Adhesive composition

Abstract

To provide an adhesive composition for laminating a support and a device layer, capable of forming an adhesive layer in which deformation due to external force is suppressed and adhesion with the device layer is enhanced.SOLUTION: An adhesive composition for forming a second adhesive layer in a laminate 100 in which a support 12, a first adhesive layer 3A, a second adhesive layer 3B, and a device layer 45 are laminated in this order, the adhesive composition containing a block copolymer having a first block and a second block, in which the first block is a block constituted by a polymer having a repeating structure of a constituent unit (u1) derived from norbornene which may have substituents, and a modulus of elasticity at 260 °C is greater than or equal to 20MPa.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition for forming a second adhesive layer in a laminate in which a support, a first adhesive layer, a second adhesive layer, and a device layer are laminated in this order. [Background technology]

[0002] Semiconductor packaging technology not only protects IC chips from external impacts, but also allows for versatile semiconductor products to be created by using different chip placement methods and various wiring processing methods. One example of semiconductor packaging technology is fan-out technology, which is being developed as a method to achieve higher integration, thinner, and smaller semiconductor packages, for example, through its application to fan-out panel level packages (PLPs), which package semiconductor elements arranged on a panel.

[0003] In order to miniaturize semiconductor packages, it is important to reduce the thickness of the substrate in which the device is incorporated. However, reducing the thickness of the substrate reduces its strength, making the substrate more susceptible to damage during semiconductor package manufacturing. To address this issue, a known technique involves temporarily bonding the substrate to a support using an adhesive to create a laminate, processing the substrate, and then separating the substrate from the support. When bonding a substrate and a support, adhesive compositions containing a polymer having a cycloolefin structure have conventionally been widely used as temporary bonding agents because of their excellent light transmittance. Patent Document 1 discloses an adhesive composition containing a polymer having a cycloolefin structure to which an alkoxysilyl group is bonded. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-070766 Summary of the Invention [Problem to be solved by the invention]

[0005] In the manufacture of semiconductor packages, high-temperature processes such as sealing and thermal compression bonding (TCB) are performed to bond a substrate (device layer) to a support via an adhesive. In such high-temperature processes, the device layer is aligned and mounted on the support, and simultaneously high heat and pressure are applied to melt the solder and press it against the terminals of the support, thereby bonding the device layer to the support via an adhesive layer. However, when an adhesive layer formed using a conventional adhesive composition is used, problems arise, such as warpage of the device layer after the high-temperature process, deformation of the adhesive layer due to pressure, or peeling of the device layer.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive composition for bonding a support and a device layer, which is capable of forming an adhesive layer that is suppressed from deformation due to external forces and has improved adhesion to the device layer. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention employs the following configuration. That is, one aspect of the present invention is an adhesive composition for forming a second adhesive layer in a laminate in which a support, a first adhesive layer, a second adhesive layer, and a device layer are laminated in this order, the adhesive composition containing a block copolymer having a first block and a second block, the first block being a block composed of a polymer consisting of a repeating structure of structural unit (u1) derived from norbornene which may have a substituent, and exhibiting an elastic modulus at 260°C of 20 MPa or more. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an adhesive composition for bonding a support and a device layer, which is capable of forming an adhesive layer that is suppressed from deformation due to external forces and has improved adhesion to the device layer. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a laminate. [Figure 2A] FIG. 1 is a schematic diagram illustrating a state when a conventional laminate is used in a TCB process. [Figure 2B] 1A and 1B are schematic diagrams illustrating the state when the laminate of this embodiment is used in a TCB process. [Figure 3] FIG. 10 is a cross-sectional view showing another embodiment of the laminate. [Figure 4A] FIG. 2 is a schematic diagram showing a state in which light is irradiated onto the laminate from the support side. [Figure 4B] FIG. 2 is a schematic diagram showing a state in which the support base is separated from the laminate. [Figure 4C] FIG. 2 is a schematic diagram showing a state in which the first adhesive layer, the second adhesive layer, and the separation layer have been washed away from the device layer. DETAILED DESCRIPTION OF THE INVENTION

[0010] In this specification and claims, the term "aliphatic" is defined as a relative concept to aromatic, and refers to groups, compounds, etc. that do not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. A "halogenated alkyl group" is an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine, and iodine atoms. The term "fluorinated alkyl group" or "fluorinated alkylene group" refers to an alkyl group or alkylene group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrases "may have a substituent" or "may have a substituent" include both cases where a hydrogen atom (-H) is replaced with a monovalent group and cases where a methylene group (-CH-) is replaced with a divalent group. The term "exposure" is a general concept that includes irradiation with radiation.

[0011] The term "structural unit derived from styrene" refers to a structural unit formed by cleavage of the ethylenic double bond of styrene. The term "structural unit derived from a styrene derivative" refers to a structural unit formed by cleavage of the ethylenic double bond of a styrene derivative. The term "styrene derivative" refers to a styrene in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof. Examples of such derivatives include styrene in which the hydrogen atom at the α-position may be substituted with a substituent, but the hydrogen atom of the hydroxyl group is substituted with an organic group; and styrene in which the hydrogen atom at the α-position may be substituted with a substituent, but a substituent other than a hydroxyl group is bonded to the benzene ring. Unless otherwise specified, the α-position (the carbon atom at the α-position) refers to the carbon atom to which the benzene ring is bonded. Examples of the substituent that substitutes the hydrogen atom at the α-position of styrene include the same as those exemplified as the substituent at the α-position in the above-mentioned α-substituted acrylic ester.

[0012] The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specific examples thereof include alkyl groups having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc.). Specific examples of the halogenated alkyl group as a substituent at the α-position include groups in which some or all of the hydrogen atoms of the above-mentioned "alkyl group as a substituent at the α-position" have been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being particularly preferred. Specific examples of the hydroxyalkyl group as the substituent at the α-position include groups in which some or all of the hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α-position" have been substituted with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

[0013] The molecular weight of the resin component is determined by polystyrene-equivalent weight average molecular weight (Mw) determined by GPC (gel permeation chromatography). The glass transition point (Tg) of the resin component is a value measured by a dynamic mechanical analysis (DMA) device.

[0014] (Adhesive composition) An adhesive composition according to one aspect of the present invention is an adhesive composition for forming a second adhesive layer in a laminate having a support, a first adhesive layer, a second adhesive layer, and a device layer laminated in this order. One embodiment of the adhesive composition contains a block copolymer having a first block and a second block.

[0015] FIG. 1 shows one embodiment of a laminate to which the adhesive composition according to this embodiment is applied. The laminate 100 shown in FIG. 1 includes a support 12, a first adhesive layer 3A, a second adhesive layer 3B, and a device layer 45 laminated in this order. The support 12 includes a support base 1 and a separation layer 2. The separation layer 2 and the first adhesive layer 3A are provided adjacent to each other. The device layer 45 includes a substrate 4 and an encapsulant layer 5. The substrate 4 is provided on the second adhesive layer 3B and is encapsulated between the second adhesive layer 3B and the encapsulant layer 5. The second adhesive layer 3B is formed using the adhesive composition of this embodiment, which prevents the laminate 100 from being deformed by an external force during high-temperature treatment and improves adhesion to the device layer.

[0016] The adhesive composition of this embodiment exhibits a modulus of elasticity of 20 MPa or more at 260° C. When the adhesive composition has a modulus of elasticity at 260° C. that is equal to or greater than the lower limit of the above range, the adhesive layer formed from the adhesive composition is less likely to deform due to an external force. The adhesive composition of this embodiment has a modulus of elasticity at 260°C of 20 MPa or more, preferably 25 MPa or more, and more preferably 30 MPa or more. The upper limit of the elastic modulus at 260°C of the adhesive composition of this embodiment is substantially less than 100 MPa, and may be 90 MPa or less.

[0017] Method for measuring elastic modulus at 260°C: The elastic modulus of the adhesive composition at 260°C is measured as follows. An adhesive layer with a thickness of 50 μm is formed on a silicon wafer. A test piece (film thickness 50 μm, width 5 mm, length 40 mm) of the adhesive layer is cut out, and the tensile modulus is measured using a dynamic viscoelasticity measuring device at a frequency of 1 Hz in the range of 50 to 300° C. The measured value at 260° C. is the modulus at 260° C.

[0018] The adhesive composition of this embodiment preferably exhibits a membrane stress of 20 MPa or less, more preferably 15 MPa or less, even more preferably 10 MPa or less, and particularly preferably 5 MPa or less. When the film stress of the adhesive composition is equal to or less than the upper limit of the above-mentioned preferred range, the adhesive layer formed from the adhesive composition is less likely to deform due to an external force, and the adhesion to the device layer is likely to be improved. The lower limit of the film stress of the adhesive composition of this embodiment is substantially 1 MPa or more, and may be 2 MPa or more.

[0019] <Block copolymer (BCP component)> The adhesive composition of this embodiment contains a block copolymer having a first block and a second block. The first block is a block composed of a polymer having a repeating structure of structural units (u1) derived from norbornene, which may have a substituent.

[0020] A block copolymer is a polymer formed by combining multiple types of blocks (partial constituent components in which the same type of structural unit is repeatedly bonded). The number of blocks constituting a block copolymer may be two, three or more. One embodiment of the block copolymer (hereinafter also referred to as "(BCP) component") is a block copolymer (BCP12) having a first block and a second block. Another embodiment of the block copolymer is a block copolymer (BCP123) having a first block, a second block, and a third block. The weight average molecular weight (Mw) of the (BCP) component is, for example, 10,000 or more and 700,000 or less.

[0021] <Block 1> The first block is a block composed of a polymer having a repeating structure of a structural unit (u1) derived from norbornene which may have a substituent. Examples of the substituent that norbornene may have include alkyl groups having 1 to 16 carbon atoms, preferably alkyl groups having 1 to 12 carbon atoms, and more preferably alkyl groups having 6 to 12 carbon atoms. The structural unit (u1) is preferably a structural unit derived from unsubstituted norbornene.

[0022] Specific examples of the structural unit (u1) are shown below.

[0023] [ka]

[0024] The glass transition point (Tg) of the polymer constituting the first block is, for example, 200 to 300°C, and preferably 220 to 270°C.

[0025] <Block 2> The second block is composed of a polymer that exhibits an elastic modulus of 20 MPa or more at 260°C when an adhesive composition containing the block copolymer (BCP12) bonded to the first block forms an adhesive layer with a thickness of 50 μm. For example, the second block is preferably a block composed of a polymer consisting of a repeating structure of a structural unit (u2) derived from norbornene which may have a substituent and which has a structure different from that of the structural unit (u1). Examples of the structural unit in the second block that is derived from norbornene and that may have a substituent include the same structural units as those described above for the structural unit (u1).

[0026] The glass transition point (Tg) of the polymer constituting the second block is, for example, 100 to 180°C, and preferably 120 to 170°C.

