Adhesive film, method for producing adhesive film, adhesive resin composition, and method for producing semiconductor device

Abstract

The present invention provides an adhesive film which has an adhesive layer, wherein: the adhesive layer contains a photocurable adhesive; the peak value of probe tack of the adhesive layer at 60°C is 0.30 N / cm2 or more after irradiating the adhesive film with light having a wavelength of 405 nm and an illuminance of 100 mW / cm2 for 200 seconds using an ultra-high pressure mercury lamp so that the accumulated amount of light becomes 20,000 mJ / cm2; and the 5% weight loss temperature of the adhesive film is 390°C or higher after irradiating the adhesive film with light having a wavelength of 405 nm and an illuminance of 100 mW / cm2 for 200 seconds using an ultra-high pressure mercury lamp so that the accumulated amount of light becomes 20,000 mJ / cm2. The present invention also provides: an adhesive resin composition; and a method for producing a semiconductor device using the adhesive film.

Description

Adhesive film, method for manufacturing an adhesive film, adhesive resin composition, and method for manufacturing a semiconductor device

[0001] The present invention relates to an adhesive film. Also, the present invention relates to a method for producing the adhesive film. Furthermore, the present invention relates to an adhesive resin composition. In addition, the present invention relates to a method for producing a semiconductor device.

[0002] During processing of electronic components such as semiconductors, in order to facilitate handling of the electronic components and prevent breakage, the electronic components are fixed to a support plate via a temporary fixing material made of an adhesive resin composition, or an adhesive film having an adhesive layer is attached to the electronic components to protect them. For example, when a thick film wafer cut from a high-purity silicon single crystal or the like is ground to a predetermined thickness to obtain a thin film wafer, the thick film wafer is adhered to a support plate via an adhesive resin composition.

[0003] Thus, adhesive resin compositions and adhesive films used for electronic components are required to have high enough adhesion to firmly fix the electronic components during processing, and also to be able to be peeled off without damaging the electronic components after processing is completed (hereinafter also referred to as "high adhesion and easy peeling"). As a means for achieving high adhesion and easy peeling, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet using a pressure-sensitive adhesive in which a polyfunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to the side chain or main chain of the polymer. By utilizing the fact that the polymer has a radiation-polymerizable functional group, which hardens when irradiated with ultraviolet light, the adhesive strength is reduced by irradiating with ultraviolet light during peeling, allowing peeling without leaving any adhesive residue.

[0004] Japanese Patent Application Publication No. 5-32946

[0005] In recent years, in order to accommodate the increasing integration of semiconductors, the TBDB (Temporary Bonding / De-Bonding) process has been adopted, in which semiconductors are manufactured by supporting thin wafers with a support and a temporary fixing material such as an adhesive film. In the TBDB process, it is necessary to remove the support and the temporary fixing material from the wafer after the process is completed. When the temporary fixing material is in tape form, it is removed by peeling. Wafers often have irregularities called bumps, and it is required that the temporary fixing material be easily peeled off not only from smooth wafers but also from wafers having irregularities after the semiconductor manufacturing process.

[0006] Furthermore, when the semiconductor manufacturing process includes a thermal process, the temporary fixing material is also required to have heat resistance corresponding to the temperature at which the semiconductor is manufactured. Conventionally, resins that are hard at room temperature have often been used as the resin contained in the adhesive layer of heat-resistant temporary fixing materials. However, when a temporary fixing material using such a resin is used to temporarily fix a wafer having irregularities, the temporary fixing material is strongly adhered to the wafer having irregularities due to the anchor effect, which poses a problem that it is difficult to peel the temporary fixing material from the wafer after the semiconductor manufacturing process.

[0007] An object of the present invention is to provide an adhesive film that has excellent heat resistance and can be easily removably attached to an adherend having an uneven surface by heating. Another object of the present invention is to provide a method for producing the adhesive film. A further object of the present invention is to provide an adhesive resin composition that has excellent heat resistance and can be easily removably attached to an adherend having an uneven surface by heating. Additionally, an object of the present invention is to provide a method for producing a semiconductor device that includes a step in which an adhesive film having excellent heat resistance can be easily removably attached to an adherend having an uneven surface, even when an adhesive film having excellent heat resistance is used.

[0008] Disclosure 1 provides an adhesive film having an adhesive layer, the adhesive layer containing a photocurable adhesive, and the adhesive film is irradiated with light from an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ After irradiating for 200 seconds so as to obtain a peak probe tack value of 0.30 N / cm at 60°C of the adhesive layer.２ The adhesive film was irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２ The adhesive film has a 5% weight loss temperature of 390°C or higher after being irradiated for 200 seconds so that the 5% weight loss temperature of the adhesive film becomes 390°C or higher. Disclosure 2 is the adhesive film of Disclosure 1, wherein the photocurable adhesive comprises a curable resin, and the curable resin comprises a resin having an imide skeleton in a repeating unit of the main chain. Disclosure 3 is the adhesive film of Disclosure 1 or 2, wherein the photocurable adhesive contains an ultraviolet absorber. Disclosure 4 is the adhesive film of Disclosure 1, 2, or 3, wherein the photocurable adhesive contains a surface conditioner. Disclosure 5 is the adhesive film of Disclosure 1, 2, 3, or 4, which has a substrate. Disclosure 6 is the adhesive film of Disclosure 5, wherein the substrate contains a resin (A1) having in its main chain skeleton a repeating unit containing at least one selected from the group consisting of an ether bond, a ketone group, and an ester bond. Disclosure 7 is the adhesive film of Disclosure 5 or 6, wherein at least one surface of the substrate has an easy-adhesion layer. The present disclosure 8 is the adhesive film of the present disclosure 7, wherein the easy-adhesion layer includes at least one layer selected from a corona-treated layer, a plasma-treated layer, a sandblasted layer, a chemically etched layer, and a treatment-coated layer. The present disclosure 9 is the adhesive film of the present disclosure 5, 6, 7, or 8, which has the adhesive layer on both sides of the substrate. The present disclosure 10 is the adhesive film of the present disclosure 10, wherein the adhesive layer is formed by applying a 405 nm wavelength, 80 mW / cm illuminance, to the adhesive film using an ultra-high pressure mercury lamp. ２ The adhesive film of the present disclosure 5, 6, 7, 8 or 9, wherein the anchoring force to the substrate at 23°C after irradiating the adhesive film with light of 405 nm wavelength and 100 mW / cm irradiance at 23°C for 300 seconds is 0.10 N / 25 mm or more. ２ The cumulative light intensity is 20,000 mJ / cm ２ After irradiating for 200 seconds so as to obtain a peak probe tack value of 5.00 N / cm at 23°C of the adhesive layer. ２The adhesive film of Disclosure 12 is an adhesive film according to Disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, which is as follows: Disclosure 13 is an adhesive film according to Disclosure 12, which is characterized in that the adhesive layer is irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 80 mW / cm ２ The tensile storage modulus at 23°C after irradiation with light of 1.0 x 10 for 300 seconds was 1.0 x 10 ８ The adhesive film of Disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the adhesive film has a water absorption rate of 0.60% or less when left standing for 1 day under conditions of 23°C and 50% RH. The adhesive film of Disclosure 13, wherein the adhesive film has a water absorption rate of 0.60% or less when left standing for 1 day under conditions of 23°C and 50% RH. The adhesive film of Disclosure 14, wherein the adhesive film has a 10% weight loss temperature of 425°C or higher. The adhesive film of Disclosure 15, wherein the adhesive film of Disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, is used for temporarily fixing electronic components. Disclosure 16 is a method for producing an adhesive film according to Disclosure 7 or 8, comprising a step of performing at least one surface treatment selected from corona treatment, plasma treatment, sandblasting, chemical etching, and treatment agent application on at least one surface of the substrate. Disclosure 17 is a method for producing an adhesive film having a peak probe tack of 0.30 N / cm at 60°C after curing. ２ and a 5% weight loss temperature after curing of 390°C or higher. Disclosure 18 is an adhesive film having an adhesive layer containing the adhesive resin composition of Disclosure 17. Disclosure 19 is a method for manufacturing a semiconductor device using an adhesive film, the adhesive film having an adhesive layer, the adhesive film having a 5% weight loss temperature of 390°C or higher, and a semiconductor device having a peak probe tack value of 0.30 N / cm ２ and (II) peeling the adhesive film from the semiconductor device at a temperature T° C. or higher. Disclosure 20 is the method for producing a semiconductor device according to Disclosure 19, wherein the temperature T° C. is 60° C. or higher. The present invention will be described in detail below.

[0009] The present inventors have found that an adhesive film having an adhesive layer, which has a peak value of probe tack within a specific range, can be easily peeled from an adherend having irregularities by peeling it off while heating. Furthermore, as a result of examining the 5% weight loss temperature of the adhesive film, it has been found that an adhesive film having excellent heat resistance and which can be easily peeled off even from an adherend having irregularities by heating can be obtained, and this has led to the completion of the present invention.

[0010] The adhesive film of the present invention has an adhesive layer. The adhesive layer contains a photocurable adhesive. By containing the photocurable adhesive, the adhesive layer has photocurability, and by curing the adhesive layer by irradiation with light, it is possible to suppress increased adhesion of the adhesive film during high-temperature processing, and the adhesive film can be easily peeled off.

[0011] The photocurable adhesive preferably contains a curable resin. The curable resin preferably contains a resin having an imide skeleton in the repeating unit of the main chain. The resin having an imide skeleton in the repeating unit of the main chain has extremely excellent heat resistance due to the imide skeleton, and decomposition of the main chain is unlikely to occur even when subjected to high-temperature processing at 300°C or higher. Therefore, by containing a curable resin containing a resin having an imide skeleton in the repeating unit of the main chain, the adhesive film obtained has excellent heat resistance and can further suppress outgassing during high-temperature processing, voids between the film and the adherend, and lifting. In addition, it can prevent increased adhesion to the adherend and the generation of adhesive residue when peeled from the adherend.

[0012] The resin having the imide skeleton in the repeating unit of the main chain preferably has a constitutional unit represented by the following formula (1).

[0013]

[0014] In the above formula (1), P １ is preferably an aromatic group having 5 to 50 carbon atoms. １is an aromatic group having 5 to 50 carbon atoms, the adhesive film obtained has better heat resistance. That is, outgassing during high-temperature processing, voids between the film and the adherend, and lifting can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented.

[0015] In the above formula (1), Q １ is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having from 2 to 100 carbon atoms. １ When Q is a substituted or unsubstituted linear, branched or cyclic aliphatic group having from 2 to 100 carbon atoms, the adhesive film obtained has better light transmittance. In addition, the adhesive film obtained has better flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off. In addition, when Q is １ is preferably an aliphatic group derived from a diamine compound. In particular, from the viewpoints of light transparency, flexibility, and compatibility with solvents and other components of the resin having the imide skeleton in the main chain repeating unit, the Q １ is preferably an aliphatic group derived from a dimer diamine. The dimer diamine is a diamine compound obtained by reducing and amminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples thereof include linear, monocyclic, and polycyclic dimer diamines. The dimer diamine may contain a carbon-carbon double bond or may be a hydrogenated product to which hydrogen has been added.

[0016] The aliphatic group derived from the dimer diamine is preferably at least one group selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4). Among these, the group represented by the following formula (2-2) is more preferred.

[0017]

[0018] In formulas (2-1) to (2-4), R１ ~R １６ are each independently a linear or branched hydrocarbon group, and * represents a bond, which bonds to N in the above formula (1).

[0019] In the above formulas (2-1) to (2-4), R １ ~R １６ The hydrocarbon group represented by R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. １ and R ２ , R ３ and R ４ , R ５ and R ６ , R ７ and R ８ , R ９ and R １０ , R １１ and R １２ , R １３ and R １４ , and R １５ and R １６ The total number of carbon atoms is preferably 7 or more and 50 or less. When the total number of carbon atoms is within the above range, the resulting adhesive film will be superior in light transparency, flexibility, and compatibility with solvents and other components of the resin having the imide skeleton in the main chain repeating unit. The total number of carbon atoms is more preferably 9 or more, even more preferably 12 or more, and still more preferably 14 or more. The total number of carbon atoms is more preferably 35 or less, even more preferably 25 or less, and still more preferably 18 or less.

[0020] In the group represented by the formula (2-1), the group represented by the formula (2-2), the group represented by the formula (2-3), and the group represented by the formula (2-4), the optical isomerism is not particularly limited, and any optical isomerism is included.

[0021] The resin having an imide skeleton in the repeating unit of the main chain preferably includes a resin having no maleimide group and having an imide skeleton in the repeating unit of the main chain, and more preferably includes a resin having no polymerizable functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain.

[0022] The resin having no maleimide groups and an imide skeleton in its main chain repeating unit preferably has a weight-average molecular weight of 20,000 or more and 2,000,000 or less. When the resin having no maleimide groups and an imide skeleton in its main chain repeating unit has a weight-average molecular weight of 20,000 or more, the resulting adhesive film has better heat resistance. That is, outgassing and the occurrence of voids and lifting between the film and the adherend during high-temperature processing can be further suppressed, and increased adhesion to the adherend and the occurrence of adhesive residue upon peeling from the adherend can be further prevented. When the resin having no maleimide groups and an imide skeleton in its main chain repeating unit has a weight-average molecular weight of 2,000,000 or less, the resin having no maleimide groups and an imide skeleton in its main chain repeating unit has better compatibility with solvents and other components. The weight-average molecular weight of the resin having no maleimide group and an imide skeleton as a repeating unit in the main chain is more preferably 40,000 in lower limit, 600,000 in upper limit, 50,000 in even more preferred lower limit, and 300,000 in even more preferred upper limit. In this specification, the weight-average molecular weight is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Specifically, for example, it can be measured using an APC system (manufactured by Waters Corporation) under the following conditions: a mobile phase of THF, a flow rate of 1.0 mL / min, a column temperature of 40°C, a sample concentration of 0.2% by mass, and an RI-PDA detector. The column may be, for example, an HR-MB-M 6.0 x 150 mm (manufactured by Waters Corporation).

[0023] Specific examples of the resin that does not have a maleimide group and has an imide skeleton in the repeating unit of the main chain include resins that have a constitutional unit represented by the above formula (1) and have functional groups at both ends that do not have maleimide groups.

[0024] The resin having a structural unit represented by the above formula (1) and a functional group having no maleimide group at both ends may have a structural unit represented by the following formula (3).

[0025]

[0026] In formula (3), P２ represents an aromatic group; ２ represents a group having a substituted or unsubstituted aromatic structure.

[0027] In the above formula (3), P ２ is preferably an aromatic group having 5 to 50 carbon atoms. ２ is an aromatic group having 5 to 50 carbon atoms, the adhesive film obtained has better heat resistance. That is, it is possible to further suppress outgassing, voids, and lifting between the film and the support during high-temperature processing, and it is also possible to further prevent increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend.

[0028] In the above formula (3), Q ２ is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. ２ is a substituted or unsubstituted group having an aromatic structure having from 5 to 50 carbon atoms, the adhesive film obtained has better heat resistance. That is, it is possible to further suppress outgassing during high-temperature processing, voids between the film and the adherend, and lifting, and it is also possible to further prevent increased adhesion to the adherend and adhesive residue when peeled from the adherend.

[0029] Examples of the functional group not having a maleimide group include an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride group, and an amino group. Specific examples include an unreacted terminal group of an acid anhydride or diamine compound that serves as a raw material for a resin not having a maleimide group and having an imide skeleton in the repeating unit of its main chain. In a resin having a structural unit represented by formula (1) and functional groups not having a maleimide group at both ends, the functional groups not having a maleimide group at both ends may be the same or different.

[0030] In a resin having a structural unit represented by the formula (1) and functional groups not having maleimide groups at both ends, the content of the structural unit represented by the formula (1) is preferably 30 mol% or more, more preferably 50 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less. When a resin having a structural unit represented by the formula (1) and functional groups not having maleimide groups at both ends has a structural unit represented by the formula (3), the content of the structural unit represented by the formula (3) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. When the contents of the structural units represented by the formula (1) and the structural units represented by the formula (3) are within the above ranges, the resulting adhesive film can further suppress the occurrence of outgassing, voids, and lifting between the support and the film during high-temperature processing, and can be more easily peeled off from the adherend. The structural unit represented by the formula (1) and the structural unit represented by the formula (3) may have a block structure consisting of block components in which the respective structural units are arranged consecutively, or may have a random structure in which the respective structural units are arranged randomly.

[0031] Examples of a method for producing the resin having no maleimide group and an imide skeleton in the repeating unit of the main chain include a method of reacting a diamine compound with an aromatic acid anhydride.

[0032] As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used. By using an aliphatic diamine compound as the diamine compound, the resulting adhesive film has better light transmittance. Furthermore, the resulting adhesive film has better flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off. Furthermore, by using an aromatic diamine compound as the diamine compound, the resulting adhesive film has better heat resistance. The diamine compounds may be used alone or in combination of two or more.

[0033] Examples of the aliphatic diamine compound include 1,10-diaminodecane, 1,12-diaminododecane, dimer diamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane.

[0034] Among the aliphatic diamine compounds, dimer diamine is preferred from the viewpoints of light transparency, flexibility, and compatibility with solvents and other components of the resin that does not have a maleimide group and has an imide skeleton as a repeating unit in the main chain. Specific examples of the dimer diamine include dimer diamines that can constitute at least one group selected from the group consisting of the group represented by the above formula (2-1), the group represented by formula (2-2), the group represented by formula (2-3), and the group represented by formula (2-4).

[0035] Examples of the aromatic diamine compound include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diamino Aminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methan fluorene, bis(4-amino-3,5-diethylphenyl)methane, 9,9'-bis(4-amino-3-ethylphenyl)fluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenyl sulfone, 3,3'-diaminophenyl sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenyl)phenyl)sulfone Bis(phenoxy)phenyl)sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, Bisaniline M, Bisaniline P, 9,9-bis(4-aminophenyl)fluorene, o-tolidine sulfone, 5,5'-methylenebis(anthranilic acid), 1,Examples of suitable amines include 3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylenediamines (e.g., Jeffamine D-230, D400, D-2000, and D-4000 manufactured by Huntsman), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, and p-xylylenediamine.

[0036] Examples of the aromatic acid anhydride include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(3,4-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid), and other carboxylic acid anhydrides.

[0037] The preferred lower limit of the content of the resin having no maleimide group and an imide skeleton in the repeating unit of the main chain per 100 parts by mass of the curable resin is 10 parts by mass, and the preferred upper limit is 90 parts by mass. When the content of the resin having no maleimide group and an imide skeleton in the repeating unit of the main chain is within this range, the resulting adhesive film can be more easily peeled from the adherend. From the viewpoint of further improving removability, the more preferred lower limit of the content of the resin having no maleimide group and an imide skeleton in the repeating unit of the main chain is 20 parts by mass, and the more preferred upper limit is 80 parts by mass.

