Adhesive sheet

Abstract

The objective is to provide an adhesive sheet having a first adhesive layer with high chemical resistance, and an adhesive sheet that, when adhered to a substrate and peeled off after high-temperature treatment, leaves no residue of the second adhesive layer on the substrate. [Solution] The present invention provides an adhesive sheet comprising a base film and a first adhesive layer laminated on the first surface of the base film, wherein the base film is a polyethylene naphthalate film, and the first adhesive layer comprises a (meth)acrylic binder, a photocurable monomer, a thermosetting agent, and a photoinitiator, wherein the photocurable monomer comprises a mixture of monomers having aromatic groups, monomers having hydrophobic groups, and monomers having hydroxyl groups.

Description

[Technical Field]

[0001] This invention relates to an adhesive sheet. [Background technology]

[0002] The manufacturing of semiconductor chips can be carried out through several steps (e.g., a multi-stage process). During the semiconductor chip manufacturing process, semiconductor adhesive tape may be used to improve the handling of the semiconductor chip and prevent damage to the semiconductor chip. Generally, the semiconductor adhesive tape is a double-sided adhesive tape. After a silicon wafer is bonded to one side of the semiconductor adhesive tape, and high-temperature processing steps such as etching using an etching solution, solder formation, and chip mounting are performed, the semiconductor adhesive tape can be removed from the silicon wafer. After being bonded to the silicon wafer, the semiconductor adhesive tape can be removed from the silicon wafer through high-temperature processing.

[0003] However, in recent years, the processing temperature in the high-temperature processing step has been increasing. Also, if irregularities are formed on the surface of the silicon wafer to be adhered, the peeling force of the adhesive layer may increase after the high-temperature processing step, making it difficult to peel the semiconductor adhesive tape from the silicon wafer. Furthermore, residue of the adhesive layer may remain on the silicon wafer after the semiconductor adhesive tape has been peeled off. [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] One embodiment provides an adhesive sheet having a first adhesive layer with high chemical resistance.

[0005] Another embodiment provides an adhesive sheet that, when adhered to a substrate and peeled off after high-temperature treatment, leaves no residue of the second adhesive layer on the substrate. [Means for solving the problem]

[0006] Additional embodiments are partially described in the following description, partially evident from the description, or can be learned by practicing the embodiments presented in this disclosure.

[0007] 1. One embodiment provides an adhesive sheet comprising a base film and a first adhesive layer laminated on a first surface of the base film, wherein the base film is a polyethylene naphthalate film, and the first adhesive layer comprises a (meth)acrylic binder, a photocurable monomer, a thermosetting agent, and a photoinitiator, wherein the photocurable monomer comprises a mixture of monomers having aromatic groups, monomers having hydrophobic groups, and monomers having hydroxyl groups.

[0008] In 2.1, the monomer having an aromatic group may include the compound of the following chemical formula 1: [ka] ...chemical formula 1

[0009] In the above chemical formula 1, R 1 R is a hydrogen or methyl group, s is an integer from 0 to 10, R 2 A is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, and T is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkyleneoxy group having 1 to 6 carbon atoms.

[0010] In sections 3.1-2, the monomer having an aromatic group may include one or more of phenoxybenzyl (meth)acrylate and biphenylmethyl (meth)acrylate.

[0011] In sections 4.1 to 4.3, the monomer having an aromatic group may be included in amounts of 30 to 100 parts by weight per 100 parts by weight of the (meth)acrylic binder.

[0012] In 5.1 to 4, the monomer having a hydrophobic group may include one or more of a (meth)acrylic acid ester having a hydrophobic group at the ester site and a (meth)acrylic monomer having a morpholine group.

[0013] In 6.5, the monomer having a hydrophobic group may include one or more of isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (meth)acryloylmorpholine.

[0014] In 7.1 to 6, the monomer having a hydrophobic group may be contained in an amount of 1 part by weight to 50 parts by weight relative to 100 parts by weight of the (meth)acrylic binder.

[0015] In 8.1 to 7, the monomer having a hydroxyl group may be contained in an amount of 1 part by weight to 50 parts by weight relative to 100 parts by weight of the (meth)acrylic binder.

[0016] In 9.1 to 8, in a total of 100 parts by weight of the monomer having an aromatic group, the monomer having a hydroxyl group, and the monomer having a hydrophobic group, the content of the monomer having an aromatic group may be 50 parts by weight to 90 parts by weight, the content of the monomer having a hydroxyl group may be 1 part by weight to 40 parts by weight, and the content of the monomer having a hydrophobic group may be 5 parts by weight to 40 parts by weight.

[0017] In 10.1 to 9, one or more of the monomer having an aromatic group, the monomer having a hydrophobic group, and the monomer having a hydroxyl group may have a homopolymer glass transition temperature of 0°C or higher.

[0018] In 11.1 to 10, the photocurable monomer may be contained in an amount of 50 parts by weight to 300 parts by weight relative to 100 parts by weight of the (meth)acrylic binder.

[0019] In sections 12.1 to 11, the total amount of monomers having aromatic groups, monomers having hydrophobic groups, and monomers having hydroxyl groups may be present in the photocurable monomer at a concentration of 95% by weight or more.

[0020] In sections 13.1 to 12, the (meth)acrylic binder may be a copolymer of monomer mixtures containing (meth)acrylic acid esters having an alkyl group in the ester moiety and (meth)acrylic acid esters having one or more hydroxyl-substituted alkyl groups in the ester moiety.

[0021] In sections 14.1 to 13, the first adhesive layer is 100 parts by weight of the (meth)acrylic binder, 50 to 300 parts by weight of the aforementioned photocurable monomer, The aforementioned thermosetting agent is in an amount exceeding 0 parts by weight and not exceeding 3 parts by weight, and The photoinitiator may be included in amounts exceeding 0 parts by weight but not exceeding 3 parts by weight.

[0022] In sections 15.1 to 14, the adhesive sheet may further include a second adhesive layer laminated on the first adhesive layer, the first adhesive layer may be positioned between the base film and the second adhesive layer, and may further include a third adhesive layer laminated on the upper part of the second surface of the base film that faces away from the first surface. [Effects of the Invention]

[0023] According to one embodiment, the material has excellent chemical resistance and the first adhesive layer does not disappear during the etching process in semiconductor manufacturing, thus improving the reliability of semiconductor manufacturing.

[0024] According to one embodiment, when the second adhesive layer is bonded to the adherend and then peeled off from the adherend after high-temperature processing, there is no residue of the second adhesive layer remaining on the adherend, thereby improving semiconductor manufacturing reliability. [Brief explanation of the drawing]

[0025] [Figure 1] This is a cross-sectional view of an adhesive sheet according to one embodiment. [Figure 2] This is a cross-sectional view of an adhesive sheet according to another embodiment. [Figure 3] This is a cross-sectional view of an adhesive sheet according to another embodiment. [Modes for carrying out the invention]

[0026] Embodiments of the present invention will be described in detail below. However, these are presented as examples only and are not limited thereto, and the present invention is defined only within the scope of the claims set forth below. The accompanying drawings are provided to enhance the understanding of this disclosure, are incorporated herein, and constitute part thereof. The drawings illustrate embodiments of this disclosure and, together with the description, are helpful in illustrating the principles of this disclosure.

[0027] In this specification, unless otherwise specified, when a part such as a layer, film, region, or plate is said to be "on top of" another part, this includes not only the case where it is "immediately on top of" another part, but also the case where there is yet another part in between.

[0028] In this specification, unless otherwise specified, singular nouns may also include plural nouns. Furthermore, unless otherwise specified, "A or B" may mean "including A, including B, or including both A and B."

[0029] In this specification, “these combinations” may mean mixtures, laminates, composites, copolymers, alloys, blends, and reaction products of the constituents.

[0030] According to one embodiment, an adhesive sheet is provided.

[0031] According to one embodiment, the adhesive sheet can be used in semiconductor manufacturing.

[0032] A method for using the adhesive sheet in semiconductor manufacturing according to one embodiment will be described.

[0033] The aforementioned adhesive sheet for semiconductor manufacturing can be used in post-semiconductor manufacturing processes throughout the entire semiconductor manufacturing process.

[0034] More specifically, the process can be carried out in the following order: a silicon wafer is bonded to one side of the adhesive sheet; a glass plate is bonded to another side of the adhesive sheet; the laminate of the glass plate, the adhesive sheet, and the silicon wafer is ground and etched; a high-temperature processing step (reflow process) including solder formation is performed on the silicon wafer; the glass plate is removed from the adhesive sheet; and the silicon wafer is removed from the adhesive sheet.

[0035] In one embodiment, the glass plate can be removed from the adhesive sheet by laser treatment and / or light irradiation (e.g., UV irradiation).

