Adhesive film, temporary fixing material, cured product, laminate and method for manufacturing electronic component

Abstract

To provide an adhesive film which can efficiently peel off a support even when irradiated with low-energy laser light and has excellent peelability to an adherend even when subjected to high-temperature processing, a cured product of the same, a laminate and a method for manufacturing an electronic component.SOLUTION: There is provided an adhesive film containing an adhesive layer containing a curable adhesive, wherein the curable adhesive is a photo-curing adhesive, the adhesive layer has a gel fraction of 65 mass% or more after irradiation with light of 405 nm wavelength so that the integrated light quantity becomes 20000 mJ / cm2 and the adhesive layer has an extinction coefficient of 1.0×10-4 or more with respect to light of 308 nm wavelength after irradiation with light of 405 nm wavelength so that the integrated light quantity becomes 20000 mJ / cm2.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an adhesive film. The present invention also relates to a cured product of the adhesive film. Furthermore, the present invention relates to a laminate having the adhesive film. And the present invention relates to a method for manufacturing an electronic component using the laminate. The present invention also relates to a temporary fixing material. The present invention also relates to a cured product of the temporary fixing material. Furthermore, the present invention relates to a laminate having the cured product. And the present invention relates to a method for manufacturing an electronic component.

Background Art

[0002] When processing electronic components such as semiconductors, in order to facilitate handling of the electronic components and prevent damage, the electronic components are adhered and temporarily fixed to a support via an adhesive composition or a temporary fixing material made of an adhesive composition, or a tape-shaped temporary fixing material having an adhesive layer or an adhesive film such as an adhesive film is attached and adhered to the electronic components for protection. For example, when a thick film wafer cut out from a high-purity silicon single crystal or the like is ground to a predetermined thickness to form a thin film wafer, the thick film wafer is adhered to a support via an adhesive composition or a temporary fixing material.

[0003] Thus, the adhesive composition, adhesive film, and temporary fixing material used for electronic components are required to have high adhesiveness sufficient to firmly fix the electronic components during the processing step and to be peelable without damaging the electronic components after the step is completed (hereinafter also referred to as "high adhesion and easy peelability"). As a means for realizing high adhesion and easy peelability, for example, Patent Document 1 discloses an adhesive sheet using an adhesive in which a polyfunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to a side chain or main chain of a polymer. By utilizing the fact that the polymer is cured by ultraviolet irradiation due to having a radiation-polymerizable functional group, the adhesive force is reduced by irradiating ultraviolet rays during peeling, and peeling can be performed without adhesive residue.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Laid-Open No. 5-32946 [Summary of the Invention] [Problems to be Solved by the Invention]

[0005] In recent years, in order to cope with the high integration of semiconductors, a TBDB (Temporary bonding / de-bonding) process has been adopted for manufacturing semiconductors by supporting a thin wafer with a support and a temporary fixing material or an adhesive film. In the TBDB process, there may be a step of irradiating the entire surface of the support with laser light to peel off the support. As the laser light to be irradiated, various laser lights such as solid laser light and gas laser light are used, and laser light having a wavelength in the ultraviolet region is used to promote photolysis. Among them, excimer laser light having a wavelength of 308 nm or more and 355 nm or less is often used.

[0006] However, when peeling off the support by irradiating laser light using a conventional adhesive film such as an adhesive film or a temporary fixing material such as a tape-shaped temporary fixing material, if laser light capable of peeling off the support is continuously irradiated for a long time, the device capacity and processing capacity of the laser light irradiation device will decrease, the adhesive film and the temporary fixing material will carbonize, the support will be damaged, the adhesive film, the temporary fixing material and the support will be contaminated, and the manufacturing quality of electronic components will deteriorate due to the deterioration of the peeling performance of the support.

[0007] In addition, in semiconductor manufacturing, since a semiconductor may be integrated on a substrate by thermocompression bonding (TCB), it is required to easily peel off the adhesive film from the adherend after a high-temperature processing treatment involving a heat treatment or a heat-generating treatment. However, in a conventional adhesive film, the adhesion to the adherend may be enhanced during the high-temperature processing treatment, and the adhesive strength may not be sufficiently reduced during peeling, resulting in residue.

[0008] An object of the present invention is to provide an adhesive film that can efficiently peel a support even when irradiated with a low-energy laser beam, and further has excellent peelability with respect to an adherend even when subjected to high-temperature processing. Another object of the present invention is to provide a cured product of the adhesive film. Still another object of the present invention is to provide a laminate having a support, the adhesive film, and a semiconductor in this order. Furthermore, an object of the present invention is to provide a method for manufacturing an electronic component, which uses the laminate and has a step of efficiently peeling the support even when irradiated with a low-energy laser beam and a step of easily peeling the adherend even when subjected to high-temperature processing. Also, an object of the present invention is to provide a temporary fixing material that has excellent laser processing performance and can efficiently peel a support even when irradiated with a low-energy laser beam after curing. Another object of the present invention is to provide a cured product of the temporary fixing material. Still another object of the present invention is to provide a laminate having the cured product. Furthermore, an object of the present invention is to provide a method for manufacturing an electronic component, which has a step of efficiently peeling the support even when irradiated with a low-energy laser beam.

Means for Solving the Problems

[0009] The present disclosure 1 is an adhesive film including an adhesive layer containing a curable adhesive, wherein the curable adhesive is a photo-curable adhesive, and the adhesive layer has a gel fraction of 65% by mass or more after irradiation with light having a wavelength of 405 nm and an integrated light amount of 20000 mJ / cm 2 and the adhesive layer has an attenuation coefficient with respect to light having a wavelength of 308 nm of 1.0×10 2 or more after irradiation with light having a wavelength of 405 nm and an integrated light amount of 20000 mJ / cm -4 or more. The present disclosure 2 is an adhesive film including an adhesive layer containing a curable adhesive, wherein the curable adhesive is a photo-curable adhesive, the adhesive layer has a gel fraction of 65% by mass or more after irradiation with light, and the adhesive layer has an attenuation coefficient with respect to light having a wavelength of 308 nm of 1.0×10 -4 or more after irradiation with light. The present disclosure 3 is the adhesive film of the present disclosure 1 or 2, wherein the curable adhesive contains a curable resin and a photoinitiator. The present disclosure 4 is the adhesive film of the present disclosure 3, wherein the curable resin contains a bismaleimide compound. The present disclosure 5 is the adhesive film of the present disclosure 3 or 4, wherein the absorption coefficient of the photoinitiator at a wavelength of 405 nm is 10 ml / (g·cm) or more. The present disclosure 6 is the adhesive film of the present disclosure 3, 4 or 5, wherein the content of the photoinitiator relative to 100 parts by mass of the curable resin is 0.1 part by mass or more and 10 parts by mass or less. The present disclosure 7 is the adhesive film of the present disclosure 3, 4, 5 or 6, wherein the curable adhesive further contains an ultraviolet absorber. The present disclosure 8 is the adhesive film of the present disclosure 7, wherein the ultraviolet absorber contains a triazine-based ultraviolet absorber. The present disclosure 9 is the adhesive film of the present disclosure 7 or 8, wherein the content of the ultraviolet absorber relative to 100 parts by mass of the curable resin is 1 part by mass or more and 30 parts by mass or less. The present disclosure 10 is the adhesive film of the present disclosure 3, 4, 5, 6, 7, 8 or 9, wherein the curable adhesive further contains a release agent. The present disclosure 11 is the adhesive film of the present disclosure 10, wherein the release agent contains at least one selected from the group consisting of a silicone-based release agent and an acrylic-based release agent. The present disclosure 12 is the adhesive film of the present disclosure 10 or 11, wherein the content of the release agent relative to 100 parts by mass of the curable resin is 0.1 part by mass or more and 20 parts by mass or less. The present disclosure 13 is the adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein the gel fraction of the adhesive layer before light irradiation is 60% by mass or less. The present disclosure 14 is the adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein the attenuation coefficient of the adhesive layer before light irradiation with respect to light having a wavelength of 308 nm is 1.0×10 -4 or more. The present disclosure 15 is an adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 having a base material. The present disclosure 16 is an adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, wherein the 5% weight loss temperature is 300 ° C or higher when heated at a heating rate of 10 ° C / min in a nitrogen atmosphere after irradiation with light having a wavelength of 405 nm so that the integrated light amount becomes 20000 mJ / cm 2 The present disclosure 16 is an adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, wherein the 5% weight loss temperature is 300 ° C or higher when heated at a heating rate of 10 ° C / min in a nitrogen atmosphere after irradiation with light having a wavelength of 405 nm so that the integrated light amount becomes 20000 mJ / cm The present disclosure 17 is an adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 for temporary fixing of electronic components. The present disclosure 18 is a cured product obtained by curing the adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, and the laser processing depth when laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is 0.10 μm or more. The present disclosure 19 is a laminate having a support, an adhesive film of the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, and a semiconductor device in this order. The present disclosure 20 is a method for manufacturing an electronic component, which includes an optical irradiation step of irradiating the laminate with light from the support side using the laminate of the present disclosure 19, a high-temperature processing step of subjecting the laminate to heat treatment or a process involving heat generation, irradiating the laminate with laser light having a wavelength of 200 nm or more and 355 nm or less from the support side, peeling the support from the adhesive film, and peeling the adhesive film from the semiconductor device. The present disclosure 21 is a temporary fixing material containing a curable adhesive, wherein the curable adhesive is a photo-curable adhesive, and after curing by irradiation with light having a wavelength of 365 nm so that the integrated light amount becomes 20000 mJ / cm 2 the laser processing depth when irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2It is a temporary fixing material in which the laser processing depth when pulse-irradiated with laser light of is 0.10 μm or more. The present disclosure 22 is a temporary fixing material containing a curable adhesive, and when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after curing, the laser processing depth is 0.10 μm or more. The present disclosure 23 is the temporary fixing material according to the present disclosure 21 or 22, wherein the laser processing depth when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after curing is 1.0 μm or less. The present disclosure 24 is the temporary fixing material according to the present disclosure 21, 22, or 23, wherein the laser processing depth when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 after curing is 1.0 μm or less. The present disclosure 25 is the temporary fixing material according to the present disclosure 21, 22, 23, or 24, wherein the curable adhesive contains a curable resin, and the curable resin contains a resin having an imide skeleton as a repeating unit in the main chain. The present disclosure 26 is the temporary fixing material according to the present disclosure 25, wherein the content of the resin having an imide skeleton as a repeating unit in the main chain is 65 parts by mass or more in 100 parts by mass of the curable resin. The present disclosure 27 is the temporary fixing material according to the present disclosure 21, 22, 23, 24, 25, or 26, wherein the curable adhesive contains an ultraviolet absorber or an ultraviolet scattering agent. The present disclosure 28 is the temporary fixing material according to the present disclosure 27, wherein the ultraviolet absorber or the ultraviolet scattering agent contains a triazine-based ultraviolet absorber or titanium oxide. The present disclosure 29 is the temporary fixing material according to the present disclosure 21, 22, 23, 24, 25, 26, 27, or 28, wherein the curable adhesive contains a photopolymerization initiator. The present disclosure 30 is the temporary fixing material according to the present disclosure 21, 22, 23, 24, 25, 26, 27, 28, or 29, wherein the weight loss rate when heated at 290 °C for 30 minutes in a nitrogen atmosphere after curing is 7% or less. The cured product of the present disclosure 31 is formed by curing the temporary fixing material of the present disclosure 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. The present disclosure 32 has a support, the cured product of the present disclosure 31, and a semiconductor device in this order, and the support is a laminate having a light transmittance of 50% or more at a wavelength of 300 nm or more and 400 nm or less. The present disclosure 33 is a laminate including a support, a cured product of a temporary fixing material, and a semiconductor device in this order, and is irradiated with laser light having a wavelength of 308 nm or more and 355 nm or less, a pulse width of 100 nsec or less, and an irradiation energy density of 500 mJ / cm 2 This is a method for manufacturing an electronic component having a support peeling step of peeling the support from the laminate by pulse-irradiating the following laser light from the support side. The present invention will be described in detail below.

[0010] The inventors of the present invention have focused on the fact that in the manufacture of high heat-resistant electronic components required in recent years, the laser light irradiated for peeling the support has high energy, and damage to the device, support, temporary fixing material, etc. can be suppressed. Even when irradiating with low-energy laser light, an adhesive film or temporary fixing material that can efficiently peel the support was studied. The inventors of the present invention used an adhesive film including an adhesive layer containing a curable adhesive, and for the adhesive film after light irradiation, adjusted the gel fraction of the adhesive layer and the attenuation coefficient with respect to light of a specific wavelength within a specific range. As a result, it was found that even when irradiating with low-energy laser light, the support can be efficiently peeled, and furthermore, an adhesive film excellent in peelability with respect to the adherend can be obtained even when performing high-temperature processing, and the adhesive film of the present invention was completed. In addition, the inventors of the present invention cured a temporary fixing material containing a curable adhesive, examined the processing depth when pulse-irradiating laser light on the cured temporary fixing material, and found that when using a temporary fixing material in a specific processing state, the support can be efficiently peeled, and the temporary fixing material of the present invention was completed.

[0011] The adhesive film of the present invention includes an adhesive layer containing a curable adhesive. The curable adhesive is a photo-curable adhesive. By including an adhesive layer containing a photo-curable adhesive in the adhesive film of the present invention, it becomes possible to cure by light, and it is possible to suppress the enhancement of adhesion of the obtained adhesive film to the adherend during high-temperature processing. As a result, the obtained adhesive film has improved peelability from the adherend and can prevent the occurrence of adhesive residue when peeling from the adherend. As a method for curing the adhesive film of the present invention by light, for example, using an ultra-high pressure mercury lamp to irradiate light with a wavelength of 405 nm so that the integrated light amount is 20000 mJ / cm 2 and the like can be mentioned.

[0012] The adhesive layer according to the adhesive film of the present disclosure 2 has a lower limit of the gel fraction of 65% by mass after light irradiation. When the gel fraction of the adhesive layer after light irradiation is 65% by mass or more, the obtained adhesive film has excellent peelability from the adherend. The preferable lower limit of the gel fraction of the adhesive layer after light irradiation is 70% by mass, and the more preferable lower limit is 75% by mass. Also, in view of using a photoinitiator that is not incorporated into the crosslinking from the viewpoint of enhancing the curability of the adhesive layer, the preferable upper limit of the gel fraction of the adhesive layer after light irradiation is 99.9% by mass, and the more preferable upper limit is 99% by mass. As the light irradiation conditions for the gel fraction of the adhesive layer after light irradiation, for example, irradiating light with a wavelength of 405 nm so that the integrated light amount is 20000 mJ / cm 2 and the like can be mentioned.