[0027] <Block 3> The third block is composed of a polymer that exhibits an elastic modulus of 20 MPa or more at 260°C when an adhesive composition containing a block copolymer (BCP123) bonded to the first block and the second block forms an adhesive layer with a thickness of 50 μm. For example, the third block is preferably a block composed of a polymer consisting of a repeating structure of a structural unit (u3) derived from norbornene which may have a substituent. Examples of the structural unit (u3) in the third block include the same structural units as the structural unit (u1). Of these, the structural unit (u3) is preferably a structural unit derived from unsubstituted norbornene. The structural unit (u3) may have the same structure as the structural unit (u1), or may have a structure different from that of the structural unit (u1).

[0028] The glass transition point (Tg) of the polymer constituting the third block is, for example, 200 to 300°C, and preferably 220 to 270°C.

[0029] The block copolymer (BCP12) having a first block and a second block is preferably a block copolymer in which the first block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from unsubstituted norbornene as the structural unit (u1), and the second block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from norbornene having, as the structural unit (u2), an alkyl group having 1 to 16 carbon atoms (preferably 1 to 12 carbon atoms) as a substituent.

[0030] Specific examples of combinations of the first block and the second block are shown below: R is an alkyl group having 1 to 12 carbon atoms.

[0031] [ka]

[0032] In the block copolymer (BCP12), the molar ratio of the first block to the second block (first block / second block) is preferably 40 / 60 to 75 / 25, more preferably 45 / 55 to 70 / 30, and even more preferably 50 / 50 to 60 / 40. The weight average molecular weight of the block copolymer (BCP12) is, for example, from 10,000 to 700,000, and preferably from 50,000 to 600,000. The difference between the glass transition point of the polymer constituting the first block and the glass transition point of the polymer constituting the second block is preferably 50°C or more, more preferably 80 to 120°C.

[0033] The block copolymer (BCP123) having a first block, a second block, and a third block is preferably a block copolymer in which the first block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from unsubstituted norbornene as the structural unit (u1), the second block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from norbornene having, as the structural unit (u2), an alkyl group having 1 to 16 carbon atoms (preferably 1 to 12 carbon atoms) as a substituent, and the third block is a block composed of a polymer consisting of a repeating structure of a structural unit derived from unsubstituted norbornene as the structural unit (u3).

[0034] Specific examples of combinations of the first block, second block, and third block are shown below: R is an alkyl group having 1 to 12 carbon atoms.

[0035] [ka]

[0036] In the block copolymer (BCP123), the molar ratio of the first block to the second block to the third block (first block / second block) is preferably 40 / 60 to 75 / 25, more preferably 45 / 55 to 70 / 30, and even more preferably 50 / 50 to 60 / 40. In the block copolymer (BCP123), the molar ratio of the first block to the third block (first block / third block) is preferably 30 / 70 to 70 / 30, more preferably 40 / 60 to 60 / 40, and even more preferably 45 / 55 to 55 / 45.

[0037] The weight average molecular weight of the block copolymer (BCP123) is, for example, from 10,000 to 700,000, and preferably from 50,000 to 600,000. The difference between the glass transition point of the polymer constituting the first block and the glass transition point of the polymer constituting the second block is preferably 50°C or more, more preferably 80 to 120°C. The difference between the glass transition point of the polymer constituting the third block and the glass transition point of the polymer constituting the second block is preferably 50°C or more, more preferably 80 to 120°C.

[0038] In the adhesive composition of the present embodiment, the (BCP) component may be used alone or in combination of two or more types. The content of the (BCP) component in the adhesive composition of this embodiment is preferably 5 to 25 mass %, and more preferably 10 to 20 mass %, relative to the total amount (100 mass %) of the adhesive composition. In the adhesive composition of this embodiment, the content of the (BCP) component is preferably 90 to 99 mass %, and more preferably 92 to 97 mass %, relative to the total amount (100 mass %) of solids (the sum of all blended components excluding the solvent component from the entire adhesive composition).

[0039] The (BCP) component can be produced by a method of synthesizing the polymers constituting each block and then polymerizing them, or by a method of continuously polymerizing monomers to elongate the polymer, and can be produced by appropriately using a block copolymer synthesis method (radical polymerization, ionic polymerization, etc.).

[0040] <Other ingredients> The adhesive composition of the present embodiment may further contain other components in addition to the above-mentioned (BCP) component. Examples of such other components include resin components other than the (BCP) component, antioxidants, polymerization inhibitors, polymerization initiators, solvent components, plasticizers, adhesive aids, stabilizers, colorants, surfactants, and the like.

[0041] Resin components other than (BCP) components Examples of resin components other than the (BCP) component include cycloolefin polymers, acrylic resins, and elastomers.

[0042] Cycloolefin polymer Suitable examples of the cycloolefin polymer include a ring-opening polymer of a monomer component containing a cycloolefin monomer, and an addition polymer obtained by addition polymerization of a monomer component containing a cycloolefin monomer.

[0043] Examples of cycloolefin monomers include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and hydroxydicyclopentadiene, tetracyclic compounds such as tetracyclododecene, pentacyclic compounds such as cyclopentadiene trimer, heptacyclic compounds such as tetracyclopentadiene, and alkyl (methyl, ethyl, propyl, butyl, etc.) substituted compounds, alkenyl (vinyl, etc.) substituted compounds, alkylidene (ethylidene, etc.) substituted compounds, or aryl (phenyl, tolyl, naphthyl, etc.) substituted compounds of these polycyclic compounds.

[0044] Among the above, polymers having structural units derived from a monomer having a norbornene structure selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted derivatives thereof are particularly preferred. By using such a cycloolefin polymer having a norbornene structure, it becomes easier to obtain an adhesive composition that can form an adhesive layer that has high chemical resistance to resist solvents and is easily dissolved and removed in a hydrocarbon solvent.

[0045] The cycloolefin polymer may have, as a monomer unit, a monomer copolymerizable with the cycloolefin monomer. Suitable examples of such copolymerizable monomers include alkene monomers, which may be linear or branched and have 2 to 10 carbon atoms, and are preferably α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene, with ethylene being more preferred as the monomer unit.

[0046] Alternatively, the cycloolefin polymer may have, as a monomer unit, a structural unit represented by the following general formula (p1-1) (hereinafter also referred to as "structural unit (p1)"), a structural unit represented by the following general formula (p1-2) (hereinafter also referred to as "structural unit (p2)"), a structural unit derived from a monomer containing a maleimide skeleton (hereinafter also referred to as "structural unit (p3)"), etc. By using a cycloolefin polymer having such a monomer unit in combination, it becomes easier to obtain, for example, an adhesive composition that can form an adhesive layer that has high chemical resistance to resist solvents and is easily dissolved and removed in hydrocarbon solvents.

[0047] [ka] [In the formula, R u11 ~R u14 each independently represents an organic group having 1 to 30 carbon atoms or a hydrogen atom. u11 ~R u14 At least one of the groups is an organic group containing an alkoxysilyl group, and n is an integer of 0 to 2.]

[0048] In the formula (p1-1), R u11 ~R u14 Examples of the organic group in the formula (I) include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an organic group having a carboxy group, and an organic group having a heterocycle. R u11 ~R u14 The alkyl group in is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. R u11 ~R u14 Examples of the alkenyl group in the formula (I) include an allyl group, a pentenyl group, and a vinyl group. R u11 ~R u14The alkynyl group in the formula (I) includes, for example, an ethynyl group. R u11 ~R u14 Examples of the alkylidene group in the formula include a methylidene group and an ethylidene group. R u11 ~R u14 Examples of the aryl group in the formula (I) include a phenyl group, a naphthyl group, and an anthracenyl group. R u11 ~R u14 Examples of the aralkyl group in the formula include a benzyl group and a phenethyl group. R u11 ~R u14 Examples of the alkaryl group in the formula include a tolyl group and a xylyl group. R u11 ~R u14 Examples of the cycloalkyl group in the above formula include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. R u11 ~R u14 In the above formula, examples of the organic group having a hetero ring include an organic group having an epoxy group and an organic group having an oxetanyl group.

[0049] R u11 ~R u14 The organic group in is preferably an alkyl group, since it can further enhance solubility in hydrocarbon solvents and from the viewpoint of synthesis. In addition, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 2 to 6 carbon atoms is even more preferred, since it is easier to maintain a high glass transition temperature.

[0050] R u11 ~R u14 In the organic group, one or more hydrogen atoms may be substituted with halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms.

[0051] R u11 ~R u14At least one of the groups is an organic group containing an alkoxysilyl group. The alkoxysilyl group is an -Si(OR 1 ) m (R 2 ) 3-m A group represented by (R 1 ,R 2 are each independently an alkyl group having 1 to 30 carbon atoms; and m is an integer of 1 to 3. 1 , R 2 The alkyl group of R u11 ~R u14 The alkyl groups in R are the same as those in R. 1 , R 2 The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The organic group containing an alkoxysilyl group is preferably —Y—Si(OR 1 ) m (R 2 ) 3-m (Y is a single bond or a divalent linking group having 1 to 20 carbon atoms; R 1 , R 2 (wherein m is the same as above). Examples of the divalent linking group for Y include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, a divalent linking group having a carboxy group, and a divalent linking group having a heterocycle. Y is preferably a single bond or an alkylene group. The alkylene group for Y preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Of these, Y is preferably a single bond. Here, m is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

[0052] The organic group containing the alkoxysilyl group is R u11 ~R u14 R may be all of u11 ~R u14 R may be any three of u11 ~R u14R may be any two of u11 ~R u14 From a synthetic point of view, R u11 ~R u14 It is preferable that any one of the above is an organic group containing an alkoxysilyl group.

[0053] In order to improve the light transmittance of the adhesive layer formed using the adhesive composition, R u11 ~R u14 It is preferred that one or more of the following is a hydrogen atom.

[0054] Among the above, R u11 ~R u14 The organic group in R is preferably a combination of an alkoxysilyl group, an alkyl group, and a hydrogen atom, or a combination of an alkoxysilyl group and a hydrogen atom, and more preferably a combination of an alkoxysilyl group and a hydrogen atom. u11 ~R u14 It is preferred that one of the above is an alkoxysilyl group and the remaining three are hydrogen atoms.

[0055] In the formula (p1-1), n ​​represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0056] Specific examples of the structural unit (p1) are shown below.

[0057] [ka]

[0058] The structural unit (p1) contained in the cycloolefin polymer may be of one type or of two or more types. The proportion of the structural unit (p1) in the cycloolefin polymer can be, for example, 3 mol% or more relative to the total (100 mol%) of all structural units constituting the cycloolefin polymer. When the proportion is above the lower limit, the adhesion of the adhesive layer to the device layer is further improved. The proportion of the structural unit (p1) in the cycloolefin polymer is preferably 5 mol% or more, more preferably 8 mol% or more, even more preferably 10 mol% or more, even more preferably 12 mol% or more, and particularly preferably 14 mol% or more relative to the total (100 mol%) of all structural units constituting the cycloolefin polymer. The upper limit of the proportion of the structural unit (p1) in the cycloolefin polymer is not particularly limited, but from the viewpoint of solubility, it is preferably 30 mol% or less, more preferably 25 mol% or less, even more preferably 20 mol% or less, and particularly preferably 17 mol% or less relative to the total (100 mol%) of all structural units constituting the cycloolefin polymer. The proportion of the structural unit (p1) in the cycloolefin polymer can be, for example, 3 to 30 mol%, 5 to 25 mol%, 8 to 20 mol%, or 14 to 17 mol%, relative to the total (100 mol%) of all structural units constituting the cycloolefin polymer.