[0036] In one embodiment, the silicon wafer can be removed from the adhesive sheet by high-temperature treatment and / or light irradiation.

[0037] In one embodiment, prior to the etching step, the adhesive layer of the adhesive sheet may be photocured by light irradiation.

[0038] The adhesive sheet includes a base film and a first adhesive layer laminated on the lower surface of the base film.

[0039] In one embodiment, the adhesive sheet may further include a second adhesive layer laminated on the lower surface of the first adhesive layer. A first release film may further be laminated on the lower surface of the second adhesive layer. In some embodiments, the second adhesive layer is placed directly on the lower surface of the first adhesive layer, and the first adhesive layer is placed between the second adhesive layer and the base film.

[0040] In one embodiment, the adhesive sheet may further include a third adhesive layer laminated on the upper surface of the base film. A second release film may further be laminated on the upper surface of the third adhesive layer.

[0041] The adhesive sheet will be described in detail below.

[0042] base film The base film can support the first adhesive layer. The base film is a polyethylene naphthalate (PEN) film. The PEN film is selected so that it can be used in the post-semiconductor manufacturing process.

[0043] The base film may have a predetermined thickness ratio with respect to the first adhesive layer. For example, the thickness ratio of the base film to the first adhesive layer may be 1:0.8 to 1:1.2. Within this range, the first adhesive layer can ensure stable adhesion to the base film.

[0044] In one embodiment, the base film may have a thickness of 5 μm to 100 μm, for example, 5 μm to 80 μm or 5 μm to 50 μm. Within this range, it can be used in the adhesive sheet.

[0045] 1st adhesive layer The first adhesive layer has high chemical resistance. Therefore, the etching solution used in the etching process during the post-semiconductor manufacturing process does not penetrate the first adhesive layer, thereby increasing the reliability of the post-semiconductor manufacturing process. Specifically, when the first adhesive layer is bonded to the second adhesive layer, as described below, and then introduced into the etching process, no lifting or penetration of the etching solution occurs between the first and second adhesive layers. This prevents the first and second adhesive layers from separating from each other during the etching process, thereby increasing the reliability of the post-semiconductor manufacturing process.

[0046] The first adhesive layer ensures that when the adhesive sheet is attached to the adherend, subjected to light irradiation and high-temperature treatment, and then peeled off the adherend, no residue of the second adhesive layer remains on the adherend (for example, the second adhesive layer leaves no residue on the adherend after being peeled off). This can improve semiconductor manufacturing reliability. Hereafter, the above effect will be referred to as the "residue-free effect of the second adhesive layer."

[0047] As explained below, the adherend is bonded to the second adhesive layer in the adhesive sheet, not to the first adhesive layer. However, according to the inventors of the present invention, the first adhesive layer can provide a residue-free effect on the second adhesive layer. This is thought to be because the first adhesive layer is bonded to the second adhesive layer, and the first adhesive layer influences the peeling force of the second adhesive layer when the second adhesive layer is peeled from the adherend, but the present invention is not limited thereto.

[0048] In this specification, "adheren" may be a silicon wafer or SUS (stainless steel).

[0049] The light irradiation here may vary depending on the post-manufacturing process of the semiconductor, but it can include UV irradiation with an intensity of 2000 mJ at a wavelength of 395 nm.

[0050] Here, the high-temperature treatment can vary depending on the temperature used in the post-manufacturing process of the semiconductor, but it could include, for example, leaving it at 200°C for 60 minutes.

[0051] To prevent the first and second adhesive layers from separating when the second adhesive layer, as described below, is peeled from the adherend, the first adhesive layer may have an anchoring force of 1000 gf / inch or more on the base film after light irradiation, for example, 1000 gf / inch to 2000 gf / inch or 1500 gf / inch to 2000 gf / inch. "Anchoring force" refers to the adhesive force between the first adhesive layer and the base film, and is expressed by the peeling force (details will be described later). Within the above range, the peeling force on the base film is increased, and it is possible to prevent the base film and the first adhesive layer from separating from each other when the adhesive sheet is peeled from the adherend. Here, light irradiation can mean irradiating with light (e.g., UV) at a wavelength of 380 nm to 400 nm, for example 395 nm, and an intensity of 2000 mJ.

[0052] The first adhesive layer may have an anchoring force of 100 gf / inch or more to the substrate film before light irradiation, for example, 100 gf / inch to 300 gf / inch. Within this range, the anchoring force after light irradiation can be easily increased.

[0053] The first adhesive layer can be attached to a substrate via the second adhesive layer described below. The first adhesive layer can exert the following effects by influencing the peeling force of the second adhesive layer against the substrate.

[0054] In one embodiment, when the adhesive sheet is attached to a specimen via a second adhesive layer described below, the peeling force when the adhesive sheet is peeled off the specimen may be 10 gf / inch to 20 gf / inch, for example, 10 gf / inch to 15 gf / inch. Within this range, the adhesive sheet can adhere stably to the specimen, and the peeling force can be prevented from increasing excessively during high-temperature treatment.

[0055] In one embodiment, when a specimen in which the adhesive sheet is attached to a substrate via a second adhesive layer is irradiated with light, and the adhesive sheet is peeled off the substrate, the peeling force may be 1 gf / inch to 15 gf / inch, for example, 5 gf / inch to 15 gf / inch (e.g., before light irradiation or heat treatment). Within this range, the residue-free effect of the second adhesive layer can be achieved. Here, light irradiation can mean irradiating with light (e.g., UV) at a wavelength of 380 nm to 400 nm, for example, 395 nm, and an intensity of 2000 mJ.

[0056] In one embodiment, when a specimen in which the adhesive sheet is attached to a substrate via a second adhesive layer is irradiated with light, left at 200°C for 60 minutes, and the adhesive sheet is peeled off the substrate, the peeling force may be 20 gf / inch to 30 gf / inch, for example, 20 gf / inch to 25 gf / inch. Within this range, the residue-free effect of the second adhesive layer can be achieved. Here, light irradiation can mean irradiating with light (e.g., UV) at a wavelength of 380 nm to 400 nm, for example, 395 nm, and an intensity of 2000 mJ.

[0057] The first adhesive layer comprises a (meth)acrylic binder, a photocurable monomer, a thermosetting agent, and a photoinitiator, wherein the photocurable monomer comprises a mixture of monomers having aromatic groups, monomers having hydrophobic groups, and monomers having hydroxyl groups.

[0058] The first adhesive layer, by containing the (meth)acrylic binder, photocurable monomer, thermosetting agent, and photoinitiator, has high chemical resistance and can provide the effect of leaving no residue on the second adhesive layer.

[0059] In one embodiment, the first adhesive layer may include a cured product of a composition comprising the (meth)acrylic binder, the photocurable monomer, the thermosetting agent, and the photoinitiator. In one embodiment, the cured product may be a thermosetting product.

[0060] The first adhesive layer can be manufactured by coating the base film with the composition for the first adhesive layer to a predetermined thickness, and then heat-curing it. The heat-curing may include, but is not limited to, treatment at 100°C to 150°C for 30 seconds to 10 minutes.

[0061] The first adhesive layer may have a thickness of 5 μm to 100 μm, for example, 5 μm to 80 μm or 5 μm to 50 μm. Within this range, it can be used in post-manufacturing processes for semiconductors, and it may be easier to ensure the peeling force of the first adhesive layer.

[0062] The following describes in detail each component of the composition for the first adhesive layer.

[0063] (Meta)acrylic binder The (meth)acrylic binder may be a copolymer of monomer mixtures containing (meth)acrylic acid esters having an alkyl group in the ester moiety and (meth)acrylic acid esters having one or more hydroxyl-substituted alkyl groups in the ester moiety.

[0064] In one embodiment, the total amount of (meth)acrylic acid esters having an alkyl group in the ester moiety and (meth)acrylic acid esters having one or more hydroxyl-substituted alkyl groups in the ester moiety may be 95 mol% or more, for example, 95 mol% to 100 mol%, when the total amount of all monomers in the monomer mixture is set to 100 mol%. Within this range, the effects of the first adhesive layer described above can be easily realized.

[0065] The (meth)acrylic acid ester having an alkyl group in the ester moiety may also be a (meth)acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms in the ester moiety. For example, the (meth)acrylic acid ester may include one or more of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, iso-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate. Preferably, the (meth)acrylic acid ester may be one or more of n-butyl acrylate and 2-ethylhexyl acrylate. The (meth)acrylic acid ester may be present in the monomer mixture at an amount of 60 mol% to 99 mol%, for example, 80 mol% to 99 mol%, or 90 mol% to 99 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, the effect of the first adhesive layer can be easily achieved.