[0013] The adhesive layer according to the adhesive film of the present disclosure 1 has a wavelength of 405 nm and an integrated light amount of 20000 mJ / cm 2The lower limit of the gel fraction after irradiation so as to be [as described below, sometimes simply referred to as "the gel fraction of the adhesive layer after irradiation with light of wavelength 405 nm"] is 65% by mass. When the gel fraction of the adhesive layer after irradiation with light of wavelength 405 nm is 65% by mass or more, the resulting adhesive film has excellent peelability with respect to the adherend. The preferable lower limit of the gel fraction of the adhesive layer after irradiation with light of wavelength 405 nm is 70% by mass, and the more preferable lower limit is 75% by mass. Also, in view of using a photoinitiator that is not incorporated into crosslinking from the viewpoint of enhancing the curability of the adhesive layer, the preferable upper limit of the gel fraction of the adhesive layer after irradiation with light of wavelength 405 nm is 99.9% by mass, and the more preferable upper limit is 99% by mass. Note that the gel fraction of the adhesive layer after irradiation with light of wavelength 405 nm is measured, for example, by the following method. That is, with respect to the adhesive film, after irradiating the adhesive layer with light of wavelength 405 nm so that the integrated light amount becomes 20000 mJ / cm 2 then, after taking a mass W0 (g) of the adhesive layer after light irradiation, the taken adhesive layer is immersed in toluene at 23°C for 24 hours. After shaking, using a metal mesh (mesh opening #200 mesh, mass: W1 (g)), the adhesive layer that has absorbed and swollen with toluene is filtered, and the separated adhesive layer is dried at 110°C for 1 hour. Then, by measuring the mass W2 (g) of the adhesive layer after drying and calculating the gel fraction using the following formula, the gel fraction of the adhesive layer after irradiation with light of wavelength 405 nm can be measured. Gel fraction (% by mass) = 100×(W2 - W1) / W0 (W0: mass of the initial adhesive layer, W1: initial mass of the metal mesh, W2: mass of the adhesive layer including the metal mesh after drying)

[0014] The preferable upper limit of the gel fraction before irradiating the adhesive layer with light (hereinafter, sometimes simply referred to as "the gel fraction of the adhesive layer before light irradiation") is 60% by mass. When the gel fraction of the adhesive layer before light irradiation is 60% by mass or less, the resulting adhesive film has more excellent adhesiveness. The more preferable upper limit of the gel fraction of the adhesive layer before light irradiation is 50% by mass, and the further preferable upper limit is 40% by mass. Further, the lower limit of the gel fraction of the adhesive layer before light irradiation may be 0% by mass. However, from the viewpoints of the durability of the adhesive layer against displacement and deformation of the adherend and the adhesion of the resulting adhesive film to the adherend, the preferable lower limit of the gel fraction of the adhesive layer before light irradiation is 0.5% by mass, and the more preferable lower limit is 1% by mass. Incidentally, the gel fraction of the adhesive layer before light irradiation can be measured, for example, by carrying out the measurement method of the gel fraction of the adhesive layer after light irradiation described above without performing light irradiation.

[0015] As a method for adjusting the gel fraction of the adhesive layer after light irradiation and the gel fraction of the adhesive layer before light irradiation to the ranges described above, a method of changing the composition of the photocurable adhesive (for example, adjusting the amount of the component that does not photocure, improving the photocurability by adding a photoinitiator, etc.) is preferable.

[0016] The adhesive layer according to the adhesive film of the present disclosure 2 has a lower limit of the attenuation coefficient with respect to light having a wavelength of 308 nm after light irradiation of 1.0×10 -4 . When the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation is 1.0×10 -4 or more, the support can be efficiently peeled off even when irradiated with low-energy laser light. The preferable lower limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation is 1.0×10 -3 , the more preferable lower limit is 5.0×10 -2 , and the further preferable lower limit is 1.0×10 -1 . Also, the preferable upper limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation is 50. When the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation is 50 or less, the adhesive layer can be processed to a more sufficient depth even when irradiated with low-energy laser light, so that the support can be peeled off more efficiently. The more preferable upper limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation is 20, the further preferable upper limit is 10, and the further more preferable upper limit is 5.0. As the light irradiation conditions for the attenuation coefficient of the adhesive layer after light irradiation, for example, light with a wavelength of 405 nm is irradiated so that the integrated light amount becomes 20000 mJ / cm 2 and the like.

[0017] The adhesive layer according to the adhesive film of the present disclosure 1 has an attenuation coefficient with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm so that the integrated light amount becomes 20000 mJ / cm 2 (hereinafter, may be simply referred to as "attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm"). The lower limit is 1.0×10 -4 . When the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm is 1.0×10 -4 or more, the support can be efficiently peeled off even when irradiated with low-energy laser light. The preferable lower limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm is 1.0×10 -3 , the more preferable lower limit is 1.0×10 -2 , the further preferable lower limit is 5.0×10 -2 , and the even more preferable lower limit is 1.0×10 -1 . In addition, the preferable upper limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm is 50. When the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm is 50 or less, the adhesive layer can be processed to a more sufficient depth even when irradiated with low-energy laser light, so that the support can be peeled off more efficiently. The more preferable upper limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm is 20, the further preferable upper limit is 10, and the even more preferable upper limit is 5.0. Note that the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after irradiation with light having a wavelength of 405 nm is measured, for example, by the following method. That is, light with a wavelength of 405 nm is irradiated so that the integrated light amount becomes 20000 mJ / cm 2After irradiating so as to obtain such a state, the transmittance and reflectance of the adhesive layer are measured with a spectrophotometer (manufactured by JASCO Corporation, such as "V-670"), and the thickness is measured with a thickness gauge (manufactured by Mitutoyo Corporation, such as "Digimatic Indicator ID-H"). Using the obtained measurement results of the transmittance, reflectance, and thickness, by performing analysis with spectroscopic ellipsometry analysis software or the like, the attenuation coefficient of the adhesive layer of the present invention with respect to light having a wavelength of 308 nm after light irradiation can be measured. When the adhesive film of the present invention has a base material, the adhesive layer and the base material are separated, the transmittance, reflectance, and thickness of the separated adhesive layer are measured, and by performing analysis with spectroscopic ellipsometry analysis software using the obtained measurement results of the transmittance, reflectance, and thickness, it can be obtained. Note that at wavelengths where the transmittance is 1% or less, it may not be possible to derive an accurate value of the attenuation coefficient from the above analysis. Therefore, when the transmittance at a wavelength of 308 nm is 1% or less, assuming that it is approximated by an exponential function using the attenuation coefficient in the long-wavelength region where the transmittance is greater than 1%, the equation of the approximation curve (y = A (constant) × e ^ (B (constant) × x), y: attenuation coefficient, x: wavelength (nm)) is obtained by the least squares method, and the attenuation coefficient k at a wavelength of 308 nm is calculated from the obtained equation of the approximation curve. When the wavelength at which the transmittance becomes 1% or less is shorter than 308 nm, the attenuation coefficient k at a wavelength of 308 nm can be obtained from the above analysis results.

[0018] The preferable lower limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before irradiating the light of the adhesive layer (hereinafter, may be simply referred to as "the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation") is 1.0×10 -4 is. When the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation is 1.0×10 -4 or more, the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation of the adhesive layer can be easily adjusted within the above range. The more preferable lower limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation is 1.0×10 -3 , the further preferable lower limit is 1.0×10 -2 , and the even more preferable lower limit is 5.0×10 -2 is. Further, the preferable upper limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation is 50. When the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation is 50 or less, even when irradiating with low-energy laser light, the adhesive layer can be processed to a more sufficient depth, so that the support can be peeled off more efficiently. A more preferable upper limit of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation is 20, and an even more preferable upper limit is 10. Incidentally, the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation can be measured, for example, by performing measurement without irradiating light on the adhesive layer before measurement regarding the measurement of the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation of the adhesive layer.

[0019] As a method for adjusting the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation and the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm before light irradiation to the above-described ranges, a method of changing the type and content of the composition of the curable adhesive (for example, an ultraviolet absorber described later) is preferable.

[0020] A temporary fixing material that contains a curable adhesive and has a laser processing depth of 0.10 μm or more when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is also one of the present inventions. The temporary fixing material of the present invention has excellent laser processing performance even when irradiated with low-energy laser light after curing, and the support can be efficiently peeled off. In this specification, the "laser processing depth" refers to the removed depth of the cured temporary fixing material observed from the surface of the cured temporary fixing material on the laser light irradiation side after pulse-irradiating the cured temporary fixing material with laser light.

[0021] The above-mentioned curable adhesive may be a photocurable adhesive that cures upon irradiation with light, or may be a thermosetting adhesive that cures upon heating in a high-temperature environment. Among them, from the perspective of peelability after heating, a photocurable adhesive is preferred.

[0022] As a method for curing the above-mentioned photocurable adhesive, for example, a method of irradiating light with a wavelength of 365 nm so that the integrated light quantity becomes 20000 mJ / cm 2 a method of irradiating light with a wavelength of 405 nm so that the integrated light quantity becomes 20000 mJ / cm 2 and the like can be mentioned. As a light source in the method of irradiating the light with a wavelength of 365 nm so that the integrated light quantity becomes 20000 mJ / cm 2 for example, an ultra-high pressure mercury lamp, an LED, a metal halide lamp, etc. can be mentioned. A temporary fixing material that includes a photocurable adhesive and has a laser processing depth of 0.10 μm or more when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after irradiation so that the integrated light quantity becomes 20000 mJ / cm is also one of the present inventions. 2

[0023] As a method for curing the above-mentioned thermosetting adhesive, for example, a method of heating at 290 °C for 30 minutes in a nitrogen atmosphere, a method of heating at 150 °C for 30 minutes in an oxygen atmosphere, etc. can be mentioned.

[0024] The lower limit of the laser processing depth when the temporary fixing material according to the present disclosure 22 is pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is 0.10 μm. The laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 ​When the laser processing depth when the laser beam is pulse-irradiated is 0.10 μm or more, even when a low-energy laser beam is irradiated, the above-mentioned temporary fixing material after curing can be efficiently peeled off from the support. The laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 The preferable lower limit of the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm is 0.15 μm, and the more preferable lower limit is 0.20 μm. 2 Also, the preferable upper limit of the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is 1.0 μm. If the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is 1.0 μm or less, the above-mentioned temporary fixing material after curing has better laser processing performance and can be peeled off from the support more efficiently. The more preferable upper limit of the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm is 0.80 μm, and the even more preferable upper limit is 0.60 μm. In addition, when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated, the lower limit of the laser processing depth only needs to satisfy the above range on at least one surface of the cured temporary fixing material when the temporary fixing material of the present invention is not liquid or paste-like, but it is preferable to satisfy the above range on both surfaces of the cured temporary fixing material. Also, when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated, the upper limit of the laser processing depth only needs to satisfy the above range on at least one surface of the cured temporary fixing material when the temporary fixing material of the present invention is not liquid or paste-like, but it is more preferable to satisfy the above range on both surfaces of the cured temporary fixing material. In addition, the laser processing depth in this specification can be measured, for example, by performing step measurement on the surface of the temporarily fixed material on the laser light irradiation side after hardening, using a laser microscope, after pulse-irradiating the temporarily fixed material hardened with laser light. Examples of the laser microscope include OLS4100-SAT (manufactured by Olympus Corporation, wavelength 405 nm), etc.

[0025] The temporarily fixed material according to the present disclosure 21 has a lower limit of the laser processing depth of 0.10 μm when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after being irradiated with light having a wavelength of 365 nm so that the integrated light amount becomes 20000 mJ / cm 2 . Since the laser processing depth when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after being irradiated with light having a wavelength of 365 nm so that the integrated light amount becomes 20000 mJ / cm 2 is 0.10 μm or more, the temporarily fixed material after hardening can be efficiently peeled off from the support even when irradiated with low-energy laser light. The preferable lower limit of the laser processing depth when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after being irradiated with light having a wavelength of 365 nm so that the integrated light amount becomes 20000 mJ / cm 2 is 0.15 μm, and the more preferable lower limit is 0.20 μm. In addition, the preferable upper limit of the laser processing depth when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after being irradiated with light having a wavelength of 365 nm so that the integrated light amount becomes 20000 mJ / cm 2 is 1.0 μm. The laser processing depth when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 after being irradiated with light having a wavelength of 365 nm so that the integrated light amount becomes 20000 mJ / cm 2If the laser processing depth when the laser beam is pulse-irradiated is 1.0 μm or less, the temporary fixing material after curing has better laser processing performance and can peel off the support more efficiently. The light having a wavelength of 365 nm is irradiated so that the integrated light amount is 20,000 mJ / cm 2 After irradiation so as to be, the more preferable upper limit of the laser processing depth when the laser beam having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated is 0.80 μm, and the more preferable upper limit is 0.60 μm. In addition, when the temporary fixing material of the present invention is not in a liquid or paste state, after the light having a wavelength of 365 nm is irradiated so that the integrated light amount is 20,000 mJ / cm 2 After irradiation so as to be, the lower limit of the laser processing depth when the laser beam having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated only needs to satisfy the above range on at least one surface of the cured temporary fixing material, but it is preferable to satisfy the above range on both surfaces of the cured temporary fixing material. In addition, when the temporary fixing material of the present invention is not in a liquid or paste state, after the light having a wavelength of 365 nm is irradiated so that the integrated light amount is 20,000 mJ / cm 2 After irradiation so as to be, the upper limit of the laser processing depth when the laser beam having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated preferably satisfies the above range on at least one surface of the cured temporary fixing material, but more preferably satisfies the above range on both surfaces of the cured temporary fixing material.

[0026] The more preferable upper limit of the laser processing depth when the laser beam having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 is pulse-irradiated on the cured temporary fixing material is 1.0 μm. The laser beam having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2When the laser processing depth when the laser beam of the above is pulse-irradiated is 1.0 μm or less, the laser processing performance of the cured temporary fixing material is further improved, and the support can be peeled off more efficiently. The laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 A more preferable upper limit of the laser processing depth when the laser beam of the above is pulse-irradiated is 0.80 μm, and a further preferable upper limit is 0.60 μm. In addition, the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 A preferable lower limit of the laser processing depth when the laser beam of the above is pulse-irradiated is 0.10 μm. When the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 is 0.10 μm or more, the laser processing performance of the cured temporary fixing material is further improved, and the support can be peeled off more efficiently. The laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 A more preferable lower limit of the laser processing depth when the laser beam of the above is pulse-irradiated is 0.15 μm, and a further preferable lower limit is 0.20 μm. In addition, when the temporary fixing material of the present invention is not in a liquid or paste state, the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 is preferably within the above range on at least one surface of the cured temporary fixing material, and more preferably within the above range on both surfaces of the cured temporary fixing material.

[0027] The laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 and the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2As a method for adjusting the laser processing depth when the laser beam is pulse-irradiated, there is a method of adjusting the composition of the curable adhesive, etc. Further, when the temporary fixing material is used for the laminate described later, it can also be adjusted by using a support having a high transmittance of light with a wavelength of 308 nm.

[0028] The curable adhesive preferably contains a curable resin. The curable resin preferably includes a resin having an imide skeleton as a repeating unit in the main chain. When the curable adhesive contains a resin having an imide skeleton as a repeating unit in the main chain, the adhesive layer and the cured temporary fixing material have improved light absorbability in the ultraviolet region. Therefore, even when irradiated with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the adhesive layer and the temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the adhesive film and the cured temporary fixing material have improved peelability from the adherend, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend. In addition, the resin having an imide skeleton as a repeating unit in the main chain has extremely excellent heat resistance due to having an imide skeleton, and even when performing a high-temperature processing treatment of 300 °C or higher, the decomposition of the main chain hardly occurs. For this reason, when the photocurable adhesive contains a resin having an imide skeleton as a repeating unit in the main chain, the adhesive film and the temporary fixing material can more suppress the generation of voids and floating between the support during high-temperature processing. In addition, since the adhesive film and the temporary fixing material can more suppress the adhesion enhancement to the adherend during high-temperature processing, the peelability from the adherend is more improved, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend.

[0029] The resin having an imide skeleton as a repeating unit in the main chain preferably has a structural unit represented by the following formula (1).

[0030]

Chemical formula

[0031] In the above formula (1), P 1 is preferably an aromatic group having 5 to 50 carbon atoms. Since the above-mentioned P 1 is an aromatic group having 5 to 50 carbon atoms, the above-mentioned adhesive layer and the cured temporary fixing material have better light absorbency in the ultraviolet region. Therefore, even when irradiated with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the above-mentioned adhesive layer and the above-mentioned temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the above-mentioned adhesive film and the cured temporary fixing material have better peelability from the adherend, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend. In addition, the above-mentioned adhesive film and the cured temporary fixing material have more excellent heat resistance. That is, the generation of voids and floating between the support during high-temperature processing can be more suppressed. In addition, since the above-mentioned adhesive film and the cured temporary fixing material can more effectively suppress the adhesion enhancement to the adherend during high-temperature processing, the peelability from the adherend is more improved, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend.