[0059] [ka] [In the formula, R u21 ~R u24 each independently represents an organic group having 1 to 30 carbon atoms (excluding those containing an alkoxysilyl group) or a hydrogen atom. 2 is an integer between 0 and 2.

[0060] In the formula (p2-1), R u21 ~R u24 As the organic group in the formula (p1-1), R u11 ~R u14 The organic groups in R u21 ~R u24 The organic group in the formula does not include an alkoxysilyl group. R u21 ~Ru24 The organic group in is preferably an alkyl group, since it can further enhance solubility in hydrocarbon solvents and from the viewpoint of synthesis. In addition, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 2 to 6 carbon atoms is even more preferred, since it is easier to maintain a high glass transition temperature.

[0061] R u21 ~R u24 In the organic group, one or more hydrogen atoms may be substituted with halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms.

[0062] In order to improve the light transmittance of the adhesive layer formed using the adhesive composition, R u21 ~R u24 It is preferred that one or more of the following is a hydrogen atom. Among the above, R u21 ~R u24 The organic group in R is preferably a combination of an alkyl group and a hydrogen atom. u21 ~R u24 It is preferred that one of the groups is an alkyl group and the remaining three are hydrogen atoms.

[0063] In the formula (p2-2), n 2 is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0064] Specific examples of the structural unit (p2) are shown below.

[0065] [ka]

[0066] The structural unit (p2) contained in the cycloolefin polymer may be of one type or of two or more types. The proportion of the structural unit (p2) in the cycloolefin polymer is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, even more preferably 30 to 88 mol%, and particularly preferably 40 to 86 mol%, relative to the total (100 mol%) of all structural units constituting the cycloolefin polymer. When the proportion of the structural unit (p2) is at least as large as the lower limit of the above-mentioned preferred range, solubility in hydrocarbon solvents tends to be improved, and when it is at most the upper limit of the above-mentioned preferred range, it becomes easier to achieve a balance with other structural units.

[0067] Regarding the building block (p3) derived from a monomer containing a maleimide skeleton: By including the structural unit (p3), the cycloolefin polymer has a high glass transition temperature, and the heat resistance of the adhesive layer can be improved. A preferred example of the structural unit (p3) is a structural unit represented by the following general formula (p3-1).

[0068] [ka] [In the formula, R u10 represents an organic group having 1 to 30 carbon atoms.]

[0069] In the formula (p3-1), R u10 represents an organic group having 1 to 30 carbon atoms. u10 The organic group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. For example, R u10 Examples of the organic group in include a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, and a chain alkenyl group which may have a substituent.

[0070] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

[0071] R u10 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R u10 Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R u10 Specific examples of the aromatic hydrocarbon group in the formula (I) include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, etc.), and a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0072] R u10 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which one hydrogen atom of an aliphatic hydrocarbon ring has been substituted with an alkylene group, etc. The number of carbon atoms in this alkylene group is preferably 1 to 4. The aliphatic hydrocarbon ring preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The aliphatic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic aliphatic hydrocarbon ring is preferably one having 3 to 8 carbon atoms, and specific examples thereof include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, with cyclopentane and cyclohexane being preferred. The polycyclic aliphatic hydrocarbon ring is preferably one having 7 to 30 carbon atoms, and specifically, polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycycloalkanes having a polycyclic skeleton of a fused ring system such as a ring having a steroid skeleton are more preferred.

[0073] Among them, R u10 The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane, more preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane, still more preferably a group in which one hydrogen atom has been removed from a monocycloalkane, and particularly preferably a group in which one hydrogen atom has been removed from cyclopentane or cyclohexane.

[0074] R u10 Examples of the substituent in the cyclic group include an alkyl group, a halogen atom, and a halogenated alkyl group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of halogenated alkyl groups as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.

[0075] An optionally substituted chain alkyl group: R u10 The chain alkyl group may be either a straight chain or a branched chain. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, and a docosyl group. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and even more preferably 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0076] An optionally substituted chain alkenyl group: R u10 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of linear alkenyl groups include vinyl, propenyl (allyl), and butynyl groups. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl groups. Of the chain alkenyl groups mentioned above, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0077] R u10Examples of the substituent in the chain alkyl or alkenyl group include a halogen atom, a halogenated alkyl group, the above-mentioned R u10 Examples of the cyclic groups include the cyclic groups shown in the formula:

[0078] Among the above, R u10 is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent, and further preferably a cyclic aliphatic hydrocarbon group which may have a substituent.

[0079] Specific examples of the structural unit (p3) are shown below.

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] The structural unit (p3) contained in the cycloolefin polymer may be one type or two or more types. The proportion of the structural unit (p3) in the cycloolefin polymer is preferably 0 to 90 mol %, more preferably 0 to 70 mol %, and even more preferably 0 to 50 mol %, relative to the total (100 mol %) of all structural units constituting the cycloolefin polymer. When the proportion of the structural unit (p3) is at least as large as the lower limit of the above-mentioned preferred range, the glass transition temperature increases and the heat resistance of the adhesive layer is further improved.When the proportion is at most as large as the upper limit of the above-mentioned preferred range, it becomes easier to achieve a balance with other structural units.

[0085] Preferred examples of cycloolefin polymers include polymers having the structural unit (p3) and the structural unit (p1), and more preferred examples of cycloolefin polymers include polymers having a structural unit represented by general formula (p3-1) and a structural unit represented by general formula (p1-1).

[0086] Preferred specific examples of the cycloolefin polymer are shown below. R u10 is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent, and further preferably a cyclic aliphatic hydrocarbon group which may have a substituent. R u11 ~R u14 The organic group in R is preferably a combination of an alkoxysilyl group, an alkyl group, and a hydrogen atom, or a combination of an alkoxysilyl group and a hydrogen atom, and more preferably a combination of an alkoxysilyl group and a hydrogen atom. u11 ~R u14 It is preferred that one of the above is an alkoxysilyl group and the remaining three are hydrogen atoms.

[0087] [ka]

[0088] The weight average molecular weight (Mw) of the cycloolefin polymer (based on polystyrene equivalent by gel permeation chromatography (GPC)) is, for example, 5.0 × 10 4 ~1.0×10 6 can range from 8.0 x 10 4 ~9.0×10 5 The range of 1.0×10 5 ~8.0×10 5 The range of 2.0×10 is more preferable. 5 ~6.0×10 5 The range is more preferable. When the weight average molecular weight of the cycloolefin polymer is equal to or greater than the lower limit of the above-mentioned preferred range, the heat resistance is improved. When the weight average molecular weight is equal to or less than the upper limit of the above-mentioned preferred range, an adhesive composition capable of forming an adhesive layer that is easily dissolved and removed in a hydrocarbon solvent is easily obtained.

[0089] The dispersity (Mw / Mn) of the cycloolefin polymer can be, for example, in the range of 1.5 to 9.0, preferably in the range of 2.5 to 7.0, more preferably in the range of 3.5 to 5.5, and even more preferably in the range of 4.0 to 5.0. The dispersity indicates the width of the molecular weight distribution. Mn indicates the number average molecular weight.

[0090] The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are determined, for example, from a polystyrene-equivalent value obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement. The measurement conditions for GPC measurement are, for example, as follows: Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 2.0 mg / ml

[0091] Two or more types of cycloolefin polymers may be used in combination. The content of the cycloolefin polymer in the resin component can be 0 to 50 mass% relative to the total amount (100 mass%) of the resin component, preferably 0 to 30 mass%, more preferably 0 to 25 mass%, even more preferably 0 to 20 mass% or less, and particularly preferably 0 to 10 mass%.

[0092] Acrylic resin The adhesive composition of this embodiment contains an acrylic resin in addition to the above-mentioned (BCP) component, thereby further improving the adhesion between the support and the device layer. Examples of acrylic resins include resins (homopolymers and copolymers) polymerized using (meth)acrylic acid esters as monomers. "(Meth)acrylic" refers to at least one of acrylic and methacrylic.

[0093] Examples of the (meth)acrylic acid ester include a (meth)acrylic acid alkyl ester having a chain structure, a (meth)acrylic acid ester having an aliphatic ring, and a (meth)acrylic acid ester having an aromatic ring. Among these, it is preferable to use a (meth)acrylic acid ester having an aliphatic ring.

[0094] Examples of alkyl (meth)acrylate esters having a chain structure include acrylic alkyl esters having an alkyl group with 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms herein may be linear or branched, and examples thereof include methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, tridecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl (stearyl), n-nonadecyl, and n-eicosyl groups, with acrylic alkyl esters having an alkyl group having 15 to 20 carbon atoms being preferred.

[0095] Examples of (meth)acrylic acid esters having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. Among these, 1-adamantyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate are preferred.

[0096] In the (meth)acrylic acid ester having an aromatic ring, examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenoxymethyl group, a phenoxyethyl group, etc. The aromatic ring may have a substituent, and may have a linear or branched alkyl group having 1 to 5 carbon atoms.

[0097] In the acrylic resin, the above-mentioned (meth)acrylic acid esters may be used alone or in combination of two or more.

[0098] The acrylic resin is preferably a resin obtained by polymerizing one or more selected from the group consisting of alkyl (meth)acrylate esters having a chain structure, (meth)acrylate esters having an aliphatic ring, and (meth)acrylate esters having an aromatic ring. Among these, a resin obtained by polymerizing a (meth)acrylic acid alkyl ester and a (meth)acrylic acid ester having an aliphatic ring is more preferable.

[0099] The acrylic resin may be a resin obtained by polymerizing a (meth)acrylic acid ester monomer with another monomer polymerizable therewith. Examples of such polymerizable monomers include styrene, styrene derivatives, and monomers containing a maleimide group. The styrene derivatives herein are the same as those described above for the "styrene derivatives." The monomers containing a maleimide group herein include the same monomers as those from which the structural unit (u21) is derived.

[0100] Among acrylic resins, resins obtained by polymerizing a (meth)acrylic acid ester monomer and styrene are preferred. The presence of styrene units in acrylic resins improves the heat resistance of the acrylic resins. In addition, the compatibility with other resins and the solubility in hydrocarbon solvents are improved. Among these, the acrylic resin is particularly preferably a resin obtained by polymerizing a (meth)acrylic acid alkyl ester having a chain structure, a (meth)acrylic acid ester having an aliphatic ring, and styrene.

[0101] The solubility parameter (SP value) of the acrylic resin is preferably from 6 to 10, and more preferably from 6.5 to 9.5. When the SP value is within the above-mentioned preferred range, the compatibility of the acrylic resin with other resins is improved, making it easier to obtain a more stable adhesive composition.

[0102] The weight average molecular weight of the acrylic resin is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. When the weight average molecular weight of the acrylic resin is within the above-mentioned preferred range, it is possible to easily provide an adhesive composition having thermal fluidity suitable for bonding a substrate and a support, for example.