[0066] The (meth)acrylic acid ester having one or more hydroxyl-substituted alkyl groups in the ester moiety may also be a (meth)acrylic acid ester having one or more hydroxyl-substituted alkyl groups having 1 to 10 carbon atoms in the ester moiety. For example, the (meth)acrylic acid ester may be one or more of 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, or 1-chloro-2-hydroxypropyl (meth)acrylate. For example, the (meth)acrylic acid ester may be 4-hydroxybutyl acrylate. The (meth)acrylic acid ester may be present in the monomer mixture in an amount of 1 mol% to 40 mol%, for example, 1 mol% to 20 mol%, or 1 mol% to 10 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, the effect of the first adhesive layer can be easily achieved.

[0067] The (meth)acrylic binder can be produced by polymerizing the monomer mixture using a conventional polymerization method. The polymerization method may include conventional methods known to those skilled in the art. For example, the (meth)acrylic binder can be produced by conventional copolymer polymerization, such as suspension polymerization, emulsion polymerization, or solution polymerization, after adding an initiator to the monomer mixture. The polymerization temperature may be 60°C to 70°C, and the polymerization time may be 4 to 8 hours. Conventional initiators can be used, including azo polymerization initiators and / or peroxides such as benzoyl peroxide or acetyl peroxide.

[0068] The (meth)acrylic binder may have a weight-average molecular weight of 500,000 g / mol to 3,000,000 g / mol, for example, 500,000 g / mol to 2,000,000 g / mol or 500,000 g / mol to 1,500,000 g / mol. Within this range, the peeling force of the first adhesive layer can be easily achieved.

[0069] In this specification, "weight-average molecular weight" can be determined by the polystyrene equivalent value obtained by gel permeation chromatography.

[0070] Photocurable monomer Photocurable monomers include a mixture of monomers having aromatic groups, monomers having hydrophobic groups, and monomers having hydroxyl groups.

[0071] The composition for the first adhesive layer comprises, in addition to the (meth)acrylic binder, a mixture of photocurable monomers having aromatic groups, a monomer having hydrophobic groups, and a monomer having hydroxyl groups. A first adhesive layer using a photocurable monomer that does not contain one or two of the three types of photocurable monomers may not achieve the effects of the first adhesive layer described above. Therefore, the first adhesive layer has high chemical resistance, which allows for high reliability in etching processes during post-semiconductor manufacturing processes. Furthermore, the first adhesive layer can provide the residue-free effect of the second adhesive layer.

[0072] In one embodiment, the photocurable monomer may include a photocurable monomer having a homopolymer glass transition temperature of 0°C or higher, for example, 0°C to 150°C or 5°C to 130°C. The monomer having a homopolymer glass transition temperature of 0°C or higher may be a monomer having an aromatic group, a monomer having a hydrophobic group, or a monomer having a hydroxyl group.

[0073] In this specification, the glass transition temperature of a monomer homopolymer refers to the glass transition temperature (Tg) measured for the monomer homopolymer under test using TA Instrument's DSC Discovery. Specifically, the temperature of the monomer homopolymer under test is raised to 180°C at a heating rate of 20°C / min, then gradually cooled to -100°C, and then heated to 100°C at a heating rate of 10°C / min. After obtaining data on the endothermic transition curve, the inflection point of the endothermic transition curve can be determined as the glass transition temperature.

[0074] The photocurable monomer includes a monomer having an aromatic group. The monomer having an aromatic group is included in the first adhesive layer composition to enhance the chemical resistance of the first adhesive layer and easily provide the residue-free effect of the second adhesive layer.

[0075] The photocurable monomer includes a monomer having a hydrophobic group. The monomer having a hydrophobic group can be included in the first adhesive layer composition to easily provide the residue-free effect of the second adhesive layer. Here, the hydrophobic group may be a non-aromatic group rather than an aromatic group.

[0076] The photocurable monomer includes a monomer having a hydroxyl group. The monomer having a hydroxyl group does not excessively increase the initial peeling force of the second adhesive layer on the adherend. If the initial peeling force of the second adhesive layer on the adherend is too high, the peeling force of the second adhesive layer on the adherend will remain high even after high-temperature treatment, and residue of the second adhesive layer may remain when it is removed from the adherend.

[0077] In one embodiment, the total amount of monomers having aromatic groups, monomers having hydrophobic groups, and monomers having hydroxyl groups may be present in the photocurable monomer at a concentration of 95% by weight or more, for example, 95% to 100% by weight, or 100% by weight, when the total weight of the photocurable monomer is considered to be 100%. Within this range, the effect of the first adhesive layer may be easily achieved.

[0078] The monomer having the aromatic group may be a monofunctional or multifunctional monomer having an aromatic group in the ester moiety. Here, the "aromatic group" may be a single-ring or heterocyclic functional group having 6 to 50 carbon atoms.

[0079] In one embodiment, the monomer having an aromatic group may include, but is not limited to, the compound of the following chemical formula 1. [ka] ...chemical formula 1

[0080] In the above chemical formula 1, R 1 R is a hydrogen or methyl group, s is an integer from 0 to 10, 2 is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms, and T is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkyleneoxy group having 1 to 6 carbon atoms.

[0081] In this specification, "substituted or unsubstituted" means that one or more hydrogen atoms are substituted with a C1-C10 alkyl group, a C1-C10 thioalkyl group, a C1-C10 alkoxy group, a halogen (F, Cl, Br or I), a C3-C10 cycloalkyl group, or a C6-C20 aryl group.

[0082] For example, the monomers having the aromatic group include phenoxybenzyl(meth)acrylate, biphenylmethyl(meth)acrylate, phenoxy(meth)acrylate, 2-ethylphenoxy(meth)acrylate, benzyl(meth)acrylate, phenyl(meth)acrylate, 2-ethylthiophenyl(meth)acrylate, 2-phenylethyl(meth)acrylate, 3-phenylpropyl(meth)acrylate, 4-phenylbutyl(meth)acrylate, and 2-(2-methylphenyl)ethyl(meth)acrylate. , 2-(3-methylphenyl)ethyl (meth)acrylate, 2-(4-methylphenyl)ethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth)acrylate, 2-(4-(1-methylethyl)phenyl)ethyl (meth)acrylate, 2-(4-methoxyphenyl)ethyl (meth)acrylate, 2-(4-cyclohexylphenyl)ethyl (meth)acrylate, 2-(2-chlorophenyl)ethyl (meth)acrylate, 2-(3-chlorophenyl)ethyl (meth)acrylate, 2-(4- Chlorophenyl)ethyl (meth)acrylate, 2-(4-bromophenyl)ethyl (meth)acrylate, 2-(3-phenylphenyl)ethyl (meth)acrylate, orthobiphenyl (meth)acrylate, metabiphenyl (meth)acrylate, parabiphenyl (meth)acrylate, 2,6-terphenyl (meth)acrylate, orthoterphenyl (meth)acrylate, metaterphenyl (meth)acrylate, paraterphenyl (meth)acrylate, 4-(4-methylphenyl)phenyl (meth)acrylate It may contain one or more of the following: 4-(2-methylphenyl)phenyl(meth)acrylate, 2-(4-methylphenyl)phenyl(meth)acrylate, 2-(2-methylphenyl)phenyl(meth)acrylate, 4-(4-ethylphenyl)phenyl(meth)acrylate, 4-(2-ethylphenyl)phenyl(meth)acrylate, 2-(4-ethylphenyl)phenyl(meth)acrylate, and 2-(2-ethylphenyl)phenyl(meth)acrylate, and may contain one or more of these individually or as a mixture of two or more.

[0083] Preferably, the monomer having the aromatic group may include one or more of phenoxybenzyl acrylate and biphenylmethyl (meth)acrylate.

[0084] The monomer having the aromatic group may be present in amounts of 30 to 100 parts by weight, for example, 30 to 80 parts by weight, 30 to 70 parts by weight, or 30 to 60 parts by weight, per 100 parts by weight of the (meth)acrylic binder. Within this range, the chemical resistance of the first adhesive layer is improved, and the effect of no residue from the second adhesive layer when peeling the semiconductor manufacturing adhesive sheet from the adherend can be easily provided.

[0085] The monomer having a hydroxyl group may contain one or more (meth)acrylic acid esters having one or more hydroxyl-substituted alkyl groups in the ester moiety. The detailed types of (meth)acrylic acid esters are the same as those described above.

[0086] Preferably, the monomer having a hydroxyl group may be one or more of 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate.

[0087] The monomer having a hydroxyl group may be present in amounts of 1 to 50 parts by weight, for example, 5 to 40 parts by weight, 5 to 30 parts by weight, or 5 to 25 parts by weight, per 100 parts by weight of the (meth)acrylic binder. Within this range, the effect of no residue from the second adhesive layer can be easily provided when peeling the adhesive sheet for semiconductor manufacturing from the adherend.

[0088] The monomer having the hydrophobic group may include one or more (meth)acrylic acid esters having a hydrophobic group in the ester moiety, and (meth)acrylic monomers having a morpholine group.