[0032] In the above formula (1), Q 1 is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. Since the above-mentioned Q 1 is a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, the above-mentioned adhesive film and the above-mentioned temporary fixing material have more excellent flexibility, can exhibit high followability with respect to an adherend having unevenness, and can be more easily peeled off at the time of peeling. In addition, the above-mentioned Q 1 is preferably an aliphatic group derived from a diamine compound. Among them, from the viewpoints of flexibility and compatibility with a solvent or other components of a resin having the above-mentioned imide skeleton as a repeating unit of the main chain, the above-mentioned Q 1is preferably an aliphatic group derived from a dimer diamine. The above dimer diamine is a diamine compound obtained by reducing and aminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples thereof include linear, monocyclic, and polycyclic dimer diamines. The above dimer diamine may contain a carbon-carbon double bond or may be a hydrogenated product to which hydrogen is added.

[0033] As the aliphatic group derived from the above dimer diamine, for example, 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) is preferable. Among them, a group represented by the following formula (2-2) is more preferable.

[0034]

Chemical formula

[0035] In the above formulas (2-1) to (2-4), R 1 ~R 16 each independently represents a linear or branched hydrocarbon group, and * represents a bond. The bond * is bonded to N in the above formula (1).

[0036] In the above formulas (2-1) to (2-4), the hydrocarbon group represented by R 1 ~R 16 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Among them, R 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 16It is preferable that the total number of carbon atoms is 7 or more and 50 or less. When the total number of carbon atoms is within the above range, the resin having the imide skeleton as a repeating unit in the main chain becomes excellent in compatibility with a solvent and other components, and the adhesive film and the temporary fixing material become excellent in flexibility. The total number of carbon atoms is more preferably 9 or more, still more preferably 12 or more, and even more preferably 14 or more. The total number of carbon atoms is more preferably 35 or less, still more preferably 25 or less, and even more preferably 18 or less.

[0037] In the group represented by the above formula (2-1), the group represented by the above formula (2-2), the group represented by the above formula (2-3), and the group represented by the above formula (2-4), the optical isomerism is not particularly limited, and any optical isomer is included.

[0038] The preferable lower limit of the content of the resin having the imide skeleton as a repeating unit in the main chain in 100 parts by mass of the curable resin is 40 parts by mass, and the preferable upper limit is 100 parts by mass. When the content of the resin having the imide skeleton as a repeating unit in the main chain is within this range, the adhesive layer and the cured temporary fixing material have improved light absorption in the ultraviolet region. Even when irradiated with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the adhesive layer and the temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the adhesive film and the cured temporary fixing material have improved peelability from the adherend, and it is possible to more effectively prevent the occurrence of adhesive residue when peeling from the adherend. In addition, the adhesive film and the cured temporary fixing material are excellent in heat resistance. That is, the generation of voids and floating between the support during high-temperature processing can be more suppressed. In addition, since the adhesive film and the cured temporary fixing material during high-temperature processing can more effectively suppress the adhesion enhancement to the adherend, the peelability from the adherend is improved, and it is possible to more effectively prevent the occurrence of adhesive residue when peeling from the adherend.

[0039] The resin having the imide skeleton as a repeating unit in the main chain preferably does not have a functional group having a carbon-carbon double bond and contains a resin having the imide skeleton as a repeating unit in the main chain. The carbon-carbon double bond contained in the aromatic ring is not treated as the carbon-carbon double bond of the functional group having the carbon-carbon double bond.

[0040] The resin that does not have a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit in the main chain preferably has a lower limit of the weight-average molecular weight of 20,000 and an upper limit of 2,000,000. When the weight-average molecular weight of the resin that does not have a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit in the main chain is 20,000 or more, the above-mentioned adhesive film and the cured temporary fixing material become more excellent in heat resistance. That is, the above-mentioned adhesive film and the cured temporary fixing material can more effectively suppress the generation of voids and lifting between the support during high-temperature processing. In addition, since the above-mentioned adhesive film and the cured temporary fixing material can more effectively suppress the enhancement of adhesion to the adherend during high-temperature processing, the peelability from the adherend is further improved, and the occurrence of adhesive residue during peeling from the adherend can be more effectively prevented. When the weight-average molecular weight of the resin that does not have a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit in the main chain is 2,000,000 or less, the resin that does not have a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit in the main chain becomes more excellent in compatibility with solvents and other components. A more preferable lower limit of the weight-average molecular weight of the resin that does not have a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit in the main chain is 40,000, and a more preferable upper limit is 600,000. In the present specification, the above 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), with 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 mass%, and under the conditions of an RI·PDA detector. As the above column, HR-MB-M 6.0×150 mm (manufactured by Waters) etc. can be used.

[0041] Examples of the resin that does not have a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit in the main chain include, specifically, resins having a structural unit represented by the above formula (1) and having a functional group without a carbon-carbon double bond at both ends.

[0042] The resin having a structural unit represented by the above formula (1) and having a functional group without a carbon-carbon double bond at both ends may have a structural unit represented by the following formula (3).

[0043]

Chemical formula

[0044] In the above formula (3), P 2 represents an aromatic group, and Q 2 represents a group having a substituted or unsubstituted aromatic structure.

[0045] In the above formula (3), P 2 is preferably an aromatic group having 5 to 50 carbon atoms. The above P 2Since it is an aromatic group having 5 to 50 carbon atoms, the light absorption in the ultraviolet region of the above adhesive layer and the cured temporary fixing material is further improved. Therefore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the above adhesive layer and the above temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be further suppressed. As a result, the above adhesive film and the cured temporary fixing material have improved peelability with respect to the adherend, and it is possible to further prevent the occurrence of glue residue when peeling from the adherend. In addition, the above adhesive film and the cured temporary fixing material have more excellent heat resistance. That is, the above adhesive film and the cured temporary fixing material can further suppress the generation of voids and lifting between the support during high-temperature processing. In addition, since the above adhesive film and the cured temporary fixing material can further suppress the adhesion enhancement to the adherend during high-temperature processing, the peelability with respect to the adherend is further improved, and it is possible to further prevent the occurrence of glue residue when peeling from the adherend.

[0046] In the above formula (3), Q 2 is preferably a group having a substituted or unsubstituted aromatic structure having 5 to 50 carbon atoms. Since the above Q 2 is a group having a substituted or unsubstituted aromatic structure having 5 to 50 carbon atoms, the light absorption in the ultraviolet region of the above adhesive layer and the cured temporary fixing material is further improved. Therefore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the above adhesive layer and the above temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be further suppressed. As a result, the above adhesive film and the cured temporary fixing material have improved peelability with respect to the adherend, and it is possible to further prevent the occurrence of glue residue when peeling from the adherend. In addition, the above-mentioned adhesive film and the cured temporary fixing material will have excellent heat resistance. That is, the above-mentioned adhesive film and the cured temporary fixing material can further suppress the generation of voids and floating between the support during high-temperature processing. In addition, since the above-mentioned adhesive film and the cured temporary fixing material can further suppress the enhancement of adhesion to the adherend during high-temperature processing, the peelability from the adherend is further improved, and the occurrence of adhesive residue during peeling from the adherend can be further prevented.

[0047] Examples of the functional group having no carbon-carbon double bond include an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride group, an amino group, and the like. Specifically, examples include unreacted terminal constituent groups of acid anhydrides and diamine compounds that are raw materials of resins having no carbon-carbon double bond functional group and having an imide skeleton as a repeating unit in the main chain. In the resin having the structural unit represented by the above formula (1) and having functional groups having no carbon-carbon double bond at both ends, the functional groups having no carbon-carbon double bond at both ends may be the same or different.

[0048] In the resin having the structural unit represented by the above formula (1) and having functional groups having no carbon-carbon double bond at both ends, the content ratio of the structural unit represented by the above formula (1) is preferably 30 mol% or more, more preferably 50 mol% or more, preferably 90 mol% or less, and more preferably 80 mol% or less. When the resin having the structural unit represented by the above formula (1) and having functional groups having no carbon-carbon double bond at both ends has the structural unit represented by the above formula (3), the content ratio of the structural unit represented by the above formula (3) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, preferably 50 mol% or less, and more preferably 30 mol% or less. In the structural unit represented by the above formula (1) and the structural unit represented by the above formula (3), when the content of each structural unit is within the above range, the above adhesive film and the cured above temporary fixing material can further suppress the generation of voids and floating between the support during high-temperature processing, and can be more easily peeled off when peeled from the adherend. Note that the structural unit represented by the above formula (1) and the structural unit represented by the above formula (3) may have a block structure composed of block components in which each structural unit is continuously arranged, or may have a random structure in which each structural unit is randomly arranged.

[0049] Examples of the method for producing a resin having no functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit in the main chain include a method of reacting a diamine compound with an aromatic acid anhydride.

[0050] As the above diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used. By using an aliphatic diamine compound as the above diamine compound, the above adhesive layer and the above temporary fixing material become more excellent in flexibility, can exhibit high followability with respect to an adherend having unevenness, and can be more easily peeled off at the time of peeling. In addition, by using an aromatic diamine compound as the above diamine compound, the light absorption in the ultraviolet region of the above adhesive film and the cured above temporary fixing material is further improved. Therefore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the above adhesive layer and the above temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be further suppressed. As a result, the above adhesive film and the cured above temporary fixing material have better peelability with respect to the adherend, and can more effectively prevent the occurrence of adhesive residue when peeled from the adherend. In addition, the above adhesive film and the cured above temporary fixing material are more excellent in heat resistance. The above diamine compound may be used alone or in combination of two or more kinds.

[0051] Examples of the above 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, 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane, and the like.

[0052] Among the above aliphatic diamine compounds, from the viewpoints of flexibility, having no functional group having the above carbon-carbon double bond, and compatibility with a solvent or other components of a resin having an imide skeleton as a repeating unit of the main chain, dimer diamine is preferable. Specific examples of the above dimer diamine include, for example, a dimer diamine capable of constituting at least one kind of group selected from the group consisting of the group represented by the above 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).

[0053] 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-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bis(aminomethyl)benzene, 1,3-bis(aminomethyl)cyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, 9,9'-bis(4-amino-3-ethyldiaminofluorene), 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-aminophenoxy)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-toluidine sulfone, 5,5'-methylenebis(anthranilic acid), 1,3-Bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylene diamines (e.g., Jeffamine D-230, D-400, D-2000, D-4000, etc. manufactured by Huntsman), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, p-xylylenediamine, and the like can be mentioned.,

[0054] Examples of the aromatic carboxylic anhydride include carboxylic anhydrides such as 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’-biphenyl ether tetracarboxylic 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)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, 2,2’,3,3’-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).

[0055] In 100 parts by mass of the above curable resin, the preferable lower limit of the content of the resin having no functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain is 10 parts by mass, and the preferable upper limit is 90 parts by mass. When the content of the resin having no functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain is within this range, the above adhesive film and the cured temporary fixing material can be more easily peeled off from the adherend. From the viewpoint of further enhancing the peeling performance, the more preferable lower limit of the content of the resin having no functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain is 20 parts by mass, and the more preferable upper limit is 80 parts by mass.

[0056] The resin having an imide skeleton in the repeating unit of the main chain preferably contains a resin having a functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain. By including a resin having a functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, even when irradiated with low-energy laser light, the support can be peeled off more efficiently. In addition, the above adhesive film and the above temporary fixing material are polymerized and crosslinked uniformly and rapidly as a whole by irradiation with light or the like, and the elastic modulus increases, so that the adhesive force of the above adhesive film and the above temporary fixing material is greatly reduced. Therefore, the above adhesive film and the cured above temporary fixing material can more effectively suppress the occurrence of enhanced adhesion to the adherend during high-temperature processing, improve the peelability from the adherend, and prevent the occurrence of adhesive residue during peeling. When the resin having an imide skeleton in the repeating unit of the main chain contains a resin having no functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, in addition to the resin having no functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain, it is preferable to further contain a resin having a functional group having a carbon-carbon double bond and having an imide skeleton in the repeating unit of the main chain.

[0057] Examples of the functional group having a carbon-carbon double bond include an optionally substituted maleimide group, citraconimide group, vinyl ether group, allyl group, (meth)acryloyl group, etc. Among them, an optionally substituted maleimide group is preferable because higher heat resistance can be obtained. In the present specification, “(meth)acryloyl” means acryloyl or methacryloyl.

[0058] The resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit in the main chain preferably has a functional group equivalent weight (weight average molecular weight / number of functional groups having a carbon-carbon double bond) of the functional group having a carbon-carbon double bond of 4000 or less. When the functional group equivalent weight of the functional group having a carbon-carbon double bond is 4000 or less, the support can be peeled off more efficiently even when irradiated with low-energy laser light. In addition, since the curing of the adhesive layer and the temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the adhesive film and the cured temporary fixing material have improved peelability from the adherend, and it is possible to more effectively prevent the occurrence of adhesive residue when peeling from the adherend. In addition, the adhesive film and the cured temporary fixing material are more excellent in heat resistance. This is presumably because having a functional group having a carbon-carbon double bond at a certain density or more in the molecule of the resin shortens the crosslinking distance, thereby suppressing adhesion enhancement more effectively. The functional group equivalent weight of the functional group having a carbon-carbon double bond is more preferably 3000 or less, and even more preferably 2000 or less. In addition, there is no particular lower limit for the functional group equivalent weight of the functional group having a carbon-carbon double bond, but the substantial lower limit is about 600.

[0059] The resin having a functional group with a carbon-carbon double bond and having an imide skeleton as a repeating unit in the main chain preferably has a weight average molecular weight of 1,000 or more and 100,000 or less. When the weight average molecular weight of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton as a repeating unit in the main chain is 1,000 or more, even when irradiated with a low-energy laser beam, the support can be peeled off more efficiently. Further, since the curing of the adhesive layer and the temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the adhesive film and the cured temporary fixing material have improved peelability from the adherend, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend. Furthermore, since the film formation of the curable adhesive becomes easy and the adhesive film and the temporary fixing material exhibit a certain degree of flexibility, they can exhibit high followability with respect to an adherend having unevenness and can be more easily peeled off at the time of peeling. When the weight average molecular weight of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton as a repeating unit in the main chain is 100,000 or less, the resin having a functional group with a carbon-carbon double bond and having an imide skeleton as a repeating unit in the main chain has excellent compatibility with solvents and other components. The weight average molecular weight of the resin having a functional group with a carbon-carbon double bond and having an imide skeleton as a repeating unit in 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.

[0060] In the resin having a functional group with a carbon-carbon double bond and having an imide skeleton as a repeating unit in the main chain, the functional group with a carbon-carbon double bond may be located either in the side chain or at the terminal, but is preferably present at both terminals, and more preferably present in the side chain in addition to both terminals. The functional groups having a carbon-carbon double bond at both ends of the resin, which has a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain, have high reactivity, and the adhesive layer and the temporary fixing material can be cured more sufficiently by irradiation with light or the like. As a result, the adhesive film and the cured temporary fixing material can more effectively suppress the enhancement of adhesion to the adherend during high-temperature processing, so that the peelability from the adherend is further improved, and the occurrence of glue residue during peeling can be more effectively prevented. Also, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. Furthermore, due to the presence of a functional group having a carbon-carbon double bond in the side chain of the resin, which has a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. Also, the adhesive film and the temporary fixing material become more excellent in heat resistance. This is presumably because the enhancement of adhesion is more suppressed by shortening the crosslinking distance. Also, due to the presence of a functional group having a carbon-carbon double bond in the side chain of the resin, which has a functional group having a carbon-carbon double bond and has an imide skeleton as a repeating unit of the main chain, it becomes easy to adjust the functional group equivalent to 4000 or less while setting the weight average molecular weight to 1000 or more. Thereby, the adhesive film and the cured temporary fixing material can have sufficient initial adhesive strength and, at the same time, can more effectively prevent the occurrence of adhesion enhancement and the generation of glue residue during peeling. Furthermore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently.

[0061] As described above, in the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain, the functional group having a carbon-carbon double bond may be either in the side chain or at the terminal. When either the side chain or the terminal is a functional group other than the functional group having a carbon-carbon double bond (a functional group having no carbon-carbon double bond), examples of the functional group having no carbon-carbon double bond include an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride group, an amino group, and the like. Specifically, examples include unreacted single-terminal constituent groups of acid anhydrides and diamine compounds that are raw materials for the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain. When the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain has two or more functional groups having no carbon-carbon double bond in the side chain or at the terminal, each functional group having no carbon-carbon double bond may be the same or different.