[0103] Two or more types of acrylic resins may be used in combination. The content of the acrylic resin in the resin component can be 0 to 50 mass% relative to the total amount of the resin component (100 mass%), preferably 0 to 30 mass%, more preferably 0 to 25 mass%, even more preferably 0 to 20 mass% or less, and particularly preferably 0 to 10 mass%.

[0104] ··Elastomer Suitable examples of elastomers include those having, as a structural unit of the main chain, a structural unit derived from styrene or a structural unit derived from a styrene derivative (collectively referred to as a "styrene unit"). The elastomer is preferably a styrene-based thermoplastic elastomer, and more preferably a hydrogenated styrene-based thermoplastic elastomer. Hydrogenated elastomers have further improved thermal stability and are less susceptible to deterioration such as decomposition and polymerization. In addition, they are more preferred from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents. Among elastomers, block polymers in which both ends are styrene are more preferred. By blocking both ends with styrene, which has high thermal stability, higher heat resistance is likely to be obtained. More specifically, the elastomer is preferably a hydrogenated block copolymer of styrene and a conjugated diene. This further improves thermal stability and makes it less susceptible to degradation such as decomposition or polymerization. Furthermore, since both ends are blocked with highly thermally stable styrene, it exhibits higher heat resistance. Furthermore, this is more preferable from the viewpoints of solubility in hydrocarbon solvents and resistance to resist solvents.

[0105] Examples of commercially available elastomers that can be used as the resin component include "Septon (product name)" manufactured by Kuraray Co., Ltd., "Hybler (product name)" manufactured by Kuraray Co., Ltd., "Tuftec (product name)" manufactured by Asahi Kasei Corporation, and "Dynalon (product name)" manufactured by JSR Corporation.

[0106] Curable monomers The resin components other than the (BCP) component may be used together with a curable monomer that can serve as a matrix constituting the adhesive layer. By using a curable monomer in combination, the heat resistance of the adhesive layer can be further improved. The curable monomer is preferably a monomer that is polymerized by radical polymerization, and typically includes a polyfunctional curable monomer, with a polyfunctional (meth)acrylate monomer being particularly preferred.

[0107] Examples of polyfunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, propoxylated bisphenol A di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 5-hydroxy-1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantanetriol tri(meth)acrylate, and trimethylol. Examples of the acrylates include propane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin tri(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), and a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate.

[0108] Antioxidants The adhesive composition of the present embodiment may further contain an antioxidant in addition to the above-mentioned (BCP) component. Examples of the antioxidant include tocopherol-based compounds, phenol-based antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, benzotriazole-based antioxidants, benzophenone-based antioxidants, hydroxylamine-based antioxidants, salicylic acid ester-based antioxidants, and triazine-based antioxidants. Among these, hindered phenol-based antioxidants are preferred. Two or more antioxidants may be used in combination. The content of the antioxidant is preferably 0 to 10 parts by mass relative to 100 parts by mass of the resin component.

[0109] Polymerization inhibitor The adhesive composition of the present embodiment may further contain a polymerization inhibitor in addition to the above-mentioned (BCP) component. A polymerization inhibitor is a component that functions to prevent radical polymerization reactions caused by heat or light. Polymerization inhibitors exhibit high reactivity with radicals. Therefore, when a cycloolefin polymer is used together with the (BCP) component, the reaction between the polymerization inhibitor and radicals proceeds preferentially over the reaction between the cycloolefin polymer and radicals, inhibiting the polymerization of the cycloolefin polymers themselves. As a result, the chemical resistance of the formed adhesive layer is enhanced by heating the adhesive layer.

[0110] Polymerization initiator The adhesive composition of this embodiment may further contain a polymerization initiator in addition to the above-described (BCP) component. The polymerization initiator is a component that has the function of accelerating the polymerization reaction of the above-described curable monomer. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator. Examples of the thermal polymerization initiator include peroxides and azo-based polymerization initiators.

[0111] Solvent components The adhesive composition of this embodiment can be prepared by dissolving the (BCP) component and, if necessary, other components in a solvent component. The solvent component can be, for example, one that can dissolve each component of the adhesive composition to form a homogeneous solution, and one type may be used alone, or two or more types may be used in combination.

[0112] Examples of the solvent component include hydrocarbon solvents and petroleum-based solvents. Hereinafter, hydrocarbon solvents and petroleum-based solvents will be collectively referred to as "component (S1)." Solvent components other than component (S1) will sometimes be referred to as "component (S2)."

[0113] Examples of hydrocarbon solvents include linear, branched, and cyclic hydrocarbons, such as linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons such as isooctane, isononane, and isododecane; and cyclic hydrocarbons such as p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujane, carane, longifolene, α-terpinene, β-terpinene, γ-terpinene, α-pinene, β-pinene, α-thujone, β-thujone, cyclohexane, cycloheptane, cyclooctane, indene, pentalene, indane, tetrahydroindene, naphthalene, tetrahydronaphthalene (tetralin), and decahydronaphthalene (decalin).

[0114] Petroleum-based solvents are solvents refined from heavy oil, and examples thereof include kerosene, paraffin-based solvents, and isoparaffin-based solvents.

[0115] Furthermore, examples of the component (S2) include terpene solvents having an oxygen atom, a carbonyl group, or an acetoxy group as a polar group, such as geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, and camphor.

[0116] Examples of the component (S2) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; and monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the above polyhydric alcohols or compounds having an ester bond. Examples of suitable organic solvents include derivatives of polyhydric alcohols such as compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; and aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether.

[0117] The content of the solvent component in the adhesive composition of this embodiment may be adjusted appropriately depending on the thickness of the adhesive layer to be formed, and is preferably, for example, in the range of 75 to 90 mass % relative to the total amount (100 mass %) of the adhesive composition. That is, the adhesive composition of this embodiment preferably has a solid content (total amount of blended ingredients excluding solvent components) concentration in the range of 10 to 25 mass %. If the content of the solvent component is within the above-mentioned preferred range, viscosity adjustment becomes easy.

[0118] The adhesive composition of the present embodiment can be prepared by mixing and dissolving or dispersing the other components in the solvent component. From the viewpoint of the solubility of the resin component, it is preferable to use a solvent containing a hydrocarbon solvent, and it is more preferable to use a solvent containing a branched chain hydrocarbon or a cyclic hydrocarbon solvent. When the solvent component contains a branched or cyclic hydrocarbon solvent, clouding that can occur when the adhesive composition is stored in a liquid state (particularly at low temperatures) is more easily prevented, and storage stability can be further improved.

[0119] The solvent component preferably contains a hydrocarbon solvent that is a condensed polycyclic hydrocarbon or a branched chain hydrocarbon. In this case, the solvent component may consist solely of a solvent selected from the group consisting of condensed polycyclic hydrocarbons and branched chain hydrocarbons, or may contain other components, such as saturated aliphatic hydrocarbons, in addition to the solvent component.

[0120] As described above, the adhesive composition of this embodiment forms an adhesive layer exhibiting an elastic modulus of 20 MPa or more at 260°C. Use of such an adhesive composition increases the elastic modulus of the second adhesive layer that bonds the support and the device layer. As a result, the second adhesive layer is less likely to undergo thermal deformation or sinking during high-temperature treatment (i.e., deformation due to external forces is suppressed). Furthermore, the adhesive layer formed using the adhesive composition of this embodiment uses a block copolymer having a first block and a second block as the base material, which facilitates reducing film stress. Additionally, the first block is a block composed of a polymer having a repeating structure of structural units (u1) derived from norbornene, which may have a substituent, which enhances heat resistance. This improves adhesion between the second adhesive layer and the device layer. This suppresses peeling and cracking of the device layer.

[0121] (Laminate) As shown in FIG. 1, the laminate 100 of this embodiment is formed by laminating a support 12, a first adhesive layer 3A, a second adhesive layer 3B, and a device layer 45 in this order.

[0122] <Support> In the laminate 100 shown in FIG. 1, the support 12 includes a support base 1 and a separation layer 2 provided on the support base 1.

[0123] ≪Supporting base≫ The supporting base has the property of transmitting light. The supporting base is a member that supports the substrate, and is bonded to the substrate via a first adhesive layer and a second adhesive layer. Therefore, the supporting base preferably has the strength required to prevent damage or deformation of the substrate during thinning of the encapsulant, transportation of the substrate, mounting on the substrate, etc. Furthermore, the supporting base preferably transmits light of a wavelength that can alter the separation layer. The material of the support base may be, for example, glass, silicon, acrylic resin, etc. The shape of the support base may be, for example, rectangular, circular, etc., but is not limited to these. Furthermore, for the purpose of achieving higher density integration and improving production efficiency, the support base may be a circular support base with an enlarged size, or a large panel with a rectangular shape in plan view.

[0124] ≪Separation layer≫ The separation layer is adjacent to the first adhesive layer and is altered by irradiation with light, thereby enabling the support base to be separated from the substrate bonded to the support. This separation layer can be formed using the "separation layer-forming composition" described below, for example, by firing the components contained in the separation layer-forming composition or by chemical vapor deposition (CVD). This separation layer is suitably altered by absorbing light irradiated through the support substrate. It is preferable that the separation layer is formed only from a material that absorbs light, but it may also be a layer that contains a material that does not have a structure that absorbs light, as long as the essential property of being altered by irradiation with light is not impaired.

[0125] The term "alteration" of a separation layer refers to a phenomenon in which the separation layer is in a state where it can be destroyed by external force or where the adhesive strength between the separation layer and a layer in contact with it is reduced. The separation layer becomes brittle by absorbing light and loses the strength or adhesiveness it had before being irradiated with light. Such alteration of the separation layer occurs due to decomposition, changes in configuration, dissociation of functional groups, etc. caused by the energy of the absorbed light.

[0126] The thickness of the separation layer is preferably, for example, in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer is within the range of 0.05 μm or more and 50 μm or less, the desired alteration can be caused in the separation layer by short-term light irradiation and low-energy light irradiation. Furthermore, from the viewpoint of productivity, it is particularly preferable that the thickness of the separation layer is within the range of 1 μm or less.

[0127] It is preferable that the surface of the separation layer that comes into contact with the first adhesive layer is flat (no irregularities are formed), which makes it easy to form the first adhesive layer and to uniformly attach the support base and substrate.

[0128] <First adhesive layer> The first adhesive layer is an adhesive layer adjacent to the support, and is preferably a layer formed from a first material exhibiting the properties described below. In the laminate 100, the first adhesive layer 3A is provided adjacent to the separation layer 2 constituting the support 12. The first adhesive layer 3A is preferably removable with a cleaning solution containing an organic solvent.

[0129] The thickness of the first adhesive layer is preferably, for example, in the range of 0.1 μm to 100 μm, more preferably in the range of 1 μm to 50 μm, and even more preferably in the range of 10 μm to 40 μm. When the thickness of the first adhesive layer is within the above-mentioned preferred range, the support and the device layer can be bonded together more satisfactorily.