[0038] The resin having an imide skeleton in its main chain repeating unit preferably includes a resin having a functional group with a carbon-carbon double bond and an imide skeleton in its main chain repeating unit. By including a resin having a functional group with a carbon-carbon double bond and an imide skeleton in its main chain repeating unit, the resulting adhesive film undergoes uniform and rapid polymerization and crosslinking throughout upon irradiation with light, etc., resulting in an increase in elastic modulus and a significant decrease in adhesive strength. This further prevents increased adhesion and the occurrence of adhesive residue upon peeling. When the resin having an imide skeleton in its main chain repeating unit includes a resin that does not have the maleimide group and has an imide skeleton in its main chain repeating unit, it is preferable that the resin further includes a resin that has a functional group with a carbon-carbon double bond and has an imide skeleton in its main chain repeating unit, in addition to the resin that does not have a maleimide group and has an imide skeleton in its main chain repeating unit.

[0039] Examples of the functional group having a carbon-carbon double bond include an optionally substituted maleimide group, a citraconic imide group, a vinyl ether group, an allyl group, and a (meth)acryloyl group. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance. Note that a carbon-carbon double bond contained in an aromatic ring is not considered to be the carbon-carbon double bond of the functional group having a carbon-carbon double bond. Note that, in this specification, "(meth)acryloyl" means acryloyl or methacryloyl.

[0040] In the resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond preferably has a functional group equivalent (weight average molecular weight / number of functional groups having a carbon-carbon double bond) of 4,000 or less. When the functional group equivalent of the functional group having a carbon-carbon double bond is 4,000 or less, the resulting adhesive film has superior heat resistance. This is thought to be because the presence of functional groups having a carbon-carbon double bond at a density above a certain level in the resin molecule shortens the inter-crosslink distance, thereby further suppressing adhesion enhancement. The functional group equivalent of the functional group having a carbon-carbon double bond is more preferably 3,000 or less, and even more preferably 2,000 or less. Furthermore, there is no particular preferred lower limit for the functional group equivalent of the functional group having a carbon-carbon double bond, but the substantial lower limit is about 600.

[0041] The resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain preferably has a weight-average molecular weight of 1,000 or more and 100,000 or less. When the resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain has a weight-average molecular weight of 1,000 or more, the adhesive layer can be easily formed, and the resulting adhesive film exhibits a certain degree of flexibility, thereby exhibiting high conformability to an adherend having irregularities and allowing for easier peeling. When the resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain has a weight-average molecular weight of 100,000 or less, the solubility of the resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain in a solvent can be prevented from becoming too low. The weight average molecular weight of the resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain is more preferably 1,500 or more and 50,000 or less, and even more preferably 2,000 or more and less than 20,000.

[0042] In the resin having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond may be located either in a side chain or at a terminal, but is preferably located at both terminals, and more preferably located in both terminals and also in a side chain. The functional groups having a carbon-carbon double bond at both terminals of the resin having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain are highly reactive, allowing the adhesive film to be cured more sufficiently by irradiation with light, etc. As a result, enhanced adhesion and the occurrence of adhesive residue upon peeling can be more effectively prevented. Furthermore, the presence of a functional group having a carbon-carbon double bond in the side chain of the resin having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain results in the resulting adhesive film having superior heat resistance. This is thought to be due to the fact that enhanced adhesion is further suppressed by the shorter inter-crosslink distance. Furthermore, by having the functional group having a carbon-carbon double bond and by having the functional group having a carbon-carbon double bond in a side chain of the resin having an imide skeleton in the repeating unit of the main chain, it becomes easy to adjust the functional group equivalent to 4000 or less while maintaining the weight average molecular weight at 1000 or more. This allows the adhesive film to have sufficient initial adhesive strength, and at the same time, it is possible to further prevent increased adhesion and the occurrence of adhesive residue upon peeling.

[0043] As described above, in a resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain, the functional group having a carbon-carbon double bond may be located either in a side chain or at a terminal. When either the side chain or the terminal has a functional group other than a functional group having a carbon-carbon double bond (a functional group not having a carbon-carbon double bond), examples of the functional group not having a carbon-carbon double bond include aliphatic groups, alicyclic groups, aromatic groups, acid anhydride groups, and amino groups. Specific examples include unreacted terminal groups of acid anhydrides and diamine compounds that are raw materials for resins having the functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of their main chain. When a resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain has two or more functional groups not having a carbon-carbon double bond in a side chain or at a terminal, the functional groups not having a carbon-carbon double bond may be the same or different.

[0044] Specific examples of the resin having a functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain include resins having a constitutional unit represented by the above formula (1) and having a functional group having a carbon-carbon double bond at least in either the terminal or the side chain.

[0045] The resin having a structural unit represented by the above formula (1) and a functional group having a carbon-carbon double bond at least at either the terminal or the side chain may have at least one structural unit selected from the group consisting of a structural unit represented by the following formula (4-1) and a structural unit represented by the following formula (4-2):

[0046]

[0047] In formula (4-1), P ３ represents an aromatic group; ３ represents a group having a substituted or unsubstituted aromatic structure, and in formula (4-2), P ４ represents an aromatic group, R represents a substituted or unsubstituted branched aliphatic group or aromatic group, and X represents a functional group having a carbon-carbon double bond.

[0048] P in the above formula (4-1) ３ and P in the above formula (4-2) ４ is preferably an aromatic group having 5 to 50 carbon atoms. ３ and P ４ When is an aromatic group having 5 to 50 carbon atoms, the resulting adhesive film has better heat resistance. That is, it is possible to further suppress outgassing during high-temperature processing, voids between the film and the adherend, and lifting, and it is also possible to further prevent increased adhesion to the adherend and adhesive residue when peeled from the adherend.

[0049] In the above formula (4-1), Q ３ is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. ３ is a substituted or unsubstituted group having an aromatic structure of 5 to 50 carbon atoms, the adhesive film obtained has better heat resistance. That is, it is possible to further suppress outgassing during high-temperature processing, voids between the film and the adherend, and lifting, and it is also possible to further prevent increased adhesion to the adherend and adhesive residue when peeled from the adherend.

[0050] In the above formula (4-2), R is preferably a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms, the adhesive film obtained has better flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off.

[0051] In the above formula (4-2), R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or aromatic ether group in R is preferably bonded to X. Here, "aromatic ester group" refers to a group in which an ester group is directly bonded to an aromatic ring, and "aromatic ether group" refers to a group in which an ether group is directly bonded to an aromatic ring. By making the moiety bonded to the ester group or ether group an aromatic group, the resulting adhesive film has superior heat resistance. That is, outgassing and the occurrence of voids and lifting between the film and the adherend during high-temperature processing can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented. On the other hand, by bonding X to R via an aromatic ester group or an aromatic ether group, the carbon-carbon double bond in X is not conjugated with R, and therefore polymerization and crosslinking upon heating or light irradiation are not hindered.

[0052] The content of the structural unit represented by the formula (1) in a resin having a functional group having a carbon-carbon double bond at at least one of the terminal and the side chain is preferably 30 mol% or more, more preferably 50 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less. When a resin having a structural unit represented by the formula (1) and a functional group having a carbon-carbon double bond at at least one of the terminal and the side chain has a structural unit represented by the formula (4-1), the content of the structural unit represented by the formula (4-1) is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. When a resin having a structural unit represented by formula (1) and a functional group having a carbon-carbon double bond at at least one of the terminal and the side chain has a structural unit represented by formula (4-2), the content of the structural unit represented by formula (4-2) is preferably 10 mol% or more, more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. When the content of each of the structural units represented by formula (1), formula (4-1), and formula (4-2) is within the above range, the resulting adhesive film can further suppress outgassing during high-temperature processing, voids between the film and the adherend, and lifting, and can be more easily peeled from the adherend. The structural units represented by formula (1), formula (4-1), and formula (4-2) may have a block structure consisting of block components in which the respective structural units are arranged consecutively, or may have a random structure in which the respective structural units are arranged randomly.

[0053] Examples of methods for producing a resin having the above-mentioned functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain include the following. Specifically, first, a diamine compound is reacted with an aromatic acid anhydride to prepare an imide compound. Next, a compound having a functional group reactive with the functional group of the imide compound and a functional group having a carbon-carbon double bond (hereinafter also referred to as a "functional group-containing unsaturated compound") is reacted with the functional group of the imide compound to obtain a resin having the above-mentioned functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain. Alternatively, a resin having the above-mentioned functional group having a carbon-carbon double bond and an imide skeleton in the repeating unit of its main chain can also be obtained by reacting a diamine compound with an aromatic acid anhydride to prepare an imide compound, and then reacting the terminal of the imide compound with, for example, maleic anhydride.

[0054] The diamine compound and aromatic acid anhydride used in the method for producing a resin having a functional group with a carbon-carbon double bond and an imide skeleton in the repeating unit of the main chain may be the same as those used in the method for producing a resin having no maleimide group and an imide skeleton in the repeating unit of the main chain.

[0055] The functional group-containing unsaturated compound is selected and used depending on the functional group at the end or side chain of the imide compound.For example, when the functional group at the end or side chain of the imide compound is a hydroxyl group, the functional group-containing unsaturated compound may include a maleimide compound having a carboxyl group, a vinyl compound having an ether group, an allyl compound having a glycidyl group, an allyl ether compound having a glycidyl group, a vinyl ether compound having a glycidyl group, an allyl compound having an isocyanate group, a (meth)acryloyl compound having an isocyanate group, etc.Furthermore, when the functional group at the end or side chain of the imide compound is a carboxyl group, the functional group-containing unsaturated compound may include an allyl compound having a hydroxyl group, an allyl compound having a glycidyl group, an allyl ether compound having a glycidyl group, a vinyl ether compound having a glycidyl group, etc. Examples of the maleimide compound having a carboxy group include maleimide acetate, maleimidopropionic acid, maleimidobutyric acid, maleimidohexanoic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 19-maleimido-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid, etc. Examples of the vinyl compound having an ether group include butyl vinyl ether, etc. Examples of the allyl compound having a glycidyl group include diallyl monoglycidyl isocyanurate, etc. Examples of the allyl ether compound having a glycidyl group include allyl glycidyl ether, glycerin diallyl monoglycidyl ether, etc. Examples of the vinyl ether compound having a glycidyl group include glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, glycidyl cyclohexanedimethanol monovinyl ether, etc. Examples of the allyl compound having an isocyanate group include allyl isocyanate, etc. Examples of the (meth)acryloyl compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, etc.Examples of the allyl compound having a hydroxyl group include trimethylolpropane diallyl ether and pentaerythritol triallyl ether.

[0056] The preferred lower limit of the content of the resin having the functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain per 100 parts by mass of the curable resin is 10 parts by mass, and the preferred upper limit is 100 parts by mass. When the content of the resin having the functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain per 100 parts by mass of the curable resin is within this range, the adhesive film can be more easily peeled off. From the viewpoint of further improving removability, the preferred lower limit of the content of the resin having the functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain per 100 parts by mass of the curable resin is 20 parts by mass, even more preferably 30 parts by mass, and even more preferably 90 parts by mass, even more preferably 80 parts by mass, and even more preferably 70 parts by mass.

[0057] When the resin having an imide skeleton in the repeating unit of its main chain does not have the maleimide group and includes a resin having an imide skeleton in the repeating unit of its main chain, it is preferable that the curable resin further includes a polyfunctional monomer or polyfunctional oligomer (hereinafter simply referred to as a "polyfunctional monomer or polyfunctional oligomer") having two or more functional groups having a carbon-carbon double bond in the molecule and having a molecular weight of 5,000 or less. Also, when the curable resin includes a resin having the imide skeleton in the repeating unit of its main chain that has the functional group having a carbon-carbon double bond and has an imide skeleton in the repeating unit of its main chain, the curable resin may further include the polyfunctional monomer or polyfunctional oligomer. By including the polyfunctional monomer or polyfunctional oligomer, the adhesive film can be more efficiently three-dimensionally reticulated by irradiation with light or the like, thereby more effectively preventing enhanced adhesion and adhesive residue upon peeling.

[0058] In addition, when the resin having the imide skeleton in the repeating unit of the main chain itself is not reactive, the curable resin needs to further contain another component having a reactive functional group so that the curable resin as a whole is reactive. As such another component having a reactive functional group, it is preferable to use the polyfunctional monomer or polyfunctional oligomer. An example of a case where the resin having the imide skeleton in the repeating unit of the main chain itself is not reactive is when the resin having the imide skeleton in the repeating unit of the main chain does not have the maleimide group and only contains a resin having the imide skeleton in the repeating unit of the main chain.

[0059] Examples of the functional group having a carbon-carbon double bond in the polyfunctional monomer or polyfunctional oligomer include an optionally substituted maleimide group, a citraconic imide group, a vinyl ether group, an allyl group, and a (meth)acryloyl group. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance. In particular, the polyfunctional monomer or polyfunctional oligomer is preferably a bismaleimide compound.

[0060] The polyfunctional monomer or polyfunctional oligomer preferably has a group derived from a diamine compound. As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used, but an aliphatic diamine compound is preferred. That is, the polyfunctional monomer or polyfunctional oligomer more preferably has an aliphatic group derived from a diamine compound. By using an aliphatic diamine compound as the diamine compound, the resulting adhesive film has superior light transmittance. Furthermore, the resulting adhesive film has superior flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off.

[0061] Among the above aliphatic diamine compounds, the above-mentioned dimer diamines are preferred from the viewpoints of light transparency, flexibility, and compatibility with the solvent of the polyfunctional monomer or polyfunctional oligomer and other components.

[0062] The preferred lower limit of the content of the polyfunctional monomer or polyfunctional oligomer in 100 parts by mass of the curable resin is 5 parts by mass, and the preferred upper limit is 90 parts by mass. When the content of the polyfunctional monomer or polyfunctional oligomer is within this range, the adhesive film can be more easily peeled off. From the viewpoint of further improving removability, the more preferred lower limit of the content of the polyfunctional monomer or polyfunctional oligomer is 10 parts by mass, and the more preferred upper limit is 50 parts by mass.

[0063] When the curable resin contains a resin having the functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain, and the polyfunctional monomer or polyfunctional oligomer, the preferred lower limit of the total content of the resin having the functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain, and the polyfunctional monomer or polyfunctional oligomer, per 100 parts by mass of the curable resin, is 20 parts by mass, and the preferred upper limit is 80 parts by mass. When the total content of the resin having the functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of its main chain, and the polyfunctional monomer or polyfunctional oligomer, is within this range, the adhesive film can be more easily peeled off during peeling. From the viewpoint of further improving removability, the lower limit of the total content of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton in a repeating unit of the main chain, and the polyfunctional monomer or polyfunctional oligomer is more preferably 30 parts by mass, even more preferably 40 parts by mass, still more preferably 50 parts by mass, and more preferably 70 parts by mass.

[0064] The curable resin preferably contains a compound having a maleimide group. By containing the compound having a maleimide group, the obtained adhesive film has better heat resistance. The compound having a maleimide group is preferably a bismaleimide compound, or a resin having a maleimide group and an imide skeleton in the repeating unit of the main chain. That is, the curable resin preferably contains the bismaleimide compound as the polyfunctional monomer or polyfunctional oligomer, or the curable resin preferably contains the functional group having a carbon-carbon double bond, and the resin preferably contains a maleimide group as the functional group having a carbon-carbon double bond of the resin having an imide skeleton in the repeating unit of the main chain.

[0065] The preferred upper limit of the content of the curable resin in the photocurable adhesive is 99% by mass. By having the content of the curable resin be 99% by mass or less, the removability from an adherend having irregularities during heating can be further improved. The more preferred upper limit of the content of the curable resin is 98% by mass, an even more preferred upper limit is 96% by mass, and an even more preferred upper limit is 90% by mass. Furthermore, the preferred lower limit of the content of the curable resin is 5% by mass. By having the content of the curable resin be 5% by mass or more, adhesion enhancement during high-temperature processing can be further suppressed. The more preferred lower limit of the content of the curable resin is 10% by mass, and an even more preferred lower limit is 20% by mass.

[0066] The photocurable adhesive preferably further contains a photopolymerization initiator. By containing the photopolymerization initiator, the photocurable adhesive is more easily cured, and increased adhesion of the resulting adhesive film to the adherend during high-temperature processing can be more effectively suppressed, so that the resulting adhesive film has improved removability from the adherend and can be more easily peeled from the adherend.

[0067] Examples of the photopolymerization initiator include those that are activated by irradiation with light having a wavelength of 250 to 800 nm. Among these, the photopolymerization initiator is preferred for its molar absorption coefficient at 405 nm to be 10 ml / (g cm), more preferably 200 ml / (g cm), and even more preferably 405 ml / (g cm), since it is unlikely to overlap with the absorption wavelength of the curable resin and is sufficiently activated when the adhesive film is irradiated with light. There is no particular upper limit to the molar absorption coefficient at 405 nm, but it is preferred that it be 1.0×10 ６ The practical upper limit is about ml / (g·cm).

[0068] Examples of the photopolymerization initiator include acetophenone derivatives, benzoin ether compounds, ketal derivatives, phosphine oxide derivatives, and oxime ester compounds. Examples of the acetophenone derivatives include methoxyacetophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one. Examples of the benzoin ether compounds include benzoin propyl ether and benzoin isobutyl ether. Examples of the ketal derivatives include benzyl dimethyl ketal and acetophenone diethyl ketal. Examples of the phosphine oxide derivatives include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Examples of the oxime ester compound include 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone and 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)-1,2-octadione. Examples of the photopolymerization initiator include bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone or in combination of two or more.

[0069] The content of the photopolymerization initiator is preferably 0.1 parts by mass or less and 10 parts by mass or less per 100 parts by mass of the curable resin. By using a photopolymerization initiator within this range, the entire adhesive film is uniformly and quickly polymerized and crosslinked by light irradiation, and the elastic modulus increases, preventing a significant decrease in adhesive strength, resulting in increased adhesion, and preventing adhesive residue upon peeling. The more preferred lower limit of the photopolymerization initiator content is 0.3 parts by mass, and the more preferred upper limit is 5 parts by mass.

[0070] The photocurable adhesive preferably further contains an ultraviolet absorber, which makes the adhesive layer more flexible and improves the peak probe tack value after curing of the adhesive layer, as described below.

[0071] Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, etc. Among these, from the viewpoint of further improving the heat resistance of the adhesive film of the present invention, it is preferable that the ultraviolet absorber contains a triazine-based ultraviolet absorber.

[0072] Examples of the triazine-based ultraviolet absorber include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, Tinuvin 1577ED, and Tinuvin 1600 (all manufactured by BASF Corporation), and Adekastab LA46 and Adekastab LA-F70 (all manufactured by ADEKA Corporation). Of these, Tinuvin 400, Tinuvin 479, and Tinuvin 1600 are preferred.

[0073] The preferred lower limit of the content of the ultraviolet absorber relative to 100 parts by mass of the curable resin is 1 part by mass, and the preferred upper limit is 30 parts by mass. When the content of the ultraviolet absorber is 1 part by mass or more, the adhesive layer becomes more flexible. When the content of the ultraviolet absorber is 30 parts by mass or less, the adhesive strength of the obtained adhesive film is further improved. The more preferred lower limit of the ultraviolet absorber is 5 parts by mass, and even more preferred lower limit is 7 parts by mass, and the more preferred upper limit is 20 parts by mass, and even more preferred upper limit is 15 parts by mass.