[0062] Specific examples of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain include, for example, a resin having a structural unit represented by the above formula (1) and having a functional group having a carbon-carbon double bond in at least one of the terminal and the side chain.

[0063] The resin having a structural unit represented by the above formula (1) and having a functional group having a carbon-carbon double bond in at least one of the terminal and 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).

[0064]

Chemical formula

[0065] In formula (4-1), P 3 represents an aromatic group, and Q 3 represents a group having a substituted or unsubstituted aromatic structure. In formula (4-2), P 4represents 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.

[0066] P in the above formula (4-1) 3 and P in the above formula (4-2) 4 are preferably aromatic groups having 5 to 50 carbon atoms. The above P 3 and P 4 being aromatic groups having 5 to 50 carbon atoms improves the light absorption in the ultraviolet region of the above adhesive layer and the cured above temporary fixing material. Therefore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. Also, since the curing of the above adhesive layer and the above temporary fixing material by light irradiation becomes more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the above adhesive film and the cured above temporary fixing material have improved peelability with respect to the adherend, and it is possible to more prevent the occurrence of glue residue when peeling from the adherend. Further, the above adhesive film and the cured above temporary fixing material become more excellent in heat resistance. That is, the above adhesive film and the cured above temporary fixing material can more suppress the generation of voids and floating between the support during high-temperature processing. Also, since the above adhesive film and the cured above temporary fixing material can more suppress the adhesion enhancement to the adherend during high-temperature processing, it is possible to more prevent the occurrence of glue residue when peeling from the adherend.

[0067] In the above formula (4-1), Q 3 is preferably a group having a substituted or unsubstituted aromatic structure with 5 to 50 carbon atoms. The above Q 3Since the group has a substituted or unsubstituted aromatic structure having 5 to 50 carbon atoms, the light absorption in the ultraviolet region of the above adhesive layer and the cured temporary fixing material is further improved. Therefore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the above adhesive layer and the above temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the above adhesive film and the cured temporary fixing material have improved peelability with respect to the adherend, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend. In addition, the above adhesive film and the cured temporary fixing material become more excellent in heat resistance. That is, the above adhesive film and the cured temporary fixing material can more effectively suppress the generation of voids and peeling between the support during high-temperature processing. In addition, since the above adhesive film and the cured temporary fixing material can more effectively suppress the adhesion enhancement to the adherend during high-temperature processing, the peelability with respect to the adherend is further improved, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend.

[0068] In the above formula (4-2), R is preferably a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. Since R is a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms, the above adhesive film and the above temporary fixing material become more excellent in flexibility, can exhibit high followability with respect to an adherend having unevenness, and can be more easily peeled off during peeling.

[0069] 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 the aromatic ether group in R is preferably bonded to X. Here, the above-mentioned "aromatic ester group" means a group in which an ester group is directly bonded to an aromatic ring, and the above-mentioned "aromatic ether group" means a group in which an ether group is directly bonded to an aromatic ring. By making the portion bonded to the ester group or ether group an aromatic group in this way, the light absorbability in the ultraviolet region of the above-mentioned adhesive layer and the cured above-mentioned temporary fixing material is further improved. Therefore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the above-mentioned adhesive layer and the above-mentioned temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be more suppressed. As a result, the above-mentioned adhesive film and the cured above-mentioned temporary fixing material have improved peelability with respect to the adherend, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend. Further, the above-mentioned adhesive film and the cured above-mentioned temporary fixing material are excellent in heat resistance. That is, the above-mentioned adhesive film and the cured above-mentioned temporary fixing material can more effectively suppress the generation of voids and lifting between the support during high-temperature processing. In addition, since the above-mentioned adhesive film and the cured above-mentioned temporary fixing material can more effectively suppress the adhesion enhancement to the adherend during high-temperature processing, the peelability with respect to the adherend is further improved, and it is possible to more effectively prevent the occurrence of glue residue when peeling from the adherend. On the other hand, when X is bonded to R via an aromatic ester group or an aromatic ether group, the carbon-carbon double bond in X is not conjugated with R, so that the polymerization crosslinking when heated or irradiated with light is not hindered.

[0070] In the resin having the structural unit represented by the above formula (1) and having a functional group having a carbon-carbon double bond in at least one of the terminal and the side chain, the content ratio of the structural unit represented by the above formula (1) is preferably 30 mol% or more, more preferably 50 mol% or more, preferably 90 mol% or less, and more preferably 80 mol% or less. When the resin having the structural 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 has the structural unit represented by the above formula (4-1), the content ratio of the structural unit represented by the above formula (4-1) is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. When the resin having the structural 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 has the structural unit represented by the above formula (4-2), the content ratio of the structural unit represented by the above 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. In the structural unit represented by the above formula (1), the structural unit represented by the above formula (4-1), and the structural unit represented by the above formula (4-2), since the content of each structural unit is within the above range, the light absorbency in the ultraviolet region of the above adhesive layer and the cured above temporary fixing material is further improved. Therefore, even when irradiating with low-energy laser light, the support can be peeled off more efficiently. In addition, since the curing of the above adhesive layer and the above temporary fixing material by light irradiation is more likely to occur, the adhesion enhancement to the adherend during high-temperature processing can be further suppressed. As a result, the above adhesive film and the cured above temporary fixing material have better peelability with respect to the adherend, and it is possible to further prevent the occurrence of adhesive residue when peeling from the adherend. In addition, the above adhesive film and the cured above temporary fixing material become more excellent in heat resistance. That is, the above adhesive film and the cured above temporary fixing material can further suppress the generation of voids and floating between the support during high-temperature processing. In addition, since the above adhesive film and the cured above temporary fixing material can further suppress the adhesion enhancement to the adherend during high-temperature processing, the peelability with respect to the adherend is further improved, and it is possible to further prevent the occurrence of adhesive residue when peeling from the adherend. The structural unit represented by the above formula (1), the structural unit represented by the above formula (4-1), and the structural unit represented by the above formula (4-2) may each have a block structure composed of block components in which the respective structural units are arranged continuously, or may each have a random structure in which the respective structural units are randomly arranged.

[0071] Examples of the method for producing a resin having a functional group having a carbon-carbon double bond and an imide skeleton as a repeating unit in the main chain include the following methods. That is, first, a diamine compound and an aromatic acid anhydride are reacted to prepare an imide compound. Next, a compound having a functional group that reacts with the functional group 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, whereby a resin having a functional group having a carbon-carbon double bond and an imide skeleton as a repeating unit in the main chain can be obtained. Also, a resin having a functional group having a carbon-carbon double bond and an imide skeleton as a repeating unit in the main chain can be obtained by reacting a diamine compound and an aromatic acid anhydride to prepare an imide compound, and further reacting, for example, maleic anhydride or the like at the terminal of the imide compound.

[0072] As the diamine compound and the aromatic acid anhydride used in the method for producing a resin having a functional group having a carbon-carbon double bond and an imide skeleton as a repeating unit in the main chain, the same ones as those used in the method for producing a resin having no functional group having a carbon-carbon double bond and an imide skeleton as a repeating unit in the main chain can be used.

[0073] The functional group-containing unsaturated compound is selected and used according to the functional group at the terminal or side chain of the imide compound. For example, when the functional group at the terminal or side chain of the imide compound is a hydroxyl group, examples of the functional group-containing unsaturated compound include maleimide compounds having a carboxy group, vinyl compounds having an ether group, allyl compounds having a glycidyl group, allyl ether compounds having a glycidyl group, vinyl ether compounds having a glycidyl group, allyl compounds having an isocyanate group, (meth)acryloyl compounds having an isocyanate group, and the like. Also, for example, when the functional group at the terminal or side chain of the imide compound is a carboxy group, examples of the functional group-containing unsaturated compound include allyl compounds having a hydroxyl group, allyl compounds having a glycidyl group, allyl ether compounds having a glycidyl group, vinyl ether compounds having a glycidyl group, and the like. Examples of the maleimide compound having a carboxy group include maleimide acetate, maleimide propionic acid, maleimide butyric acid, maleimide hexanoic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 19-maleimide-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid, and the like. Examples of the vinyl compound having an ether group include butyl vinyl ether and the like. Examples of the allyl compound having a glycidyl group include diallyl monoglycidyl isocyanurate and the like. Examples of the allyl ether compound having a glycidyl group include allyl glycidyl ether, glycerin diallyl monoglycidyl ether, and the like. Examples of the vinyl ether compound having a glycidyl group include glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyldiethylene glycol vinyl ether, glycidylcyclohexanedimethanol monovinyl ether, and the like. Examples of the allyl compound having an isocyanate group include allyl isocyanate and the like. Examples of the (meth)acryloyl compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and the like. Examples of the allyl compound having a hydroxyl group include trimethylolpropane diallyl ether, pentaerythritol triallyl ether and the like.

[0074] The preferable lower limit of the content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain in 100 parts by mass of the curable resin is 10 parts by mass, and the preferable upper limit is 100 parts by mass. When the content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain is within this range, the adhesive film and the cured temporary fixing material can be more easily peeled off at the time of peeling. From the viewpoint of further enhancing the peeling performance, the more preferable lower limit of the content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain is 20 parts by mass, and the further preferable lower limit is 30 parts by mass. The more preferable upper limit is 90 parts by mass, the further preferable upper limit is 80 parts by mass, and the even more preferable upper limit is 70 parts by mass.

[0075] When the resin having an imide skeleton as a repeating unit of the main chain does not have a functional group having a carbon-carbon double bond and includes a resin having an imide skeleton as a repeating unit of the main chain, the curable resin preferably further contains a polyfunctional monomer or polyfunctional oligomer (hereinafter, also simply referred to as "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 5000 or less. Also, when the resin having an imide skeleton as a repeating unit of the main chain has a functional group having a carbon-carbon double bond and includes a resin having an imide skeleton as a repeating unit of the main chain, the curable resin may further contain the polyfunctional monomer or polyfunctional oligomer. By containing the above-mentioned polyfunctional monomer or polyfunctional oligomer, the above-mentioned adhesive layer and the above-mentioned temporary fixing material can be three-dimensionally crosslinked more efficiently by irradiation with light or the like, and the adhesion enhancement of the above-mentioned adhesive film and the cured above-mentioned temporary fixing material to the adherend can be more suppressed. Therefore, the peelability from the adherend is further improved, and it is possible to more effectively prevent the occurrence of adhesive residue during peeling.

[0076] In addition, when the resin having the imide skeleton as the repeating unit of the main chain itself has no reactivity, the photocurable adhesive needs to have reactivity as a whole by further containing other components having reactive functional groups. As such other components having reactive functional groups, it is preferable to use the above-mentioned polyfunctional monomer or polyfunctional oligomer. Examples of the case where the resin having the imide skeleton as the repeating unit of the main chain itself has no reactivity include, for example, the case where the resin having the imide skeleton as the repeating unit of the main chain does not have a functional group having a carbon-carbon double bond and contains only the resin having the imide skeleton as the repeating unit of the main chain.

[0077] Examples of the functional group having a carbon-carbon double bond in the above-mentioned polyfunctional monomer or polyfunctional oligomer include, for example, an optionally substituted maleimide group, citraconimide group, vinyl ether group, allyl group, (meth)acryloyl group, etc. Among them, an optionally substituted maleimide group is preferable because higher heat resistance can be obtained. In particular, the above-mentioned polyfunctional monomer or polyfunctional oligomer is preferably a bismaleimide compound.

[0078] The above-mentioned polyfunctional monomer or polyfunctional oligomer preferably has a group derived from a diamine compound. As the above-mentioned diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used, but an aliphatic diamine compound is preferred. That is, it is more preferable that the above-mentioned polyfunctional monomer or polyfunctional oligomer has an aliphatic group derived from a diamine compound. By using an aliphatic diamine compound as the above-mentioned diamine compound, the above-mentioned adhesive film and the above-mentioned temporary fixing material become more excellent in flexibility, can exhibit high followability with respect to an adherend having irregularities, and can be more easily peeled off at the time of peeling.

[0079] Among the above-mentioned aliphatic diamine compounds, dimer diamine as described above is preferred from the viewpoints of flexibility and compatibility with a solvent or other components of the above-mentioned polyfunctional monomer or polyfunctional oligomer.

[0080] The preferable lower limit of the content of the above-mentioned polyfunctional monomer or polyfunctional oligomer in 100 parts by mass of the above-mentioned curable resin is 5 parts by mass, and the preferable upper limit is 90 parts by mass. When the content of the above-mentioned polyfunctional monomer or polyfunctional oligomer is within this range, the above-mentioned adhesive film and the cured above-mentioned temporary fixing material can be more easily peeled off at the time of peeling. From the viewpoint of further enhancing the peeling performance, the more preferable lower limit of the content of the above-mentioned polyfunctional monomer or polyfunctional oligomer is 10 parts by mass, and the more preferable upper limit is 50 parts by mass.

[0081] When the curable adhesive contains a resin having no functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain, a resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain, and the polyfunctional monomer or polyfunctional oligomer, the lower limit of the total content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer in 100 parts by mass in total thereof is preferably 20 parts by mass, and the upper limit is preferably 80 parts by mass. When the total content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer is within this range, the adhesive film and the cured temporary fixing material can be more easily peeled off at the time of peeling. From the viewpoint of further improving the peeling performance, the more preferable lower limit of the total content of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer is 30 parts by mass, the further preferable lower limit is 40 parts by mass, the even more preferable lower limit is 50 parts by mass, and the more preferable upper limit is 70 parts by mass.

[0082] The curable resin preferably contains a compound having a maleimide group. By containing the compound having a maleimide group, the adhesive film and the cured temporary fixing material become more excellent in heat resistance. The compound having a maleimide group is preferably a bismaleimide compound or a resin having a maleimide group and having an imide skeleton as a repeating unit of the main chain. That is, the curable resin preferably contains the bismaleimide compound as the polyfunctional monomer or polyfunctional oligomer, or contains a resin having a maleimide group as the functional group having a carbon-carbon double bond of the resin having a functional group having a carbon-carbon double bond and having an imide skeleton as a repeating unit of the main chain.

[0083] The curable adhesive preferably further contains a polymerization initiator. Since the above-mentioned curable adhesive contains a polymerization initiator, the above-mentioned adhesive layer and the above-mentioned temporary fixing material are more likely to cure, and the above-mentioned adhesive film and the cured above-mentioned temporary fixing material can more effectively suppress the enhancement of adhesion to the adherend during high-temperature processing. Therefore, the peelability from the adherend is further improved, and it can be more easily peeled off when peeled from the adherend. The above-mentioned polymerization initiator may be a thermal polymerization initiator or a photoinitiator, but a photoinitiator is preferred.

[0084] Examples of the above-mentioned photoinitiator include those activated by irradiation with light having a wavelength of 250 to 800 nm. In the adhesive film of the present invention, since it hardly overlaps with the absorption wavelength of the resin having the above-mentioned imide skeleton as a repeating unit of the main chain, the above-mentioned polyfunctional monomer or polyfunctional oligomer, and is sufficiently activated when the above-mentioned adhesive layer is irradiated with light, the above-mentioned photoinitiator preferably contains a compound having a molar extinction coefficient of 10 ml / (g·cm) or more at a wavelength of 405 nm. The above-mentioned photoinitiator more preferably contains a compound having a molar extinction coefficient of 50 ml / (g·cm) or more at a wavelength of 405 nm, and still more preferably contains a compound having a molar extinction coefficient of 100 ml / (g·cm) or more at a wavelength of 405 nm. There is no particular upper limit to the molar extinction coefficient of the compound having a molar extinction coefficient of 1 or more at a wavelength of 405 nm at a wavelength of 405 nm, but the substantial upper limit is 1.0×10 6 ml / (g·cm). In the temporary fixing material of the present invention, since the resin having the imide skeleton as a repeating unit of the main chain, the above-mentioned polyfunctional monomer or polyfunctional oligomer hardly overlap with the absorption wavelength and is sufficiently activated when the temporary fixing material is irradiated with light, it is preferable that the above-mentioned photoinitiator contains a compound having a molar extinction coefficient of 1 or more at 405 nm. More preferably, the photoinitiator contains a compound having a molar extinction coefficient of 200 or more at 405 nm, and still more preferably, a compound having a molar extinction coefficient of 350 or more at 405 nm. There is no particular upper limit on the molar extinction coefficient at 405 nm of the compound having a molar extinction coefficient of 1 or more at 405 nm, but the substantial upper limit is 2000.