[0130] <Ingredient 1> The first material may be an adhesive composition containing a resin component and other components (hereinafter also referred to as "adhesive composition (1)"). The first material may be, for example, a material that exhibits an elastic modulus of 0.1 MPa or less under the temperature conditions (hereinafter also referred to as "attachment temperature") when the support and the device layer are attached to each other. The attachment temperature is set appropriately depending on, for example, the resin component contained in the adhesive composition (1).

[0131] The elastic modulus of the first material at the application temperature is preferably 0.1 MPa or less, more preferably 0.075 MPa or less, and even more preferably 0.05 MPa or less. If the modulus of elasticity at the attachment temperature is equal to or less than the upper limit of the range, the adhesive layer formed from the first material will be less susceptible to deformation due to external forces. The lower limit of the elastic modulus at the application temperature is substantially 0.001 MPa or more, and may be 0.002 MPa or more.

[0132] Method for measuring modulus of elasticity at application temperature: The elastic modulus of the first material at the application temperature is measured as follows. An adhesive layer with a thickness of 50 μm is formed on a silicon wafer. A test piece (film thickness 50 μm, width 5 mm, length 40 mm) of the adhesive layer is cut out, and the tensile modulus is measured using a dynamic viscoelasticity measuring device at a frequency of 1 Hz in the range of 50 to 300° C. The tensile modulus under the temperature conditions when the support and the device layer are bonded together is defined as the modulus at the bonding temperature.

[0133] The adhesive composition (1) exemplified as the first material may be an adhesive composition containing a thermoplastic resin, or may be an adhesive composition containing a thermosetting resin. As the adhesive composition (1), various adhesive compositions known in the art, such as acrylic, novolac, naphthoquinone, hydrocarbon, polyimide, elastomer, polysulfone, and urethane adhesive compositions, can be used.

[0134] Such adhesive composition (1) may include, for example, one containing a thermoplastic resin, a diluent, and other components such as additives (hereinafter also referred to as "adhesive composition (11)"). The content of the thermoplastic resin in the adhesive composition (11) is preferably 50 to 95 mass %, more preferably 60 to 90 mass %, relative to the total amount (100 mass %) of the adhesive composition (11). As the thermoplastic resin, for example, hydrocarbon resin, acrylic-styrene resin, maleimide resin, elastomer, polysulfone resin, or a combination thereof can be preferably used.

[0135] Dilution solvent Examples of dilution solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, isononane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons having 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujane, carane, longifolene, and geraniol. Terpene solvents such as ethanol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, and dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n ketones such as 2-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers, monomethyl ethers, monoethyl ethers, monopropyl ethers, and monobutyl ethers of the above polyhydric alcohols or compounds having an ester bond, or monophenyl ethers (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane; and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate;Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether;

[0136] Other ingredients The adhesive composition (11) may further contain other compatible substances to the extent that the essential properties are not impaired. For example, various commonly used additives such as additional resins for improving the performance of the adhesive, curable monomers, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, and surfactants may be further used.

[0137] The adhesive composition (1) may contain, for example, a thermosetting resin, a crosslinking agent component, a polymerization initiator, and other components such as additives (hereinafter also referred to as "adhesive composition (12)"). For example, a urethane resin or the like can be preferably used as the thermosetting resin.

[0138] Urethane resin Suitable examples of the urethane resin include urethane resins containing polymerizable carbon-carbon double bonds (hereinafter also referred to as "component (P1)"). The (P1) component can polymerize and harden via the polymerizable carbon-carbon double bond to form a second adhesive layer. This allows for temporary bonding of a semiconductor substrate or electronic device to a support. Furthermore, the urethane bond in the (P1) component is decomposable by acid or alkali. Therefore, the second adhesive layer can be easily removed using a treatment solution containing acid or alkali. The component (P1) can be synthesized by a polymerization addition reaction between a polyisocyanate compound (hereinafter also referred to as "component (I)") and a polyol (hereinafter also referred to as "component (O)"). At least one of the components (I) and (O) preferably contains a polymerizable carbon-carbon double bond. Components that fall under the category of a crosslinking agent component (component (M)) described below are excluded from component (P1).

[0139] Crosslinking agent component The adhesive composition (12) may contain, in addition to the component (P1), a crosslinking agent component (hereinafter also referred to as "component (M)"), such as caprolactone-modified urethane acrylate.

[0140] Polymerization initiator (component (A)) The polymerization initiator (hereinafter also referred to as "component (A)") is a component that has the function of accelerating a polymerization reaction. Examples of component (A) include a thermal polymerization initiator and a photopolymerization initiator.

[0141] Other ingredients In addition to the components (P1), (M), and (A), the adhesive composition (12) may further contain optional components that are compatible with the components (P1), (M), and (A) to the extent that the essential properties are not impaired. The optional components include, but are not limited to, polymerization inhibitors, silane coupling agents, surfactants, solvents, plasticizers, adhesive aids, stabilizers, colorants, etc.

[0142] <Second adhesive layer> The second adhesive layer is an adhesive layer provided between the first adhesive layer and the device layer and adjacent to the device layer, and is a layer formed from the adhesive composition of the above-mentioned embodiment. In the laminate 100, the substrate 4 is provided on the second adhesive layer 3B, and the substrate 4 is sealed between the second adhesive layer 3B and the sealant layer 5. The second adhesive layer 3B can be removed with a cleaning liquid containing an organic solvent.

[0143] The thickness of the second adhesive layer is preferably, for example, in the range of 0.1 μm to 100 μm, more preferably in the range of 1 μm to 50 μm, and even more preferably in the range of 10 μm to 40 μm. When the thickness of the second adhesive layer is within the above-mentioned preferred range, the support and the device layer can be bonded together more satisfactorily.

[0144] Regarding the combination of the first adhesive layer and the second adhesive layer: In the laminate of this embodiment, preferred combinations of the first adhesive layer and the second adhesive layer are listed below.

[0145] Combination (1): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (11) containing a thermoplastic resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP12).

[0146] Combination (2): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (11) containing a thermoplastic resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP123).

[0147] Combination (3): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (11) containing a thermoplastic resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP12), another cycloolefin polymer, and an antioxidant.

[0148] Combination (4): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (11) containing a thermoplastic resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP12), an acrylic resin, and an antioxidant.

[0149] Combination (5): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (12) containing a thermosetting resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP12).

[0150] Combination (6): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (12) containing a thermosetting resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP123).

[0151] Combination (7): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (12) containing a thermosetting resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP12), another cycloolefin polymer, and an antioxidant.

[0152] Combinations (8): The first adhesive layer is a layer formed from a first material, which is an adhesive composition (12) containing a thermosetting resin, and the second adhesive layer is a layer formed from an adhesive composition containing a block copolymer (BCP12), an acrylic resin, and an antioxidant.

[0153] In the laminate of this embodiment, the thickness ratio between the first adhesive layer and the second adhesive layer is preferably first adhesive layer / second adhesive layer = 1 / 9 to 9 / 1. When the thickness ratio is within the above-mentioned preferred range, deformation due to external force is easily suppressed while maintaining adhesion between the support and the device layer. The thickness ratio is more preferably first adhesive layer / second adhesive layer = 3 / 7 to 7 / 3.

[0154] <Device Layer> The device layer is a composite of a member made of a metal or a semiconductor and a resin that seals or insulates the member. Specifically, the device layer includes at least one of an encapsulant layer and a rewiring layer, and may further include a substrate. In the laminate 100 shown in FIG. 1, the device layer 45 is composed of a substrate 4 and an encapsulant layer 5.

[0155] <Substrate> The substrate (bare chip) is supported by a support and is subjected to processes such as thinning, mounting, etc. Structures such as integrated circuits and metal bumps are mounted on the substrate. The substrate is typically a silicon wafer substrate, but is not limited to this, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like.

[0156] The substrate may be a semiconductor element or other element, and may have a single-layer or multi-layer structure. When the substrate is a semiconductor element, the electronic component obtained by dicing the device layer becomes a semiconductor device. Preferably, the substrate is a semiconductor element.

[0157] ≪Encapsulation material layer≫ The encapsulant layer is provided to encapsulate the substrate and is formed using an encapsulant that can insulate or encapsulate a member made of metal or semiconductor. As the sealing material, for example, a resin composition containing a resin is used. The resin used for the sealing material is not particularly limited as long as it can seal and / or insulate metals or semiconductors, and examples thereof include epoxy resins. The sealing material may contain other components such as a filler in addition to the resin. Examples of the filler include spherical silica particles.

[0158] <Laminate manufacturing method (1)> The laminate 100 shown in FIG. 1 can be produced, for example, by a production method including a separation layer forming step, an adhesive layer forming step, a device layer forming step, and a device layer fixing step.

[0159] [Separation layer formation process] The separation layer forming step is a step of forming a separation layer on one surface of a support substrate using the [separation layer forming composition] described below, thereby producing a support 12 composed of a support substrate 1 and a separation layer 2.

[0160] The method for forming the separation layer 2 on the support base 1 is not particularly limited, but examples thereof include spin coating, dipping, roller blade coating, spray coating, slit coating, and chemical vapor deposition (CVD). For example, in the separation layer forming process, the support 12 can be obtained by removing the solvent component from the coating layer of the separation layer forming composition applied to the support substrate 1 in a heated environment or a reduced pressure environment to form a film, or by forming a film on the support substrate 1 by a vapor deposition method.

[0161] [Adhesive layer formation process] The adhesive layer forming step includes an adhesive layer forming operation (1) for forming a first adhesive layer and an adhesive layer forming operation (2) for forming a second adhesive layer.

[0162] Adhesive layer forming operation (1): In the adhesive layer forming operation (1), a first adhesive layer 3A is formed on the separation layer 2 of the support 12 using an adhesive composition, which is a first material.

[0163] The method for forming the first adhesive layer 3A on the support 12 is not particularly limited, and examples thereof include spin coating, dipping, roller blade coating, spray coating, slit coating, etc. Then, the first material is applied to the support 12 and heated, or the solvent component contained in the first material is removed under a reduced pressure environment.

[0164] Thereafter, when the first adhesive layer 3A contains a curable monomer and a thermal polymerization initiator, the curable monomer may be polymerized by heating. The conditions for heating the first adhesive layer 3A may be appropriately set based on the one-minute half-life temperature and one-hour half-life temperature of the thermal polymerization initiator. Heating is preferably performed at a temperature in the range of, for example, 50 to 300°C under vacuum or in an inert gas atmosphere such as nitrogen gas, and more preferably in an inert gas atmosphere.

[0165] Furthermore, when the first adhesive layer 3A contains a curable monomer and a photopolymerization initiator, the curable monomer may be polymerized by exposure to light in an inert gas atmosphere such as nitrogen gas. The exposure conditions may be appropriately set depending on the type of photopolymerization initiator, etc.

[0166] Adhesive layer forming operation (2): In the adhesive layer forming operation (2), the second adhesive layer 3B is formed on the device layer 45 or the first adhesive layer 3A using the adhesive composition of the above-described embodiment. When forming the second adhesive layer 3B, the second adhesive layer 3B may be formed on the device layer 45 (sealant) using the adhesive composition of the above-mentioned embodiment, or the second adhesive layer 3B may be formed on the first adhesive layer 3A using the adhesive composition of the above-mentioned embodiment.