[0074] The photocurable adhesive preferably further contains a surface conditioner. By including a surface conditioner in the photocurable adhesive, the surface conditioner bleeds out to the adherend interface, thereby further improving the removability of the resulting adhesive film. Examples of the surface conditioner include silicone-based surface conditioners, fluorine-based surface conditioners, and acrylic-based surface conditioners. These surface conditioners have excellent heat resistance, so by including a surface conditioner in the photocurable adhesive, the photocurable adhesive can be prevented from burning even after high-temperature processing at 300°C or higher. Furthermore, the surface conditioner bleeds out to the adherend interface during peeling of the resulting adhesive film, making peeling easier. Among these, silicone-based surface conditioners are preferred from the standpoints of environmental friendliness and ease of disposal. Acrylic-based surface conditioners are also preferred from the standpoints of preventing silicone contamination of the adherend and further improving the peak value of the probe tack after curing of the adhesive film, as described below.

[0075] The surface conditioner may have a functional group capable of crosslinking with a resin having the imide skeleton in its main chain repeating unit. When the surface conditioner has a functional group capable of crosslinking with a resin having the imide skeleton in its main chain repeating unit, the surface conditioner chemically reacts with the resin having the imide skeleton in its main chain repeating unit or the polyfunctional monomer or polyfunctional oligomer upon irradiation with light or reaction with a crosslinking agent, etc., and is incorporated into the resin. This prevents the surface conditioner from adhering to and contaminating the adherend. Examples of functional groups capable of crosslinking with the resin having the imide skeleton in its main chain repeating unit or the polyfunctional monomer or polyfunctional oligomer include a carboxy group, a functional group having a radically polymerizable unsaturated bond (e.g., a vinyl group, a (meth)acryloyl group, or an optionally substituted maleimide group), a hydroxy group, an amide group, an isocyanate group, and an epoxy group.

[0076] Examples of the acrylic surface conditioner include acrylic copolymers used to impart leveling properties, and specific examples include BYK-394, BYK-350, BYK-381 (all manufactured by BYK-Chemie), Disparlon 1970 (manufactured by Kusumoto Chemicals Co., Ltd.), and the like.

[0077] Examples of the silicone surface conditioner include silicone oil, silicone diacrylate, and silicone graft copolymer. Specifically, a silicone compound having a siloxane skeleton in the main chain and a functional group having a carbon-carbon double bond in the side chain or at the terminal is preferred. As the silicone compound having a siloxane skeleton in the main chain and a functional group having a carbon-carbon double bond in the side chain or at the terminal, at least one selected from the group consisting of a silicone compound represented by the following formula (5-1), a silicone compound represented by the following formula (5-2), and a silicone compound represented by the following formula (5-3) is preferred. These silicone compounds have particularly excellent heat resistance and are highly polar, so they easily bleed out from the adhesive layer.

[0078]

[0079] X in the above formulas (5-1) to (5-3) and Y in the above formulas (5-1) and (5-3) each independently represent an integer of 0 or more and 1200 or less, and R in the above formulas (5-1) to (5-3) represents a functional group having a carbon-carbon double bond.

[0080] In the above formulas (5-1) to (5-3), examples of the functional group having a carbon-carbon double bond represented by R include an optionally substituted maleimide group, a citraconic imide group, a vinyl ether group, an allyl group, and a (meth)acryloyl group. Among these, an optionally substituted maleimide group is preferred because the resulting adhesive film has better heat resistance. Note that when multiple R are present in the above formulas (5-1) to (5-3), the respective R may be the same or different.

[0081] Among the silicone compounds represented by the above formulas (5-1) to (5-3), commercially available examples include EBECRYL350 and EBECRYL1360 (both manufactured by Daicel-Allnex Co., Ltd.), etc. Other examples include BYK-UV3500 (manufactured by BYK-Chemie Co., Ltd.) and TEGO RAD2250 (manufactured by Evonik Co., Ltd.) (in both cases, R is an acryloyl group).

[0082] Examples of the fluorine-based surface conditioner include hydrocarbon compounds having fluorine atoms.

[0083] The content of the surface conditioner is preferably 0.1 parts by mass at its lower limit and 20 parts by mass at its upper limit relative to 100 parts by mass of the curable resin. By using the surface conditioner in this range, the resulting adhesive film will have excellent removability without contaminating the adherend. From the viewpoint of further improving removability while suppressing contamination, the lower limit of the content of the surface conditioner is more preferably 0.3 parts by mass, and the upper limit is more preferably 10 parts by mass. Since the adhesive film of the present invention has excellent heat resistance, it can exert sufficient effects even if the content of the surface conditioner is relatively small. Therefore, the possibility of contamination by the silicone compound or fluorine compound can be further reduced.

[0084] The photocurable adhesive preferably further contains an inorganic filler, which can prevent the resulting adhesive film from decreasing in elastic modulus at high temperatures and can further prevent peeling during high-temperature processing, even when the adhesive film is subjected to high-temperature processing at 300°C or higher.

[0085] Examples of the inorganic filler include inorganic fillers consisting of at least one selected from the group consisting of oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconia, and composites thereof. Among these, silica and talc are preferred because they are commercially available at low cost and easily available.

[0086] The inorganic filler may be surface-modified. Examples of the functional group that may be used to modify the surface of the inorganic filler include an alkylsilane group, a methacryloyl group, and a dimethylsiloxane group. Among these, a dimethylsiloxane group is preferred because it has appropriate hydrophobicity.

[0087] The preferred lower limit of the average particle size of the inorganic filler is 5 nm, and the preferred upper limit is 30 μm. By having the average particle size of the inorganic filler within this range, the resulting adhesive film can be more effectively prevented from peeling during high-temperature processing, and can be easily peeled off by peel treatment when peeling. The more preferred lower limit of the average particle size of the inorganic filler is 10 nm, and the more preferred upper limit is 20 μm, and the even more preferred lower limit is 15 nm, and the even more preferred upper limit is 15 μm. The average particle size can be determined, for example, by observing 50 particles of any inorganic filler using an electron microscope or an optical microscope, calculating the average particle size of each inorganic filler, or by performing laser diffraction particle size distribution measurement.

[0088] The content of the inorganic filler is preferably 1 part by mass at the lower limit and 20 parts by mass at the upper limit relative to 100 parts by mass of the curable resin. By having the content of the inorganic filler within this range, the adhesive film obtained can be more effectively prevented from peeling during high-temperature processing, and can be easily peeled by peel treatment when peeled. The content of the inorganic filler is more preferably 3 parts by mass at the lower limit and 15 parts by mass at the upper limit, and even more preferably 5 parts by mass at the lower limit and 10 parts by mass at the upper limit.

[0089] The photocurable adhesive may further contain a gas generating agent. By containing the gas generating agent, even after high-temperature processing at 300°C or higher, gas generated by irradiation with light or the like is released at the interface with the adherend, making it possible to peel the adhesive film from the adherend more easily and without leaving any adhesive residue. Furthermore, even when peeling the adhesive film from a thin adherend after high-temperature processing at 300°C or higher, damage to the adherend can be prevented.

[0090] The gas generating agent preferably has a weight loss rate of 5% or less when heated from 30°C to 300°C at a temperature increase rate of 10°C / min in a nitrogen atmosphere as measured by TG-DTA (thermogravimetry-differential thermal analysis). If the weight loss rate is 5% or less, decomposition of the gas generating agent is unlikely to occur even when high-temperature processing is performed at 300°C or higher, and the adhesive film has superior heat resistance. In other words, peeling can be further suppressed during high-temperature processing, and increased adhesion and adhesive residue upon peeling can be further prevented. The TG-DTA (thermogravimetry-differential thermal analysis) measurement can be performed using, for example, a TG-DTA device ("STA7200RV" manufactured by Hitachi High-Tech Science Corporation).

[0091] Examples of the gas generating agent include a gas generating agent that generates gas upon heating and a gas generating agent that generates gas upon irradiation with light. These gas generating agents may be used alone or in combination of two or more. Among them, from the viewpoint of preventing decomposition of the gas generating agent in a high-temperature processing step, a gas generating agent that generates gas upon irradiation with light is preferred, and a gas generating agent that generates gas upon irradiation with ultraviolet light is more preferred. Examples of the gas generating agent include a tetrazole compound or a salt thereof, a triazole compound or a salt thereof, an azo compound, an azide compound, xanthone acetate, a carbonate, and the like. These gas generating agents may be used alone or in combination of two or more. Among them, a tetrazole compound or a salt thereof is preferred because of its particularly excellent heat resistance.

[0092] The content of the gas generating agent is preferably 5 parts by mass or less and 50 parts by mass or less per 100 parts by mass of the curable resin. When the content of the gas generating agent is within this range, the resulting adhesive film has particularly excellent removability. The more preferred lower limit of the content of the gas generating agent is 8 parts by mass or less and the more preferred upper limit is 30 parts by mass or less.

[0093] The photocurable adhesive may contain known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, surfactants, waxes, etc., as long as the effects of the present invention are not impaired.

[0094] The adhesive layer was formed by irradiating the adhesive film with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ The lower limit of the peak probe tack value at 60°C after irradiating for 200 seconds so as to satisfy the condition (hereinafter, sometimes simply referred to as "peak probe tack value at 60°C after curing of the adhesive layer") is 0.30 N / cm ２ After curing, the adhesive layer had a peak probe tack of 0.30 N / cm at 60°C. ２As a result, the adhesive film of the present invention can be easily peeled off even from an adherend having unevenness by heating during peeling. The preferred lower limit of the peak value of the probe tack at 60°C after curing of the adhesive layer is 0.40 N / cm ２ , and a more preferable lower limit is 0.50 N / cm ２ The preferred upper limit of the peak value of the probe tack at 60°C after curing of the adhesive layer is 5.00 N / cm ２ After curing, the adhesive layer had a peak probe tack of 5.00 N / cm at 60°C. ２ The upper limit of the peak probe tack value at 60°C after curing of the adhesive layer is more preferably 4.00 N / cm ２ , and a more preferable upper limit is 2.00 N / cm ２ In this specification, the term "peak probe tack value" refers to the maximum load applied to a probe when the probe is brought into contact with an adhesive layer using a probe tack measurement device and then pulled up, and specifically refers to the peak tack value measured using a probe tack measurement device (such as the "Tacking Tester TAC-2" manufactured by RHESCA) under measurement conditions of a probe diameter of 5 mm, a pressing speed of 0.5 mm / sec, a pressing load of 98 gf, a contact time of 10 seconds, and a lifting speed of 0.1 mm / s. As a specific measurement method, first, an ultra-high pressure mercury lamp is used, and the wavelength is 405 nm and the illuminance is 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ The cured adhesive layer is irradiated for 200 seconds so as to obtain a value of 25 mm in width and 50 mm in length, and the cured adhesive layer is cut into a test piece having a size of 25 mm in width and 50 mm in length. The test piece thus prepared is then measured using the above-mentioned probe tack measurement device under the above-mentioned measurement conditions in an environment of 60°C and 50% RH, thereby obtaining the tackiness.

[0095] The adhesive layer was formed by irradiating the adhesive film with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２The preferred upper limit of the peak probe tack value at 23°C after irradiating for 200 seconds so as to achieve a value of 5.00 N / cm (hereinafter, sometimes simply referred to as "peak probe tack value at 23°C after curing of the adhesive layer") is 5.00 N / cm ２ After curing, the adhesive layer had a peak probe tack of 5.00 N / cm at 23°C. ２ The upper limit of the peak probe tack value at 23°C after curing of the adhesive layer is more preferably 3.00 N / cm. ２ , and a more preferable upper limit is 1.00 N / cm ２ The preferred lower limit of the peak value of the probe tack at 23°C after curing of the adhesive layer is 0.10 N / cm ２ After curing, the adhesive layer had a peak probe tack of 0.10 N / cm at 23°C. ２ By setting the value to 0.20 N / cm or more, the adhesive strength at room temperature is further improved. A more preferable lower limit of the peak value of probe tack at 23°C after curing of the adhesive layer is 0.20 N / cm ２ , and a more preferable lower limit is 0.25 N / cm ２ The peak value of the probe tack at 23°C after the adhesive layer has cured can be measured by setting the measurement temperature at 23°C for the peak value of the probe tack at 60°C after the adhesive layer has cured.

[0096] The adhesive layer has a ratio (V1) of the peak probe tack value at 60°C after curing of the adhesive layer to the peak probe tack value at 23°C after curing of the adhesive layer ((peak probe tack value at 60°C after curing of the adhesive layer) / (peak probe tack value at 23°C after curing of the adhesive layer)), which preferably has a lower limit of 1.0 and an upper limit of 10.0. When V1 is within the above range, the adhesive film of the present invention can achieve both high heat resistance and excellent removability from an adherend having unevenness. A more preferred lower limit of V1 is 2.0, a more preferred upper limit is 8.0, an even more preferred lower limit is 3.0, and an even more preferred upper limit is 6.0.

[0097] Methods for adjusting the peak probe tack value at 60°C after curing of the adhesive layer and the peak probe tack value at 23°C after curing of the adhesive layer include, for example, changing the composition of the adhesive layer (for example, adding a heat-resistant low molecular weight compound (such as an ultraviolet absorber) to the adhesive layer, changing the surface conditioner, adding an inorganic filler, etc.).

[0098] When the adhesive film has a substrate, the adhesive layer, in an uncured state, has a preferred lower limit of anchor strength to the substrate at 23°C of 0.03 N / 25 mm. When the adhesive layer has an anchor strength to the substrate at 23°C of 0.03 N / 25 mm or more, peeling at the interface between the adhesive layer and the substrate can be suppressed, and the handleability of the resulting adhesive film is further improved. A more preferred lower limit of the anchor strength of the adhesive layer to the substrate at 23°C is 0.05 N / 25 mm. There is no particular preferred upper limit of the anchor strength of the adhesive layer to the substrate at 23°C, but about 20 N / 25 mm is a practical upper limit. The anchor strength of the adhesive layer to the substrate at 23°C is measured by the following method. That is, one side of a commercially available double-sided tape (manufactured by Sekisui Chemical Co., Ltd., "3810H") was adhered to a stainless steel plate that had been washed with ethanol and then wiped dry. The adhesive layer of the adhesive film of the present invention that was not to be measured was then placed on the other side of the double-sided tape, with the side of the adhesive film of the present invention with the adhesive layer to be measured facing up. A 25 mm-wide silicone tape (manufactured by Sliontec Co., Ltd., "6260-01") was then pressed against the adhesive layer of the adhesive film of the present invention by rolling a 2 kg hand roller back and forth once at a speed of 300 mm / min. A 25 mm-wide cut was made along the silicone tape in the adhesive layer pressed against the silicone tape, and the adhesive was then aged at 23°C and 50% RH for 1 hour to prepare a test sample. The obtained test sample is subjected to a 180° peel test in accordance with JIS Z0237 using a tensile tester (Shimadzu Corporation, "AG-IS" or the like) under conditions of 23°C, 50% RH, and a peel rate of 300 mm / min, and the 90° peel strength of the adhesive layer to the substrate is measured by peeling the adhesive layer pressed onto the silicone tape from the substrate. The obtained 90° peel strength is taken as the anchor strength of the adhesive layer to the substrate at 23°C.

[0099] When the adhesive film of the present invention is a single-sided adhesive film, the anchoring strength of the adhesive layer to the substrate at 23°C is measured by the following method. Specifically, one side of a commercially available double-sided tape (manufactured by Sekisui Chemical Co., Ltd., "3810H") is adhered to a stainless steel plate that has been washed with ethanol and then wiped dry. The adhesive-free side of the substrate of the adhesive film of the present invention is then placed over the other side of the double-sided tape, with the side of the adhesive film of the present invention with the adhesive layer to be measured facing up. Furthermore, a 25 mm-wide silicone tape (manufactured by Sliontec Co., Ltd., "6260-01") is pressed against the adhesive layer of the adhesive film of the present invention by rolling it back and forth once at a speed of 300 mm / min. A 25 mm-wide cut is made along the silicone tape in the adhesive layer pressed against the silicone tape, and the adhesive layer is then aged for 1 hour at 23°C and 50% RH to prepare a test sample. The obtained test sample is subjected to a 90° peel test in accordance with JIS Z0237 using a tensile tester (Shimadzu Corporation, "AG-IS" or the like) under conditions of 23°C, 50% RH, and a peel rate of 300 mm / min, and the 90° peel strength of the adhesive layer to the substrate is measured by peeling the adhesive layer pressed onto the silicone tape from the substrate. The obtained 90° peel strength is taken as the anchor strength of the adhesive layer to the substrate at 23°C.

[0100] When the adhesive film has a substrate, the adhesive layer in the adhesive film of the present invention is formed by irradiating the adhesive film with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 80 mW / cm. ２The preferred lower limit of the anchoring force to the substrate at 23°C after irradiation with light of 405 nm wavelength for 300 seconds (hereinafter sometimes simply referred to as "anchoring force of the adhesive layer to the substrate at 23°C after irradiation with light of 405 nm wavelength") is 0.10 N / 25 mm. When the anchoring force of the adhesive layer to the substrate at 23°C after irradiation with light of 405 nm wavelength is 0.10 N / 25 mm or more, peeling at the interface between the adhesive layer and the substrate can be suppressed, and the handleability of the resulting adhesive film can be further improved. A more preferred lower limit of the anchoring force of the adhesive layer to the substrate at 23°C after irradiation with light of 405 nm wavelength is 0.15 N / 25 mm. There is no particular preferred upper limit of the anchoring force of the adhesive layer to the substrate at 23°C after irradiation with light of 405 nm wavelength, but about 20 N / 25 mm is a practical upper limit. The anchoring strength of the adhesive layer to the substrate at 23°C after irradiation with light of 405 nm wavelength was measured by the method described above, in which light of 405 nm wavelength was irradiated from an ultra-high pressure mercury lamp at an illuminance of 80 mW / cm. ２ The measurement can be carried out using the adhesive film irradiated with light having a wavelength of 405 nm from an ultra-high pressure mercury lamp for 300 seconds. When the adhesive film is a single-sided adhesive film, the direction in which the adhesive film is irradiated with light having a wavelength of 405 nm from an ultra-high pressure mercury lamp may be from the substrate side or from the adhesive layer side. When irradiating with light from the adhesive layer side, irradiation is carried out without removing a separator such as a release PET film that protects the adhesive layer.

[0101] Methods for adjusting the anchoring strength of the adhesive layer to a substrate at 23°C and the anchoring strength of the adhesive layer to a substrate at 23°C after irradiation with light having a wavelength of 405 nm include, for example, a method of directly applying an adhesive to a substrate when producing an adhesive film, a method of subjecting a substrate to surface treatment such as corona treatment, plasma treatment, sandblasting, chemical etching, or application of a treatment agent when producing an adhesive film, a method of adjusting the glass transition temperature (Tg) of the adhesive layer, and adjusting the type and content of an adhesive strength adjuster.