[0089] In one embodiment, the monomer having the hydrophobic group may include one or more (meth)acrylic acid esters and (meth)acryloylmorpholine having a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in the ester moiety. For example, the monomer having the hydrophobic group may include one or more bornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (meth)acryloylmorpholine.

[0090] The monomer having the hydrophobic group may be present in amounts of 1 to 50 parts by weight, for example, 5 to 40 parts by weight, 5 to 30 parts by weight, or 10 to 30 parts by weight, per 100 parts by weight of the (meth)acrylic binder. Within this range, the chemical resistance of the first adhesive layer is improved, and the effect of no residue from the second adhesive layer when peeling the semiconductor manufacturing adhesive sheet from the adherend can be easily provided.

[0091] In one embodiment, of a total of 100 parts by weight of the monomer having an aromatic group, the monomer having a hydroxyl group, and the monomer having a hydrophobic group, the monomer having an aromatic group may be present in 50 to 90 parts by weight, for example, 50 to 80 parts by weight; the monomer having a hydroxyl group may be present in 1 to 40 parts by weight, for example, 5 to 30 parts by weight; and the monomer having a hydrophobic group may be present in 5 to 40 parts by weight, for example, 10 to 40 parts by weight. Within this range, the chemical resistance of the first adhesive layer is improved, and it becomes easier to prevent residue from the second adhesive layer from remaining when peeling the semiconductor manufacturing adhesive sheet from the adherend.

[0092] The photocurable monomer may be present in amounts of 50 to 300 parts by weight, for example, 50 to 200 parts by weight, 50 to 100 parts by weight, or 50 to 90 parts by weight, per 100 parts by weight of the (meth)acrylic binder. Within this range, the effect of the first adhesive layer can be easily achieved.

[0093] Thermosetting agent The thermosetting agent can help to provide anchoring force for the first adhesive layer to the substrate film and peeling force for the first adhesive layer to the second adhesive layer by thermal curing the (meth)acrylic binder, thereby forming the matrix of the first adhesive layer.

[0094] The thermosetting agent may include one or more of the following: isocyanate-based curing agents, metal chelate-based curing agents, carbodiimide-based curing agents, aziridine-based curing agents, and epoxy-based curing agents. Preferably, the thermosetting agent may be an isocyanate-based curing agent alone.

[0095] The isocyanate-based curing agent may include two or more functional isocyanate-based curing agents, specifically two- to six-functional isocyanate-based curing agents. In one embodiment, the isocyanate-based curing agent may include one or more xylene diisocyanates, such as m-xylene diisocyanate; methylenebis(phenyl isocyanate), such as 4,4'-methylenebis(phenyl isocyanate); naphthalene diisocyanate; tolylene diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; or adducts thereof. For example, the adduct may be a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate, a trimethylolpropane adduct of xylene diisocyanate, an isocyanurate of tolylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, or an isocyanurate of isophorone diisocyanate. The isocyanate-based curing agent may contain one or more of the above compositions.

[0096] The thermosetting agent may be present in an amount exceeding 0 parts by weight but not exceeding 3 parts by weight per 100 parts by weight of the (meth)acrylic binder, for example, 0.001 parts by weight to 3 parts by weight, or 0.01 parts by weight to 2 parts by weight. Within this range, the reliability of the first adhesive layer can be improved.

[0097] Photoinitiator The photoinitiator acts during the photoirradiation step in the post-semiconductor manufacturing process described above, thereby photocuring the first adhesive layer. Photoirradiation of the first adhesive layer can increase the crosslinking density of the first adhesive layer and improve its chemical resistance.

[0098] The photoinitiator may include one or more photoradical initiators and cationic photoinitiators.

[0099] In one embodiment, the photoinitiator may include a photoinitiator having the maximum absorption wavelength within the irradiation wavelength range applied during the above-described light irradiation. For example, the photoinitiator may have the maximum absorption wavelength at a wavelength of 280 nm to 430 nm. Within this range, the photocuring effect of the binder can be obtained by light irradiation. Specifically, the photoinitiator may include, but is not limited to, phosphorus-based initiators, ketone-based initiators, etc.

[0100] The photoinitiator may be present in an amount greater than 0 parts by weight and less than or equal to 3 parts by weight per 100 parts by weight of the (meth)acrylic binder, for example, 0.05 parts by weight to 3 parts by weight, or 0.1 parts by weight to 3 parts by weight. Within this range, it is possible to provide a uniform curing effect of the (meth)acrylic binder by light irradiation and an effect of preventing a decrease in the transparency of the first adhesive layer due to the remaining amount of initiator.

[0101] The first adhesive layer composition may further contain additives typically found in adhesive layers. For example, these additives may include, but are not limited to, surfactants, heat stabilizers, light stabilizers, pigments, dispersants, and the like.

[0102] 2nd adhesive layer The second adhesive layer can be attached to the substrate in a post-semiconductor manufacturing process and then removed from the substrate.

[0103] The second adhesive layer may contain a (meth)acrylic binder having (meth)acrylate groups in its side chains, a silicon oligomer, a thermosetting agent, and a photoinitiator.

[0104] In one embodiment, the second adhesive layer may include a cured product of a composition comprising a (meth)acrylic binder having (meth)acrylate groups in its side chains, a silicon oligomer, a thermosetting agent, and a photoinitiator. In one embodiment, the cured product may be a thermosetting product.

[0105] The second adhesive layer may have a thickness of 5 μm to 300 μm, for example, 50 μm to 300 μm or 50 μm to 200 μm. Within this range, it can be used in the adhesive sheet and may have an excellent effect in protecting the adherend or the terminals formed on the adherend.

[0106] The second adhesive layer can be manufactured by coating the composition onto a release film (for example, the first release film described below) to a predetermined thickness, and then heat-curing it. The heat-curing may include, but is not limited to, treatment at 100°C to 150°C for 30 seconds to 10 minutes.

[0107] (meth)acrylic binder having (meth)acrylate groups in the side chain The binder has (meth)acrylate groups in its side chains. Therefore, the binder can be further cured by light irradiation as described in the post-semiconductor manufacturing process, which increases the crosslinking density and thus the chemical resistance of the second adhesive layer.

[0108] In one embodiment, the binder may contain the units of the following chemical formula 2. [ka] ...Chemical formula 2

[0109] In the above chemical formula 1, * represents the bonding site of an element, R,R 1 and R 2 Each of these is independently either a hydrogen atom or a methyl group, and L is a divalent organic group.

[0110] In the above Chemical Formula 2, L may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. In the above Chemical Formula 2, L may further have an amide group or an ester group.

[0111] In one embodiment, the binder may include a unit represented by the following Chemical Formula 2-1.

Chemical Formula

[0112] In the above Chemical Formula 2-1, * represents a bonding site of an element, and R, R 1 and R 2 are each independently hydrogen or a methyl group, L 12 is hydrogen, or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and L 11 and L 13 are each independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

[0113] For example, in the above Chemical Formula 2-1, L 11 and L 13 may each independently be a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.

[0114] The binder may have a higher weight average molecular weight than the oligomer. For example, the binder may have a weight average molecular weight of 100,000 g / mol or more, for example, 100,000 g / mol to 1,000,000 g / mol, or 100,000 g / mol to 800,000 g / mol. Within the above range, the second adhesive layer can be easily provided with peel force.

[0115] The binder may include a polymer of a monomer mixture containing a monomer having a (meth)acrylate group in its side chain. The monomer having a (meth)acrylate group in its side chain may include one or more of the following Chemical Formula 3.

Chemical Formula

[0116] In the aforementioned chemical formula 3, R 1 ,R 2 , and L are the same as those defined in chemical formula 2 above.

[0117] In the aforementioned chemical formula 3, L may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. In the aforementioned chemical formula 3, L may further have an amide group or an ester group.

[0118] In one embodiment, the monomer having a (meth)acrylate group in the side chain may include one or more of those shown in the following chemical formula 3-1. [ka] ...Chemical formula 3-1

[0119] In the aforementioned chemical formula 3-1, R 1 ,R 2 ,L 11 ,L 12 , and L 13 These are the same as those defined in the chemical formula 2-1 above.

[0120] For example, in the above chemical formula 3-1, L 11 and L 13 Each of these may independently be a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.

[0121] The binder may produce a prepolymer and may contain a reaction product of the prepolymer and a monomer having a (meth)acrylate group in its side chain. This can prevent side reactions from occurring during polymerization. For example, the monomer having a (meth)acrylate group in its side chain may be 2-isocyanate ethyl (meth)acrylate.

[0122] Specifically, the prepolymer may be a prepolymer of monomer mixtures containing (meth)acrylic acid esters having an alkyl group in the ester moiety, and (meth)acrylic acid esters having one or more hydroxyl-substituted alkyl groups in the ester moiety.