[0085] Examples of the photoinitiator include acetophenone derivatives, benzoin ether compounds, ketal derivatives, phosphine oxide derivatives, oxime ester compounds, and the like. Examples of the acetophenone derivative include methoxyacetophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, and the like. Examples of the benzoin ether compound include benzoin propyl ether, benzoin isobutyl ether, and the like. Examples of the ketal derivative include benzyldimethyl ketal, acetophenone diethyl ketal, and the like. Examples of the phosphine oxide derivative include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like. Examples of the oxime ester compound include 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)-1,2-octadione, and the like. In addition, examples of the above-mentioned photopolymerization initiator include bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenylpropane, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

[0086] With respect to 100 parts by mass of the above-mentioned curable resin, the preferable lower limit of the content of the above-mentioned polymerization initiator is 0.1 part by mass, and the preferable upper limit is 10 parts by mass. When the content of the above-mentioned polymerization initiator is within this range, the entire adhesive layer and the above-mentioned temporary fixing material are uniformly and rapidly polymerized and crosslinked by irradiation with light, heating, etc., and the elastic modulus increases, so that an adhesive film can be obtained, and the adhesive force of the above-mentioned temporary fixing material is greatly reduced. Therefore, it is possible to further prevent the occurrence of enhanced adhesion or the generation of glue residue during peeling. The more preferable lower limit of the content of the above-mentioned polymerization initiator is 0.5 part by mass, the further preferable lower limit is 1 part by mass, the more preferable upper limit is 7 parts by mass, and the further preferable upper limit is 5 parts by mass.

[0087] In the adhesive film of the present invention, when the above-mentioned curable adhesive contains the above-mentioned photopolymerization initiator, it is preferably further contained with an ultraviolet absorber. When the above-mentioned curable adhesive contains an ultraviolet absorber, the light absorption property of the above-mentioned adhesive layer in the ultraviolet region is further enhanced, so that even when irradiated with low-energy laser light, the support can be peeled off more efficiently.

[0088] The above-mentioned curable adhesive preferably contains an ultraviolet absorber or an ultraviolet scattering agent. When the curable adhesive contains an ultraviolet absorber, the cured temporary fixing material is excellent in ultraviolet absorption, the laser processing performance is further improved, and the support can be peeled off more efficiently. When the curable adhesive contains an ultraviolet scattering agent, the laser processing performance on the surface of the cured temporary fixing material is further improved, and the support can be peeled off more efficiently. Further, the curable adhesive may contain both an ultraviolet absorber and an ultraviolet scattering agent.

[0089] Examples of the ultraviolet absorber in the adhesive film of the present invention include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like. Among them, from the viewpoint of heat resistance, the ultraviolet absorber preferably contains a triazine-based ultraviolet absorber.

[0090] Examples of the ultraviolet absorber in the temporary fixing material of the present invention include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like. Examples of the ultraviolet scattering agent include titanium oxide, zinc oxide, and the like. Among them, from the viewpoint of heat resistance, the ultraviolet absorber or the ultraviolet scattering agent preferably contains a triazine-based ultraviolet absorber or titanium oxide.

[0091] Examples of the triazine-based ultraviolet absorber include Tinuvin400, Tinuvin405, Tinuvin460, Tinuvin477, Tinuvin479, Tinuvin1577ED, Tinuvin1600 (all manufactured by BASF), Adeka Stab LA46, Adeka Stab LA-F70 (all manufactured by ADEKA). Among them, Tinuvin400, Tinuvin479, and Tinuvin1600 are preferable.

[0092] With respect to 100 parts by mass of the above curable resin, the preferable lower limit of the content of the above ultraviolet absorber or ultraviolet scattering agent is 1 part by mass, and the preferable upper limit is 30 parts by mass. If the content of the above ultraviolet absorber or ultraviolet scattering agent is 1 part by mass or more, the absorbability of light in the ultraviolet region of the above adhesive layer and the cured above temporary fixing material is further enhanced, so that even when irradiating with low-energy laser light, the support can be peeled off more efficiently. If the content of the above ultraviolet absorber or ultraviolet scattering agent is 30 parts by mass or less, the above adhesive film and the cured above temporary fixing material can be easily peeled off from the adherend even after the heating step. The more preferable lower limit of the above ultraviolet absorber or ultraviolet scattering agent is 5 parts by mass, the further preferable lower limit is 7 parts by mass, the more preferable upper limit is 20 parts by mass, and the further preferable upper limit is 15 parts by mass.

[0093] The above photocurable adhesive preferably further contains a release agent. Examples of the above release agent include silicone-based release agents, fluorine-based release agents, acrylic-based release agents, etc. Since these release agents are excellent in heat resistance, when the above curable adhesive contains a release agent, charring of the above adhesive layer is prevented even after a high-temperature processing treatment of 300 °C or higher, and it bleeds out to the adherend interface during peeling of the obtained adhesive film, making peeling easier. Among them, silicone-based release agents are preferable from the viewpoint of being environmentally friendly and easy to dispose of. Also, acrylic-based release agents are preferable from the viewpoint of preventing contamination of the adherend by silicone.

[0094] The release agent may have a functional group capable of crosslinking with a resin having an imide skeleton as a repeating unit of the main chain. Since the release agent has a functional group capable of crosslinking with a resin having an imide skeleton as a repeating unit of the main chain, the release agent is chemically reacted and incorporated with the resin having an imide skeleton as a repeating unit of the main chain or the polyfunctional monomer or polyfunctional oligomer by irradiation with light or reaction with a crosslinking agent or the like. Therefore, it is possible to suppress the release agent from adhering to and contaminating the adherend. Examples of the functional group capable of crosslinking with the resin having an imide skeleton as a repeating unit of the main chain or the polyfunctional monomer or polyfunctional oligomer include a carboxy group, a functional group having a radically polymerizable unsaturated bond (for example, a vinyl group, a (meth)acryloyl group, an optionally substituted maleimide group), a hydroxy group, an amide group, an isocyanate group, an epoxy group, and the like.

[0095] Examples of the silicone-based release agent include silicone oil, silicone diacrylate, silicone-based graft copolymers, and the like. 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 preferable. 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 preferable. These silicone compounds are particularly excellent in heat resistance and have a high polarity, so that bleed-out from the adhesive film and the temporary fixing material is easy.

[0096]

Chemical formula

[0097] In the above formulas (5-1) to (5-3), X, and in the above formulas (5-1) and (5-3), Y each independently represents an integer of 0 or more and 1,200 or less. In the above formulas (5-1) to (5-3), R represents a functional group having a carbon-carbon double bond.

[0098] Examples of the functional group having a carbon-carbon double bond represented by R in the above formulas (5-1) to (5-3) include an optionally substituted maleimide group, a citraconimide group, a vinyl ether group, an allyl group, a (meth)acryloyl group, and the like. Among them, since the above adhesive film and the above temporary fixing material are excellent in heat resistance, an optionally substituted maleimide group is preferable. In the above formulas (5-1) to (5-3), when there are a plurality of Rs, each R may be the same or different.

[0099] Examples of commercially available silicone compounds represented by the above formulas (5-1) to (5-3) include EBECRYL350, EBECRYL1360 (both manufactured by Daicel Ornex Co., Ltd.), and the like. Also, BYK-UV3500 (manufactured by BYK Chemie), TEGO RAD2250 (manufactured by Evonik) (both with R being an acryloyl group), and the like can be mentioned.

[0100] Examples of the above fluorine-based release agent include hydrocarbon compounds having a fluorine atom, and the like.

[0101] Examples of the above acrylic-based release agent include BYK-394, BYK-350, BYK-381 (all manufactured by BYK Chemie), Disparon 1970 (manufactured by Kusumoto Chemicals, Ltd.), and the like.

[0102] The content of the release agent preferably has a lower limit of 0.1 part by mass and an upper limit of 20 parts by mass with respect to 100 parts by mass of the curable resin. When the content of the release agent is within this range, the adhesive film and the temporary fixing material after curing will have excellent peeling performance without contaminating the adherend. From the perspective of further enhancing the peeling performance while suppressing contamination, the more preferable lower limit of the content of the release agent is 0.3 part by mass, and the more preferable upper limit is 10 parts by mass.

[0103] The curable adhesive may further contain a gas generating agent. When the curable adhesive contains a gas generating agent, even after undergoing a high-temperature processing treatment at 300°C or higher, the gas generated by irradiating light or the like is released at the interface with the adherend. Therefore, the adhesive film and the temporary fixing material can be more easily peeled from the adherend without leaving any adhesive residue. Also, when peeling a thin adherend after performing a high-temperature processing treatment at 300°C or higher, damage to the adherend can be prevented.

[0104] The gas generating agent preferably has a weight loss rate of 5% or less at 300°C when heated at a heating rate of 10°C / min from 30°C to 300°C in a nitrogen atmosphere by TG-DTA (thermogravimetry-differential thermal analysis) measurement. If the weight loss rate is 5% or less, the decomposition of the gas generating agent is less likely to occur even when performing a high-temperature processing treatment at 300°C or higher, and the adhesive film and the cured temporary fixing material will have more excellent heat resistance. That is, peeling during the high-temperature processing can be further suppressed, and it is also possible to more effectively prevent adhesive enhancement and the occurrence of adhesive residue during peeling. The TG-DTA (thermogravimetry-differential thermal analysis) measurement can be performed, for example, using a TG-DTA apparatus (manufactured by Hitachi High-Tech Science Corporation, "STA7200RV") or the like.

[0105] Examples of the gas generating agent include, for example, a gas generating agent that generates gas by heating, a gas generating agent that generates gas by irradiating light, and the like. Among them, a gas generating agent that generates gas by irradiating light is preferable, and a gas generating agent that generates gas by irradiating ultraviolet light is more preferable. Examples of the gas generating agent include, for example, a tetrazole compound or a salt thereof, a triazole compound or a salt thereof, an azo compound, an azide compound, xanthone acetic acid, 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 preferable because of its particularly excellent heat resistance.

[0106] The content of the gas generating agent preferably has a lower limit of 5 parts by mass and an upper limit of 50 parts by mass with respect to 100 parts by mass of the curable resin. When the content of the gas generating agent is within this range, the adhesive film and the cured temporary fixing material are particularly excellent in peeling performance. A more preferable lower limit of the content of the gas generating agent is 8 parts by mass, and a more preferable upper limit is 30 parts by mass.

[0107] The photocurable adhesive may further contain an inorganic filler. By containing the inorganic filler, the adhesive layer and the temporary fixing material can suppress a decrease in the elastic modulus at high temperatures, and the adhesive film and the cured temporary fixing material can further suppress peeling during high-temperature processing even when a high-temperature processing treatment of 300 °C or higher is performed.

[0108] Examples of the inorganic filler include an inorganic filler composed of at least one selected from the group consisting of oxides of silicon, aluminum, calcium, boron, magnesium, and zirconia, and composites thereof. Among them, silica and talc are preferable because they are inexpensive and easily available as commercial products.

[0109] The above inorganic filler may be surface-modified. Examples of the modifying functional group for surface-modifying the inorganic filler include an alkylsilane group, a methacryloyl group, and a dimethylsiloxane group. Among them, the dimethylsiloxane group is preferred because it has appropriate hydrophobicity.

[0110] The preferred lower limit of the average particle diameter of the above inorganic filler is 5 nm, and the preferred upper limit is 30 μm. When the average particle diameter of the above inorganic filler is within this range, the above adhesive film and the cured temporary fixing material can further suppress peeling during high-temperature processing, and can be peeled by a peeling process during peeling. The more preferred lower limit of the average particle diameter of the above inorganic filler is 10 nm, the further preferred lower limit is 15 nm, the more preferred upper limit is 20 μm, and the further preferred upper limit is 15 μm. The average particle diameter can be determined, for example, by observing 50 arbitrary inorganic fillers with an electron microscope or an optical microscope and calculating the average value of the particle diameters of each inorganic filler, or by performing laser light diffraction particle size distribution measurement.

[0111] The content of the above inorganic filler preferably has a lower limit of 1 part by mass and an upper limit of 20 parts by mass with respect to 100 parts by mass of the above curable resin. When the content of the above inorganic filler is within this range, the above adhesive film and the cured temporary fixing material can further suppress peeling during high-temperature processing, and can be peeled by a peeling process during peeling. The more preferred lower limit of the content of the above inorganic filler is 3 parts by mass, the further preferred lower limit is 5 parts by mass, the more preferred upper limit is 15 parts by mass, and the further preferred upper limit is 10 parts by mass.

[0112] The above curable adhesive may contain known additives such as a photosensitizer, a heat stabilizer, an antioxidant, an antistatic agent, a plasticizer, a resin, a surfactant, and a wax.

[0113] The adhesive film of the present invention may or may not have a base material. When not having the above base material, it is not necessary to select a base material having both light transmissibility and heat resistance, and the adhesive film of the present invention can have a cheaper and simpler configuration. When having the above base material, the handleability of the adhesive film of the present invention is further improved. Further, the adhesive film of the present invention is preferably in the form of a tape from the viewpoint of handleability. When having the above base material, the adhesive film of the present invention may have the above photocurable adhesive on one or both surfaces of the base material. Examples of the base material include resin sheets such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, polyether ether ketone (PEEK), and polyamide (PA). A resin sheet with high light transmissibility can be preferably used. Also, a sheet having a mesh-like structure, a sheet with holes, glass, etc. can also be used. From the viewpoint of enhancing flexibility, the preferable lower limit of the thickness of the above base material is 5 μm, the more preferable lower limit is 10 μm, the preferable upper limit is 150 μm, and the more preferable upper limit is 100 μm.

[0114] The temporary fixing material of the present invention may be in a liquid or paste form, or may be a temporary fixing material such as a tape having an adhesive layer containing a curable adhesive, and is preferably a tape-shaped temporary fixing material. In this case, the above tape may have the above adhesive layer on one or both surfaces of the base material, or may not have a base material. When not having the above base material, it is not necessary to select a base material having both light transmissibility and heat resistance, and the above tape can have a cheaper and simpler configuration. When having the above base material, the handleability of the temporary fixing material of the present invention is further improved. When having the above-mentioned substrate, examples of the substrate include resin sheets such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, polyether ether ketone (PEEK), polyamide (PA), etc. A resin sheet with high light transmittance can be preferably used. In addition, a sheet having a mesh-like structure, a sheet with holes, glass, etc. can also be used. From the viewpoint of enhancing flexibility, the preferable lower limit of the thickness of the above-mentioned substrate is 5 μm, more preferably 10 μm, the preferable upper limit is 150 μm, and more preferably 100 μm.

[0115] The method for manufacturing the adhesive film of the present invention is not particularly limited and can be manufactured by a conventionally known method. Specifically, for example, first, a resin having an imide skeleton as a repeating unit in the main chain and additives to be blended as required are mixed using a bead mill, ultrasonic dispersion, homogenizer, high-output disperser, roll mill, etc. to prepare the above-mentioned curable adhesive. Next, the prepared curable adhesive is applied with a doctor knife on the release-treated surface of a 50-μm-thick release polyethylene terephthalate (PET) film subjected to one-sided release treatment, and heated at 130°C for 10 minutes to dry the coating solution to form an adhesive layer, and then a 50-μm-thick release PET film is overlapped so that the release-treated surface faces the adhesive layer, whereby it can be obtained. Also, when the adhesive film of the present invention has a substrate, a laminated film having an adhesive layer formed by applying the prepared curable adhesive with a doctor knife on the release-treated surface of a 50-μm-thick release polyethylene terephthalate (PET) film subjected to one-sided release treatment and heating at 130°C for 10 minutes to dry the coating solution is prepared, and the adhesive layer of the laminated film is overlapped on the surface of the substrate layer, whereby it can be obtained.