[0102] The adhesive layer has a shear storage modulus at 23°C of preferably 1 x 10 ４ The shear storage modulus of the adhesive layer at 23°C is 1 × 10 ４ When the shear storage modulus of the adhesive layer is 5×10 Pa or more, the obtained adhesive film has better heat resistance. ４ Pa, and a more preferable lower limit is 1×10 ５ The preferred upper limit of the shear storage modulus of the adhesive layer at 23°C is 5 x 10 ７ The shear storage modulus of the adhesive layer at 23°C is 5 × 10 ７ When the adhesive film has a substrate, the adhesive layer has a stronger anchoring force to the substrate, and the adhesive film has a stronger handleability. ７ Pa, and a more preferable upper limit is 1×10 ７ Pa. The shear storage modulus of the adhesive layer at 23°C can be measured, for example, by dynamic viscoelasticity measurement. Specifically, for example, a measurement sample of only the adhesive layer is prepared by stacking the adhesive layers to a thickness of about 1 mm, and the prepared sample is subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (manufactured by IT Measurement Control Co., Ltd., "DVA-200" or the like) under measurement conditions of shear mode, heating rate of 10°C / min, measurement temperature of 0°C to 300°C, and frequency of 10 Hz.

[0103] In the adhesive film of the present invention, the adhesive layer is irradiated with a 405 nm wavelength, 80 mW / cm irradiance, irradiated by an ultra-high pressure mercury lamp. ２ The preferred lower limit of the tensile storage modulus at 23°C after irradiation with light having a wavelength of 405 nm for 300 seconds (hereinafter, may be simply referred to as "the tensile storage modulus at 23°C after irradiation with light having a wavelength of 405 nm of the adhesive layer") is 1.0 × 10 ８ The adhesive layer has a tensile storage modulus of 1.0 × 10 at 23°C after being irradiated with light having a wavelength of 405 nm. ８The more preferable lower limit of the tensile storage modulus at 23°C after irradiation of the adhesive layer with light having a wavelength of 405 nm is 1.5 × 10 ８ N / 25 mm, and a more preferable lower limit is 2.0 × 10 ８ The preferred upper limit of the tensile storage modulus of the adhesive layer at 23° C. after irradiation with light having a wavelength of 405 nm is 5.0×10 ９ The adhesive layer has a tensile storage modulus of 5.0 × 10 at 23°C after irradiation with light having a wavelength of 405 nm. ９ When the adhesive film has a substrate, the adhesive layer has a stronger anchoring force with respect to the substrate, and the adhesive film has a stronger handleability. A more preferred upper limit of the tensile storage modulus at 23°C after irradiation of the adhesive layer with light having a wavelength of 405 nm is 4.0 × 10 ９ N / 25 mm, and a more preferable upper limit is 3.0 × 10 ９ The tensile storage modulus at 23°C after irradiation of the adhesive layer with light having a wavelength of 405 nm was measured by the above-mentioned method for measuring the shear storage modulus at 23°C of the adhesive layer, in which the integrated light intensity of light having a wavelength of 405 nm was 20,000 mJ / cm using an ultra-high pressure mercury lamp. ２ The measured value can be obtained by using a measurement sample irradiated so that the measured value satisfies the above equation and performing measurement in a tensile mode instead of a shear mode.

[0104] Methods for adjusting the shear storage modulus of the adhesive layer at 23°C and the tensile storage modulus of the adhesive layer at 23°C after irradiation with light having a wavelength of 405 nm include, for example, changing the composition of the adhesive layer (for example, adding an inorganic filler), adjusting the glass transition temperature (Tg) of the adhesive layer, and adjusting the degree of crosslinking of the curable resin.

[0105] The adhesive layer preferably has a glass transition temperature (Tg) in an uncured state greater than 0°C and less than 100°C. When the adhesive layer has a glass transition temperature greater than 0°C, the heat resistance of the resulting adhesive film is further improved. When the adhesive layer has a glass transition temperature less than 100°C, the anchoring force of the adhesive layer to the substrate is further improved when the adhesive film has a substrate. The glass transition temperature of the adhesive layer is more preferably 5°C in lower limit, more preferably 95°C in upper limit, even more preferably 8°C in lower limit, and even more preferably 90°C in upper limit. The glass transition temperature of the adhesive layer can be measured, for example, by dynamic viscoelasticity measurement. Specifically, for example, a measurement sample of only the adhesive layer is prepared by stacking the adhesive layers to a thickness of about 1 mm. The temperature at which the loss tangent becomes maximum can be measured by performing dynamic viscoelasticity measurement on the obtained measurement sample using a dynamic viscoelasticity measuring device (such as "DVA-200" manufactured by IT Measurement Control Co., Ltd.) under measurement conditions of shear mode, a heating rate of 10°C / min, a measurement temperature of 0°C to 300°C, and a frequency of 10 Hz.

[0106] The adhesive layer was irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 80 mW / cm ２The glass transition temperature (Tg) after irradiating with light having a wavelength of 405 nm for 300 seconds (hereinafter sometimes simply referred to as "glass transition temperature of the adhesive layer after irradiating with light having a wavelength of 405 nm") is preferably 0°C in lower limit and 100°C in upper limit. When the adhesive layer has a glass transition temperature of 0°C or higher after curing by irradiation with light having a wavelength of 405 nm, the heat resistance of the resulting adhesive film is further improved. When the adhesive layer has a glass transition temperature of 100°C or lower after curing by irradiation with light having a wavelength of 405 nm, the anchoring force of the adhesive layer to the substrate is further improved, and the handleability of the resulting adhesive film is further improved. The glass transition temperature of the adhesive layer after irradiating with light having a wavelength of 405 nm is more preferably 5°C in lower limit and more preferably 95°C in upper limit, even more preferably 8°C in lower limit and even more preferably 90°C in upper limit. The glass transition temperature of the adhesive layer after irradiation with light having a wavelength of 405 nm was measured using an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 80 mW / cm in the above-described method for measuring the glass transition temperature of the adhesive layer. ２ The measurement can be performed by irradiating a measurement sample with light of 1000 kJ / s for 300 seconds.

[0107] Methods for adjusting the glass transition temperature of the adhesive layer and the glass transition temperature of the adhesive layer after irradiation with light having a wavelength of 405 nm include, for example, changing the composition of the adhesive layer (for example, adding an inorganic filler) and adjusting the degree of crosslinking of the curable resin.

[0108] The adhesive layer preferably has an upper limit of 1.0% water absorption rate (hereinafter sometimes simply referred to as "water absorption rate of the adhesive layer") when left uncured for one day under conditions of 23°C and 50% RH. When the water absorption rate of the adhesive layer is 1.0% or less, the water absorption rate of the resulting adhesive film can be more easily adjusted to within the above-mentioned range. A more preferred upper limit of the water absorption rate of the adhesive layer is 0.9%, and an even more preferred upper limit is 0.8%. There is no particular lower limit for the water absorption rate of the adhesive layer, but approximately 0.2% is a practical lower limit. The water absorption rate of the adhesive layer can be measured by the following method. That is, the adhesive layer is cut into a size of 20 mm wide x 50 mm long to prepare a test piece, and the test piece is dried for one hour under an environment of 130°C and 50% RH. The mass W of the test piece immediately after drying is ０ Furthermore, the mass W ０ After the measurement, the test piece was left standing for one day under the conditions of 23°C and 50% RH, and the mass W １ The obtained W ０ , W １ The water absorption rate is calculated using the following formula (i): Water absorption rate (%) = {(W １ -W ０ ) / W ０}×100 (i) (W ０ : Mass of the test piece immediately after drying for 1 hour under an environment of 130 ° C. and 50% RH, W １ : Mass of the test piece after leaving it for 1 day under the conditions of 23 ° C and 50% RH)

[0109] The adhesive layer preferably has a thickness of 1 μm at its lower limit and 500 μm at its upper limit. By ensuring that the thickness of the adhesive layer is within the above range, the resulting adhesive film has sufficient adhesive strength at room temperature. Furthermore, the water absorption of the resulting adhesive film can be more easily adjusted within the above range. The adhesive layer more preferably has a thickness of 5 μm at its lower limit and 250 μm at its upper limit, and even more preferably 10 μm at its lower limit and 200 μm at its upper limit.

[0110] The adhesive film of the present invention preferably has a substrate. By having the adhesive film of the present invention have a substrate, the adhesive film can be more easily re-peeled without a backing when peeled off by heating, and the handleability of the adhesive film of the present invention is further improved.

[0111] The substrate preferably contains a resin material having excellent heat resistance. Examples of the resin material include a resin (A1) having a repeating unit containing at least one selected from the group consisting of an ether bond, a ketone group, and an ester bond in its main chain skeleton, a polyimide, a polyamide, and the like. Among these, the substrate preferably contains the resin (A1). When the substrate contains the resin (A1), the light transmittance of the substrate is improved, allowing the adhesive layer to be photocured through the substrate. In addition, the water absorption of the substrate, as described below, is reduced, thereby further suppressing the occurrence of foaming during high-temperature processing, and further preventing peeling during high-temperature processing. Such resin materials may be used alone or in combination of two or more.

[0112] Examples of the resin (A1) include polyether ether ketone (PEEK), polyethylene naphthalate (PEN), and polyetherimide (PEI).

[0113] It is preferable that at least one surface of the substrate has an easy-adhesion layer. By having at least one surface of the substrate have an easy-adhesion layer, the adhesion between the adhesive layer and the substrate is further improved, and the anchoring force of the adhesive layer to the substrate at 23°C is further improved. As a result, the handleability of the obtained adhesive film is further improved.

[0114] The adhesion-enhancing layer preferably includes at least one layer selected from a corona-treated layer, a plasma-treated layer, a sandblasted layer, a chemically etched layer, and a treatment-coated layer. By including at least one layer selected from a corona-treated layer, a plasma-treated layer, a sandblasted layer, a chemically etched layer, and a treatment-coated layer, the adhesion between the adhesive layer and the substrate is further improved, thereby further improving the anchoring force of the adhesive layer to the substrate at 23°C and further improving the handleability of the resulting adhesive film. It is particularly preferred that the adhesion-enhancing layer include a corona-treated layer. Examples of methods for forming the corona-treated layer include using a high-frequency power supply (e.g., "AGI-020" manufactured by Kasuga Electric Co., Ltd.) to perform corona treatment on the substrate under conditions of an output of 0.3 kW, an electrode distance of 1 mm, and a speed of 2 m / min to form a corona-treated layer. Alternatively, commercially available products in which the substrate has been subjected to corona treatment may be used. Examples of the treating agent that forms the treating agent coating layer include polyethyleneimine graft polymers, acrylic polymers, polyimides, bismaleimide resins, silane coupling agents, titanium coupling agents, other known adhesion-imparting agents, and pressure-sensitive adhesives.

[0115] When the easy-adhesion layer is a treatment agent coating layer, the thickness of the treatment agent coating layer preferably has a lower limit of 0.1 μm and an upper limit of 1000 μm. When the thickness of the treatment agent coating layer is within the above range, the adhesion between the adhesive layer and the substrate is further improved, and the anchoring force of the adhesive layer to the substrate at 23° C. is further improved. As a result, the handleability of the obtained adhesive film is further improved. A more preferred lower limit of the thickness of the treatment agent coating layer is 1 μm, a more preferred upper limit is 100 μm, and an even more preferred upper limit is 50 μm. When the easy-adhesion layer is other than a treatment agent coating layer, the thickness of the easy-adhesion layer is not particularly limited, but is substantially 1 nm or more and 100 μm or less.

[0116] The substrate preferably has a lower limit of the glass transition temperature (Tg) of 100°C. When the substrate has a glass transition temperature of 100°C or higher, the heat resistance of the adhesive film obtained is further improved. A more preferred lower limit of the glass transition temperature of the substrate is 120°C. Furthermore, the upper limit of the glass transition temperature of the substrate is not particularly limited, but a substantial upper limit is 300°C. The glass transition temperature of the substrate can be measured, for example, by dynamic viscoelasticity measurement. Specifically, for example, the glass transition temperature of the substrate can be measured as the temperature at which the loss tangent becomes maximum by performing dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (such as "DVA-200" manufactured by IT Measurement Control Co., Ltd.) under measurement conditions of shear mode, a heating rate of 10°C / min, a measurement temperature of 0°C to 300°C, and a frequency of 10 Hz.

[0117] The preferred lower limit of the melting point of the substrate is 150°C. When the melting point of the substrate is 150°C or higher, the heat resistance of the resulting adhesive film is further improved. There are no particular restrictions on the upper limit of the melting point of the substrate, but the practical upper limit is 400°C. The melting point of the substrate can be measured, for example, by the following method. That is, the substrate is subjected to differential scanning calorimetry using a differential scanning calorimeter (DSC) (manufactured by Hitachi High-Tech Science Corporation, "DSC-7020") under measurement conditions of a nitrogen atmosphere, a heating rate of 10°C / min, and a measurement temperature of 30°C to 500°C, and the melting point of the substrate can be measured by reading the temperature showing the endothermic peak from the obtained differential scanning calorimetry curve.

[0118] The substrate preferably has a lower limit of 50% for light transmittance at a wavelength of 405 nm (hereinafter sometimes simply referred to as "light transmittance of the substrate"). When the light transmittance of the substrate is 50% or more, a sufficient amount of light can be irradiated onto the adhesive layer, making it possible to easily cure the adhesive layer of the adhesive film. A more preferred lower limit of the light transmittance of the substrate is 60%, and an even more preferred lower limit is 65%. Furthermore, the preferred upper limit of the light transmittance of the substrate is 70%. When the light transmittance of the substrate is 70% or less, it is possible to prevent light from being irradiated onto the adherend when irradiating the adhesive film with light, thereby making it possible to cure the adhesive film while preventing deterioration in the quality of the adherend. Note that, in this specification, the light transmittance at a wavelength of 405 nm can be measured using a spectrophotometer (such as the "V-670" manufactured by JASCO Corporation), for example.

[0119] The substrate preferably has a thickness upper limit of 100 μm. When the substrate has a thickness of 100 μm or less, the resulting adhesive film becomes flexible and can be stored in a rolled state. In addition, the adhesive film has better ultraviolet transmittance. The substrate more preferably has a thickness upper limit of 75 μm, and even more preferably 50 μm. In addition, the substrate preferably has a thickness lower limit of 5 μm. When the substrate has a thickness of 5 μm or more, the resulting adhesive film has stiffness and is easier to handle. The substrate more preferably has a lower limit of 10 μm, and even more preferably 15 μm.

[0120] The preferred lower limit of the thickness ratio of the substrate relative to the total thickness of the adhesive film of the present invention is 5%. When the thickness ratio of the substrate is 5% or more, the water absorption rate of the adhesive film described below can be easily adjusted to an appropriate range. A more preferred lower limit of the thickness ratio of the substrate is 8%, and an even more preferred lower limit is 10%. Furthermore, a preferred upper limit of the thickness ratio of the substrate is 50%. When the thickness ratio of the substrate is 50% or less, the adhesive film of the present invention does not become too rigid as a whole, and the adhesive film has excellent followability to a release film that protects the adhesive layer and to a core material used when the adhesive film is rolled. A more preferred upper limit of the thickness ratio of the substrate is 40%, and an even more preferred upper limit is 35%.

[0121] When the adhesive film of the present invention has a substrate, it may be a single-sided adhesive film having the adhesive layer on one side of the substrate, or a double-sided adhesive film having the adhesive layer on both sides of the substrate. In particular, from the viewpoint of being able to use a rigid support such as glass to support a thin adherend having a thickness of 50 μm or less, the adhesive film of the present invention is preferably a double-sided adhesive film having the adhesive layer on both sides of the substrate.

[0122] The method for producing the adhesive film of the present invention is not particularly limited, and it can be produced using a conventionally known method. Specifically, for example, the curable resin and optional additives are first mixed using a bead mill, ultrasonic dispersion, homogenizer, high-power disperser, roll mill, or the like to prepare an adhesive solution. Next, the obtained adhesive solution is applied to a release PET film and dried at 130°C for 10 minutes to produce a laminated film having an adhesive layer, and a total of two laminated films are produced in the same manner. Then, a double-sided adhesive film having a substrate and adhesive layers on both sides of the substrate can be produced by, for example, stacking the laminated film on both sides of the substrate so that the adhesive layers face each other.

[0123] When producing an adhesive film, it is preferable to form an adhesive layer by directly applying an adhesive solution to a substrate. By directly applying an adhesive solution to a substrate to form an adhesive layer, the adhesion between the adhesive layer and the substrate is further improved, so that the anchoring force of the adhesive layer to the substrate at 23°C is further improved, and the handleability of the resulting adhesive film is further improved.

[0124] When producing an adhesive film, it is preferable to subject the substrate to a surface treatment before use. By subjecting the substrate to a surface treatment, the adhesion between the adhesive layer and the substrate is further improved, thereby further improving the anchoring force of the adhesive layer to the substrate at 23°C, and further improving the handleability of the resulting adhesive film. Examples of surface treatments include corona treatment, plasma treatment, sandblasting, chemical etching, and application of a treatment agent (e.g., polyethyleneimine graft polymer, acrylic polymer, polyimide, bismaleimide resin, silane coupling agent, titanium coupling agent, other known adhesion-imparting agent, pressure-sensitive adhesive, etc.) (treatment agent application). Of these, corona treatment is preferred. Examples of methods for corona treatment include corona treatment of the substrate using a high-frequency power supply (e.g., "AGI-020" manufactured by Kasuga Electric Co., Ltd.) under conditions of an output of 0.3 kW, an electrode distance of 1 mm, and a speed of 2 m / min. Commercially available products in which the substrate has been corona-treated may also be used. The present invention also provides a method for producing an adhesive film of the present invention having a substrate, which includes a step of performing at least one surface treatment selected from corona treatment, plasma treatment, sandblasting, chemical etching, and application of a treatment agent on at least one surface of the substrate.

[0125] When producing an adhesive film, it is preferable to dry the substrate before use. By drying the substrate before use, the moisture content of the substrate in the resulting adhesive film is reduced, thereby making it possible to further suppress the occurrence of foaming during high-temperature processing. As a result, the heat resistance of the resulting adhesive film is further improved, and the resulting adhesive film is further prevented from peeling in a high-temperature environment. Drying conditions include, for example, leaving the film standing for 10 minutes in an environment of 130°C and 50% RH. In addition, in the drying treatment of the substrate described above, the substrate alone may be placed in an oven to dry, or a laminate formed by laminating the substrate and the adhesive layer may be placed in an oven to dry.