[0123] The (meth)acrylic acid ester having an alkyl group in the ester moiety may be an (meth)acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms in the ester moiety. The specific types of the (meth)acrylic acid ester are the same as those described above. For example, the (meth)acrylic acid ester may include one or more of 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methyl acrylate, and methyl methacrylate. The alkyl group-containing (meth)acrylic acid ester may be present in the monomer mixture for the prepolymer in an amount of 60 mol% to 95 mol%, for example, 70 mol% to 95 mol%, or 80 mol% to 95 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, the formation of the second adhesive layer may be facilitated.

[0124] The (meth)acrylic acid ester having one or more hydroxyl-substituted alkyl groups in the ester moiety may also be a (meth)acrylic acid ester having one or more hydroxyl-substituted C1-C10 alkyl groups in the ester moiety. The specific types of the (meth)acrylic acid ester are the same as those described above. For example, the (meth)acrylic acid ester may include one or more of 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate. The (meth)acrylic acid ester having hydroxyl-substituted alkyl groups may be present in the monomer mixture for the prepolymer in amounts of 5 mol% to 40 mol%, for example, 5 mol% to 30 mol%, or 5 mol% to 20 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, it is possible to provide initial tackiness for the second adhesive layer and reaction sites with monomers having (meth)acrylate groups in the side chains.

[0125] In one embodiment, the total of (meth)acrylic acid esters having an alkyl group in the ester moiety and (meth)acrylic acid esters having one or more hydroxyl-substituted alkyl groups in the ester moiety may be present in the monomer mixture for the prepolymer in an amount of 95 mol% or more, for example, 95 mol% to 100 mol%, or 100 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%.

[0126] The monomer having a (meth)acrylate group in the side chain may also be a monomer having a functional group that can react with the hydroxyl group. For example, the monomer may be 2-isocyanate ethyl (meth)acrylate.

[0127] In one embodiment, the monomer having a (meth)acrylate group in its side chain may be present in 1 to 10 parts by weight, for example, 1 to 5 parts by weight, per 100 parts by weight of the monomer mixture for the prepolymer. Within this range, the effect of the first adhesive layer may be facilitated.

[0128] The binder can be produced by manufacturing a prepolymer from a monomer mixture for the prepolymer, and by reacting the prepolymer with a monomer having a (meth)acrylate group in its side chain.

[0129] Silicon-based oligomers By containing silicon, the silicon-based oligomer can suppress the increase in peeling force of the second adhesive layer after high-temperature processing in the semiconductor manufacturing process.

[0130] In one embodiment, the silicon-based oligomer may have (meth)acrylate groups in its side chains. Therefore, by further curing the silicon-based oligomer with light irradiation as described in the post-semiconductor process, the crosslinking density of the second adhesive layer can be increased, thereby improving the chemical resistance of the second adhesive layer. The weight-average molecular weight of the oligomer may be 200,000 g / mol or less, for example, 10,000 g / mol to 200,000 g / mol or 10,000 g / mol to 100,000 g / mol.

[0131] The oligomer may include an oligomer or polymer of monomer mixtures.

[0132] The monomer mixture may contain a silicon-containing (meth)acrylate. The silicon-containing (meth)acrylate may contain one or more compounds of the following chemical formula 4. [ka] ...chemical formula 4

[0133] In the aforementioned chemical formula 4, R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 , and R 17 Each of these is independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted C5-C10 cycloalkyl group, and R 18 R is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. 19 is a hydrogen atom or a methyl group, and n is an integer greater than or equal to 1.

[0134] The aforementioned silicon-containing (meth)acrylate is manufactured by a conventional method known to those skilled in the art, or is a commercially available product.

[0135] The silicon-containing (meth)acrylate may be present in the monomer mixture in an amount of 0.01 mol% to 30 mol%, for example, 0.1 mol% to 20 mol%, 0.1 mol% to 10 mol%, or 0.1 mol% to 5 mol%, when the total amount of all monomers in the monomer mixture of the silicone oligomer is taken as 100 mol%. Within this range, the peeling force of the second adhesive layer can be ensured, and the increase in peeling force during high-temperature processes can be easily reduced.

[0136] The monomer mixture may further comprise a (meth)acrylic acid ester having an alkyl group in the ester moiety, and a (meth)acrylic acid ester having one or more hydroxyl-substituted alkyl groups in the ester moiety.

[0137] The (meth)acrylic acid ester having an alkyl group in the ester moiety may also be a (meth)acrylic acid ester having an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms in the ester moiety. The specific types of the (meth)acrylic acid ester are the same as those described above. For example, the (meth)acrylic acid ester may include one or more of 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate.

[0138] The alkyl group-containing (meth)acrylic acid ester may be present in the monomer mixture in an amount of 80 mol% to 99 mol%, for example, 85 mol% to 99 mol%, or 80 mol% to 95 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, the formation of the second adhesive layer may be facilitated.

[0139] The (meth)acrylic acid ester having one or more hydroxyl-substituted alkyl groups in the ester moiety may be a (meth)acrylic acid ester having one or more hydroxyl-substituted C1-C10 alkyl groups in the ester moiety. The specific types of the (meth)acrylic acid ester are the same as those described above. For example, the (meth)acrylic acid ester may contain one or more of 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.

[0140] The (meth)acrylic acid ester having a hydroxyl group-substituted alkyl group may be present in the monomer mixture in an amount of 0.1 mol% to 40 mol%, for example, 0.1 mol% to 10 mol%, or 0.1 mol% to 5 mol%, when the total monomers in the monomer mixture are considered to be 100 mol%. Within this range, it is possible to provide the initial tackiness of the second adhesive layer and to provide reaction sites with the monomer having a (meth)acrylate group in its side chain.

[0141] In one embodiment, the oligomer can be produced by polymerizing the monomer mixture.

[0142] In another embodiment, the oligomer can be produced by preparing a pre-oligomer from the monomer mixture and reacting the pre-oligomer with a monomer having a (meth)acrylate group in its side chain.

[0143] The monomer having a (meth)acrylate group in the side chain may also be a monomer having a functional group that can react with the hydroxyl group. For example, the monomer may be 2-isocyanate ethyl (meth)acrylate.

[0144] In one embodiment, the monomer having a (meth)acrylate group in its side chain may be present in 1 to 10 parts by weight, for example, 1 to 5 parts by weight, per 100 parts by weight of the monomer mixture for the oligomer. Within this range, the effect of the first adhesive layer may be facilitated.

[0145] The silicon oligomer may be present in amounts of 0.01 to 10 parts by weight, for example, 0.01 to 5 parts by weight, 0.1 to 5 parts by weight, or 0.5 to 3 parts by weight, per 100 parts by weight of the (meth)acrylic binder. Within this range, it is possible to prevent an increase in the peeling force of the second adhesive layer described above.

[0146] Thermosetting agent The thermosetting agent can help provide initial peeling force for the second adhesive layer by thermally curing the (meth)acrylic binder and the silicone oligomer to form the matrix of the second adhesive layer.

[0147] The thermosetting agent may include one or more of the following: isocyanate-based curing agents, metal chelating curing agents, carbodiimide-based curing agents, aziridine-based curing agents, and epoxy-based curing agents. Preferably, the thermosetting agent may be a mixture of an isocyanate-based curing agent and a metal chelating curing agent. The isocyanate-based curing agent is substantially the same as that described above. The metal chelating curing agent may include, but is not limited to, a chelating curing agent having aluminum, tin, etc.

[0148] The thermosetting agent may be present in an amount greater than 0 parts by weight and less than or equal to 3 parts by weight per 100 parts by weight of the (meth)acrylic binder, for example, 0.001 parts by weight to 3 parts by weight, or 0.01 parts by weight to 2 parts by weight. Within this range, the reliability of the second adhesive layer can be improved.

[0149] Photoinitiator The photoinitiator can improve the chemical resistance of the second adhesive layer to etching solutions by photocuring the (meth)acrylic binder and increasing the crosslinking density of the second adhesive layer. The photoinitiator is substantially the same as that described above.

[0150] The photoinitiator may be present in an amount greater than 0 parts by weight and less than or equal to 3 parts by weight per 100 parts by weight of the (meth)acrylic binder, for example, 0.05 parts by weight to 3 parts by weight, or 0.1 parts by weight to 3 parts by weight. Within this range, it is possible to provide a uniform curing effect of the (meth)acrylic binder by light irradiation and an effect of preventing a decrease in the transparency of the second adhesive layer due to the remaining amount of initiator.

[0151] The second adhesive layer composition may further contain conventional additives included in the adhesive layer. These additives may include, but are not limited to, antistatic agents, surfactants, dispersants, and release agents.