[0116] As a method for manufacturing the temporary fixing material, for example, when the temporary fixing material is in a liquid or paste state, a resin having the imide skeleton as a repeating unit of the main chain and, if necessary, an additive to be blended are mixed using a bead mill, ultrasonic dispersion, homogenizer, high-output disperser, roll mill, or the like. Further, when the temporary fixing material is a tape-shaped temporary fixing material having an adhesive layer containing a curable adhesive, it can be manufactured by the same method as the above-described adhesive film.

[0117] The preferable lower limit of the total thickness of the adhesive film of the present invention (when having a base material, the combined thickness of the adhesive layer and the base material) is 5 μm, and the preferable upper limit is 550 μm. When the total thickness of the adhesive film of the present invention is 5 μm or more, sufficient pressure-sensitive or heat-sensitive adhesive force can be obtained initially. When the total thickness of the adhesive film of the present invention is 550 μm or less, high flexibility can be exhibited, high followability can be exhibited with respect to an adherend having unevenness, and it can be more easily peeled off at the time of peeling. The more preferable lower limit of the total thickness of the adhesive film of the present invention is 10 μm, the further preferable lower limit is 20 μm, the more preferable upper limit is 400 μm, and the further preferable upper limit is 300 μm.

[0118] The adhesive film of the present invention, after being irradiated with light having a wavelength of 405 nm so that the integrated light amount becomes 20000 mJ / cm 2 When heated at a temperature rising rate of 10 °C / min in a nitrogen atmosphere, the preferable lower limit of the 5% weight loss temperature (hereinafter, may be simply referred to as "the 5% weight loss temperature when heated at a temperature rising rate of 10 °C / min in a nitrogen atmosphere after light irradiation") is 300 °C. If the 5% weight loss temperature when the adhesive film of the present invention is heated at a temperature rising rate of 10 °C / min in a nitrogen atmosphere after light irradiation is 300 °C or higher, the obtained adhesive film is more excellent in heat resistance and can further suppress peeling during high-temperature processing. The more preferable lower limit of the 5% weight loss temperature when the adhesive film of the present invention is heated at a temperature rising rate of 10 °C / min in a nitrogen atmosphere after light irradiation is 350 °C, and the further preferable lower limit is 375 °C. In addition, when the adhesive film of the present invention is heated at a heating rate of 10 °C / min in a nitrogen atmosphere after light irradiation, there is no particular upper limit for the 5% weight loss temperature, but the substantial upper limit is 600 °C. Incidentally, the 5% weight loss temperature when the adhesive film of the present invention is heated at a heating rate of 10 °C / min in a nitrogen atmosphere after light irradiation can be measured by TG-DTA (thermogravimetry-differential thermal analysis) using, for example, a TG-DTA apparatus (manufactured by Hitachi High-Tech Science Corporation, "STA7200RV").

[0119] The preferred upper limit of the weight loss rate when the temporary fixing material of the present invention is heated at 290 °C for 30 minutes in a nitrogen atmosphere after curing is 7%. If the above weight loss rate is 7% or less, the cured temporary fixing material will be more excellent in heat resistance and can further suppress peeling during high-temperature processing. The more preferred upper limit of the above weight loss rate is 5%, and the further preferred upper limit is 3%. In addition, although there is no particular lower limit for the above weight loss rate, the substantial lower limit is 0.01%. Incidentally, the weight loss rate when heated at 290 °C for 30 minutes in the above nitrogen atmosphere can be measured by TG-DTA (thermogravimetry-differential thermal analysis) using, for example, a TG-DTA apparatus (manufactured by Hitachi High-Tech Science Corporation, "STA7200RV").

[0120] The preferred lower limit of the ultraviolet absorption rate of the temporary fixing material of the present invention after curing is 80%. If the above ultraviolet absorption rate is 80% or more, the cured temporary fixing material will be more excellent in ultraviolet absorption, the laser processing performance will be further improved, and the support can be peeled off more efficiently. In addition, the peeling performance of the cured temporary fixing material is further improved, and the adhesive residue of the cured temporary fixing material can be further suppressed. The preferred lower limit of the above ultraviolet absorption rate is 90%, and the further preferred lower limit is 95%. In addition, although there is no particular upper limit for the above ultraviolet absorption rate, the substantial upper limit is 100%. The ultraviolet absorption rate can be measured using a spectrophotometer. The optical path length at this time is the thickness of the temporary fixing material after curing. Examples of the spectrophotometer include U-3900 (manufactured by Hitachi High-Technologies Corporation) and the like.

[0121] For the temporary fixing material of the present invention, the preferable lower limit of the gel fraction after curing is 50% by mass, and the preferable upper limit is 99% by mass. When the gel fraction of the temporary fixing material after curing is within the above range, it can be more easily peeled off when peeled from the adherend. A more preferable lower limit of the gel fraction of the cured product is 60% by mass, and a more preferable upper limit is 95% by mass. Note that the gel fraction of the temporary fixing material after curing is measured, for example, by the following method. That is, a cured temporary fixing material with a mass of W0 (g) is sampled, and the sampled cured temporary fixing material is immersed in toluene at 23°C for 24 hours. After shaking and soaking, using a metal mesh (mesh size #200 mesh, mass: W1 (g)), the cured temporary fixing material that has absorbed and swollen with toluene is filtered, and the separated cured temporary fixing material is dried at 110°C for 1 hour. Then, the mass W2 (g) of the cured temporary fixing material after drying is measured, and the gel fraction of the cured temporary fixing material after curing can be measured by calculating the gel fraction using the following formula. Gel fraction (% by mass) = 100×(W2 - W1) / W0 (W0: mass of the temporary fixing material after initial curing, W1: initial mass of the metal mesh, W2: mass of the cured temporary fixing material including the metal mesh after drying)

[0122] When the temporary fixing material of the present invention is not in a liquid or paste form (for example, in the case of a tape-like temporary fixing material), the preferable lower limit of the thickness after curing is 5 μm, and the preferable upper limit is 550 μm. When the thickness of the temporary fixing material after curing is 5 μm or more, the temporary fixing material can have sufficient pressure-sensitive or heat-sensitive adhesive force initially. When the thickness of the temporary fixing material after curing is 550 μm or less, the temporary fixing material can exhibit high flexibility even after curing, can exhibit high followability with respect to an adherend having irregularities, and can be more easily peeled off at the time of peeling. The more preferable lower limit of the thickness of the temporary fixing material after curing is 10 μm, the further preferable lower limit is 20 μm, and the even more preferable lower limit is 30 μm. The more preferable upper limit of the thickness of the temporary fixing material after curing is 400 μm, the further preferable upper limit is 300 μm, the even more preferable upper limit is 200 μm, and the particularly preferable upper limit is 150 μm.

[0123] The adhesive film of the present invention can easily peel off the support even when irradiated with low-energy laser light, and can also easily peel off the adhesive film from the adherend even when performing high-temperature processing. Therefore, the adhesive film of the present invention can be suitably used for the manufacture of electronic components having a support peeling step by irradiation with laser light or a high-temperature processing step. In particular, it can be suitably used for temporarily fixing electronic components in the manufacture of electronic components such as semiconductor devices.

[0124] The temporary fixing material of the present invention can easily peel off the support by having appropriate laser processing performance even when irradiated with low-energy laser light after curing. Therefore, the temporary fixing material of the present invention can be suitably used for the manufacture of electronic components having a support peeling step by irradiation with laser light. In particular, it can be suitably used in the manufacture of semiconductor devices.

[0125] The adhesive film of the present invention, or a cured product obtained by curing the temporary fixing material of the present invention is also one of the present inventions. Even when irradiated with low-energy laser light, the cured product of the present invention has appropriate processing performance, so that the support can be easily peeled off. Therefore, the cured product can be suitably used in the manufacture of electronic components having a support peeling step by irradiation with laser light. In particular, it can be suitably used in the manufacture of semiconductor devices.

[0126] The cured product of the present invention may be one obtained by curing a temporary fixing material such as a liquid or paste, or may be one obtained by curing a temporary fixing material such as an adhesive film or tape. Among them, it is preferably one obtained by curing an adhesive film or tape-shaped temporary fixing material. When the adhesive film or the temporary fixing material has photocurability, the cured product can be obtained, for example, by irradiating the temporary fixing material with ultraviolet light having a wavelength of 365 nm so that the integrated light amount becomes 20000 mJ / cm 2 and curing the temporary fixing material. When the adhesive film or the temporary fixing material has thermosetting properties, the cured product can be obtained, for example, by heating the temporary fixing material at 290 ° C. for 30 minutes in a nitrogen atmosphere to cure the temporary fixing material.

[0127] The cured product obtained by curing the adhesive film has a preferable lower limit of the laser processing depth of 0.10 μm when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 When the laser processing depth of the cured product when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is 0.10 μm or more, the cured product can be peeled off from the support more efficiently even when irradiated with low-energy laser light. A more preferable lower limit of the laser processing depth of the cured product when pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is 0.15 μm, and a further preferable lower limit is 0.20 μm. Incidentally, for the cured product obtained by curing the above adhesive film, when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated, it is preferable that the lower limit of the laser processing depth satisfies the above range on at least one surface of the cured product, and it is more preferable that the above range is satisfied on both surfaces of the cured product. For the cured product obtained by curing the above temporary fixing material, the lower limit of the laser processing depth when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated is 0.10 μm. When the laser processing depth when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 of the cured product is pulse-irradiated is 0.10 μm or more, even when low-energy laser light is irradiated, the cured product can be efficiently peeled off from the support. The preferable lower limit of the laser processing depth when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 of the cured product is pulse-irradiated is 0.15 μm, and the more preferable lower limit is 0.20 μm. Incidentally, when the cured product is not a cured product of a liquid or paste-like temporary fixing material, the lower limit of the laser processing depth when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 is pulse-irradiated only needs to satisfy the above range on at least one surface of the cured product, but it is preferable that the above range is satisfied on both surfaces of the cured product.

[0128] The preferable upper limit of the laser processing depth when the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 of the cured product is pulse-irradiated is 1.0 μm. When the laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2When the laser processing depth when the laser beam of 2 is pulse-irradiated is 1.0 μm or less, the above-mentioned temporary fixing material after curing has better laser processing performance and can peel off the support more efficiently. A more preferable upper limit of the laser processing depth when the laser beam of wavelength 308 nm, pulse width 10 nsec, and irradiation energy density 300 mJ / cm is pulse-irradiated is 0.80 μm, and a further preferable upper limit is 0.60 μm. 2 When the cured product is not a cured product of a liquid or paste-like temporary fixing material, the upper limit of the laser processing depth when the laser beam of wavelength 308 nm, pulse width 10 nsec, and irradiation energy density 300 mJ / cm

[0129] is pulse-irradiated preferably satisfies the above range on at least one surface of the cured product, and more preferably satisfies the above range on both surfaces of the cured product. 2 A more preferable upper limit of the laser processing depth when the laser beam of wavelength 308 nm, pulse width 10 nsec, and irradiation energy density 400 mJ / cm 2 is pulse-irradiated is 1.0 μm. When the laser processing depth when the laser beam of wavelength 308 nm, pulse width 10 nsec, and irradiation energy density 400 mJ / cm 2 is pulse-irradiated is 1.0 μm or less, the laser processing performance of the above-mentioned cured product is further improved, and the support can be peeled off more efficiently. A more preferable upper limit of the laser processing depth when the laser beam of wavelength 308 nm, pulse width 10 nsec, and irradiation energy density 400 mJ / cm of the cured product is 0.80 μm, and a further preferable upper limit is 0.60 μm. 2 A preferable lower limit of the laser processing depth when the laser beam of wavelength 308 nm, pulse width 10 nsec, and irradiation energy density 400 mJ / cm 2If the laser processing depth when the laser beam is pulse-irradiated is 0.10 μm or more, the laser processing performance for the above curing is further improved, and the support can be peeled off more efficiently. For the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 A more preferable lower limit of the laser processing depth when the laser beam is pulse-irradiated is 0.15 μm, and a further more preferable lower limit is 0.20 μm. When the cured product is not a cured product of a liquid or paste-like temporary fixing material, the laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm 2 is pulse-irradiated preferably satisfies the above range on at least one surface of the cured product, and more preferably satisfies the above range on both surfaces of the cured product.

[0130] The adhesive film of the present invention is preferably used in a laminate having a support, the adhesive film of the present invention, and a semiconductor device in this order. If the adhesive film of the present invention is used in a laminate having the above-described configuration, it can be more suitably used in the manufacture of electronic components. A laminate having a support, the adhesive film of the present invention, and a semiconductor device in this order (hereinafter, may also be referred to as "laminate (a)") is also one of the present inventions.

[0131] The cured product of the temporary fixing material of the present invention is preferably used in a laminate having a support, the cured product, and a semiconductor device in this order. If the cured product of the temporary fixing material of the present invention is used in a laminate having the above configuration, even when irradiated with a low-energy laser beam, the support can be peeled off more efficiently, so that it can be suitably used in the manufacture of electronic components. A laminate having a support, the cured product of the temporary fixing material of the present invention, and a semiconductor device in this order, and the support having a light transmittance of 50% or more at a wavelength of 300 nm or more and 400 nm or less (hereinafter, may also be referred to as "laminate (b)") is also one of the present inventions.

[0132] Hereinafter, for matters common to the above laminate (a) and the above laminate (b), unless otherwise specified, they shall be simply described as "the above laminate".

[0133] As the material of the above support, a material with a high light transmittance is preferred, and examples thereof include glass, quartz, sapphire, etc.

[0134] In the above laminate (a), the preferred lower limit of the light transmittance of the above support at a wavelength of 200 nm or more and 355 nm or less is 20%. If the light transmittance of the above support at a wavelength of 200 nm or more and 355 nm or less is 20% or more, the above support can be efficiently peeled off from the above adhesive film. The more preferred lower limit of the light transmittance of the above support at a wavelength of 200 nm or more and 355 nm or less is 30%, and the further preferred lower limit is 50%. Also, there is no particular upper limit for the light transmittance of the above support at a wavelength of 200 nm or more and 355 nm or less, but the practical upper limit is 95%.

[0135] In the above laminate (b), the preferred lower limit of the light transmittance of the above support at a wavelength of 300 nm or more and 400 nm or less is 50%. If the light transmittance of the above support at a wavelength of 300 nm or more and 400 nm or less is 50% or more, the laser processing performance of the above cured product is further improved, and the above support can be peeled off more efficiently. The more preferred lower limit of the light transmittance of the above support at a wavelength of 300 nm or more and 400 nm or less is 60%, and the further preferred lower limit is 70%. Also, there is no particular upper limit for the light transmittance of the above support at a wavelength of 300 nm or more and 400 nm or less, but the practical upper limit is 95%.

[0136] The upper limit of the haze of the above support is not particularly limited, but from the viewpoint of irradiating the laser light from the above support side to the cured product of the above adhesive film or the above temporary fixing material, it is preferable that the haze of the above support is small. The preferred upper limit of the haze of the above support is 10%, and the more preferred upper limit is 5%. Also, there is no particular preferred lower limit for the haze of the above support, but the substantial lower limit is 0.001%. Note that the haze of the above support can be measured using, for example, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., "NDH4000") or the like.

[0137] The above laminate (a) only needs to have the support, the adhesive film of the present invention, and the semiconductor device in this order, and may further have other layers as long as the effects of the present invention are not impaired. Also, the above laminate (b) only needs to have the support, the cured product of the temporary fixing material, and the semiconductor device in this order, and may further have other layers as long as the effects of the present invention are not impaired.