[0126] The adhesive film of the present invention is irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ The lower limit of the 5% weight loss temperature after 200 seconds of irradiation so as to obtain a temperature (hereinafter, sometimes simply referred to as "5% weight loss temperature after curing the adhesive layer of the adhesive film of the present invention") is 390°C. When the 5% weight loss temperature after curing the adhesive layer of the adhesive film of the present invention is 390°C or higher, the adhesive film of the present invention has excellent heat resistance. A preferred lower limit of the 5% weight loss temperature after curing the adhesive layer of the adhesive film of the present invention is 400°C, and a more preferred lower limit is 420°C. There is no particular upper limit to the 5% weight loss temperature after curing the adhesive layer of the adhesive film of the present invention, but the practical upper limit is about 600°C. The 5% weight loss temperature after curing the adhesive layer of the adhesive film of the present invention can be measured by simultaneous differential thermal and thermogravimetry measurement. Specifically, it can be measured, for example, by the following method. That is, the adhesive film is cut into a size of 25 mm wide x 50 mm long to prepare a test piece. The obtained test piece was irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２The adhesive layer is cured by irradiating for 200 seconds so that the temperature becomes equal to the cured temperature. The test piece with the cured adhesive layer is weighed into an aluminum pan, and the aluminum pan is set in a differential thermal and thermogravimetric simultaneous analyzer. The temperature is increased from 30°C to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere. The temperature at which the mass of the adhesive film decreases by 5% compared to the mass before heating can be obtained as the 5% weight loss temperature. As the differential thermal and thermogravimetric simultaneous analyzer, for example, a STA7200RV (manufactured by Hitachi High-Tech Science Corporation) can be used. Note that no release PET film to protect the adhesive layer is laminated on the test piece.

[0127] Methods for adjusting the 5% weight loss temperature after curing of the adhesive layer of the adhesive film of the present invention to fall within the above-mentioned range include, for example, changing the composition of the adhesive layer (for example, by adding an inorganic filler), changing the type of substrate, etc.

[0128] The adhesive film of the present invention has a preferred lower limit of the 10% weight loss temperature of 425°C. When the adhesive film of the present invention has a 10% weight loss temperature of 425°C or higher, the adhesive film of the present invention has better heat resistance. The lower limit of the 10% weight loss temperature of the adhesive film of the present invention is more preferably 440°C, and even more preferably 450°C. There is no particular preferred upper limit of the 10% weight loss temperature of the adhesive film of the present invention, but the substantial upper limit is about 600°C. At the 10% weight loss temperature of the adhesive film of the present invention described above, the adhesive layer of the adhesive film is an uncured adhesive layer that has not been subjected to a curing operation. The 10% weight loss temperature of the adhesive film of the present invention can be measured using a simultaneous differential thermal and thermogravimetric analyzer. Specifically, it can be measured by the following method. That is, the adhesive film is cut into a size of 5 mm wide x 10 mm long to prepare a test piece. The obtained test piece is weighed into an aluminum pan, and the aluminum pan is set in a differential thermal and thermogravimetric simultaneous analyzer. The temperature is increased from 30°C to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere. The temperature at which the mass of the adhesive film decreases by 10% compared to the mass before heating can be obtained as the 10% weight loss temperature. As the differential thermal and thermogravimetric simultaneous analyzer, for example, a STA7200RV (manufactured by Hitachi High-Tech Science Corporation) can be used. Note that no release PET film to protect the adhesive layer is laminated on the test piece.

[0129] Methods for adjusting the 10% weight loss temperature of the adhesive film of the present invention within the above-mentioned range include, for example, changing the composition of the adhesive layer (for example, by adding an inorganic filler), changing the type of substrate, or changing the thickness ratio of the adhesive layer to the substrate.

[0130] In the adhesive film of the present invention, the light transmittance at a wavelength of 405 nm is preferably 10% at a lower limit. A light transmittance of 10% or more at a wavelength of 405 nm allows a sufficient amount of light to be irradiated onto the adhesive layer, thereby enabling the adhesive layer to be sufficiently cured. A more preferred lower limit of the light transmittance is 15%, and an even more preferred lower limit is 20%. Furthermore, a preferred upper limit of the light transmittance at a wavelength of 405 nm is 70%. A light transmittance of 70% or less can prevent light from irradiating the adherend when irradiating the adhesive film with light, thereby enabling the adhesive film to be peeled off while preventing deterioration in the quality of the adherend. A more preferred upper limit of the light transmittance at a wavelength of 405 nm is 60%, and an even more preferred upper limit is 50%.

[0131] The adhesive film of the present invention has a preferred lower limit of the total thickness of 30 μm and a preferred upper limit of 500 μm. When the adhesive film of the present invention has a total thickness of 30 μm or more, the adhesive film can initially have sufficient pressure-sensitive or heat-sensitive adhesive strength. When the adhesive film has a total thickness of 500 μm or less, the adhesive film can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off. The adhesive film's total thickness is more preferably 50 μm lower limit, more preferably 300 μm upper limit, even more preferably 75 μm lower limit, and even more preferably 200 μm upper limit.

[0132] The adhesive film of the present invention preferably has a water absorption rate of 0.60% or less when left standing for 1 day under conditions of 23°C and 50% RH. A water absorption rate of 0.60% or less can suppress foaming between film layers during high-temperature processing, thereby preventing the adhesive film of the present invention from peeling off during high-temperature processing. A more preferred upper limit of the water absorption rate of the adhesive film of the present invention is 0.40%. There is no particular preferred lower limit for the water absorption rate of the adhesive film of the present invention, but the substantial lower limit is about 0.10%. The water absorption rate of the adhesive film of the present invention can be measured by the same method as for the water absorption rate of the adhesive layer described above.

[0133] Methods for adjusting the water absorption rate of the adhesive film to fall within the above-mentioned range include, for example, changing the composition of the adhesive layer, changing the type of substrate, using a substrate that has been dried during the production of the adhesive film, and changing the ratio of the thickness of the substrate to the total thickness of the film.

[0134] Because the adhesive film of the present invention has high heat resistance, it can be suitably used for protecting, adhering, and temporarily fixing adherends that undergo high-temperature processing at 300°C or higher. For example, during processing of electronic components such as semiconductors, the adhesive film of the present invention can be used to temporarily fix electronic components to a support plate via the adhesive film of the present invention, or to protect electronic components by attaching the adhesive film of the present invention to the electronic components, in order to facilitate handling and prevent damage to the electronic components. In particular, the adhesive film of the present invention has excellent removability, making it particularly suitable for temporary fixing of electronic components. Note that, because the adhesive film of the present invention requires heating for re-peeling, it has adequate adhesive strength at room temperature and can be used for permanent bonding of adherends in some applications without any problems. Examples of such high-temperature processing include heat-resistant treatment of semiconductors.

[0135] After curing, the peak probe tack at 60°C was 0.30 N / cm ２The present invention also provides an adhesive resin composition that has the above properties and a 5% weight loss temperature after curing of 390° C. or higher. The adhesive resin composition of the present invention has excellent heat resistance and can be easily removed from even uneven adherends by heating.

[0136] The adhesive resin composition of the present invention may be a photocurable type that is cured by irradiation with light, or may be a thermosetting type that is cured by heating to a high temperature.

[0137] The adhesive resin composition of the present invention preferably contains a curable resin. The curable resin preferably contains a resin having an imide skeleton in the repeating unit of its main chain. The resin having an imide skeleton in the repeating unit of its main chain has extremely excellent heat resistance due to the imide skeleton, and is less likely to decompose the main chain even when subjected to high-temperature processing at 300°C or higher. Therefore, by including a curable resin containing a resin having an imide skeleton in the repeating unit of its main chain, the adhesive resin composition obtained has excellent heat resistance, and can further suppress outgassing during high-temperature processing and the occurrence of voids and lifting between the adhesive and the adherend. In addition, it can prevent increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend.

[0138] Examples of the resin having an imide skeleton in the repeating unit of the main chain include the same resins as those used in the adhesive film of the present invention described above.

[0139] The curable resin preferably further contains the polyfunctional monomer or polyfunctional oligomer used in the adhesive film of the present invention described above. By containing the polyfunctional monomer or polyfunctional oligomer in the curable resin, three-dimensional reticulation proceeds more efficiently as curing progresses, and the adhesive resin composition of the present invention can be more effectively prevented from increasing adhesion or leaving adhesive residue upon peeling.

[0140] The curable resin preferably contains a compound having a maleimide group. By containing the compound having a maleimide group, the adhesive resin composition of the present invention has better heat resistance. Examples of the compound having a maleimide group include the same compounds as those used in the adhesive film of the present invention described above.

[0141] The adhesive resin composition of the present invention preferably further contains a polymerization initiator. By containing the polymerization initiator in the adhesive resin composition, the adhesive resin composition becomes more easily cured and the adhesion of the adhesive resin composition to the adherend during high-temperature processing can be more effectively suppressed, so that the adhesive resin composition obtained has improved removability from the adherend and can be more easily peeled from the adherend.

[0142] The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator. Examples of the photopolymerization initiator include those similar to those used in the adhesive film of the present invention.

[0143] Examples of the thermal polymerization initiator include Perbutyl H and Percumyl H (both manufactured by NOF Corporation).

[0144] When the adhesive resin composition of the present invention is a photocurable type, it preferably further contains an ultraviolet absorber. By containing an ultraviolet absorber in the adhesive resin composition of the present invention, curing of the adhesive resin composition proceeds more efficiently. In addition, since the adhesive layer becomes more flexible, the probe tack peak value after curing of the adhesive resin composition of the present invention, which will be described later, is further improved.

[0145] Examples of the ultraviolet absorber include the same ones as those used in the adhesive film of the present invention.

[0146] The adhesive resin composition of the present invention preferably further contains a surface conditioner. When the adhesive resin composition of the present invention contains a surface conditioner, the surface conditioner bleeds out to the interface with the adherend, thereby further improving the removability of the adhesive resin composition of the present invention.

[0147] Examples of the surface conditioner include the same ones as those used in the adhesive film of the present invention.

[0148] The adhesive resin composition of the present invention may further contain a gas generating agent. By containing the gas generating agent, even after high-temperature processing at 300°C or higher, gas generated by irradiation with light or the like is released at the interface with the adherend, making it possible to peel the adherend more easily and without leaving any adhesive residue. Furthermore, even when peeling a thin adherend after high-temperature processing at 300°C or higher, damage to the adherend can be prevented.

[0149] Examples of the gas generating agent include the same as those used in the adhesive film of the present invention described above.

[0150] The adhesive resin composition of the present invention preferably further contains an inorganic filler. By containing the inorganic filler, the adhesive resin composition of the present invention can suppress a decrease in elastic modulus at high temperatures, and can further suppress peeling during high-temperature processing even when subjected to high-temperature processing at 300°C or higher.

[0151] Examples of the inorganic filler include the same ones as those used in the adhesive film of the present invention.

[0152] The adhesive resin composition of the present invention may contain known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, surfactants, and waxes, as long as the effects of the present invention are not impaired.

[0153] The method for producing the adhesive resin composition of the present invention is not particularly limited, and it can be produced by using a conventionally known method. Specifically, for example, the above-mentioned curable resin and additives to be blended as necessary can be first mixed using a bead mill, ultrasonic dispersion, homogenizer, high-power disperser, roll mill, etc. to prepare a solution containing the adhesive resin composition.

[0154] The adhesive resin composition of the present invention has a lower limit of the peak probe tack at 60°C after curing of 0.30 N / cm ２The adhesive resin composition of the present invention, after curing, has a peak probe tack value of 0.30 N / cm at 60°C. ２ Because of the above, the adhesive resin composition of the present invention can be easily re-peeled from an adherend having unevenness by heating during peeling. A preferred lower limit of the peak value of probe tack at 60°C after curing of the adhesive resin composition of the present invention is 0.40 N / cm ２ , and a more preferable lower limit is 0.50 N / cm ２ The preferred upper limit of the peak value of the probe tack at 60°C after curing of the adhesive resin composition of the present invention is 5.00 N / cm ２ The adhesive resin composition of the present invention, after curing, has a peak probe tack value of 5.00 N / cm at 60°C. ２ The adhesive resin composition of the present invention has excellent heat resistance when the adhesive layer is cured at 60°C. A more preferable upper limit of the peak value of the probe tack at 60°C after curing is 4.00 N / cm. ２ , and a more preferable upper limit is 2.00 N / cm ２ The method for measuring the peak probe tack value at 60°C after curing of the adhesive resin composition of the present invention includes first coating a solution containing the adhesive resin composition of the present invention prepared by the above-mentioned method onto a release PET film or the like, and drying at 130°C for 10 minutes to prepare a film of the adhesive resin composition. Next, the prepared film of the adhesive resin composition is cured and measured in the same manner as the above-mentioned method for measuring the peak probe tack value at 60°C after curing of the adhesive layer in the adhesive film of the present invention.

[0155] The adhesive resin composition of the present invention has a peak probe tack value of preferably 5.00 N / cm at 23°C after curing. ２ The adhesive resin composition of the present invention, after curing, has a peak probe tack value of 5.00 N / cm at 23°C. ２ The adhesive resin composition of the present invention has a more preferable upper limit of the peak value of the probe tack at 23°C after curing of the adhesive resin composition of the present invention of 3.00 N / cm or less.２ , and a more preferable upper limit is 1.00 N / cm ２ The preferred lower limit of the peak value of the probe tack at 23°C after curing of the adhesive resin composition of the present invention is 0.10 N / cm ２ The adhesive resin composition of the present invention, after curing, has a peak probe tack value of 0.10 N / cm at 23°C. ２ The adhesive resin composition of the present invention has a more improved adhesive strength at room temperature. A more preferred lower limit of the peak probe tack value at 23°C after curing is 0.20 N / cm ２ , and a more preferable lower limit is 0.25 N / cm ２ The method for measuring the probe tack peak value at 23°C after curing of the adhesive resin composition of the present invention includes first coating a solution containing the adhesive resin composition of the present invention prepared by the above-mentioned method onto a release PET film or the like, and drying at 130°C for 10 minutes to prepare a film of the adhesive resin composition. Next, the prepared film of the adhesive resin composition is used to cure and measure the probe tack peak value at 23°C after curing of the adhesive layer in the adhesive film of the present invention as described above.

[0156] In the adhesive resin composition of the present invention, the ratio (V2) of the peak probe tack value at 60°C after curing to the peak probe tack value at 23°C after curing ((peak probe tack value at 60°C after curing) / (peak probe tack value at 23°C after curing)) preferably has a lower limit of 1.00 and an upper limit of 10.0. When V2 is within the above range, the resulting adhesive resin composition has superior heat resistance and superior removability from an adherend having unevenness. The lower limit of V2 is more preferably 2.00, and the upper limit is more preferably 8.00, and the even more preferably 3.00 and 6.00, respectively.

[0157] Examples of methods for adjusting the peak value of the probe tack at 60°C after curing of the adhesive resin composition of the present invention and the peak value of the probe tack at 23°C after curing of the adhesive resin composition of the present invention include methods of changing the composition (for example, a method of adding a low molecular weight compound having heat resistance (such as an ultraviolet absorber), a method of changing the surface conditioner, or a method of adding an inorganic filler).

[0158] The adhesive resin composition of the present invention has a lower limit of the 5% weight loss temperature after curing of 390°C. When the adhesive resin composition of the present invention has a 5% weight loss temperature after curing of 390°C or higher, the adhesive resin composition of the present invention has excellent heat resistance. The lower limit of the 5% weight loss temperature after curing of the adhesive resin composition of the present invention is preferably 400°C, more preferably 420°C. There is no particular preferred upper limit of the 5% weight loss temperature after curing of the adhesive resin composition of the present invention, but the practical upper limit is about 600°C. The 5% weight loss temperature after curing of the adhesive resin composition of the present invention can be measured by applying a solution containing the adhesive resin composition prepared by the above-mentioned method to a release PET film and drying at 130°C for 10 minutes to produce a film of the adhesive resin composition. The adhesive layer of the adhesive film of the present invention can then be cured and measured in the same manner as in the measurement of the 5% weight loss temperature after curing.

[0159] Examples of methods for adjusting the 5% weight loss temperature after curing of the adhesive resin composition of the present invention to fall within the above-mentioned range include methods of changing the composition (for example, a method of incorporating an inorganic filler, etc.).

[0160] The curing conditions for the adhesive resin composition of the present invention at the peak probe tack value at 60°C after curing, the peak probe tack value at 23°C after curing, and the 5% weight loss temperature after curing are, for example, as follows: That is, when the adhesive resin composition of the present invention is a photocurable type, the curing conditions are: a wavelength of 405 nm, an illuminance of 100 mW / cm ２ The accumulated light intensity is 20,000 mJ / cm ２The wavelength was 365 nm and the illuminance was 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ In the case where the adhesive resin composition of the present invention is a thermosetting type, examples of the method include heating at 150°C for 30 minutes or at 200°C for 30 minutes.

[0161] The adhesive resin composition of the present invention may be used as a liquid adhesive or in an adhesive film having an adhesive layer containing the adhesive resin composition of the present invention. In particular, from the viewpoint of further improving handleability, it is preferably used in an adhesive film having an adhesive layer containing the adhesive resin composition of the present invention.

[0162] When the adhesive resin composition of the present invention is used for an adhesive film, the adhesive film may be a non-support type having no substrate, or a supported type having a substrate. In particular, the adhesive film is preferably a supported type having a substrate, from the viewpoint that the adhesive film can be peeled off without a backing when heated and the handleability of the adhesive film is further improved.

[0163] Examples of the substrate include those similar to those used in the adhesive film of the present invention.

[0164] Adhesives and adhesive films using the adhesive resin composition of the present invention have high heat resistance and can suppress peeling during high-temperature processing, making them suitable for use in protecting, adhering, and temporarily fixing adherends that undergo high-temperature processing at 300°C or higher. For example, during processing of electronic components such as semiconductors, these adhesives or adhesive films can be used to temporarily fix electronic components to a support plate via the adhesive or adhesive film, or to protect electronic components by attaching the adhesive or adhesive film to them, in order to facilitate handling and prevent damage to the electronic components. In particular, these adhesives and adhesive films have excellent removability and are therefore more suitable for temporary fixing of electronic components. Note that these adhesives and adhesive films require heating for removability, but they have adequate adhesive strength at room temperature and can be used without problems for permanent bonding of adherends, depending on the application.

[0165] A method for manufacturing a semiconductor device using an adhesive film, the method comprising the steps of: (I) temporarily fixing a semiconductor device using an adhesive film having an adhesive layer, the adhesive film having a 5% weight loss temperature of 390°C or higher, and a peak probe tack value of the adhesive layer of 0.30 N / cm ２ and (II) peeling the adhesive film from the semiconductor device at a temperature T° C. or higher. The method for producing a semiconductor device of the present invention includes a step of easily peeling the adhesive film from an adherend having irregularities, even when an adhesive film having excellent heat resistance is used, and thereby the semiconductor device produced is free from adhesive residue and has excellent production quality.

[0166] The adhesive film in the method for manufacturing a semiconductor device of the present invention has an adhesive layer. The adhesive layer preferably contains a curable adhesive. The curable adhesive may be a photocurable adhesive that cures upon irradiation with light, or a thermosetting adhesive that cures upon heating. Examples of the photocurable adhesive include the same as the photocurable adhesive in the adhesive film of the present invention described above. Examples of the thermosetting adhesive include an adhesive containing a thermosetting adhesive resin composition of the adhesive resin composition of the present invention described above.

[0167] Examples of the adhesive layer include the same adhesive layer as in the adhesive film of the present invention described above, and the adhesive layer in the adhesive film of the present invention described above, where the photocurable adhesive is changed to a thermosetting adhesive, etc. Examples of the adhesive film include adhesive films having such an adhesive layer.