[0152] 3rd adhesive layer The third adhesive layer can be bonded to the glass plate in a post-processing step of semiconductor manufacturing and then removed from the glass plate.

[0153] The third adhesive layer may have a thickness of 1 μm to 100 μm, for example, 1 μm to 80 μm or 10 μm to 70 μm. Within this range, a high degree of support to the glass plate can be achieved, and the effect of making it easier to remove from the glass plate later can be obtained.

[0154] The third adhesive layer is not particularly limited as long as it has high peeling force to the base film and can be peeled off the glass plate after adhering to the glass plate by any process, for example, high-temperature treatment and / or light irradiation.

[0155] In one embodiment, the third adhesive layer may include a (meth)acrylic binder having (meth)acrylate groups in its side chains, a silicon oligomer, an oligomer with a high glass transition temperature, a thermosetting agent, and a photoinitiator.

[0156] In one embodiment, the third adhesive layer may include a cured product of a composition comprising a (meth)acrylic binder having (meth)acrylate groups in its side chains, a silicon oligomer, an oligomer with a high glass transition temperature, a thermosetting agent, and a photoinitiator. The cured product may be a thermosetting product.

[0157] The third adhesive layer can be manufactured by coating the composition onto a release film to a predetermined thickness and then heat-curing it. The heat-curing may include, but is not limited to, treatment at 100°C to 150°C for 30 seconds to 10 minutes.

[0158] The (meth)acrylic binder having a (meth)acrylate group in the side chain is substantially the same as that described above.

[0159] The aforementioned silicon-based oligomer is substantially the same as that described above.

[0160] The silicon oligomer may be present in amounts of 0.01 to 10 parts by weight, for example, 0.01 to 5 parts by weight, 0.1 to 5 parts by weight, or 0.5 to 3 parts by weight, per 100 parts by weight of the (meth)acrylic binder having (meth)acrylate groups in its side chains. Within this range, it is possible to prevent an increase in the peeling force of the third adhesive layer described above.

[0161] The oligomer with a high glass transition temperature can improve the chemical resistance of the third adhesive layer.

[0162] In one embodiment, the oligomer with a high glass transition temperature may have a glass transition temperature that is higher than that of the (meth)acrylic binder or the silicon oligomer.

[0163] In one embodiment, the oligomer with a high glass transition temperature may have a glass transition temperature of 10°C or higher. Within this range, the chemical resistance of the third adhesive layer may be improved. For example, the oligomer may have a glass transition temperature of 10°C to 50°C, for example, 10°C to 30°C or 10°C to 20°C.

[0164] The oligomer may have a weight-average molecular weight of 5,000 g / mol to 100,000 g / mol, for example, 10,000 g / mol to 100,000 g / mol or 50,000 g / mol to 100,000 g / mol. Within this range, the glass transition temperature can be easily reached without affecting the peeling force of the third adhesive layer.

[0165] The oligomer may be present in amounts less than 20 parts by weight per 100 parts by weight of the (meth)acrylic binder. Within this range, the chemical resistance can be improved without increasing the haze of the third adhesive layer. For example, the oligomer may be present in amounts of 1 to 15 parts by weight or 5 to 15 parts by weight per 100 parts by weight of the binder. Within this range, the chemical resistance of the third adhesive layer can be improved.

[0166] In one embodiment, the oligomer may be a non-silicone oligomer that does not contain silicon.

[0167] The oligomer can be produced by polymerizing a monomer mixture. The type and content of monomers in the monomer mixture can be appropriately controlled, as long as it has the glass transition temperature range.

[0168] The monomer mixture may include monomers whose homopolymer glass transition temperature is 20°C or higher. Monomers whose homopolymer glass transition temperature is 20°C or higher can easily reach the glass transition temperature of the oligomer. For example, the monomers may have homopolymer glass transition temperatures of 20°C to 110°C, for example, 50°C to 100°C.

[0169] In one embodiment, the monomer of the homopolymer having a glass transition temperature of 20°C or higher may include a (meth)acrylic acid ester having an alicyclic group in the ester moiety. When the (meth)acrylic acid ester having an alicyclic group in the monomer of the homopolymer having a glass transition temperature of 20°C or higher is combined with a (meth)acrylic binder having a (meth)acrylate group in the side chain and a silicon oligomer, as described below, the effect of the third adhesive layer can be enhanced.

[0170] The (meth)acrylic acid ester may be a (meth)acrylic acid ester having a substituted or unsubstituted alicyclic group having 6 to 20 carbon atoms in the ester moiety. For example, the (meth)acrylic acid ester may include one or more of isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and bornyl (meth)acrylate.

[0171] The (meth)acrylic acid ester may be present in the monomer mixture in an amount of 30 mol% or more. Within this range, the glass transition temperature of the oligomer can be easily reached.

[0172] The (meth)acrylic acid ester may be present in the monomer mixture in an amount of 30 mol% to 80 mol%, for example, 40 mol% to 80 mol%, or 40 mol% to 60 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, the glass transition temperature of the oligomer can be provided, and the initial tackiness of the third adhesive layer can be easily reached.

[0173] The monomer mixture may further comprise a comonomer polymerizable with the (meth)acrylic acid ester. The comonomer may include a (meth)acrylic acid ester having an alkyl group in the ester moiety, and a (meth)acrylic acid ester having one or more hydroxyl-substituted alkyl groups in the ester moiety.

[0174] The (meth)acrylic acid ester having an alkyl group in the ester moiety is substantially the same as that described above. For example, the (meth)acrylic acid ester may include one or more of 2-ethylhexyl acrylate and n-butyl acrylate. The (meth)acrylic acid ester may be present in the monomer mixture in amounts of 5 mol% to 30 mol%, for example, 5 mol% to 25 mol%, or 10 mol% to 25 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, the glass transition temperature of the oligomer can be provided, and the tackiness of the third adhesive layer can be easily reached.

[0175] The (meth)acrylic acid ester having one or more hydroxyl-substituted alkyl groups in the ester moiety is substantially the same as that described above. For example, the (meth)acrylic acid ester may be 2-hydroxyethyl methacrylate. The (meth)acrylic acid ester may be present in the monomer mixture in amounts of 5 mol% to 50 mol%, for example, 5 mol% to 40 mol%, or 10 mol% to 40 mol%, when the total amount of all monomers in the monomer mixture is 100 mol%. Within this range, the glass transition temperature of the oligomer can be provided, and the initial tackiness of the third adhesive layer can be easily reached.

[0176] In one embodiment, the total of (meth)acrylic acid esters having a substituted or unsubstituted alicyclic group having 6 to 20 carbon atoms in the ester moiety, (meth)acrylic acid esters having an alkyl group in the ester moiety, and (meth)acrylic acid esters having an alkyl group with one or more hydroxyl groups substituted in the ester moiety may be present in the monomer mixture in an amount of 95 mol% or more, for example, 95 mol% to 100 mol%, or 100 mol%, when the total amount of all monomers in the monomer mixture is taken as 100 mol%.

[0177] The oligomer can be produced by polymerizing the monomer mixture using a conventional polymerization method. The polymerization method may include conventional methods known to those skilled in the art. For example, the oligomer can be produced by conventional copolymer polymerization, such as suspension polymerization, emulsion polymerization, or solution polymerization, after adding an initiator to the monomer mixture. The polymerization temperature may be 60°C to 70°C, and the polymerization time may be 4 to 8 hours. Conventional initiators can be used, including azo polymerization initiators and / or peroxides such as benzoyl peroxide or acetyl peroxide.

[0178] The aforementioned thermosetting agent is substantially the same as the thermosetting agent described above.

[0179] The thermosetting agent may be present in an amount exceeding 0 parts by weight but not exceeding 3 parts by weight per 100 parts by weight of the (meth)acrylic binder, for example, 0.001 parts by weight to 3 parts by weight, or 0.01 parts by weight to 2 parts by weight. Within this range, the reliability of the third adhesive layer can be improved.

[0180] The aforementioned photoinitiator is substantially the same as the photoinitiator described above.

[0181] The photoinitiator may be present in an amount greater than 0 parts by weight and less than or equal to 3 parts by weight per 100 parts by weight of the (meth)acrylic binder, for example, 0.05 parts by weight to 3 parts by weight or 0.1 parts by weight to 3 parts by weight. Within this range, a uniform curing effect of the (meth)acrylic binder by light irradiation can be obtained, and an effect of preventing a decrease in the transparency of the third adhesive layer due to residual initiator can be provided.

[0182] First release film The first release film can protect the second adhesive layer from external foreign matter.

[0183] The first release film may include an optically transparent resin film. For example, the first release film may be the polyester resin film described above.

[0184] The first release film may include one or more silicone-based coating layers and fluorine-based coating layers on its surface to facilitate release from the second adhesive layer.