[0138] A method for manufacturing an electronic component having a light irradiation step of irradiating the above laminate (a) with light from the above support side, a high-temperature processing step of subjecting the above laminate to a heat treatment or a process accompanied by heat generation, irradiating the above laminate (a) with laser light having a wavelength of 200 nm or more and 355 nm or less from the above support side, and peeling the above support from the above adhesive film (hereinafter, may also be referred to as "support peeling step (a)"), and an adhesive film peeling step of peeling the above adhesive film from the above semiconductor device is also one of the present inventions. The method for manufacturing an electronic component of the present invention can efficiently peel the above support from the above adhesive film even when irradiating with low-energy laser light, and can also efficiently peel the above adhesive film from the above semiconductor device even when performing a high-temperature processing step. As a result, the electronic component can be manufactured without deteriorating the processing quality of the electronic component due to carbonization of the adhesive film, damage to the support, contamination of the adhesive film and the support, deterioration of the peeling performance of the support, and occurrence of glue residue during peeling of the adhesive film.

[0139] Examples of the light source of the light irradiated in the above light irradiation step include an ultra-high pressure mercury lamp and an LED. Among them, an ultra-high pressure mercury lamp is preferable from the viewpoint of easily curing the above photocurable adhesive.

[0140] The wavelength of the light irradiated in the above light irradiation step preferably has a lower limit of 356 nm and an upper limit of 500 nm. When the wavelength of the light irradiated in the above light irradiation step is within the above range, the adhesive film can be photocured more efficiently in the above light irradiation step, and the adhesive film can be easily peeled off in the above adhesive film peeling step. Further, in the above support peeling step, the support can be peeled off from the adhesive film more efficiently using a laser beam having a wavelength within the range described later. The more preferable lower limit of the wavelength of the light irradiated in the above light irradiation step is 360 nm, and the further preferable lower limit is 375 nm, and the more preferable upper limit is 450 nm, and the further preferable upper limit is 420 nm.

[0141] The integrated light amount of the light irradiated in the above light irradiation step preferably has a lower limit of 1000 mJ / cm 2 and an upper limit of 30000 mJ / cm 2 . By irradiating so that the integrated light amount of the light irradiated in the above light irradiation step is 1000 mJ / cm 2 or more, the adhesive film can be cured more sufficiently. By irradiating so that the integrated light amount of the light irradiated in the above light irradiation step is 30000 mJ / cm 2 or less, photodegradation of low molecular weight compounds can be suppressed, and it can be applied at a higher temperature in the above high-temperature processing step. The more preferable lower limit of the integrated light amount of the light irradiated in the above light irradiation step is 3000 mJ / cm 2 , and the further preferable lower limit is 5000 mJ / cm 2 , and the more preferable upper limit is 25000 mJ / cm 2 , and the further preferable upper limit is 20000 mJ / cm 2 .

[0142] Examples of the above high-temperature processing step include processes such as reflow, sputtering, and thermocompression bonding (TCB).

[0143] The wavelength of the laser light irradiated in the support peeling step (a) preferably has a lower limit of 200 nm and an upper limit of 355 nm. When the wavelength of the laser light irradiated in the support peeling step (a) is within the above range, damage to the support and the like can be further suppressed, and the support can be more efficiently peeled from the adhesive film.

[0144] The preferable upper limit of the irradiation energy density of the laser light irradiated in the support peeling step (a) is 500 mJ / cm 2 When the irradiation energy density of the laser light irradiated in the support peeling step (a) is 500 mJ / cm 2 or less, damage to the support and the like can be further suppressed, and the support can be more efficiently peeled from the adhesive film. The more preferable upper limit of the irradiation energy density of the laser light irradiated in the support peeling step (a) is 400 mJ / cm 2 and the further preferable upper limit is 300 mJ / cm 2 . Moreover, although there is no preferable lower limit for the irradiation energy density of the laser light irradiated in the support peeling step (a), the substantial lower limit is 100 mJ / cm 2 .

[0145] The laser light irradiated in the support peeling step (a) may be a CW (Continuous Wave) laser or a pulsed laser.

[0146] When the laser light irradiated in the support peeling step (a) is a pulsed laser, the preferable upper limit of the pulse width is 100 nsec. When the pulse width of the laser light irradiated in the support peeling step (a) is 100 nsec or less, damage to the support and the like can be further suppressed, and the support can be more efficiently peeled from the adhesive film. The more preferable upper limit of the pulse width of the laser light irradiated in the support peeling step (a) is 50 nsec, and the further preferable upper limit is 20 nsec. There is no particular preferable lower limit for the pulse width of the laser light irradiated in the support peeling step (a), but the substantial lower limit is 5 fsec.

[0147] In a laminate including a support, a cured product of a temporary fixing material, and a semiconductor device in this order, laser light having a wavelength of 308 nm or more and 355 nm or less, a pulse width of 100 nsec or less, and an irradiation energy density of 500 mJ / cm 2 By pulse-irradiating the following laser light from the support side, a method for manufacturing an electronic component having a support peeling step (hereinafter, may also be referred to as "support peeling step (b)") of peeling the support from the laminate is also one of the present inventions. The method for manufacturing an electronic component of the present invention is to irradiate a laminate including a support, a cured product of a temporary fixing material, and a semiconductor device in this order with laser light having a wavelength of 308 nm or more and 355 nm or less, a pulse width of 100 nsec or less, and an irradiation energy density of 500 mJ / cm 2 including a support peeling step of pulse-irradiating the following laser light from the support side to peel the support. By including the support peeling step (b) in the manufacturing method, even when irradiating a low-energy laser, the support can be efficiently peeled, and the electronic component can be manufactured without degrading the processing quality of the electronic component due to carbonization of the temporary fixing material, support damage, contamination of the temporary fixing material or support, and deterioration of the support peeling performance.

[0148] In the method for manufacturing an electronic component of the present invention, a laminate similar to the laminate including the support, the cured product of the temporary fixing material, and the semiconductor device described above in this order is preferably used.

[0149] The wavelength of the laser light irradiated in the support peeling step (b) has a lower limit of 308 nm and an upper limit of 355 nm. By the wavelength of the laser light irradiated in the support peeling step (b) being within the above range, the laser processing performance of the cured product is improved, and the support can be efficiently peeled.

[0150] The upper limit of the pulse width of the laser light irradiated in the support peeling step (b) is 100 nsec. If the pulse width of the laser light irradiated in the support peeling step (b) is 100 nsec or less, the laser processing performance of the cured product is improved, and while suppressing damage to the support, etc., the support can be efficiently peeled off. The preferable upper limit of the pulse width of the laser light irradiated in the support peeling step (b) is 50 nsec, and the more preferable upper limit is 20 nsec. There is no particular lower limit for the pulse width of the laser light irradiated in the support peeling step (b), but the substantial lower limit is 50 fsec.

[0151] The upper limit of the irradiation energy density of the laser light irradiated in the support peeling step (b) is 500 mJ / cm 2 is. If the irradiation energy density of the laser light irradiated in the support peeling step (b) is 500 mJ / cm 2 or less, the laser processing performance of the cured product is improved, and the support can be efficiently peeled off. The preferable upper limit of the irradiation energy density of the laser light irradiated in the support peeling step (b) is 400 mJ / cm 2 , and the more preferable upper limit is 300 mJ / cm 2 is. Also, there is no particular lower limit for the irradiation energy density of the laser light irradiated in the support peeling step (b), but the substantial lower limit is 100 mJ / cm 2 is.

[0152] The method for manufacturing an electronic component of the present invention has a step of curing a temporary fixing material before the support peeling step (b). The curing step preferably has, for example, a photocuring step of irradiating light to cure the temporary fixing material and / or a thermocuring step of heating the temporary fixing material to cure the temporary fixing material.

[0153] The intensity distribution in the preferable irradiation shape of the laser light irradiated in the support peeling step (a) and the support peeling step (b) changes according to the purpose, but it is preferably a Gaussian waveform or is subjected to a flattening process. When the intensity distribution in the irradiation shape of the laser beam irradiated in the support peeling step is a Gaussian waveform, processing by irradiation with one pulse of the laser beam can be performed into a uniform circle. When the intensity distribution in the irradiation shape of the laser beam irradiated in the support peeling step is flattened, it is not necessary to irradiate the laser beam repeatedly, and the laser beam can be irradiated more uniformly. Examples of the flattening method include a method using a splitter or a mask.

[0154] The irradiation shape of the laser beam irradiated in the support peeling step (a) and the support peeling step (b) is preferably a rectangle. By the irradiation shape of the laser beam being a rectangle, the laser beam can be irradiated more uniformly without gaps.

[0155] In the support peeling step (a) and the support peeling step (b), it is preferable to irradiate the entire surface of the support of the laminate with the laser beam by moving the laser beam irradiation device or the stage on which the laminate is placed in the vertical and horizontal directions. At this time, an offset may be applied to the laminate, and the laser beam may be irradiated so as to overlap with the offset.

[0156] When the laser beam is irradiated in the support peeling step (a) and the support peeling step (b), white smoke may be generated. When the white smoke is generated, the laser beam is blocked, and the processing performance of the laser beam irradiation device is reduced. Therefore, in the support peeling step (a) and the support peeling step (b), it is preferable to perform ventilation when irradiating the laser beam.

Effects of the Invention

[0157] According to the present invention, even when irradiating with a low-energy laser beam, the support can be efficiently peeled off, and further, even when performing high-temperature processing, an adhesive film excellent in peelability with respect to the adherend can be provided. Further, according to the present invention, a cured product of the adhesive film can be provided. Furthermore, according to the present invention, a laminate having a support, the adhesive film, and a semiconductor in this order can be provided. Moreover, according to the present invention, a method for manufacturing an electronic component having a step of efficiently peeling off the support even when irradiating with a low-energy laser beam and a step of easily peeling off the adherend even when performing high-temperature processing using the laminate can be provided. Also, according to the present invention, even when irradiating with a low-energy laser beam after curing, a temporary fixing material excellent in laser processing performance and capable of efficiently peeling off the support can be provided. Further, according to the present invention, a cured product of the temporary fixing material can be provided. Furthermore, according to the present invention, a laminate having the cured product can be provided. Moreover, according to the present invention, a method for manufacturing an electronic component having a step of efficiently peeling off the support even when irradiating with a low-energy laser beam can be provided.

Mode for Carrying Out the Invention

[0158] Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples.

[0159] (Synthesis Example 1) 250 ml of toluene was charged into a 500-ml round-bottom flask equipped with a Teflon (registered trademark) stirrer. 31.9 g (0.06 mol) of diaminodimer (manufactured by Klochner, "Primene 1075"), 5.5 g (0.015 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, and 39.8 g (0.0765 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)phthalic 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 then cooled to room temperature. Polyimide A having a structural unit represented by the following formula (6-1) and a structural unit represented by the following formula (6-2) in the form of a brown solid was obtained. For the obtained polyimide A, when measured by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (manufactured by Waters) as the column, the weight average molecular weight was 78,000.

[0160] [Chemical formula]

[0161] (Synthesis Example 2) 250 ml of toluene was charged into a 500-ml round-bottom flask equipped with a Teflon (registered trademark) stirrer. 56 g (0.1 mol) of diaminodimer (manufactured by Klochner, "Primene 1075") and 19.6 g (0.2 mol) of maleic anhydride were added, and then 5 g of methanesulfonic anhydride was added. After the resulting solution was refluxed for 12 hours, it was cooled to room temperature, 300 ml of toluene was added to the flask, and the layers were separated by standing to remove the lower layer which was an impurity. The obtained solution was filtered through a glass frit funnel filled with silica gel, and then the solvent was removed under vacuum to obtain a brown liquid bismaleimide compound D represented by the following formula (7).

[0162] [Chemical formula]

[0163] (Synthesis Example 3) 250 ml of toluene was charged into a 500-ml round-bottom flask containing a Teflon (registered trademark) stirrer. 39.9 g (0.075 mol) of diaminodiphenylmethane (manufactured by Kureha Corporation, "Priamine 1075") and 39.8 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. Polyimide B having a structural unit represented by the following formula (8) in the form of a brown solid was obtained. When the obtained polyimide B was measured by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (manufactured by Waters Corporation) as the column, the weight average molecular weight was 90,000.

[0164]

Chemical formula

[0165] In Tables 1 to 8, bismaleimide C was a bismaleimide compound represented by the following formula (9) (manufactured by Designer Molecules, "BMI-3000GEL").

[0166]

Chemical formula

[0167] In formula (9), n is the number of repetitions.

[0168] (Synthesis of acrylic copolymer E) A reactor equipped with a thermometer, a stirrer, and a cooling pipe was prepared. 94 parts by mass of 2-ethylhexyl acrylate, 6 parts by mass of hydroxyethyl methacrylate, 0.01 part by mass of lauryl mercaptan, and 80 parts by mass of ethyl acetate were added into this reactor, and then the reactor was heated to start reflux. Subsequently, 0.01 part by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added into the said reactor as a polymerization initiator, and polymerization was started under reflux. Next, 0.01 part by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added also 1 hour and 2 hours after the start of polymerization, and further, 0.05 part by mass of t-hexyl peroxypivalate was added 4 hours after the start of polymerization to continue the polymerization reaction. And 8 hours after the start of polymerization, an ethyl acetate solution containing a functional group-containing acrylic polymer with a solid content of 55% by mass and a weight average molecular weight of 500,000 was obtained. To 100 parts by mass of the resin solid content of the obtained ethyl acetate solution containing the functional group-containing acrylic polymer, 3.5 parts by mass of 2-isocyanatoethyl methacrylate was added and reacted to obtain an acrylic copolymer D. The weight average molecular weight of the acrylic copolymer was 550,000. Regarding the weight average molecular weight of the obtained acrylic copolymer, it was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters)) using THF as the eluent and HR-MB-M 6.0×150 mm (manufactured by Waters) as the column.

[0169] (Examples 1-1 to 1-23, Comparative Examples 1-1 to 1-7) (Production of Adhesive Film) Each material described in Tables 1 to 2 and 4 was added to 150 ml of toluene and mixed to prepare a toluene solution of a photocurable adhesive. The toluene solution of the obtained photocurable adhesive was applied with a doctor knife onto the release-treated surface of a 50-μm-thick release polyethylene terephthalate (PET) film with one-sided release treatment so that the dry film thickness was 80 μm, and then heated at 130 °C for 10 minutes to dry the coating solution and obtain a laminated film. Further, a 50-μm-thick release PET film with one-sided release treatment was overlaid on the laminated film so that the release-treated surface faced the dry film, thereby obtaining an adhesive film with a release PET film.

[0170] (Gel fraction of the adhesive layer) One of the PET films of the obtained adhesive film was peeled off, and a mass W0 (g) of the adhesive layer was sampled. The sampled photocurable adhesive was immersed in toluene at 23 °C for 24 hours. After shaking, the toluene-absorbed and swollen adhesive layer was filtered using a metal mesh (mesh opening #200 mesh, mass: W1 (g)), and the separated photocurable adhesive was dried at 110 °C for 1 hour. Then, the mass W2 (g) of the dried adhesive layer was measured, and the gel fraction before light irradiation of the adhesive layer was measured by calculating the gel fraction using the following formula. The results are shown in Tables 1 to 2 and 4. Gel fraction (mass%) = 100×(W2 - W1) / W0 (W0: mass of the initial adhesive layer, W1: initial mass of the metal mesh, W2: mass of the adhesive layer including the dried metal mesh) Also, after irradiating the obtained adhesive film with light having a wavelength of 405 nm from an ultra-high pressure mercury lamp so that the integrated light quantity was 20000 mJ / cm 2 One of the PET films of the adhesive film was peeled off, and the gel fraction of the adhesive layer after light irradiation was measured in the same manner as the gel fraction of the adhesive layer before light irradiation described above. The results are shown in Tables 1 to 2 and 4.

[0171] (Attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm) (A) Measurement of transmittance X Regarding the obtained adhesive film (adhesive layer), after cutting it into a flat rectangular shape with a plane length of 20 mm × 30 mm, a measurement sample with the PET films on both sides peeled off was attached to the opening of the integrating sphere ISN-723 of the spectrophotometer V-670 (both manufactured by JASCO Corporation), and the transmittance X of light from a wavelength of 220 nm to 1500 nm was measured with the incident angle of the measurement light set to 0°.