[0167] The method for forming the second adhesive layer 3B on the device layer 45 or the first adhesive layer 3A is not particularly limited, but examples include spin coating, dipping, roller blade, spray coating, slit coating, chemical vapor deposition (CVD), etc. For example, in the adhesive layer formation operation (2), the second adhesive layer 3B can be formed on the device layer 45 or the first adhesive layer 3A by removing the solvent component from the coating layer of the adhesive composition applied to the device layer 45 or the first adhesive layer 3A under a heated or reduced pressure environment to form a film.

[0168] [Device layer formation process] The device layer forming step is a step of forming a device layer which is a composite of a member made of a metal or semiconductor and a resin that seals or insulates the member. The device layer formation step may include a sealing operation of sealing the substrate with an encapsulant.

[0169] Sealing operation: In the sealing operation, the substrates are sealed with a sealing material to produce a sealed body. The sealed body is used as device layer 45 in the method for producing a laminate according to this embodiment. The number of substrates to be sealed with the sealing material is not particularly limited, and may be the number necessary to form the desired device layer.

[0170] In the sealing operation, for example, a substrate is placed on a holding plate, and a sealing material heated to 130 to 170°C is supplied onto the holding plate so as to cover the substrate while maintaining a high viscosity, and then compression-molded to produce a sealed body. At this time, the temperature condition is, for example, 130 to 170°C. The pressure applied to the substrate is, for example, 50 to 500 N / cm 2 is.

[0171] [Device layer fixing process] The device layer fixing step is a step of fixing the device layer (encapsulated body) onto the support via an adhesive layer, thereby obtaining a laminate. In manufacturing the laminate 100, the device layer 45 is fixed onto the support 12 via the first adhesive layer 3A and the second adhesive layer 3B, thereby obtaining the laminate 100.

[0172] The method for fixing the device layer 45 on the support 12 is not particularly limited, and any known method used for bonding substrates or the like may be used. For example, the first adhesive layer 3A and the second adhesive layer 3B are placed opposite each other, and the device layer 45 is placed at a predetermined position on the support 12. Next, the support 12 and the substrate 4 are pressure-bonded together using a die bonder or the like while being heated under vacuum (for example, at about 100°C) (a so-called TCB process), thereby fixing the device layer 45 on the support 12. The temperature and pressure conditions in the TCB process are, for example, 200 to 350°C and 0.5 to 3.0 N / mm 2 The pressing time is 0.5 to 20 seconds.

[0173] As described above, in the laminate of this embodiment, the support and the device layer are bonded together via an adhesive layer, which is composed of a first adhesive layer adjacent to the support and a second adhesive layer adjacent to the device layer. The second adhesive layer is a layer formed from the adhesive composition of the above-mentioned embodiment. By adopting this configuration, the laminate is less likely to deform due to external forces (effect (i)), and the adhesive layer has good washability (effect (ii)).

[0174] Regarding effect (i): Figure 2A is a schematic diagram showing a state where a conventional laminate is used in a TCB process, and Figure 2B is a schematic diagram showing a state where laminate 100 is used in a TCB process.

[0175] In manufacturing the laminate, for example, die bonding may be performed on a device layer 45 (also called a bump substrate) that includes a substrate on which metal bumps are mounted.

[0176] FIG. 2A shows a case where a support 12 and a bump substrate are bonded together using a conventional laminate in a TCB process, and die bonding is performed on the bump substrate. The adhesive layer 3' in the laminate is, for example, a single layer formed from the first material described above. In this case, during die bonding, the adhesive layer 3' may be thermally deformed, sinking, causing the bumps to come into contact with the support 12, resulting in warping of the substrate and damage to the bumps.

[0177] FIG. 2B shows a case where the support 12 and the bump substrate are bonded together using the laminate 100 in the TCB process, and die bonding is performed on the bump substrate. In the laminate 100, the first adhesive layer 3A is a layer formed from a first material exhibiting an elastic modulus of 0.1 MPa or less under the temperature conditions when the support 12 and the device layer 45 (bump substrate) are bonded together. The second adhesive layer 3B is a layer formed from an adhesive composition containing a block copolymer having a first block and a second block and exhibiting an elastic modulus of 20 MPa or more at 260°C. In this case, the increased elastic modulus of the second adhesive layer 3B makes the second adhesive layer 3B less susceptible to thermal deformation and sinking during die bonding (i.e., deformation due to external forces is suppressed). This prevents contact between the bumps and the support 12. In addition, the second adhesive layer 3B has increased adhesion to the device layer 45 (bump substrate), making it less likely to peel from the bump substrate. Furthermore, the laminate 100 also suppresses gas generation from the encapsulant during heat treatment.

[0178] (Another embodiment of the laminate) FIG. 3 shows another embodiment of the laminate. The laminate 200 shown in FIG. 3 has the same configuration as the laminate 100 , except that the device layer is a device layer 456 made up of a substrate 4 , a sealing material layer 5 , and a rewiring layer 6 .

[0179] <Device Layer in Other Embodiments of the Laminate> In the stacked body 200 shown in FIG. 3, the device layer 456 is composed of a substrate 4, a sealing material layer 5, and a rewiring layer 6. The substrate 4 and the sealing material layer 5 are the same as those described above for the <<substrate>> and <<sealing material layer>>.

[0180] ≪Rewiring layer≫ The redistribution layer (RDL) is a thin-film wiring body that forms wiring connected to a substrate and may have a single-layer or multi-layer structure. The redistribution layer may be, but is not limited to, wiring formed by a conductor (for example, metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy) between patterned resin materials (such as photosensitive polyimide and photosensitive acrylic resin).

[0181] <Laminate manufacturing method (2)> The laminate 200 shown in FIG. 3 can be manufactured by a manufacturing method including, as an example, a separation layer forming step, an adhesive layer forming step, a device layer forming step, a device layer fixing step, a grinding step, and a rewiring layer forming step.

[0182] The separation layer forming step, adhesive layer forming step, device layer forming step, and device layer fixing step are the same as those described for the separation layer forming step, adhesive layer forming step, device layer forming step, and device layer fixing step in the above-mentioned <Laminate manufacturing method (1)>.

[0183] [Grinding process] The grinding step is a step in which, after the above-mentioned sealing operation, the sealant portion of the sealant (sealant layer 5) is ground so that part of the substrate 4 is exposed. Grinding of the sealing material portion is carried out by grinding the sealing material layer 5 until it has a thickness substantially equal to that of the substrate 4, for example, as shown in FIG.

[0184] [Rewiring layer formation process] The rewiring formation step is a step of forming a rewiring layer 6 on the exposed substrate 4 after the grinding step. The redistribution layer (RDL) is a thin-film wiring body that forms wiring connected to elements and can have a single-layer or multi-layer structure. For example, the redistribution layer can be made of a dielectric (silicon oxide (SiO x The wiring may be formed on a conductive material (metals such as aluminum, copper, titanium, nickel, gold, silver, and alloys such as silver-tin alloy) made of a conductive material (such as a photosensitive resin, photosensitive epoxy, etc.), but is not limited to this.

[0185] The rewiring layer 6 is formed by first depositing silicon oxide (SiO x ), a dielectric layer of a photosensitive resin or the like is formed. The dielectric layer of silicon oxide can be formed by, for example, a sputtering method, a vacuum deposition method, or the like. The dielectric layer of a photosensitive resin can be formed by applying the photosensitive resin onto the sealing material layer 5 by, for example, a method such as spin coating, dipping, roller blade, spray coating, or slit coating.

[0186] Subsequently, wiring is formed on the dielectric layer using a conductor such as a metal. The wiring can be formed by known semiconductor process techniques such as lithography processes such as photolithography (resist lithography), etching processes, etc. Examples of such lithography processes include lithography processes using a positive resist material and lithography processes using a negative resist material. Thus, when performing photolithography processing, etching processing, etc., the laminate is exposed to an acid such as hydrofluoric acid, an alkali such as tetramethylammonium hydroxide (TMAH), or a resist solvent for dissolving the resist material, and is also treated at high temperatures.

[0187] The method (2) for manufacturing a laminate explained above may further include a step of forming a bump on the rewiring layer 6 or mounting an element thereon, in addition to the above-mentioned embodiment. The elements can be mounted on the rewiring layer 6 using, for example, a chip mounter.

[0188] Regarding the laminate manufacturing method (2), in the above-described embodiment, the grinding step and the rewiring layer forming step are performed after the device layer forming step, but the grinding operation of the sealing material portion and the rewiring layer forming operation may also be performed during the device layer forming step.

[0189] (Electronic component manufacturing method) According to another aspect of the present invention, a method for manufacturing an electronic component is a manufacturing method including a separation step and a removal step after obtaining a laminate by the above-mentioned <Laminate manufacturing method (2)>.

[0190] 4A to 4C are schematic process diagrams illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Fig. 4A shows a state in which light is irradiated onto the laminate from the support side. Fig. 4B shows a state in which the support base has been separated from the laminate. Fig. 4C shows a state in which the first adhesive layer, the second adhesive layer, and the separation layer have been removed by washing from the device layer.

[0191] [Separation process] The separation step is a step in which light (arrow) is irradiated onto separation layer 2 through support base 1 to alter separation layer 2, thereby separating device layer 456 from support base 1. In FIG. 4A, separation layer 2 is irradiated with light (arrow) through support base 1, thereby altering separation layer 2.

[0192] The wavelength capable of altering the separation layer 2 is, for example, in the range of 600 nm or less. The type and wavelength of the light to be irradiated may be appropriately selected depending on the transparency of the support base 1 and the material of the separation layer 2, and may include, for example, laser light or non-laser light, such as a solid-state laser such as a YAG laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, or fiber laser, a liquid laser such as a dye laser, a gas laser such as a CO2 laser, excimer laser, Ar laser, or He-Ne laser, a semiconductor laser, or a free electron laser. This alters the separation layer 2, making it possible to easily separate the support base 1 and the device layer 456.

[0193] When irradiating with laser light, the following conditions can be given as an example of the laser light irradiation conditions. The average output power of the laser beam is preferably 1.0 W or more and 7.0 W or less, and more preferably 3.0 W or more and 7.0 W or less. The repetition frequency of the laser beam is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10,000 mm / s or less.

[0194] Separation layer 2 is irradiated with light (arrow) to alter the properties of separation layer 2, and then supporting base 1 is separated from device layer 456 as shown in FIG. 4B. For example, the support base 1 and the device layer 456 are separated by applying a force in a direction that moves them apart. Specifically, the support base 1 and the device layer 456 can be separated by fixing one of the support base 1 and the device layer 456 to a stage and lifting the other while suction-holding it with a separation plate equipped with an adsorption pad such as a bellows pad. The force applied to the laminate 200 can be adjusted appropriately depending on the size of the laminate 200, etc., and is not limited to any particular value. For example, for a laminate with a diameter of approximately 300 mm, the support base 1 and the device layer 456 can be suitably separated by applying a force of approximately 0.1 to 5 kgf (0.98 to 49 N).

[0195] [Removal process] The removal step is a step of removing the separation layer, the first adhesive layer, and the second adhesive layer attached to the device layer after the separation step. FIG. 4B shows a state in which the separation layer 2, the first adhesive layer 3A, and the second adhesive layer 3B remain attached to the device layer 456 after the separation step.