[0168] The adhesive layer has a probe tack peak value at 60°C of preferably 0.30 N / cm ２ The peak probe tack value of the adhesive layer at 60°C is 0.30 N / cm ２ By virtue of the above, in the step (II) described below, the adhesive film can be more easily peeled off by heating it during peeling, thereby further improving the manufacturing quality of the semiconductor device to be manufactured. A preferable lower limit of the peak value of the probe tack of the adhesive layer at 60°C is 0.40 N / cm ２ , and a more preferable lower limit is 0.50 N / cm ２ The preferred upper limit of the peak value of the probe tack of the adhesive layer at 60°C is 5.00 N / cm ２ The peak probe tack value of the adhesive layer at 60°C is 5.00 N / cm ２ When the adhesive film has a peak probe tack value of 4.00 N / cm at 60° C., the adhesive film has a suitable heat resistance and can be suitably used in the method for manufacturing a semiconductor device of the present invention. ２ , and a more preferable upper limit is 2.00 N / cm ２In the manufacturing method of the present invention, with regard to the peak probe tack value at 60°C of the adhesive layer, the adhesive layer may be in an uncured state or after curing, but from the viewpoint of making it possible to more easily peel off the adhesive film during semiconductor manufacturing, it is more preferable that the peak probe tack value at 60°C of the adhesive layer after curing satisfies the above-mentioned range. Furthermore, the method for measuring the peak probe tack value at 60°C of the adhesive layer can be the same as the method for measuring the peak probe tack value at 60°C of the adhesive layer in the adhesive film of the present invention described above.

[0169] The adhesive film has a lower limit of 5% weight loss temperature of 390°C. When the adhesive film has a 5% weight loss temperature of 390°C or higher, the adhesive film has excellent heat resistance, and the manufacturing quality of the semiconductor device manufactured by the manufacturing method of the semiconductor device of the present invention is improved. The lower limit of the 5% weight loss temperature of the adhesive film is preferably 400°C, more preferably 420°C. There is no particular preferred upper limit of the 5% weight loss temperature, but the practical upper limit is about 600°C. Regarding the 5% weight loss temperature of the adhesive layer in the manufacturing method of the semiconductor device of the present invention, the adhesive layer may be in an uncured state or a cured state. However, from the viewpoint of making the adhesive film more easily peelable and further improving the manufacturing quality of the semiconductor device, it is more preferable that the 5% weight loss temperature of the adhesive layer after curing satisfies the above-mentioned range. The 5% weight loss temperature of the adhesive film can be measured by the same method as the 5% weight loss temperature after curing of the adhesive layer of the adhesive film of the present invention described above.

[0170] In the adhesive film of the method for producing a semiconductor device of the present invention, when measuring the peak value of the probe tack at 60°C of the adhesive layer and the 5% weight loss temperature of the adhesive film, examples of the curing conditions for the adhesive layer include the following: That is, when the adhesive resin composition of the present invention is a photocurable type, the curing conditions are: wavelength 405 nm, illuminance 100 mW / cm ２The cumulative light intensity is 20,000 mJ / cm ２ The wavelength was 365 nm and the illuminance was 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ When the adhesive resin composition of the present invention is a thermosetting type, examples of the method include heating at 150°C for 30 minutes or at 200°C for 30 minutes.

[0171] The method for producing a semiconductor device of the present invention includes the steps of: (I) temporarily fixing a semiconductor device using the adhesive film; and (II) forming a semiconductor device on the adhesive layer such that the peak probe tack of the adhesive layer is 0.30 N / cm. ２ and step (II) of peeling the adhesive film from the semiconductor device at a temperature T° C. or higher. By including the steps (I) and (II) in the method for producing a semiconductor device of the present invention, the adhesive film can be easily peeled from the semiconductor device, thereby improving the production quality of the semiconductor device produced.

[0172] The temperature T°C in the step (II) is preferably 60°C or higher. When the temperature T°C is 60°C or higher, the adhesive film that temporarily fixed the semiconductor device in the step (I) can be more easily peeled off. The temperature T°C is more preferably 65°C or higher, and even more preferably 70°C or higher.

[0173] According to the present invention, an adhesive film having excellent heat resistance and capable of being easily re-detached from an adherend having irregularities by heating can be provided. Furthermore, according to the present invention, a method for producing the adhesive film can be provided. Furthermore, according to the present invention, an adhesive resin composition having excellent heat resistance and capable of being easily re-detached from an adherend having irregularities by heating can be provided. Additionally, according to the present invention, a method for producing a semiconductor device can be provided, which includes a step of easily re-detaching an adhesive film from an adherend having irregularities, even when an adhesive film having excellent heat resistance is used.

[0174] The following examples will explain the present invention in more detail, but the present invention is not limited to these examples.

[0175] (Synthesis of Polyimide Compounds 1-A, 2-A, and 3-A) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 39.9 g (0.075 mol) of dimer diamine ("Priamine 1075" manufactured by Croda) and 39 g (0.0765 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A brown solid toluene solution of resins (polyimide compounds 1-A, 2-A, and 3-A) having a structural unit represented by the following formula (6), no maleimide group, and an imide skeleton in the main chain repeating unit was obtained. The weight average molecular weight of the obtained polyimide compounds 1-A, 2-A, and 3-A was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M 6.0 × 150 mm (manufactured by Waters Corporation) as a column, and was found to be 90,000.

[0176]

[0177] (Synthesis of Polyimide Compounds 1-C and 2-C) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 39.9 g (0.075 mol) of dimer diamine (manufactured by Croda, "Priamine 1075") and 23.732 g (0.0765 mol) of 4,4'-oxydiphthalic anhydride were added in this order. A degassing tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A brown solid toluene solution of resins (polyimide compounds 1-C and 2-C) having a structural unit represented by the following formula (7), no maleimide group, and an imide skeleton in the main chain repeating unit was obtained. The weight-average molecular weights of the obtained polyimide compounds 1-C and 2-C were measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M 6.0 × 150 mm column (manufactured by Waters Corporation), and were found to be 110,000.

[0178]

[0179] (Synthesis of Polyimide Compound 2-D) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 39.9 g (0.075 mol) of dimer diamine (manufactured by Croda, "Priamine 1075"), 31.2 g (0.0612 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, and 3.335 g (0.0153 mol) of pyromellitic anhydride were added in this order. A detachment tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A toluene solution of a brown solid resin (polyimide compound 2-D) having structural units represented by the following formulas (8-1) and (8-2), no maleimide group, and an imide skeleton in the main chain repeating unit was obtained. The weight average molecular weight of the obtained polyimide compound 2-D was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M 6.0 × 150 mm (manufactured by Waters Corporation) as a column, and was found to be 100,000.

[0180]

[0181] (Synthesis of Polyimide Compound 2-E) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 39.9 g (0.075 mol) of dimer diamine (manufactured by Croda, "Priamine 1075"), 11.7 g (0.0230 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, and 11.674 g (0.0536 mol) of pyromellitic anhydride were added in this order. A detachment tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A toluene solution of a brown solid resin (polyimide compound 2-E) having structural units represented by the following formulas (9-1) and (9-2), no maleimide group, and an imide skeleton in the main chain repeating unit was obtained. The weight average molecular weight of the obtained polyimide compound 2-E was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M 6.0 × 150 mm (manufactured by Waters Corporation) as a column, and was found to be 98,000.

[0182]

[0183] (Synthesis of Bismaleimide Compound 2-F) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 56 g (0.1 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 19.6 g (0.2 mol) of maleic anhydride were added, followed by 5 g of methanesulfonic anhydride. The resulting solution was refluxed for 12 hours, cooled to room temperature, and 300 mL of toluene was added to the flask. The solution was allowed to stand to separate the layers, and the lower layer, which was an impurity, was removed. The resulting solution was filtered through a glass-fritted funnel filled with silica gel, and the solvent was removed under vacuum to obtain bismaleimide compound 2-F represented by the following formula (10) as a brown liquid.

[0184]

[0185] (Synthesis of Acrylic Copolymer 1-E) A reactor equipped with a thermometer, a stirrer, and a cooling tube was prepared. 94 parts by mass of 2-ethylhexyl acrylate, 6 parts by mass of hydroxyethyl methacrylate, 0.01 parts by mass of lauryl mercaptan, and 80 parts by mass of ethyl acetate were added to the reactor, and the reactor was heated to initiate reflux. Subsequently, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added as a polymerization initiator to initiate polymerization under reflux. Next, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added one hour and two hours after the start of polymerization, and then 0.05 parts by mass of t-hexylperoxypivalate was added four hours after the start of polymerization to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution containing a functional group-containing acrylic polymer with a solids content of 55% by mass and a weight-average molecular weight of 500,000 was obtained. 3.5 parts by mass of 2-isocyanatoethyl methacrylate was added to 100 parts by mass of the resin solids content of the obtained ethyl acetate solution containing the functional group-containing acrylic polymer and reacted to obtain acrylic copolymer 1-E. The weight-average molecular weight of acrylic copolymer 1-E was 550,000. The weight-average molecular weight of the obtained acrylic copolymer 1-E was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC System (manufactured by Waters Corporation)) using THF as the eluent and an HR-MB-M 6.0 x 150 mm column (manufactured by Waters Corporation).

[0186] (Synthesis of Acrylic Copolymer 2-G) A reactor equipped with a thermometer, a stirrer, and a cooling tube was prepared. 93 parts by mass of 2-ethylhexyl acrylate, 1 part by mass of acrylic acid, 6 parts by mass of hydroxyethyl methacrylate, 0.01 parts by mass of lauryl mercaptan, and 80 parts by mass of ethyl acetate were added to the reactor, and the reactor was heated to initiate reflux. Subsequently, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added as a polymerization initiator to initiate polymerization under reflux. Next, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added one hour and two hours after the start of polymerization, and then 0.05 parts by mass of t-hexylperoxypivalate was added four hours after the start of polymerization to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution containing a functional group-containing (meth)acrylic polymer with a solids content of 55% by mass and a weight-average molecular weight of 600,000 was obtained. 3.5 parts by mass of 2-isocyanatoethyl methacrylate was added to 100 parts by mass of the resin solids content of the obtained ethyl acetate solution containing the functional group-containing (meth)acrylic polymer, and the mixture was allowed to react to obtain an acrylic copolymer (acrylic copolymer 2-G) with a weight-average molecular weight of 800,000 and double bonds in the side chains. The weight-average molecular weight of the obtained acrylic copolymer 2-G was measured by gel permeation chromatography (GPC) using THF as the eluent and an HR-MB-M (product name, manufactured by Waters Corporation) column.

[0187] (Synthesis of Acrylic Copolymer 2-H) Acrylic copolymer 2-H was synthesized in the same manner as in the above-mentioned "(Synthesis of Acrylic Copolymer 2-G)," except that a monomer mixture containing 70 parts by mass of ethyl acrylate and 23 parts by mass of methyl methacrylate was used instead of 93 parts by mass of 2-ethylhexyl acrylate, and the weight-average molecular weight was measured. The weight-average molecular weight of acrylic copolymer 2-H was 500,000.

[0188] Examples 1-1 to 1-13, Comparative Examples 1-1 to 1-4 Preparation of adhesive resin composition, production of adhesive film Each material listed in Table 1 was added to 150 mL of toluene and mixed to prepare a solution containing an adhesive resin composition. Note that polyimide compound 1-B is a polyimide compound having a maleimide group represented by the following formula (11) (manufactured by Designer Molecules, "BMI-3000GEL"), and bismaleimide compound 1-D is a bismaleimide compound represented by the above formula (10) (manufactured by Designer Molecules, "BMI-689"). The solution containing the obtained adhesive resin composition was applied with a doctor knife to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been release-treated on one side, so that the dried thickness was as shown in Table 1, and the coating solution was dried by heating at 130°C for 10 minutes to form an adhesive layer. Furthermore, a separately prepared release PET film was overlaid with the release-treated surface facing the adhesive layer, thereby obtaining an adhesive film with a release PET film. For Comparative Examples 1-1 and 1-2, in which the adhesive layer contained a crosslinking agent, the release PET film was overlaid with the release-treated surface facing the adhesive layer, and then the film was further aged at 40°C for 3 days to obtain an adhesive film with a release PET film.

[0189]

[0190] In formula (11), n ​​is the number of repetitions.

[0191] (Measurement of peak probe tack value after curing of adhesive layer) (1) Peak probe tack value at 23°C The obtained adhesive layer was irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２The cured adhesive layer was irradiated for 200 seconds so that the cured adhesive layer was 25 mm wide x 50 mm long to prepare a test piece. The prepared test piece was measured using a probe tack measurement device (manufactured by RHESCA, "Tacking Tester TAC1000") under the following measurement conditions: 23°C, humidity 50%, probe diameter 5 mm, pressing speed 0.5 mm / sec, pressing load 98 gf, contact time 10 seconds, and lifting speed 0.1 mm / s, to measure the peak probe tack value at 23°C. The results are shown in Table 1.

[0192] (2) Peak probe tack value at 60° C. The peak probe tack value at 60° C. was measured in the same manner as in the above-mentioned “(1) Peak probe tack value at 23° C.,” except that the measurement temperature was changed from 23° C. to 60° C. The results are shown in Table 1.

[0193] (Measurement of 5% weight loss temperature after curing the adhesive layer of the adhesive film) The obtained adhesive film was cut into a size of 25 mm wide x 50 mm long to prepare a test piece, and the obtained test piece was irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２ The adhesive layer was cured by irradiating the adhesive film for 200 seconds so that the temperature reached 10°C. The test piece with the cured adhesive layer was weighed into an aluminum pan, and the aluminum pan was set in a differential thermal-thermogravimetric simultaneous analyzer ("STA7200RV" manufactured by Hitachi High-Tech Science Corporation). The temperature was increased from 30°C to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere. The temperature at which the mass of the adhesive film decreased by 5% compared to the mass before heating was defined as the 5% weight loss temperature. Note that no release PET film protecting the adhesive layer was laminated on the test piece. The results are shown in Table 1.

[0194] (Measurement of 10% Weight Loss Temperature of Adhesive Film) Each adhesive film obtained was cut into a size of 5 mm wide x 10 mm long to prepare a test specimen. The obtained test specimen was weighed into an aluminum pan, and the aluminum pan was set in a differential thermal-thermogravimetric simultaneous analyzer ("STA7200RV" manufactured by Hitachi High-Tech Science Corporation). The temperature was increased at a temperature increase rate of 10°C / min over a temperature range from 30°C to 500°C under a nitrogen atmosphere. The temperature at which the mass of the adhesive film decreased by 10% compared to the mass before heating was defined as the 10% weight loss temperature (°C). Note that no release PET film protecting the adhesive layer was laminated on the test specimen. The results are shown in Table 1.

[0195] (Measurement of tensile storage modulus at 23°C after irradiating adhesive layer with light having a wavelength of 405 nm) The obtained adhesive layers were stacked to a thickness of about 1 mm to prepare a laminate consisting of only the adhesive layers. The prepared laminate was irradiated with light having a wavelength of 405 nm and an illuminance of 80 mW / cm using an ultra-high pressure mercury lamp. ２ A measurement sample was prepared by irradiating the adhesive layer with light of 405 nm wavelength for 300 seconds. Dynamic viscoelasticity measurements were performed on the prepared measurement sample using a dynamic viscoelasticity measuring device (manufactured by IT Measurement & Control Co., Ltd., "DVA-200") under measurement conditions of tensile mode, heating rate of 10°C / min, measurement temperature of 0°C to 300°C, and frequency of 10 Hz, thereby obtaining the tensile storage modulus (Pa) at 23°C after irradiation of the adhesive layer with light of 405 nm wavelength. The results are shown in Table 1.

[0196] (Measurement of water absorption rate of adhesive film when left standing for 1 day under the conditions of 23°C and 50% RH) The obtained adhesive film was cut into a size of 20 mm in width x 50 mm in length to prepare a test piece, and then the test piece was dried for 1 hour under an environment of 130°C and 50% RH, and the mass W of the test piece immediately after drying was ０ Furthermore, the mass W ０ After the measurement, the test piece was left standing for one day under the conditions of 23°C and 50% RH, and the mass W １ The obtained W ０ , W １Using the above, the water absorption rate (%) of the adhesive film when left standing for 1 day under the conditions of 23°C and 50% RH was calculated by the following formula (i). Note that no release PET film to protect the adhesive layer was laminated on the test piece. The results are shown in Table 1. Water absorption rate (%) = {(W １ -W ０ ) / W ０}×100 (i) (W ０ : Mass of the test piece immediately after drying for 1 hour under an environment of 130 ° C. and 50% RH, W １ : Mass of the test piece after leaving it for 1 day under the conditions of 23 ° C and 50% RH)

[0197] (Examples 1-14 to 1-15, 1-17 to 1-19, Comparative Examples 1-5 to 1-6) (Preparation of adhesive resin composition, production of adhesive film) Solutions containing adhesive resin compositions having the compositions shown in Table 2 were prepared in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4. The solutions containing the prepared adhesive resin compositions were applied with a doctor knife to the release-treated surface of a 50 μm thick PET film (release PET film) that had been subjected to one-side release treatment so that the dried thickness was as shown in Table 2, and the coating solution was dried by heating at 130 ° C. for 10 minutes, thereby producing a laminate film (a) having an adhesive layer 1 formed thereon. The obtained laminate film (a) was laminated on one side of the substrate shown in Table 2 so as to face the adhesive layer 1. Using a similar method, a laminate film (b) having an adhesive layer 2 formed thereon and having the composition and thickness shown in Table 2 was prepared, and the laminate film (b) was laminated on the other side of the substrate so as to face the adhesive layer 2, thereby obtaining an adhesive film having adhesive layers on both sides of the substrate. For Comparative Examples 1-5 and 1-6, which had adhesive layers containing a crosslinking agent, the laminate film (a) and the laminate film (b) were laminated on the substrate, and then the laminate film was further aged at 40°C for 3 days, thereby obtaining an adhesive film having adhesive layers on both sides of the substrate. In the evaluations described below, adhesive layer 1 was used as the adhesive layer that adheres to the wafer.

[0198] (Measurement of peak probe tack value after adhesive layer curing) An ultra-high pressure mercury lamp was used from the adhesive layer 2 side at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２The adhesive layer was cured by irradiating the adhesive with light for 200 seconds so that the peak probe tack value at 23°C after curing of the adhesive layer and the peak probe tack value at 60°C after curing of the adhesive layer were measured in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4. The results are shown in Table 2.

[0199] (Measurement of 5% weight loss temperature after curing the adhesive layer of the adhesive film) The temperature was measured from the adhesive layer 2 side using an ultra-high pressure mercury lamp with a wavelength of 405 nm and an illuminance of 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ The adhesive layer was cured by irradiating the adhesive film with light for 200 seconds so that the temperature reached 5% weight loss. The adhesive film was then cured in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4, and the 5% weight loss temperature was measured after the adhesive layer of the adhesive film was cured. The results are shown in Table 2.

[0200] (Measurement of 10% weight loss temperature of adhesive film) The 10% weight loss temperature of the adhesive film was measured in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4. The results are shown in Table 2.