[0185] Second release film The second release film can protect the third adhesive layer from external foreign matter.

[0186] The second release film is substantially identical to the first release film.

[0187] Figures 1 and 2 are cross-sectional views of an adhesive sheet according to one embodiment.

[0188] Referring to Figure 1, the adhesive sheet may include a base film 10 and a first adhesive layer 20 laminated on the lower surface of the base film 10.

[0189] Referring to Figure 2, the adhesive sheet may include a base film 10, a first adhesive layer 20 laminated on the lower surface of the base film 10, a second adhesive layer 30 laminated on the lower surface of the first adhesive layer, and a third adhesive layer 40 laminated on the upper surface of the base film 10.

[0190] Referring to Figure 3, the adhesive sheet may include a base film 10, a first adhesive layer 20 laminated on the lower surface of the base film 10, a second adhesive layer 30 laminated on the lower surface of the first adhesive layer, a first release film 50 laminated on the lower surface of the second adhesive layer 30, a third adhesive layer 40 laminated on the upper surface of the base film 10, and a second release film 60 laminated on the upper surface of the third adhesive layer 40. [Examples]

[0191] Examples and comparative examples of the present invention are described below. However, the following examples are merely one embodiment of the present invention, and the present invention is not limited to these examples.

[0192] Example 1 (1) Manufacturing of a laminate of the first adhesive layer and the base film A monomer mixture containing 97 mol% n-butyl acrylate and 3 mol% 4-hydroxybutyl acrylate, along with 100 parts by weight of ethyl acetate as a solvent, was added to a 1 L reactor equipped with a cooling device for easy temperature control and reflux of nitrogen gas. After replacing the reactor with nitrogen gas for 1 hour to remove oxygen, the temperature was maintained at 62°C. After uniformly stirring the monomer mixture, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and the mixture was reacted for 8 hours to produce a (meth)acrylic binder with a weight-average molecular weight of 1,000,000 g / mol. Subsequently, the obtained binder solution was diluted with ethyl acetate to produce a (meth)acrylic binder solution with a solid content of 24% by weight.

[0193] In terms of solids content, 100 parts by weight of the manufactured (meth)acrylic binder, 0.5 parts by weight of TD-75 (Soken, NCO reactive curing agent, 75% solids) as a thermosetting agent, and 0.3 parts by weight of TPO (BASF) as a photoinitiator were mixed. Then, a mixture of photocurable monomers containing 50 parts by weight of 3-phenoxybenzyl acrylate (POBA) as an aromatic monomer, 10 parts by weight of 4-hydroxybutyl acrylate (4-HBA) as a hydroxyl monomer, and 20 parts by weight of isobornyl acrylate (IBXA) as a hydrophobic monomer was added, and the mixture was diluted with methyl ethyl ketone to make the total solids content of the first adhesive layer composition 25%.

[0194] The first adhesive layer composition prepared above was applied to a PEN (TOYOBO, Q8300, thickness: 25 μm) film that had been corona-treated on one side using an applicator, and the mixture was dried in a 110°C oven for 4 minutes to produce a laminate of the first adhesive layer (thickness: 25 μm) and the PEN film (thickness: 25 μm).

[0195] (2) Manufacturing of the second adhesive layer Ethyl acetate was added to a 1 L reactor equipped with a cooling device for easy temperature control and refluxing nitrogen gas. 100 parts by weight of a monomer mixture containing 75 mol% 2-ethylhexyl acrylate, 15 mol% methyl acrylate, and 10 mol% 4-hydroxybutyl acrylate was added to the reactor. To remove oxygen from the monomer mixture, nitrogen gas was introduced into the reactor for 30 minutes to purge it, and then the internal temperature of the reactor was maintained at 62°C. After uniformly stirring the monomer mixture, 0.07 parts by weight of AIBN was added as an initiator and the reaction was allowed to proceed for 8 hours. Ethyl acetate was added to produce a 30% by weight (meth)acrylic prepolymer solution. To 100 parts by weight of the resin solids of the obtained (meth)acrylic prepolymer solution, 4.5 parts by weight of 2-isocyanate ethyl methacrylate was added and reacted to obtain a (meth)acrylic binder having (meth)acrylate groups in the side chains (weight-average molecular weight: 100,000 g / mol).

[0196] Ethyl acetate was added to a 1 L reactor equipped with a cooling device for easy temperature control and refluxing nitrogen gas. 100 parts by weight of a monomer mixture containing 95 mol% 2-ethylhexyl acrylate, 4.5 mol% 4-hydroxybutyl acrylate, and 0.5 mol% silicon-based acrylate (KF-2012, Shin-etsu Co., Ltd.) was added to the reactor. To remove oxygen from the monomer mixture, nitrogen gas was introduced into the reactor for 30 minutes to purge it, and then the internal temperature of the reactor was maintained at 62°C. After uniformly stirring the monomer mixture, 0.07 parts by weight of AIBN was added as an initiator and the reaction was allowed to proceed for 8 hours. Ethyl acetate was added to produce a 30% by weight silicon-based pre-oligomer solution. To 100 parts by weight of the solid content of the obtained silicon-based pre-oligomer solution, 2 parts by weight of 2-isocyanate ethyl methacrylate were added and reacted to obtain a silicon-based oligomer having (meth)acrylate groups in its side chains (weight-average molecular weight: 80,000 g / mol).

[0197] Based on solid content, 100 parts by weight of the manufactured (meth)acrylic binder, 1 part by weight of the manufactured silicone oligomer, 0.7 parts by weight of isocyanate curing agent TD-75 and 0.5 parts by weight of metal chelate curing agent BXX-4805 as thermosetting agents, and 0.1 parts by weight of TPO-L as a photoinitiator were added and stirred to produce a composition for the second adhesive layer.

[0198] The manufactured second adhesive layer composition was applied to one side of a release-treated polyethylene terephthalate film (first release film) to a thickness of 100 μm using an applicator, and dried in an oven at 110°C for 5 minutes to produce a second adhesive layer with a thickness of 100 μm.

[0199] (3) Manufacturing of the third adhesive layer (2) Similarly, a (meth)acrylic binder having (meth)acrylate groups in the side chain was prepared.

[0200] (2) A silicon-based oligomer was manufactured in the same manner as in (2).

[0201] Ethyl acetate was added to a 1 L reactor equipped with a cooling device for easy temperature control and refluxing nitrogen gas. 100 parts by weight of a monomer mixture containing 20 mol% 2-ethylhexyl acrylate, 50 mol% isobornyl acrylate (IBXA), and 30 mol% 2-hydroxyethyl methacrylate (2-HEMA) was added to the reactor. To remove oxygen from the monomer mixture, nitrogen gas was introduced into the reactor for 30 minutes to purge it, and then the internal temperature of the reactor was maintained at 62°C. After uniformly stirring the monomer mixture, 0.07 parts by weight of AIBN was added as an initiator, and the mixture was reacted for 8 hours to produce an oligomer with a high glass transition temperature. The molecular weight of the oligomer, measured using GPC, was 80,000 g / mol, and the glass transition temperature was 15°C.

[0202] Based on solid content, 100 parts by weight of the manufactured (meth)acrylic binder, 1 part by weight of the manufactured silicon oligomer, 5 parts by weight of the manufactured oligomer with a high glass transition temperature, 0.7 parts by weight of isocyanate curing agent TD-75 and 0.5 parts by weight of metal chelating curing agent BXX-4805 as thermosetting agents, and 0.1 parts by weight of TPO-L as a photoinitiator were added and stirred to produce a composition for the third adhesive layer.

[0203] The manufactured third adhesive layer composition was applied to one surface of a release-treated polyethylene terephthalate film (second release film) to a thickness of 25 μm using an applicator, and dried in an oven at 110°C for 5 minutes to produce a third adhesive layer with a thickness of 25 μm.

[0204] (4) Manufacturing of adhesive sheets In a laminate of the PEN film manufactured in (1) and the first adhesive layer, the second adhesive layer and the first release film manufactured in order were bonded to the first adhesive layer, and the third adhesive layer and the second release film manufactured in order were bonded to the PEN film, thereby manufacturing an adhesive sheet laminated in the order of second release film - third adhesive layer - PEN film - first adhesive layer - second adhesive layer - first release film.

[0205] Examples 2-3 In Example 1, an adhesive sheet was manufactured using the same method as in Example 1, except that the composition of the first adhesive layer composition was changed as shown in Table 1 below.

[0206] Comparative Examples 1 to 6 In Example 1, an adhesive sheet was manufactured using the same method as in Example 1, except that the composition of the first adhesive layer composition was changed as shown in Table 1 below.

[0207] The following physical properties were evaluated using the semiconductor manufacturing adhesive sheets produced in the examples and comparative examples.