[0196] A method for removing the first adhesive layer 3A and the second adhesive layer 3B attached to the device layer 456 includes, for example, a method of removing the separation layer 2, the first adhesive layer 3A and the second adhesive layer 3B using a cleaning solution. The cleaning liquid preferably contains an organic solvent.

[0197] Regarding effect (ii): In FIG. 4C, in the removal step, the separation layer 2, the first adhesive layer 3A, and the second adhesive layer 3B attached to the device layer 456 are removed, thereby obtaining the electronic component 50. In the laminate 200, the second adhesive layer 3B adjacent to the device layer 456 is a layer formed from an adhesive composition containing a block copolymer having a first block and a second block and exhibiting an elastic modulus of 20 MPa or more at 260°C. The second adhesive layer 3B contains a specific block copolymer, i.e., the first block is a block composed of a polymer consisting of a repeating structure of structural units (u1) derived from norbornene, which may have a substituent, making it easily soluble in the cleaning solution. This allows the adhesive layer to be easily removed by cleaning from the device layer 456.

[0198] That is, according to the laminate to which the present invention is applied, it is possible to provide a laminate in which deformation due to an external force is suppressed and the adhesive layer is easily removable by washing.

[0199] Other embodiments: In the laminate 100 shown in FIG. 1 and the laminate 200 shown in FIG. 3, the support 12 is composed of a support base 1 and a separation layer 2, but is not limited to this, and the support may be composed of only a support base by using a first adhesive layer or a second adhesive layer that also functions as a separation layer.

[0200] In the laminate 100 and the laminate 200, the support base 1 and the separation layer 2 are adjacent to each other, but this is not limiting, and other layers may be provided between the support base 1 and the separation layer 2. In this embodiment, the other layers only need to be made of a material that transmits light. This allows layers that impart desirable properties to the laminate to be added as appropriate without preventing light from entering the separation layer 2. The wavelengths of light that can be used vary depending on the type of material that constitutes the separation layer 2. Therefore, the material that constitutes the other layers does not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of wavelengths that can alter the material that constitutes the separation layer 2.

[0201] In the method for manufacturing an electronic component according to the embodiment described above, after the removal step, the electronic component 50 may be further subjected to processes such as solder ball formation, dicing, and oxide film formation.

[0202] [Composition for forming separation layer] The separation layer-forming composition, which is a material for forming the separation layer, may contain, for example, a fluorocarbon, a polymer having a repeating unit including a structure having light absorption properties, an inorganic substance, a compound having an infrared absorbing structure, an infrared absorbing substance, a reactive polysilsesquioxane, or a resin component having a phenol skeleton. The separation layer-forming composition may also contain optional components such as a filler, a plasticizer, a thermal acid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a component that can improve the separability of the supporting substrate.

[0203] Fluorocarbon The separation layer may contain a fluorocarbon. A separation layer made of a fluorocarbon is altered by absorbing light, and as a result, loses the strength or adhesiveness it had before being irradiated with light. Therefore, by applying a slight external force (for example, by lifting the support), the separation layer is destroyed, making it easier to separate the support and the device layer. The fluorocarbon that constitutes the separation layer can be suitably formed into a film by a plasma CVD method. Fluorocarbons absorb light within a specific wavelength range depending on the type of fluorocarbon. By irradiating the separation layer with light within the range of wavelengths absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be suitably altered. The light absorption rate of the separation layer is preferably 80% or more.

[0204] The light to be irradiated onto the separation layer may be laser light, such as a solid-state laser (e.g., YAG laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, fiber laser), a liquid laser (e.g., dye laser), a gas laser (e.g., CO2 laser, excimer laser, Ar laser, He-Ne laser), a semiconductor laser, a free electron laser, or a non-laser light, depending on the wavelength that can be absorbed by the fluorocarbon. Wavelengths that can alter the fluorocarbon include, for example, wavelengths in the range of 600 nm or less.

[0205] Polymers having repeating units containing light-absorbing structures The separation layer may contain a polymer having a repeating unit containing a structure having light absorption properties, and the polymer is altered when irradiated with light. Examples of the light-absorbing structure include an atomic group containing a conjugated π-electron system consisting of a substituted or unsubstituted benzene ring, a fused ring, or a heterocyclic ring. More specific examples of the light-absorbing structure include a cardo structure, or a benzophenone structure, a diphenylsulfoxide structure, a diphenylsulfone structure (bisphenylsulfone structure), a diphenyl structure, or a diphenylamine structure present in the side chain of the polymer. The light-absorbing structure can absorb light having a wavelength in a desired range depending on the type of the structure. For example, the wavelength of light that can be absorbed by the light-absorbing structure is preferably in the range of 100 to 2000 nm, and more preferably in the range of 100 to 500 nm.

[0206] Examples of light that can be absorbed by the light-absorbing structure include light emitted from a high-pressure mercury lamp (wavelength of 254 nm or more and 436 nm or less), a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), an F2 excimer laser (wavelength of 157 nm), a XeCl laser (wavelength of 308 nm), a XeF laser (wavelength of 351 nm), or a solid-state UV laser (wavelength of 355 nm), or g-line (wavelength of 436 nm), h-line (wavelength of 405 nm), or i-line (wavelength of 365 nm).

[0207] ·Inorganic matter The separation layer may be made of an inorganic material. The inorganic material may be any material that changes its properties by absorbing light, and suitable examples include one or more materials selected from the group consisting of metals, metal compounds, and carbon. Metal compounds are compounds containing metal atoms, and examples include metal oxides and metal nitrides. Such inorganic materials include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO2, SiN, Si3N4, TiN, and carbon. The term "carbon" is a concept that may include allotropes of carbon, such as diamond, fullerene, diamond-like carbon, and carbon nanotubes. The inorganic substances absorb light having wavelengths in a specific range depending on the type of inorganic substance.

[0208] The light to be irradiated onto the separation layer made of an inorganic material may be laser light such as a solid laser such as a YAG laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, or fiber laser, a liquid laser such as a dye laser, a gas laser such as a CO2 laser, excimer laser, Ar laser, or He-Ne laser, a semiconductor laser, or a free electron laser, or non-laser light, depending on the wavelength that can be absorbed by the inorganic material. The inorganic separation layer can be formed on the support substrate by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating.

[0209] Compounds with infrared absorbing structures The separation layer may contain a compound having an infrared absorbing structure, which is altered by absorbing infrared rays. Examples of structures having infrared absorption properties or compounds having such structures include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulenic, cyclic), alkynes (monosubstituted, disubstituted), monocyclic aromatics (benzene, monosubstituted, disubstituted, trisubstituted), alcohols or phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetals, ketals, aliphatic ethers, aromatic ethers, vinyl ethers, oxirane ring ethers, peroxide ethers, ketones, dialkyl carbonyls, aromatic carbonyls, enols of 1,3-diketones, o-hydroxyaryl ketones, dialkyl aldehydes, aromatic aldehydes, carboxylic acids (dimers, carboxylic acid anions), formates, acetates, conjugated esters, non-conjugated esters, aromatic esters, lactones (β-, γ-, δ-), aliphatic acid chlorides, and aromatic acid salts. compounds, acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amides, secondary amides, lactams, primary amines (aliphatic, aromatic), secondary amines (aliphatic, aromatic), tertiary amines (aliphatic, aromatic), primary amine salts, secondary amine salts, tertiary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, isocyanates, thiocyanates, aliphatic isothiocyanates, aromatic isothiocyanates, aliphatic nitro compounds, aromatic nitro compounds, nitroamines, nitrosamines, nitrates, nitrites, nitroso bonds (aliphatic, aromatic, monomers, dimers), sulfur compounds such as mercaptans, thiophenols, or thiolic acids, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary sulfonamides, secondary sulfonamides, sulfates, carbon-halogen bonds, Si-A 1 Join(A 1 is H, C, O or halogen), PA 2 Join(A 2 is a H, C or O) or Ti—O bond.

[0210] Examples of the structure containing the carbon-halogen bond include -CH2Cl, -CH2Br, -CH2I, -CF2-, -CF3, -CH=CF2, -CF=CF2, aryl fluoride, and aryl chloride.

[0211] The above Si-A 1 Examples of structures containing bonds include SiH, SiH2, SiH3, Si-CH3, Si-CH2-, Si-C6H5, SiO-aliphatic, Si-OCH3, Si-OCH2CH3, Si-OC6H5, Si-O-Si, Si-OH, SiF, SiF2, and SiF3. Si-A 1 As the structure containing the bond, it is particularly preferable that a siloxane skeleton or a silsesquioxane skeleton is formed.

[0212] The above PA 2 Examples of structures containing bonds include PH, PH2, P-CH3, P-CH2-, P-C6H5, and A 3 3-PO(A 3 is an aliphatic group or an aromatic group), (A 4 O)3-PO(A 4 is an alkyl group), P-OCH3, P-OCH2CH3, P-OC6H5, POP, P-OH, or O=P-OH.

[0213] Examples of the compounds containing the Ti-O bond include: (i) alkoxytitanium compounds such as tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and titanium-i-propoxyoctylene glycolate; (ii) chelate titanium compounds such as di-i-propoxy bis(acetylacetonato)titanium and propanedioxytitanium bis(ethylacetoacetate); and (iii) i-C3H7O-[-Ti(Oi-C3H7)2-O-]. n -i-C3H7 or n-C4H9O-[-Ti(On-C4H9)2-O-] n(iv) titanium acylates such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, and (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium; and (v) water-soluble titanium compounds such as di-n-butoxybis(triethanolaminato)titanium. Among them, di-n-butoxybis(triethanolaminato)titanium (Ti(OC4H9)2[OC2H4N(C2H4OH)2]2) is preferred as a compound containing a Ti-O bond.

[0214] The infrared absorbing structure can absorb infrared rays having wavelengths in a desired range depending on the type of structure selected. Specifically, the infrared absorbing structure can absorb infrared rays having wavelengths in the range of 1 to 20 μm, for example, and more preferably in the range of 2 to 15 μm. Furthermore, when the structure is an Si—O bond, an Si—C bond, or a Ti—O bond, the thickness is preferably within the range of 9 to 11 μm.

[0215] Those skilled in the art can easily understand the infrared wavelengths that can be absorbed by each of the above structures. For example, the absorption bands of each structure can be found in the non-patent literature, "Spectroscopic Identification of Organic Compounds (5th Edition) - Combined Use of MS, IR, NMR, and UV" (published in 1992), pages 146 to 151, by Silverstein, Bassler, and Morrill.

[0216] The compound having an infrared absorbing structure used to form the separation layer is not particularly limited, as long as it can be dissolved in a solvent for application and solidified to form a solid layer among the compounds having the structure described above. However, in order to effectively alter the compound in the separation layer and facilitate separation of the support substrate and the device layer, it is preferable that the separation layer has high infrared absorption, that is, low infrared transmittance when irradiated with infrared rays. Specifically, the infrared transmittance of the separation layer is preferably less than 90%, and more preferably less than 80%.