[0201] (Measurement of tensile storage modulus at 23°C after irradiating adhesive layer with light of wavelength 405 nm) A laminate in which adhesive layer 1 was laminated to a thickness of 1 mm was irradiated with light of wavelength 405 nm by an ultra-high pressure mercury lamp at an illuminance of 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ The measurement samples were irradiated for 200 seconds so that the tensile storage modulus was measured at 23°C after irradiating the adhesive layer with light having a wavelength of 405 nm in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4. The results are shown in Table 2.

[0202] (Measurement of anchoring strength to substrate at 23°C after irradiating adhesive layer with light of wavelength 405 nm) The adhesive film was irradiated from the adhesive layer 2 side with a super high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 80 mW / cm ２An adhesive film was prepared by irradiating it with light for 300 seconds. One side of a commercially available double-sided tape (manufactured by Sekisui Chemical Co., Ltd., "3810H") was attached to a stainless steel plate that had been washed with ethanol and then wiped dry. Then, adhesive layer 2 of the adhesive film irradiated with light as described above was overlapped with the other side of the double-sided tape, with adhesive layer 1 (the surface to be measured) of the adhesive film facing up. Furthermore, a 25 mm-wide silicone tape (manufactured by Sliontec Co., Ltd., "6260-01") was pressed onto the exposed adhesive layer 1 of the adhesive film by rolling a 2 kg hand roller back and forth at a speed of 10 mm / min. A 25 mm-wide cut was made along the silicone tape in adhesive layer 1 pressed onto the silicone tape, and the adhesive layer was then aged for 1 hour at 23 °C and 50% RH to prepare a test sample. The obtained test samples were subjected to a 90° peel test in accordance with JIS Z0237 using a tensile tester (Shimadzu Corporation, "Autograph AGS-X") under conditions of 23°C, 50% RH, and a peel rate of 300 mm / min. The 90° peel strength (N / 25 mm) of the adhesive layer to the substrate was measured by peeling the adhesive layer 1 pressure-bonded to the silicone tape from the substrate. The obtained 90° peel strength was taken as the anchor strength of the adhesive layer to the substrate at 23°C after irradiating it with light having a wavelength of 405 nm. The results are shown in Table 2.

[0203] (Measurement of water absorption rate of adhesive film when left standing for 1 day under conditions of 23°C and 50% RH) In the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4, the water absorption rate of adhesive films when left standing for 1 day under conditions of 23°C and 50% RH was measured. The results are shown in Table 2.

[0204] (Example 1-16) In the above-mentioned "(Measurement of peak value of probe tack after curing of adhesive layer)" and "(Measurement of 5% weight loss temperature after curing of adhesive layer of adhesive film)", an ultra-high pressure mercury lamp was used at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２Adhesive films were prepared and measurements were carried out in the same manner as in Examples 1-14 to 1-15, 1-17 to 1-19 and Comparative Examples 1-5 to 1-6, except that the adhesive layer was cured by heating at 150°C for 30 minutes in an oven instead of irradiating for 200 seconds so that the adhesive layer became irradiated. The results are shown in Table 2.

[0205] The abbreviations for the resins contained in the substrates and the types of substrates shown in Table 2 are as follows: PEN: polyethylene naphthalate PEEK: polyether ether ketone PI: polyimide PET: polyethylene terephthalate PEN-containing substrate: Teonex Q83C (manufactured by Teijin Ltd.) PEEK-containing substrate: EXPEEK (manufactured by Kurabo Industries Ltd.) PI-containing substrate: Upilex 25U (manufactured by UBE Co., Ltd.) PET-containing substrate: LS-PET (manufactured by Toyo Cross Co., Ltd.)

[0206]

[0207]

[0208] (Example 2-1) (Preparation of adhesive resin composition, production of adhesive film) Each material listed in Table 3 was added to 150 mL of toluene and mixed to prepare a solution containing an adhesive resin composition. Note that polyimide compound 2-B listed in Table 3 is a polyimide compound having a maleimide group represented by the above formula (11) (manufactured by Designer Molecules, "BMI-3000GEL"). The solution containing the obtained adhesive resin composition was applied with a doctor knife to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been prepared and had been subjected to a release treatment on one side, so that the dried thickness was as listed in Table 3. The coating solution was dried by heating at 130 ° C. for 10 minutes, thereby obtaining a laminated film having an adhesive layer. Another identical laminated film was produced by the same method. A laminated film was placed on one side and the other side of a substrate of the type and thickness shown in Table 3, with the adhesive layer facing the substrate, and the substrate was left to cure for 1 hour in an environment of 23°C, thereby obtaining an adhesive film having adhesive layers on both sides of the substrate.

[0209] (Measurement of shear storage modulus of adhesive layer (uncured state) at 23°C) The obtained adhesive layers were stacked to a thickness of about 1 mm to prepare a measurement sample of only the adhesive layer. The prepared measurement sample was subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (manufactured by IT Measurement Control Co., Ltd., "DVA-200") under measurement conditions of shear mode, heating rate of 10°C / min, measurement temperature 0°C to 300°C, and frequency 10 Hz, to measure the shear storage modulus (Pa) of the adhesive layer (uncured state) at 23°C. The results are shown in Table 3.

[0210] (Measurement of tensile storage modulus at 23°C after irradiating adhesive layer with light having a wavelength of 405 nm) Before setting the obtained measurement sample in the dynamic viscoelasticity measuring device, the adhesive layer was irradiated with light having a wavelength of 405 nm and an illuminance of 80 mW / cm using an ultra-high pressure mercury lamp. ２ The tensile storage modulus (Pa) of the adhesive layer at 23°C after irradiation with light of a wavelength of 405 nm was obtained by the same method as in "(Measurement of the shear storage modulus of the adhesive layer (uncured state) at 23°C)" described above, except that a measurement sample irradiated with light of a wavelength of 405 nm for 300 seconds was used and that the dynamic viscoelasticity measurement was performed in tension mode instead of shear mode. The results are shown in Table 3.

[0211] (Measurement of the tensile storage modulus at 23°C of the adhesive layer that was in contact with the glass after bonding the adhesive layer to glass and irradiating it with light from the adhesive layer side) One surface of the measurement sample obtained in the above-mentioned "(Measurement of the shear storage modulus of the adhesive layer (uncured state) at 23°C)" was bonded to glass, and light was irradiated from the surface of the measurement sample that was not in contact with the glass at a wavelength of 405 nm and an illuminance of 80 mW / cm ２ The adhesive layer was attached to glass, and the tensile storage modulus (Pa) of the adhesive layer in contact with the glass after irradiating light from the adhesive layer side was obtained in the same manner as in "(Measurement of shear storage modulus of adhesive layer (uncured state) at 23°C)" above, except that the measurement sample was irradiated with light for 300 seconds, and then removed from the glass and subjected to dynamic viscoelasticity measurement, and that the measurement was performed in tension mode instead of shear mode in the dynamic viscoelasticity measurement. The results are shown in Table 3.

[0212] (Measurement of anchoring strength of adhesive layer (uncured state) to substrate at 23°C) One side of a commercially available double-sided tape (manufactured by Sekisui Chemical Co., Ltd., "3810H") was attached to a SUS plate that had been washed with ethanol and then wiped dry, and then the adhesive layer of the resulting adhesive film on the side not being measured was overlapped with the other side of the double-sided tape, with the adhesive layer of the adhesive film to be measured facing up. Furthermore, a 25 mm wide silicone tape (manufactured by Sliontec Co., Ltd., "6260-01") was pressed against the exposed adhesive layer of the adhesive film to be measured by moving a 2 kg hand roller back and forth once at a speed of 10 mm / min. A 25 mm wide cut was made along the silicone tape in the adhesive layer pressed against the silicone tape, and the adhesive was then aged for 1 hour at 23°C and 50% RH to prepare a test sample. The obtained test samples were subjected to a 90° peel test in accordance with JIS Z0237 using a tensile tester (Shimadzu Corporation, "Autograph AGS-X") under conditions of 23°C, 50% RH, and a peel rate of 300 mm / min. The adhesive layer pressed onto the silicone tape was peeled from the substrate to measure the 90° peel strength (N / 25 mm) of the adhesive layer against the substrate. The obtained 90° peel strength was taken as the anchor strength of the adhesive layer (uncured state) against the substrate at 23°C. The results are shown in Table 3.

[0213] (Measurement of anchoring strength to substrate at 23°C after irradiating adhesive layer with light of wavelength 405 nm) Before one side of a commercially available double-sided tape was attached to an SUS plate that had been washed with ethanol and then wiped dry, the adhesive film was irradiated with light of wavelength 405 nm from an ultra-high pressure mercury lamp at an illuminance of 80 mW / cm. ２ The anchoring strength (N / 25 mm) of the adhesive layer to the substrate at 23°C after irradiation with light of a wavelength of 405 nm was measured in the same manner as in "(Measurement of anchoring strength of adhesive layer (uncured state) to substrate at 23°C)" above, except that an adhesive film irradiated with light of a wavelength of 405 nm for 300 seconds was used. The results are shown in Table 3.

[0214] (Measurement of anchoring strength of the adhesive layer in contact with the glass to the substrate at 23°C after the adhesive film was attached to the glass and irradiated with light from the adhesive film side) The adhesive film was attached to the glass, and the surface of the adhesive film not in contact with the glass was irradiated with light at a wavelength of 405 nm and an illuminance of 80 mW / cm ２ The adhesive film of the adhesive layer was attached to glass, and the adhesive film was irradiated with light from the adhesive film side, and the anchoring strength (N / 25 mm) of the adhesive layer that was in contact with the glass to the substrate at 23°C was obtained in the same manner as in "(Measurement of anchoring strength of adhesive layer (uncured state) to the substrate at 23°C)" above, except that the adhesive film was irradiated with light from the adhesive film side for 300 seconds and then removed from the glass to measure the 90° peel strength of the adhesive layer that was in contact with the glass to the substrate. The results are shown in Table 3.

[0215] (Measurement of Glass Transition Temperature of Adhesive Layer (Uncured State)) A measurement sample was prepared using the same method as in "(Measurement of Shear Storage Modulus of Adhesive Layer (Uncured State) at 23°C)" described above. The obtained measurement sample was subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (manufactured by IT Measurement & Control Co., Ltd., "DVA-200") under the measurement conditions of shear mode, heating rate of 10°C / min, measurement temperature 0°C to 300°C, and frequency 10 Hz, to measure the glass transition temperature (°C) of the adhesive layer (uncured state). The results are shown in Table 3.

[0216] (Measurement of Glass Transition Temperature of Substrate) For the substrates shown in Table 3, dynamic viscoelasticity measurement was performed using a dynamic viscoelasticity measuring device (manufactured by IT Measurement & Control Co., Ltd., "DVA-200") under measurement conditions of a tensile mode, a heating rate of 10°C / min, a measurement temperature of 0°C to 400°C, and a frequency of 10 Hz, to measure the glass transition temperature (°C) of the substrate. The results are shown in Table 3.

[0217] (Measurement of melting point of substrate) For the substrates shown in Table 3, differential scanning calorimetry (DSC) was performed using a differential scanning calorimeter (DSC-7020, manufactured by Hitachi High-Tech Science Corporation) under measurement conditions of a nitrogen atmosphere, a heating rate of 10°C / min, and a measurement temperature of 30°C to 500°C. From the obtained differential scanning calorimetry curve, the temperature showing an endothermic peak was taken as the melting point (°C) of the substrate. The results are shown in Table 3.

[0218] (Measurement of peak probe tack value after adhesive layer curing) An ultra-high pressure mercury lamp was used from one adhesive layer side (the adhesive layer side not being measured) at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２ The adhesive layer was cured by irradiating with light for 200 seconds so that the peak probe tack value was measured for the adhesive layer on the side that was not irradiated with light. Except for this, the peak probe tack value at 23°C after curing of the adhesive layer and the peak probe tack value at 60°C after curing of the adhesive layer were measured in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4. The results are shown in Table 3.

[0219] (Measurement of 5% weight loss temperature after curing the adhesive layer of the adhesive film) An ultra-high pressure mercury lamp was irradiated from one adhesive layer side at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The cumulative light intensity is 20,000 mJ / cm ２ The adhesive layer was cured by irradiating the film with light for 200 seconds so that the temperature reached 5% weight loss, and the measurement was then carried out. Except for this, the adhesive layer of the adhesive film was cured in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4, and the 5% weight loss temperature was measured. The results are shown in Table 3.

[0220] (Measurement of 10% weight loss temperature of adhesive film) The 10% weight loss temperature of the adhesive film was measured in the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4. The results are shown in Table 3.

[0221] (Measurement of water absorption rate of adhesive film when left standing for 1 day under conditions of 23°C and 50% RH) In the same manner as in Examples 1-1 to 1-13 and Comparative Examples 1-1 to 1-4, the water absorption rate of adhesive films when left standing for 1 day under conditions of 23°C and 50% RH was measured. The results are shown in Table 3.

[0222] (Example 2-2) In the above-mentioned "(Preparation of adhesive resin composition, production of adhesive film)", an adhesive film was produced and measurements were carried out in the same manner as in Example 2-1, except that a substrate whose surface had been subjected to corona treatment as shown in Table 3 was used, using a high-frequency power supply device ("AGI-020" manufactured by Kasuga Electric Co., Ltd.) under conditions of an output of 0.3 kW, an electrode distance of 1 mm, and a speed of 2 m / min. The results are shown in Table 3.

[0223] (Examples 2-3, 2-7) A solution containing an adhesive resin composition was prepared in the same manner as in "(Preparation of adhesive resin composition, production of adhesive film)" above. The solution containing the prepared adhesive resin composition was directly applied to one surface of the substrate shown in Table 3 so that the dry thickness was 50 μm, and the substrate was dried at 130°C for 10 minutes to form an adhesive layer. Then, a release-treated surface of a release PET film was placed on top of the substrate so that it faced the adhesive layer. An adhesive layer prepared in the same manner was also placed on the other surface of the substrate, and the substrate was then aged for 1 hour in an environment of 23°C to obtain an adhesive film having adhesive layers on both surfaces of the substrate. Measurements were performed in the same manner as in Example 2-1, except for the method of producing the adhesive film. The results are shown in Table 3.

[0224] (Examples 2-4 to 2-6, 2-8, 2-10 to 2-14, Comparative Examples 2-1 to 2-2) Adhesive films were prepared and measurements were carried out in the same manner as in Example 2-1, except that in the above-mentioned "(Preparation of adhesive resin composition, production of adhesive film)", the type of substrate and the composition of the adhesive layer were changed as shown in Tables 3 and 4. The results are shown in Tables 3 and 4.

[0225] (Example 2-9) (Preparation of adhesive resin composition, production of adhesive film) An adhesive film having an adhesive layer on only one side of the substrate was obtained in the same manner as in Example 2-1, except that the laminated film was overlaid on only one side of the substrate.

[0226] (Measurement of anchoring strength of adhesive layer (uncured state) to substrate at 23°C) One side of a commercially available double-sided tape (manufactured by Sekisui Chemical Co., Ltd., "3810H") was attached to a SUS plate that had been washed with ethanol and then wiped dry. The substrate side of the adhesive film of Example 2-9 that did not have an adhesive layer was then overlapped with the other side of the double-sided tape, with the adhesive layer of the adhesive film to be measured facing up. Furthermore, a 25 mm wide silicone tape (manufactured by Sliontec Co., Ltd., "6260-01") was pressed onto the exposed adhesive layer of the adhesive film by moving a 2 kg hand roller back and forth once at a speed of 10 mm / min. A 25 mm wide cut was made along the silicone tape in the adhesive layer pressed onto the silicone tape, and the adhesive was then aged for 1 hour at 23°C and 50% RH to prepare a test sample. The obtained test samples were subjected to a 90° peel test in accordance with JIS Z0237 using a tensile tester (Shimadzu Corporation, "Autograph AGS-X") under conditions of 23°C, 50% RH, and a peel rate of 300 mm / min, and the adhesive layer pressed onto the silicone tape was peeled from the substrate to measure the anchoring strength of the adhesive layer (in an uncured state) to the substrate at 23°C. The results are shown in Table 3.

[0227] The measurements were carried out in the same manner as in Example 2-1, except for "(Preparation of adhesive resin composition, production of adhesive film)" and "Measurement of anchoring strength of adhesive layer (uncured state) to substrate at 23°C." The results are shown in Table 3.

[0228] The abbreviations for the resins contained in the substrates and the types of substrates shown in Tables 3 and 4 are as follows: PEEK: Polyether ether ketone PET: Polyethylene terephthalate PEN: Polyethylene naphthalate LDPE: Low-density polyethylene PEEK-containing substrate: EXPEEK (manufactured by Kurabo Industries, Ltd.) Polyimide-containing substrate: Upilex 25U (manufactured by UBE Co., Ltd.) Polyamide-containing substrate: Uniamide EX-25 (manufactured by Unitika Ltd.) PET film: Lumirror S-10 (manufactured by Toray Industries, Inc.) PEN-containing substrate: Teonex Q83C (manufactured by Toyobo Co., Ltd.) LDPE-containing substrate: LLDPE film A-1 (manufactured by Tamapoly Co., Ltd.)

[0229]

[0230]

[0231] (Examples 3-1 to 3-5, 3-9 to 3-11) (Preparation of adhesive resin composition, production of adhesive film) Each material listed in Table 5 was added to 150 mL of toluene and mixed to prepare a solution containing an adhesive resin composition. Note that bismaleimide compound 3-B in Table 5 is a bismaleimide compound represented by the above formula (10) ("BMI-689" manufactured by Designer Molecules). The solution containing the obtained adhesive resin composition was applied with a doctor knife to the release-treated surface of a 50 μm thick PET film (release PET film) that had been subjected to one-side release treatment so that the dried thickness was as listed in Table 5, and the coating solution was dried by heating at 130 ° C. for 10 minutes to obtain a laminate film (a) having an adhesive layer. Further, a laminate film (b) having an adhesive layer with the thickness shown in Table 5 was produced by the same method. An adhesive film having adhesive layers on both sides of the substrate was obtained by stacking laminate film (a) on one side and laminate film (b) on the other side of a substrate of the type and thickness shown in Table 5 so that the adhesive layer faced the substrate, and curing the resulting film at 40° C. for 24 hours. In the evaluations described below, the adhesive layer derived from laminate film (a) will be referred to as adhesive layer 2 for bonding to glass, and the adhesive layer derived from laminate film (b) will be referred to as adhesive layer 1 for bonding to a wafer.

[0232] (Measurement of 10% weight loss temperature of adhesive film) Each adhesive film obtained was cut into a size of 5 mm wide x 10 mm long to prepare a test piece. The obtained test piece was weighed into an aluminum pan, and the aluminum pan was set in a differential thermal-thermogravimetric simultaneous analyzer (Hitachi High-Tech Science Corporation, "STA7200RV"), and the temperature was increased at a heating rate of 10°C / min over a temperature range from 30°C to 500°C under a nitrogen atmosphere. The temperature at which the mass of the adhesive film decreased by 10% compared to the mass before heating was defined as the 10% weight loss temperature (°C). Note that no release PET film protecting the adhesive layer was laminated on the test piece. The results are shown in Table 5.

