent content was measured using the same method as above and is listed in Table 1 below.

[0145] Experimental Example 3. Tack Measurement

[0146] Samples were prepared according to UV irradiation doses (0, 300, 700, and 1000 mJ). The tack values ​​of the samples were measured using a SUS ball probe in a texture analyzer under the conditions of a measurement speed of 10 mm / sec, a force of 500 g, and a contact time of 10 seconds.

[0147] For samples with changed thermosetting agent content, the Tack value according to UV irradiation dose was measured using the same method as above and is listed in Table 1 below.

[0148] Experimental Example 4. Measurement of residue and ball pressure

[0149] Wafers measuring 50 mm x 50 mm were prepared. Samples measuring 25 mm x 150 mm were attached to the wafer using a 2 kg roller. After 1 hour, the sample was irradiated with UV light and removed. The sample residue and ball pressure were checked under a microscope.

[0150] For samples with changed thermosetting agent content, the gelation degree before and after UV exposure was measured using the same method as above, and is listed in Table 1 below.

[0151]

[0152] Through the above Table 1, it can be confirmed that the gelation degree, tack ratio, tensile strength, presence of residue, and occurrence of ball compression change depending on the content ratio of the thermosetting agent and photoinitiator used in the manufacture of the adhesive layer.

[0153] Specifically, when the photoinitiator is included in an amount of 4000 parts by weight or more per 100 parts by weight of the heat curing agent (Comparative Examples 1 to 4), it can be confirmed that the gelation degree, tack ratio, and tensile strength are reduced, and residue and ball compression occur, making it unsuitable as an adhesive film for protecting the surface of a semiconductor wafer.

[0154] In addition, when a monomer other than the amide group-containing monomer (dimethylacrylamide) is used (Comparative Examples 5 to 7), the gelation degree and tack ratio are reduced and residue and ball pressure are generated, so it can be confirmed that it is not suitable as an adhesive film for protecting the surface of a semiconductor wafer.

Claims

1. A thermosetting resin comprising an amide group-containing monomer and a hydroxyl group-containing monomer; thermosetting agent; and In a composition for an adhesive film containing a photoinitiator, A composition for an adhesive film, wherein the composition for an adhesive film comprises more than 100 parts by weight and less than 4,000 parts by weight of the photoinitiator relative to 100 parts by weight of the thermosetting agent.

2. A composition for an adhesive film according to claim 1, wherein the composition for an adhesive film further comprises at least one of a delay agent and a solvent.

3. A composition for an adhesive film according to claim 1, wherein the amide group-containing monomer is at least one selected from the group consisting of (meth)acrylamide, dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

4. A composition for an adhesive film according to claim 1, wherein the hydroxyl group-containing monomer is at least one selected from the group consisting of unsaturated alcohols, hydroxyalkyl (meth)acrylates, and polypropylene glycol mono (meth)acrylate.

5. A composition for an adhesive film according to claim 1, wherein the thermosetting resin further comprises an alkyl (meth)acrylate monomer.

6. In claim 1, the composition for an adhesive film has a gelation degree of 97% or more after UV irradiation of 700 mJ.

7. An adhesive layer comprising a composition for an adhesive film according to any one of claims 1 to 6 or a cured product thereof.

8. An adhesive film for protecting a semiconductor wafer surface, comprising a substrate layer; an intermediate layer; and an adhesive layer according to claim 7.

9. In claim 8, the substrate layer is at least one selected from the group consisting of polyethylene terephthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polyether ether ketone resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, polystyrene resin, polycarbonate resin, fluorine-based resin, and cellulose-based resin. An adhesive film for protecting a semiconductor wafer surface.

10. An adhesive film for protecting a semiconductor wafer surface, wherein the intermediate layer comprises a composition for forming an intermediate layer containing an amide group-containing monomer and a hydroxyl group-containing monomer, or a cured product thereof, according to claim 8.

11. An adhesive film for protecting a semiconductor wafer surface, wherein the adhesive layer has a gelation degree of 97% or more after irradiation with UV of 700 mJ in claim 8.

12. In claim 8, the adhesive film is an adhesive film for protecting a semiconductor wafer surface, wherein the adhesive film has a tensile strength of 5.6 Mpa or more after irradiation with UV of 700 mJ.

13. In claim 8, the adhesive film is an adhesive film for protecting a semiconductor wafer surface, wherein the adhesive film has a tensile strength of 6.2 Mpa or more after irradiation with UV of 1000 mJ.

14. In claim 8, the adhesive film is an adhesive film for protecting a semiconductor wafer surface, wherein the adhesive film has a Tack ratio of 48 or more when exposed to 0 mJ of UV irradiation and when exposed to 1000 mJ of UV irradiation.

15. A method for manufacturing an adhesive film for protecting a semiconductor wafer surface, comprising the step of forming an adhesive layer by applying a composition for an adhesive film on a substrate layer, The composition for the adhesive film comprises a thermosetting resin including an amide group-containing monomer and a hydroxyl group-containing monomer, a thermosetting agent, and a photoinitiator, A method for producing an adhesive film for protecting a semiconductor wafer surface, wherein the composition for the adhesive film contains the photoinitiator in an amount of more than 100 parts by weight and less than 4,000 parts by weight relative to 100 parts by weight of the thermal curing agent.

16. A method for manufacturing an adhesive film for protecting a semiconductor wafer surface, wherein the step of forming an adhesive layer by applying a composition for an adhesive film on the substrate layer according to claim 15 comprises the step of forming an intermediate layer on the substrate layer; and the step of forming an adhesive layer by applying a composition for an adhesive film on the intermediate layer.

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