[0217] Infrared absorbing materials The separation layer may contain an infrared absorbing material, which may be any material that changes its properties when it absorbs light, and suitable examples of such materials include carbon black, iron particles, and aluminum particles. Each type of infrared absorbing material absorbs light having a specific range of wavelengths. By irradiating the separation layer with light having a wavelength within the range absorbed by the infrared absorbing material used in the separation layer, the infrared absorbing material can be suitably altered.

[0218] Reactive polysilsesquioxane The separation layer can be formed by polymerizing a reactive polysilsesquioxane, and the resulting separation layer has high chemical resistance and high heat resistance.

[0219] The term "reactive polysilsesquioxane" refers to a polysilsesquioxane having a silanol group or a functional group capable of forming a silanol group upon hydrolysis at the end of the polysilsesquioxane skeleton. The silanol groups or the functional groups capable of forming a silanol group can be polymerized with each other by condensing them. Furthermore, as long as the reactive polysilsesquioxane has a silsesquioxane skeleton with a random structure, a cage structure, a ladder structure, or the like, it is possible to use a reactive polysilsesquioxane having a silanol group or a functional group capable of forming a silanol group.

[0220] The siloxane content of the reactive polysilsesquioxane is preferably 70 to 99 mol %, and more preferably 80 to 99 mol %. When the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferred range, a separation layer can be formed that can be suitably altered by irradiation with infrared rays (preferably far infrared rays, more preferably light with a wavelength of 9 to 11 μm).

[0221] The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, and more preferably 1,000 to 10,000. When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferred range, it can be suitably dissolved in a solvent and can be suitably applied onto a support plate.

[0222] Examples of commercially available reactive polysilsesquioxanes that can be used include SR-13, SR-21, SR-23, and SR-33 (trade names) manufactured by Konishi Chemical Industry Co., Ltd.

[0223] Resin components with a phenolic skeleton The separation layer may contain a resin component having a phenol skeleton, which is easily altered (oxidized, etc.) by heating or the like, thereby increasing photoreactivity. Here, "having a phenol skeleton" means containing a hydroxybenzene structure. The resin component having a phenol skeleton has film-forming ability and preferably has a molecular weight of 1,000 or more. When the molecular weight of the resin component is 1,000 or more, the film-forming ability is improved. The molecular weight of the resin component is more preferably 1,000 to 30,000, further preferably 1,500 to 20,000, and particularly preferably 2,000 to 15,000. When the molecular weight of the resin component is equal to or less than the upper limit of the above-mentioned preferred range, the solubility of the separation layer-forming composition in a solvent is increased.

[0224] Examples of resin components having a phenol skeleton include novolac phenol resins, resol phenol resins, hydroxystyrene resins, hydroxyphenyl silsesquioxane resins, hydroxybenzyl silsesquioxane resins, acrylic resins containing a phenol skeleton, etc. Among these, novolac phenol resins and resol phenol resins are more preferred. [Example]

[0225] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0226] <Preparation of Adhesive Composition> (Examples 1 to 6, Comparative Examples 1 and 2) The components shown in Table 1 were mixed and dissolved to prepare adhesive compositions of each example (resin component concentration: approximately 14% by mass).

[0227] [Table 1]

[0228] In Table 1, the abbreviations have the following meanings: The numbers in brackets [ ] are the blend amounts (parts by mass).

[0229] P-1: Block copolymer represented by the following chemical formula (BCP-1). Weight average molecular weight (Mw) 320,000; n / m = 1 / 1 (molar ratio), R is a linear alkyl group with 10 carbon atoms. PRZ-X10495 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0230] [ka]

[0231] P-2: Block copolymer represented by the following chemical formula (BCP-2). Weight average molecular weight (Mw) 410,000; n / m / l = 1 / 1 / 1 (molar ratio), R is a linear alkyl group with 10 carbon atoms. PRZ-X10496 (manufactured by Sumitomo Bakelite Co., Ltd.)

[0232] [ka]

[0233] P-3: Homopolymer (poly n-butylnorbornene) represented by the following chemical formula (P2-1). Weight average molecular weight (Mw) 500,000. P-4: Random copolymer represented by the following chemical formula (P2-2). Weight average molecular weight (Mw) approximately 100,000; m / n = 80 / 20 (molar ratio).

[0234] [ka]

[0235] P-5: Copolymer represented by the following formula (P2-3). Weight average molecular weight (Mw) is about 8000. 1 / m = 65 / 35 (molar ratio); R u10 is a methyl group; R u11 is a hydrogen atom, R u12 is a hydrogen atom, R u13 is a hydrogen atom, R u14 is a butyl group; n is 1

[0236] P-6: Acrylic resin represented by the following formula (P2-4). Weight average molecular weight (Mw) approximately 10,000. l / m / n = 60 / 20 / 20 (molar ratio).

[0237] [ka]

[0238] Add-1: An antioxidant having a structure represented by the following chemical formula (x). Add-2: An antioxidant having a structure represented by the following chemical formula (y). Add-3: An antioxidant having a structure represented by the following chemical formula (z).

[0239] [ka]

[0240] S-1: Decahydronaphthalene

[0241] <Evaluation> The adhesive composition was evaluated by measuring the modulus of elasticity at 260° C. The second adhesive layer was evaluated by measuring the film stress, the amount of warpage, and the adhesion.

[0242] [Elastic modulus at 260℃] Each adhesive composition of each example was spin-coated onto a silicon wafer by a spin coater method, and baked at temperatures of 90°C, 160°C, and 220°C for 4 minutes, respectively, to form an adhesive layer with a thickness of 50 μm. A test piece (film thickness 50 μm, width 5 mm, length 40 mm) of the adhesive layer was cut out, and the tensile modulus was measured at a frequency of 1 Hz in the range of 50 to 300° C. using Rheogel-E4000 (manufactured by UBM). The modulus at 260° C. is shown in Table 2.

[0243] [Membrane stress, warpage] The "warpage amount" of an 8-inch silicon wafer with a thickness of 725 μm±25 μm was measured in advance using a residual stress measuring device (manufactured by Tencor Corporation, model name FLX3300-T). The adhesive composition of each example was spin-coated onto the 8-inch silicon wafer and baked at temperatures of 90°C, 160°C, and 220°C for 4 minutes, respectively, to form an adhesive layer with a thickness of 50 µm. The amount of warpage [μm] of the 8-inch silicon wafer on which the adhesive layer was formed was measured using the residual stress measurement device, and the film stress [MPa] generated between the 8-inch silicon wafer and the adhesive layer was evaluated. The film stress [MPa] and the amount of warpage [μm] are shown in Table 2.

[0244] [Adhesion] The adhesive composition of each example was applied onto a silicon substrate (size 6 inches, thickness 675 μm) by spin coating while rotating at 1000 rpm. Next, each of the silicon substrates coated with the adhesive composition was preheated at 90° C. for 4 minutes to form an adhesive layer with a thickness of 35 μm. Next, the adhesive layer was linearly cut using a cutter. The cutting line of the adhesive layer thus formed was set to cross the silicon substrate. The distance [mm] from the cutting line to which the adhesive layer peeled was measured, and the adhesion between the silicon substrate and the adhesive layer was evaluated. The results are shown in Table 2. A shorter peel distance indicates better adhesion of the adhesive layer to the silicon substrate.

[0245] [Virtual TCB Test] Each laminate was produced using the adhesive composition of each example, and then the 8-inch silicon wafer (device layer) constituting each laminate was ground to a thickness of 50 μm. After grinding, a Si chip cut to 2 mm x 2 mm was attached to the device layer surface with a force of 3 N / mm using a benchtop die bonder T-3000-FC3 with a stage temperature of 100°C and a bonder terminal temperature of 300°C. 2 The device was pressed down with a force of 1000 for 5 seconds. This Si chip pressing operation was repeated eight times. After that, the depth [μm] of the second adhesive layer pressed by the Si chip was measured. The results are shown in Table 2 as virtual TCB test [μm]. It is considered that there is no problem if the pressing depth is 3 μm or less, and the second adhesive layer is unlikely to deform during the thermal process.

[0246] The laminate was produced as follows. The separation layer-forming composition was spin-coated on an 8-inch glass (support), baked at 90°C for 3 minutes, and then baked in an oven at 320°C for 60 minutes to form a separation layer. Meanwhile, the adhesive composition of each example was spin-coated onto an 8-inch silicon wafer (device layer) and baked for 3 minutes at temperatures of 90°C, 160°C, and 220°C, respectively, to form a second adhesive layer with a film thickness of 30 μm. Next, the first material was applied onto the second adhesive layer and baked at temperatures of 90°C, 160°C, and 220°C for 3 minutes each to form a first adhesive layer with a film thickness of 30 μm. Next, the support on which the separation layer was formed was laminated on the first adhesive layer to obtain a laminate in which the support, separation layer, first adhesive layer, second adhesive layer and device layer were laminated in this order.

[0247] As the first material, an elastomer adhesive containing a hydrogenated styrene-based thermoplastic elastomer: TZNR-A4035 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. The separation layer-forming composition used was TZNR-CTRL9 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.).

[0248] [Table 2]

[0249] The results shown in Table 2 confirm that the adhesive compositions of Examples 1 to 6 are able to form adhesive layers that are resistant to deformation (warping, indentation) due to external forces and have improved adhesion between the silicon substrate and the adhesive layer. [Explanation of symbols]

[0250] 1 Supporting base 2 separation layer 3' adhesive layer 3A First Adhesive Layer 3B Second adhesive layer 4 boards 5 Encapsulant layer 6 Redistribution layer 12 Support 45 Device Layer 50 Electronic Components 100 laminate 200 laminate 456 Device Layer

Claims

1. An adhesive composition for forming a second adhesive layer in a laminate in which a support, a first adhesive layer, a second adhesive layer, and a device layer are laminated in this order, comprising: A block copolymer having a first block and a second block, the first block is a block constituted by a polymer having a repeating structure of a structural unit (u1) derived from norbornene which may have a substituent, An adhesive composition having an elastic modulus of 20 MPa or more at 260°C.

2. 2. The adhesive composition according to claim 1, wherein the second block is a block constituted of a polymer comprising a repeating structure of a structural unit (u2) derived from norbornene which may have a substituent and which has a different structure from the structural unit (u1).

3. The adhesive composition according to claim 1 or 2, wherein the structural unit (u1) is a structural unit derived from unsubstituted norbornene.

4. The adhesive composition according to claim 3, wherein the structural unit (u2) is a structural unit derived from norbornene having an alkyl group having 1 to 16 carbon atoms as a substituent.

5. the block copolymer further comprises a third block; 3. The adhesive composition according to claim 1, wherein the third block is a block constituted by a polymer having a repeating structure of a structural unit (u3) derived from norbornene which may have a substituent.

6. The adhesive composition according to claim 5 , wherein the structural unit (u3) is a structural unit derived from unsubstituted norbornene.

7. The adhesive composition according to claim 1 , wherein the block copolymer has a weight average molecular weight (Mw) of 10,000 or more and 700,000 or less.

8. The adhesive composition according to claim 1 , further comprising an antioxidant.

Images