[0208] (1) Anchor force (unit: gf / inch): One side of polyethylene terephthalate (PET) film is 100 W / m / m 2 Corona treatment was performed under (Does power) conditions. The corona-treated PET film and the laminates of the first adhesive layer and PEN produced according to the examples and comparative examples were bonded together and left at room temperature for 30 minutes to produce a laminate in which the PET film, first adhesive layer, and PEN film were laminated in that order. The produced laminate was cut to a size of 25 mm x 200 mm in width x length to produce test pieces, and the peel force when the first adhesive layer was peeled from the PET film was measured using a tensile testing machine (Texture Analyzer, TA Industry) at 25°C with a peeling speed of 300 mm / min and a peeling angle of 180°, in accordance with JIS Z 2037.

[0209] After irradiating the aforementioned specimen with 2000 mJ of UV light through a UV exposure machine (UV irradiation with a wavelength of 395 nm), the peeling force was measured using the same method as described above.

[0210] (2) Chemical resistance: The first release film was removed from the adhesive sheets manufactured in the examples and comparative examples, and the second adhesive layer was bonded to a 4-inch silicon wafer using a mounter. The wafers were then irradiated with 2000 mJ of UV light through a UV exposure machine (wavelength 395 nm) and immersed in either the solution under condition 1) or condition 2) below. Microscopic examination was performed to check for diluent penetration between the first and second adhesive layers, or for any lifting of the first adhesive layer. The evaluation was OK if there was no diluent penetration or lifting, and NG if there was diluent penetration and / or lifting. Condition 1) NMP (N-methyl-2-pyrrolidone), 15 minutes at 70°C Condition 2) DMSO (dimethyl sulfoxide), 15 minutes at 70°C

[0211] (3) Peeling force (unit: gf / inch): (i) Preparation of specimens: The adhesive sheets of the examples and comparative examples were cut to a size of 25 mm x 200 mm in width x length to prepare specimens. The first release film was peeled off at 23°C and 50% relative humidity to expose the second adhesive layer. The exposed second adhesive layer was pressed onto a silicon wafer using a 2 kg roller to prepare specimens. After preparing the specimens, they were left at 23°C and 50% relative humidity for 30 minutes.

[0212] (ii) Initial peel force: For the specimens described above, the peel force was evaluated using a tensile testing machine (Texture Analyzer, TA Industry) in accordance with JIS Z 2037, when the second adhesive layer was peeled from the silicon wafer at 25°C, a peeling speed of 300 mm / min, and a peeling angle of 180°.

[0213] (iii) Peeling force after pre-UV treatment: The specimens were irradiated with 2000 mJ of UV light through a UV exposure machine (wavelength 395 nm). Based on JIS Z 2037, the peeling force was evaluated when the second adhesive layer was peeled from the silicon wafer at 25°C, a peeling speed of 300 mm / min, and a peeling angle of 180° using a tensile testing machine (Texture Analyzer, TA Industry).

[0214] (iv) Peeling force after high-temperature process: After manufacturing the specimens, they were irradiated with 2000 mJ of UV light through a UV exposure machine (wavelength 395 nm). The specimens were then left in an oven at 200°C for 60 minutes. In accordance with JIS Z 2037, the peeling force was evaluated when the second adhesive layer was peeled from the silicon wafer at 25°C with a peeling speed of 300 mm / min and a peeling angle of 180° using a tensile testing machine (Texture Analyzer, TA Industry).

[0215] (4) Residue after peeling After preparing the specimens according to (i) of (3), they were irradiated with 2000 mJ of UV light through a UV exposure machine (wavelength 395 nm). Then, the specimens were left in an oven at 200°C for 60 minutes, and then left at 23°C and 50% relative humidity for 30 minutes before the silicon wafer was peeled off the second adhesive layer. The silicon wafer was evaluated as follows: × if there was no residue of the second adhesive layer, △ if there was a small amount of residue of the second adhesive layer, and ○ if there was a large amount of residue of the second adhesive layer.

[0216] [Table 1]

[0217] Table 1: POBA: Phenoxybenzyl acrylate, 4-HBA: 4-hydroxybutyl acrylate, IBXA: Isobornyl acrylate, ACMO: Acryloylmorpholine, DCPA: Dicyclopentenyl acrylate

[0218] As shown in Table 1, the adhesive sheet of the example can adhere to the substrate film with high reliability due to its high initial anchoring force, and its high anchoring force after pre-UV treatment may be advantageous in improving chemical resistance. As shown in Table 1, the adhesive sheet of the example showed high chemical resistance under all two evaluation conditions. As shown in Table 1, the adhesive sheet of the example has the effect of eliminating residue in the second adhesive layer after peeling off the silicon wafer.

[0219] On the other hand, as shown in Table 1 above, the adhesive sheets of the comparative examples have poor chemical resistance, and residue remains in the second adhesive layer after peeling off the silicon wafer, which can reduce the reliability of the semiconductor manufacturing process.

[0220] Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto and can be implemented in various ways within the scope of the claims, the detailed description of the invention, and the accompanying drawings, and it is clear that these also fall within the scope of the present invention.

Claims

1. Substrate film, and The base film includes a first adhesive layer laminated on the first surface, The aforementioned base film is a polyethylene naphthalate film. The first adhesive layer comprises a (meth)acrylic binder, a photocurable monomer, a thermosetting agent, and a photoinitiator. The photocurable monomer comprises a mixture of monomers having aromatic groups, monomers having hydrophobic groups, and monomers having hydroxyl groups, in an adhesive sheet.

2. The adhesive sheet according to claim 1, wherein the monomer having the aromatic group comprises a compound of the following chemical formula 1. 【Chemistry 1】 ...Chemical formula 1 (In the above chemical formula 1, R １ is a hydrogen or methyl group, s is an integer between 0 and 10. R ２ This is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 50 carbon atoms. T is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted alkylene oxy group having 1 to 6 carbon atoms.

3. The adhesive sheet according to claim 1, wherein the monomer having the aromatic group comprises one or more phenoxybenzyl (meth)acrylate and biphenylmethyl (meth)acrylate.

4. The adhesive sheet according to claim 1, wherein the monomer having the aromatic group is contained in an amount of 30 to 100 parts by weight per 100 parts by weight of the (meth)acrylic binder.

5. The adhesive sheet according to claim 1, wherein the monomer having a hydrophobic group comprises one or more (meth)acrylic acid esters having a hydrophobic group in the ester moiety, and (meth)acrylic monomers having a morpholine group.

6. The adhesive sheet according to claim 5, wherein the monomer having a hydrophobic group comprises one or more isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (meth)acryloylmorpholine.

7. The adhesive sheet according to claim 1, wherein the monomer having the hydrophobic group is contained in an amount of 1 to 50 parts by weight per 100 parts by weight of the (meth)acrylic binder.

8. The adhesive sheet according to claim 1, wherein the monomer having a hydroxyl group is contained in an amount of 1 to 50 parts by weight per 100 parts by weight of the (meth)acrylic binder.

9. The adhesive sheet according to claim 1, wherein in a total of 100 parts by weight of the monomer having an aromatic group, the monomer having a hydroxyl group, and the monomer having a hydrophobic group, the monomer having an aromatic group is present in an amount of 50 to 90 parts by weight, the monomer having a hydroxyl group is present in an amount of 1 to 40 parts by weight, and the monomer having a hydrophobic group is present in an amount of 5 to 40 parts by weight.

10. The adhesive sheet according to claim 1, wherein one or more of the monomer having an aromatic group, the monomer having a hydrophobic group, and the monomer having a hydroxyl group have a homopolymer glass transition temperature of 0°C or higher.

11. The adhesive sheet according to claim 1, wherein the photocurable monomer is contained in an amount of 50 to 300 parts by weight per 100 parts by weight of the (meth)acrylic binder.

12. The adhesive sheet according to claim 1, wherein the total amount of the monomer having an aromatic group, the monomer having a hydrophobic group, and the monomer having a hydroxyl group is contained in the photocurable monomer in an amount of 95% by weight or more.

13. The adhesive sheet according to claim 1, wherein the (meth)acrylic binder is a copolymer of monomer mixtures containing a (meth)acrylic acid ester having an alkyl group in the ester moiety and a (meth)acrylic acid ester having one or more alkyl groups substituted with hydroxyl groups in the ester moiety.

14. The first adhesive layer is 100 parts by weight of the (meth)acrylic binder, 50 to 300 parts by weight of the aforementioned photocurable monomer, The aforementioned thermosetting agent is more than 0 parts by weight and 3 parts by weight or less, and The adhesive sheet according to claim 1, comprising more than 0 parts by weight and 3 parts by weight or less of the photoinitiator.

15. The adhesive sheet according to claim 1, further comprising a second adhesive layer laminated on the lower surface of the first adhesive layer and a third adhesive layer laminated on the upper surface of the base film.

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