[0233] (Measurement of water absorption rate of adhesive film when left standing for 1 day under the condition of 23°C, 50% RH) Each adhesive film obtained was cut into a size of 20 mm in width x 50 mm in length to prepare a test piece, and then the test piece was dried for 1 hour under an environment of 130°C, 50% RH, and the mass W of the test piece immediately after drying was ０ Furthermore, the mass W ０ After the measurement, the test piece was left standing for one day under the conditions of 23°C and 50% RH, and the mass W １ The obtained W ０ , W １ Using the above, the water absorption rate (%) of the adhesive film when left standing for 1 day under the conditions of 23°C and 50% RH was calculated by the following formula (i). Note that no release PET film to protect the adhesive layer was laminated on the test piece. The results are shown in Table 5. Water absorption rate (%) = {(W １ -W ０ ) / W ０}×100 (i) (W ０ : Mass of the test piece immediately after drying for 1 hour under an environment of 130 ° C. and 50% RH, W １ : Mass of the test piece after leaving it for 1 day under the conditions of 23 ° C and 50% RH)

[0234] (Measurement of UV transmittance of adhesive film at wavelength of 405 nm) Each of the obtained adhesive films was cut into a size of 50 mm wide x 50 mm long to prepare a test piece. The UV transmittance (%) of the prepared test piece at wavelength of 405 nm was measured using a spectrophotometer (manufactured by JASCO Corporation, "V-670"). Note that no release PET film to protect the adhesive layer was laminated on the test piece. The results are shown in Table 5.

[0235] (Measurement of peak probe tack value after curing of adhesive layer) In the same manner as in Examples 1-14 to 1-15, 1-17 to 1-19 and Comparative Examples 1-5 to 1-6, the peak probe tack value at 23°C after curing of the adhesive layer and the peak probe tack value at 60°C after curing of the adhesive layer were measured. The results are shown in Table 5.

[0236] (Measurement of 5% weight loss temperature after curing of adhesive layer of adhesive film) The 5% weight loss temperature after curing of the adhesive layer of the adhesive film was measured in the same manner as in Examples 1-14 to 1-15, 1-17 to 1-19 and Comparative Examples 1-5 to 1-6. The results are shown in Table 5.

[0237] (Measurement of tensile storage modulus at 23°C after irradiation of adhesive layer with light having a wavelength of 405 nm) The tensile storage modulus at 23°C after irradiation of the adhesive layer with light having a wavelength of 405 nm was measured in the same manner as in Examples 1-14 to 1-15, 1-17 to 1-19, and Comparative Examples 1-5 to 1-6. The results are shown in Table 5.

[0238] (Measurement of anchoring strength to substrate at 23°C after irradiation of adhesive layer with light having a wavelength of 405 nm) The anchoring strength to substrate at 23°C after irradiation of adhesive layer with light having a wavelength of 405 nm was measured in the same manner as in Examples 1-14 to 1-15, 1-17 to 1-19 and Comparative Examples 1-5 to 1-6. The results are shown in Table 5.

[0239] (Examples 3-6 to 3-8) For the substrates shown in Table 5, a pretreatment of drying for 10 minutes under an environment of 130 ° C. and 50% RH was performed, and then the laminate film (a) and the laminate film (b) were laminated on the substrate. Except for this, adhesive films were produced in the same manner as in Examples 3-1 to 3-5, 3-9 to 3-11, and various measurements were carried out in the same manner as in Examples 3-1 to 3-5, 3-9 to 3-11.

[0240] The abbreviations for the resin materials contained in the substrates and the types of substrates shown in Table 5 are as follows: PEEK: Polyether ether ketone PEN: Polyethylene naphthalate PET: Polyethylene terephthalate PEEK-containing substrate: EXPEEK (manufactured by Kurabo Industries, Ltd.) PEN-containing substrate: Teonex Q83C (manufactured by Teijin Limited) Polyamide-containing substrate: Uniamide EX-25 (manufactured by Unitika Ltd.) Polyimide-containing substrate: Upilex 25U (manufactured by UBE Co., Ltd.) PET film: LS-PET (manufactured by Toyo Cross Co., Ltd.)

[0241]

[0242] <Evaluation> The adhesive films obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Tables 6 to 10.

[0243] (1) Heat Resistance One release PET film was peeled off from the obtained adhesive film, and the film was attached to a 200 mm diameter, 600 μm thick glass (manufactured by SCHOTT, "Tempax") under vacuum and at a temperature of 40°C, and the adhesive film was cut into the shape of a silicon wafer. Next, the other release PET film from the attached adhesive film was peeled off, and a 200 mm diameter, 700 μm thick silicon wafer was attached to the surface opposite to the surface attached to the glass under vacuum and at 90°C using a pressure lamination device (manufactured by Takatori, "GWSM-300M") to produce a laminate. An ultra-high pressure mercury lamp was used to illuminate the glass side of the obtained laminate with a wavelength of 405 nm and an illuminance of 100 mW / cm. ２ The cumulative light intensity is 20,000 mJ / cm ２ The adhesive layer was cured by irradiating the laminate for 200 seconds so that the temperature reached 0°C. The prepared laminate was heated at 250°C using a hot plate (MSA Factory, "PH224 / 225"), and the time until the adhesive film of the laminate peeled or deformed was measured, with the time when heating of the laminate began being set to 0 seconds. The heat resistance of the adhesive film was evaluated by rating it as "○" if the adhesive film of the laminate did not peel or deform even after 30 minutes, rating it as "△" if the time until the adhesive film of the laminate peeled or deformed was 15 minutes or more but less than 30 minutes, and rating it as "×" if the time until the adhesive film of the laminate peeled or deformed was less than 15 minutes. Furthermore, for Examples 1-14 to 1-19, Comparative Examples 1-5 to 1-6, and Examples 3-1 to 3-11, the adhesive layer 1 side was attached to a silicon wafer and the adhesive layer 2 side was attached to glass, and the evaluation was performed.

[0244] (2) Removability from Concave and Convex Substrate (2-1) With Backing Instead of a silicon wafer, a test patterned wafer having a PBO film on its surface (Waltz Corporation, "WALTS-TEG FBW100A-0001JY", Cu pillar height: 35 μm, SnAg height on Cu pillar: 15 μm) was used, and a laminate was produced in the same manner as in "(1) Heat Resistance" above, except that an adhesive film was attached to the surface of the wafer having the Cu pillars. Using an ultra-high pressure mercury lamp, a wavelength of 405 nm and an illuminance of 100 mW / cm were used from the glass side of the obtained laminate. ２ The cumulative light intensity is 20,000 mJ / cm ２ After the adhesive layer was cured by irradiating the laminate for 200 seconds, the laminate was heated at 250°C for 30 minutes using a hot plate (MSA Factory, "PH224 / 225"). After natural air cooling, the laminate was irradiated from the glass side with a wavelength of 355 nm and an irradiation energy density of 700 mJ / cm. ２A pulsed laser with a frequency of 60 kHz was irradiated onto the entire glass surface, and the glass was peeled off from the adhesive film. After the glass was peeled off, polyimide tape (3M Corporation, "5413", width 25 mm) was attached to the adhesive film of the laminate, and the adhesive film was cut to the same width as the polyimide tape to prepare a backing sample for peelability evaluation. For the obtained peelability evaluation sample, the adhesive film was heated to 60°C, and the peel angle was adjusted to 180° using an angle-flexible adhesive / film peeling analyzer VPA-2S (Kyowa Interface Science Co., Ltd.), and the adhesive film was peeled off from the uneven wafer, and the 180° peel force (N / inch) was measured. The removability of the adhesive film from the uneven substrate was evaluated by assigning an "○" if the obtained 180° peel force was less than 20 N / inch, an "△" if it was 20 N / inch or more but less than 30 N / inch, and an "×" if it was 30 N / inch or more. For Comparative Examples 1-1 to 1-2, 1-5 to 1-6, and 2-1 to 2-2, the evaluation of "(1) Heat resistance" described above was "x," so this evaluation was not performed. Furthermore, for Examples 1-14 to 1-19, Comparative Examples 1-5 to 1-6, and Examples 3-1 to 3-11, the adhesive layer 1 side was attached to a wafer with a test pattern having a PBO film on its surface, and the adhesive layer 2 side was attached to glass, and the evaluation was performed.

[0245] (2-2) No Backing The removability of the adhesive film from the uneven substrate was evaluated in the same manner as in the evaluation of "(1) With Backing" above, except that the adhesive film after peeling the glass from the laminate was not backed with polyimide tape. Note that this evaluation was only performed on adhesive films having a substrate, that is, Examples 1-14 to 1-19, Examples 2-1 to 2-14, and Examples 3-1 to 3-11. For Comparative Examples 1-5 to 1-6 and Comparative Examples 2-1 to 2-2, the evaluation of "(1) Heat Resistance" above was "x", so this evaluation was not performed.

[0246] (3) Handling Ease The obtained adhesive film was cut into a size of 30 cm wide x 30 cm long to prepare a test piece, and the PET film protecting the adhesive layer was gently peeled off by hand from one corner of the test piece. The adhesive film was visually observed during and after peeling of the PET film, and the handling ease of the adhesive film was evaluated according to the following criteria: ○: The PET film was peeled off without any problems. ×: When peeling the PET film, the adhesive layer peeled off from the substrate or some lift occurred. Note that even if the evaluation is "X," the adhesive film of the present invention can be used without any problems depending on the application. Furthermore, this evaluation was performed only on adhesive films having a substrate, i.e., Examples 1-14 to 1-19, Comparative Examples 1-5 to 1-6, Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-2, and Examples 3-1 to 3-11. In addition, for Examples 1-14 to 1-19, Comparative Examples 1-5 to 1-6, and Examples 3-1 to 3-11, the PET film on the adhesive layer 1 side was peeled off before the evaluation.

[0247] For Examples 1-14 to 1-19, Comparative Examples 1-4 to 1-6, Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-2, and Examples 3-1 to 3-11, which have a substrate, the following optional evaluations (4-1) to (4-3) were performed to further evaluate heat resistance at high temperatures. If the evaluation of "(1) Heat Resistance" above is not "X", the adhesive film of the present invention has excellent heat resistance. Therefore, even if the evaluations of the following (4-1) to (4-3) are "X", the adhesive film of the present invention can be used without problems depending on the application. If the evaluations of the following (4-1) to (4-3) are not "X", the adhesive film of the present invention has even better heat resistance.

[0248] (4-1) Heat Resistance Test at 260°C The separator on one side of the adhesive film obtained in Examples 2-1 to 2-14 and Comparative Examples 2-1 to 2-2 was peeled off, and the film was manually bonded to a quartz glass sheet having a diameter of 8 inches and a thickness of 800 μm. Furthermore, the separator on the other side of the adhesive film bonded to the quartz glass sheet was peeled off, and an 8-inch diameter bare silicon wafer was bonded to the film using a vacuum bonding device (manufactured by Takatori Corporation, "GWSM-300M") under conditions of a vacuum of 100 Pa, a temperature of 80°C, and a pressure of 0.5 MPa x 300 sec, to obtain a glass wafer laminate. An ultra-high pressure mercury lamp was used from the glass side of the obtained glass wafer laminate at a wavelength of 405 nm and an illuminance of 80 mW / cm. ２ For Example 2-9 having an adhesive layer on only one side, the separator of the adhesive film was peeled off, and the adhesive film was bonded to an 8-inch diameter silicon bare wafer using a vacuum bonding device (manufactured by Takatori Corporation, "GWSM-300M") under conditions of a vacuum of 100 Pa, a temperature of 40°C, and a pressure of 0.5 MPa x 300 sec., and then irradiated from the substrate side with light at a wavelength of 405 nm and an illuminance of 80 mW / cm. ２ A test sample was obtained by irradiating the test sample with light of 1000 nm for 300 seconds. The prepared test sample was placed in an oven heated to 260°C and left to stand in an environment of 260°C for 30 minutes, thereby conducting a heat resistance test. After the heat resistance test, the glass wafer laminate was removed from the oven, and the adhesive surfaces on both sides of the adhesive film were visually observed to confirm the ratio of the area where the adhesive film had peeled to the entire adhesive surface (peeled area). The heat resistance of the adhesive film at ultra-high temperatures was evaluated according to the following criteria: ○: The peeled area was about 5% or less. △: The peeled area was more than 5% but less than 30%. ×: The peeled area was about 30% or more.

[0249] (4-2) Weight loss rate of adhesive layer at 300 °C The adhesive films obtained in Examples 2-1 to 2-14 and Comparative Examples 2-1 to 2-2 were cut to a size of φ4 mm to prepare test specimens. The obtained test specimens were weighed into an aluminum pan, and the aluminum pan was set in a differential thermal-thermogravimetric simultaneous analyzer "STA7200RV (manufactured by Hitachi High-Tech Science Corporation)". The weight loss rate (%) of the adhesive layer at 300 °C was measured by comparing the weight when heated from 30 °C to 300 °C at a heating rate of 10 °C / min under a nitrogen atmosphere with the weight before heating. Note that no release PET film to protect the adhesive layer was laminated on the test specimen. Heat resistance was evaluated by marking "○" when the weight loss rate (%) of the obtained adhesive layer at 300 °C was 4% or less and "×" when it was greater than 4%.

[0250] (4-3) Film peeling at 300 ° C. The adhesive films obtained in Examples 1-14 to 1-19, Comparative Examples 1-5 to 1-6, Examples 2-1 to 2-14, Comparative Examples 2-1 to 2-2, and Examples 3-1 to 3-11 having a substrate were cut into circles with a diameter of 200 mm. Next, one release PET film was peeled from the cut adhesive film and attached to a silicon wafer with a diameter of 200 mm and a thickness of 700 μm under vacuum and 40 ° C. conditions. Next, the other release PET film was peeled off, and a glass sheet with a diameter of 200 mm and a thickness of 600 μm (manufactured by SCHOTT, "Tempax") was attached to the surface opposite the surface attached to the silicon wafer under vacuum and 90 ° C. conditions using a pressure lamination device (manufactured by Takatori, "GWSM-300M") to obtain a laminate. The obtained laminate was heated for 30 minutes using a 300°C hot plate (manufactured by ASONE, "ND-3HA"). The heated laminate was observed from the glass side using a stereomicroscope and evaluated according to the following criteria. ◯: There was no change in appearance of the adhesive layer of the adhesive film and the adhesive surface between the glass and the adhesive film. Δ: There was no change in appearance of the adhesive layer of the adhesive film and the adhesive surface between the glass and the adhesive film, but the substrate was melted. ×: The adhesive layer of the adhesive film was melted, or bubbles were generated on the adhesive surface between the glass and the adhesive film. Furthermore, for Examples 1-14 to 1-19, Comparative Examples 1-5 to 1-6, and Examples 3-1 to 3-11, the adhesive layer 1 side was attached to a silicon wafer and the adhesive layer 2 side was attached to glass, and the evaluation was performed.

[0251]

[0252]

[0253]

[0254]

[0255]

[0256] According to the present invention, an adhesive film having excellent heat resistance and capable of being easily re-detached from an adherend having irregularities by heating can be provided. Furthermore, according to the present invention, a method for producing the adhesive film can be provided. Furthermore, according to the present invention, an adhesive resin composition having excellent heat resistance and capable of being easily re-detached from an adherend having irregularities by heating can be provided. Additionally, according to the present invention, a method for producing a semiconductor device can be provided, which includes a step of easily re-detaching an adhesive film from an adherend having irregularities, even when an adhesive film having excellent heat resistance is used.

Claims

1. An adhesive film having an adhesive layer, the adhesive layer containing a photocurable adhesive, and the adhesive film is irradiated with a super-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm. ２ The accumulated light intensity is 20,000 mJ / cm ２ After irradiating for 200 seconds so as to obtain a peak probe tack value of 0.30 N / cm at 60° C. ２ The adhesive film is irradiated with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The accumulated light intensity is 20,000 mJ / cm ２ and a 5% weight loss temperature of the adhesive film after 200 seconds of irradiation so as to obtain a temperature of 390° C. or higher.

2. The adhesive film according to claim 1, wherein the photocurable adhesive contains a curable resin, and the curable resin contains a resin having an imide skeleton in the repeating unit of the main chain.

3. An adhesive film according to claim 1 or 2, wherein the photocurable adhesive contains an ultraviolet absorbing agent.

4. An adhesive film according to claim 1, 2 or 3, wherein the photocurable adhesive contains a surface conditioner.

5. The adhesive film according to claim 1, 2, 3 or 4, which has a substrate.

6. An adhesive film according to claim 5, wherein the substrate contains a resin (A1) having in its main chain skeleton a repeating unit containing at least one type selected from the group consisting of an ether bond, a ketone group, and an ester bond.

7. The adhesive film according to claim 5 or 6, wherein at least one surface of the substrate has an easy-adhesion layer.

8. The adhesive film according to claim 7, wherein the easy-adhesion layer comprises at least one layer selected from the group consisting of a corona-treated layer, a plasma-treated layer, a sandblasted layer, a chemically etched layer, and a treatment-coated layer.

9. The adhesive film according to claim 5, 6, 7 or 8, which has the adhesive layer on both sides of the substrate.

10. The adhesive layer is formed by irradiating the adhesive film with an ultra-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 80 mW / cm. ２ 10. An adhesive film according to claim 5, 6, 7, 8 or 9, which has an anchoring strength to said substrate of 0.10 N / 25 mm or more at 23° C. after irradiation with light of 1000 nm for 300 seconds.

11. The adhesive film is irradiated with a super-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 100 mW / cm ２ The accumulated light intensity is 20,000 mJ / cm ２ After irradiating for 200 seconds so as to obtain a peak probe tack value of 5.00 N / cm at 23° C. ２ The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein:

12. The adhesive layer is irradiated with a super-high pressure mercury lamp at a wavelength of 405 nm and an illuminance of 80 mW / cm ２ The tensile storage modulus at 23°C after irradiation with light of 1.0 x 10 for 300 seconds was 1.0 x 10 ８ 12. The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, having a modulus of elasticity of 1 Pa or more.

13. An adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, which has a water absorption rate of 0.60% or less when left standing for one day under conditions of 23°C and 50% RH.

14. The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein the adhesive film has a 10% weight loss temperature of 425°C or higher.

15. The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, which is used for temporarily fixing electronic parts.

16. A method for producing an adhesive film according to claim 7 or 8, comprising a step of performing at least one surface treatment selected from corona treatment, plasma treatment, sandblasting, chemical etching, and application of a treatment agent on at least one surface of the substrate.

17. Peak probe tack value at 60°C after curing is 0.30 N / cm ２ and a 5% weight loss temperature after curing is 390° C. or higher.

18. An adhesive film having an adhesive layer containing the adhesive resin composition according to claim 17.

19. A method for manufacturing a semiconductor device using an adhesive film, comprising the steps of: (I) temporarily fixing a semiconductor device using the adhesive film; (II) forming a semiconductor device on the adhesive film; and (III) forming a semiconductor device on the adhesive film; and (IV) forming a semiconductor device on the adhesive film. ２ (II) peeling the adhesive film from the semiconductor device at a temperature T° C. or higher.

20. The method of manufacturing a semiconductor device according to claim 19, wherein said temperature T°C is 60°C or higher.

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