[0172] (B) Measurement of reflectance Y The absolute reflectance measurement unit ARSN-733 (both manufactured by JASCO Corporation) was attached to the spectrophotometer V-670. The PET film on one side of the adhesive film (adhesive layer) was peeled off, and a black vinyl tape (manufactured by Sekisui Chemical Co., Ltd., "Esron Tape No. 360", black, width 19 mm) was attached to cut the reflection from the back surface. The PET film on the side of the adhesive film opposite to the side where the black vinyl tape was attached was peeled off. The adhesive film was set on the sample stage using a leaf spring (an accessory of the absolute reflectance measurement unit ARSN-733) so that the measurement light was incident from the side opposite to the side where the black vinyl tape was attached, and the reflectance Y of light from a wavelength of 220 nm to 1500 nm was measured with the incident angle of the measurement light set to 5° and the reflection angle set to 5°.

[0173] (C) Measurement of the thickness of the adhesive layer The PET films on both sides of the adhesive film (adhesive layer) were peeled off, and the thickness of the adhesive layer was measured. A thickness gauge (manufactured by Mitutoyo Corporation, "Digimatic Indicator ID-H") was used for the thickness measurement.

[0174] (D) Derivation of the attenuation coefficient Using the measured transmittance X, reflectance Y, and the thickness of the adhesive layer, the refractive index n and extinction coefficient k were analyzed by spectroscopic ellipsometry analysis software (manufactured by J.A. Woollam, "WVASE32"). By approximating the refractive index in the visible region (wavelength from 380 nm to 780 nm) with a Cauchy polynomial, the value of the refractive index n1 from the absorption edge to a wavelength of 780 nm was obtained using the transmittance X. With the obtained refractive index n1 fixed and used as the refractive index of light from a wavelength of 220 nm to 1500 nm, the extinction coefficient k1 was calculated using the transmittance X. Further, the reflectance y1 was calculated using the calculated refractive index n1 and extinction coefficient k1. Since the reflection of light on the surface of the adhesive layer is not a perfect specular reflection and the measured reflectance Y is lower than the ideal reflectance, the reflectance Y in the visible region was adjusted to match the reflectance y1 to obtain the reflectance y2. Next, with the extinction coefficient k1 fixed, the refractive index n2 from a wavelength of 220 nm to 1500 nm was calculated using the reflectance y2. This procedure was repeated until the measured value and the calculated value of the reflectance matched to obtain the refractive index n and extinction coefficient k from a wavelength of 220 nm to 1500 nm. In this example and the comparative examples, except for Comparative Examples 1-4, the transmittance at a wavelength of 308 nm was 1% or less. Therefore, assuming an approximation with an exponential function using the extinction coefficient in the long-wavelength region where the transmittance is greater than 1% (the extinction coefficient from a wavelength of 395 nm to 425 nm), the equation of the approximate curve (y = A (constant) × e ^ (B (constant) × x), y: extinction coefficient, x: wavelength (nm)) was obtained by the least squares method. The extinction coefficient k at a wavelength of 308 nm was obtained from the equation of the obtained approximate curve. When the wavelength at which the transmittance becomes 1% or less is shorter than 308 nm, the extinction coefficient k at a wavelength of 308 nm was obtained from the above analysis results. In Comparative Examples 1-4, since the transmittance at a wavelength of 308 nm was more than 1%, the extinction coefficient k at a wavelength of 308 nm was obtained from the above analysis results. By performing the above analysis, the extinction coefficient of the adhesive layer for light at a wavelength of 308 nm before light irradiation was obtained. The results are shown in Tables 1-2 and 4.

[0175] Also, the obtained adhesive film (adhesive layer) was irradiated with light having a wavelength of 405 nm from an ultra-high pressure mercury lamp with an integrated light amount of 20000 mJ / cm 2After irradiation so as to achieve the above, the same methods as the above-mentioned “(A) Measurement of transmittance X”, “(B) Measurement of reflectance Y”, “(C) Measurement of the thickness of the adhesive film”, and “(D) Derivation of attenuation coefficient” were carried out, and the attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation was measured. The results are shown in Tables 1 to 2 and 4.

[0176] (5% weight loss temperature when heated at a heating rate of 10 °C / min in a nitrogen atmosphere after light irradiation of the adhesive film) After cutting the obtained adhesive film into a flat rectangular shape of 100 mm × 200 mm, light having a wavelength of 405 nm was irradiated onto the cut adhesive film with an integrated light amount of 20000 mJ / cm 2 The adhesive film irradiated with light was weighed into an aluminum pan, the PET films on both sides of the adhesive film were peeled off, and after setting the aluminum pan in a differential thermal thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Science Corporation, “STA7200”), thermogravimetric analysis was performed at a heating rate of 10 °C / min in a nitrogen atmosphere. The temperature at which the weight of the adhesive film became 95% of the initial weight was defined as the 5% weight loss temperature when heated at a heating rate of 10 °C / min in a nitrogen atmosphere after light irradiation of the adhesive film, and the results are shown in Tables 1 to 2 and 4.

[0177] <Evaluation> For the adhesive films obtained in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7, the following evaluations were carried out. The results are shown in Tables 1 to 2 and 4.

[0178] (Fabrication of laminate) One release PET film of the obtained adhesive film was peeled off, and it was attached to a silicon wafer having a diameter of 200 mm and a thickness of 700 μm under vacuum and 40 °C conditions, and the adhesive film was cut into the shape of the silicon wafer. Next, the other release PET film of the attached adhesive film was peeled off, and a glass (manufactured by SCHOTT, “Tempax”) having a diameter of 200 mm and a thickness of 600 μm was attached to the surface opposite to the surface attached to the silicon wafer under vacuum and 90 °C conditions using a pressure bonding device (manufactured by Takatori Corporation, “GWSM-300M”) to obtain a laminate. Also, from the glass side of the obtained laminate, using an ultra-high pressure mercury lamp, light with a wavelength of 405 nm was irradiated so that the integrated light quantity became 20000 mJ / cm 2 And a treatment of heating for 30 minutes was performed using a hot plate (manufactured by MSA Factory, "PH224 / 225") at 290°C under a nitrogen atmosphere.

[0179] (Peelability of the support) After performing the above-described light irradiation treatment and heat treatment and allowing natural air cooling, for the laminate, from the glass side, a pulsed laser with a wavelength of 308 nm, an irradiation energy density of 250 mJ / cm 2 and a pulse width of 20 nsec was irradiated over the entire glass surface. Then, the silicon wafer side was fixed to the adsorption stage, a suction cup hook was attached to the glass side, and a digital force gauge (manufactured by IMADA, "ZTS-50N") was hooked to the hook. In this way, the peel force for peeling the glass from the adhesive film was measured with the digital force gauge. When the obtained peel force was 20 N / inch or less, it was rated as "◎", when it was greater than 20 N / inch and 30 N / inch or less, it was rated as "○", and when it was greater than 30 N / inch, it was rated as "×", and the peelability of the support was evaluated.

[0180] (Peelability of the adhesive film) For the laminate after peeling the support used in the above-described "(Peelability of the support)", the adhesive film on the laminate was cut to a width of 25 mm, and using a tensile tester (manufactured by Shimadzu Corporation, "AG-IS"), the 180° peel force of the adhesive film was measured by peeling the adhesive film from the semiconductor device under the conditions of a peel rate of 300 mm / min and a peel angle of 180°. When the obtained 180° peel force was 1.0 N / inch or less, it was rated as "○", when it was greater than 1.0 N / inch and 3.0 N / inch or less, it was rated as "△", and when it was greater than 3.0 N / inch, it was rated as "×", and the peelability of the adhesive film was evaluated.

[0181] (Examples 1-24 to 1-26) (Production of the adhesive film) In the same manner as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7, two laminated films were produced, and then one laminated film was overlapped on each of the two surfaces of the base materials shown in Table 3 so that the dry films faced each other, thereby obtaining an adhesive film having a base material and an adhesive layer having the same composition and thickness on both sides of the base material.

[0182] Note that the types of the base materials shown in Table 3 are as follows. · PA (polyamide)-containing base material (manufactured by Unitika Ltd., "Unitamide (registered trademark)") · Transparent PI (polyimide)-containing base material (manufactured by I.S.T. Co., Ltd., "TORMED (registered trademark)") · PEEK (polyetheretherketone)-containing base material (manufactured by Kurashiki Boseki Co., Ltd., "Expeek / EXPEEK")

[0183] (Gel fraction of the adhesive layer) In the same manner as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7, the gel fraction of the adhesive layer before light irradiation and the gel fraction of the adhesive layer after light irradiation were obtained. The results are shown in Table 3.

[0184] (Attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm) A cutter knife was inserted between the base material and the adhesive layer in the obtained adhesive film to separate the base material and the adhesive layer. For the separated adhesive layer, the transmittance X, reflectance Y, and thickness were measured in the same manner as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-3, 1-5 to 1-7, and the attenuation coefficient was derived. The results are shown in Table 3.

[0185] (5% weight loss temperature when heated at a heating rate of 10 ° C / min in a nitrogen atmosphere after light irradiation of the adhesive film) In the same manner as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7, the 5% weight loss temperature when heated at a heating rate of 10 ° C / min in a nitrogen atmosphere after light irradiation of the adhesive film was measured. The results are shown in Table 3.

[0186] For the evaluation, it was carried out in the same manner as in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-7. The results are shown in Table 3.

[0187]

Table 1

[0188]

Table 2

[0189]

Table 3

[0190]

Table 4

[0191] (Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, Comparative Examples 2-1 to 2-2) (Preparation of temporary fixing material) To 150 mL of toluene, each material described in Tables 5 to 6 and 8 was added and mixed to prepare a toluene solution of a curable adhesive. The obtained toluene solution of the curable adhesive was applied with a doctor knife on the release-treated surface of a 50-μm-thick release polyethylene terephthalate (PET) film having a single-sided release treatment so that the thickness of the dry film was 80 μm, and heated at 130°C for 10 minutes to dry the applied solution to obtain a laminated film. Further, a 50-μm-thick release PET film having a single-sided release treatment was overlaid on the laminated film so that the release-treated surface faced the dry film, thereby obtaining a temporary fixing material with a release PET film.

[0192] (Laser processing depth after curing the temporary fixing material) One of the release PET films was peeled off from the obtained temporary fixing material, and it was attached to a silicon wafer with a diameter of 200 mm and a thickness of 700 μm under vacuum at 40 °C. The temporary fixing material was cut into the shape of the silicon wafer. From the side of the other release PET film of the temporary fixing material attached to the silicon wafer, ultraviolet light with a wavelength of 365 nm was irradiated with an integrated light quantity of 20,000 mJ / cm 2 so that it became. Further, after irradiating with ultraviolet light, the other release PET film was peeled off, and heat treatment was performed for 30 minutes using a hot plate (manufactured by MSA Factory, "PH224 / 225") at 290 °C under a nitrogen atmosphere to cure the temporary fixing material. The cured temporary fixing material was pulse-irradiated with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 . After pulse-irradiating the laser light, the laser processing depth was measured by measuring the step using a laser microscope (manufactured by Olympus, "OLS4100-SAT", wavelength 405 nm) on the surface of the cured product on the laser light irradiation side. Also, the laser processing depth when irradiated with laser light having an irradiation energy density of 400 mJ / cm 2 was measured in the same manner. The obtained laser processing depths are shown in Tables 5 to 6 and 8.

[0193] (Weight loss rate when heated at 290 °C for 30 minutes in a nitrogen atmosphere after curing the temporary fixing material) Regarding the obtained temporary fixing material, after irradiating with ultraviolet light having a wavelength of 365 nm with an integrated light quantity of 20,000 mJ / cm 2 so that it became, heat treatment was performed for 30 minutes using a hot plate (manufactured by MSA Factory, "PH224 / 225") at 290 °C under a nitrogen atmosphere to cure the temporary fixing material. One of the release PET films of the cured temporary fixing material was peeled off, the cured temporary fixing material was weighed into an aluminum pan with a mass of W5 (mg), and after setting the aluminum pan in a differential thermal thermogravimetric simultaneous measurement device (manufactured by Hitachi High-Tech Sciences, "STA7200"), it was heated at 290 °C for 30 minutes under a nitrogen atmosphere, and then the weight W6 (mg) of the cured temporary fixing material was measured. The weight loss rate was calculated from the following calculation formula. The results are shown in Tables 5 to 6 and 8. Weight reduction rate (%) = 100×(W5 - W6) / W5

[0194] <Evaluation> For the temporary fixing materials obtained in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2, the following evaluations were performed. The results are shown in Tables 5 to 6 and 8.

[0195] (Fabrication of laminate) One of the release PET films of the obtained temporary fixing material was peeled off, and it was attached to a silicon wafer with a diameter of 200 mm and a thickness of 700 μm under vacuum and at 40 °C using a vacuum laminator (manufactured by Takatori Corporation, "ATM-812M"), and the temporary fixing material was cut into the shape of the silicon wafer. Next, the other release PET film of the attached temporary fixing material was peeled off, and a glass (manufactured by SCHOTT, "Tempax") with a diameter of 200 mm and a thickness of 600 μm was attached to the surface opposite to the surface attached to the silicon wafer under vacuum and at 90 °C using a pressure laminating device (manufactured by Takatori Corporation, "GWSM-300M"). From the glass side of the temporary fixing material to which the silicon wafer and the glass were attached, ultraviolet light with a wavelength of 365 nm was irradiated using an ultra-high pressure mercury lamp so that the integrated light amount was 20000 mJ / cm 2 After irradiation, the laminate was obtained by heating for 30 minutes using a hot plate (manufactured by MSA Factory, "PH224 / 225") at 290 °C under a nitrogen atmosphere.

[0196] (Laser lift-off evaluation) For the obtained laminate, laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 was pulse-irradiated onto the entire glass surface. Then, the silicon wafer side of the laminate was fixed to the adsorption stage, a suction cup hook was attached to the glass side of the laminate, and a digital force gauge (manufactured by IMADA, "ZTS-50N") was hooked onto the hook. In this way, the peeling force for peeling the glass from the cured product was measured with a digital force gauge, and the laser lift-off evaluation was performed. When the obtained peeling force was 20 N / inch or less, it was rated as "◎"; when it was greater than 20 N / inch and 30 N / inch or less, it was rated as "○"; and when it was greater than 30 N / inch, it was rated as "×", and the support peeling performance of the cured product was evaluated accordingly.

[0197] (Examples 2-3 to 2-5) In the above-mentioned "(Laser processing depth after curing the temporary fixing material)", "(Weight loss rate when heated at 290 °C for 30 minutes in a nitrogen atmosphere after curing the temporary fixing material)", and "(Fabrication of the laminate)", except that the step of irradiating ultraviolet light with a wavelength of 365 nm was not performed, temporary fixing materials and laminates were fabricated and evaluated in the same manner as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16 and Comparative Examples 2-1 to 2-2. The results are shown in Table 5.

[0198] (Example 2-6) In the above-mentioned "(Laser processing depth after curing the temporary fixing material)", "(Weight loss rate when heated at 290 °C for 30 minutes in a nitrogen atmosphere after curing the temporary fixing material)", and "(Fabrication of the laminate)", except that the step of heat treatment after ultraviolet irradiation was not performed, temporary fixing materials and laminates were fabricated and evaluated in the same manner as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16 and Comparative Examples 2-1 to 2-2. The results are shown in Table 6.

[0199] (Example 2-9) In the above-mentioned "(Laser processing depth after curing the temporary fixing material)", "(Weight loss rate when heated at 290 °C for 30 minutes in a nitrogen atmosphere after curing the temporary fixing material)", and "(Fabrication of the laminate)", except that an LED was used instead of the ultra-high pressure mercury lamp and ultraviolet light with a wavelength of 365 nm was irradiated so that the integrated light quantity became 20000 mJ / cm 2 temporary fixing materials and laminates were fabricated and evaluated in the same manner as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16 and Comparative Examples 2-1 to 2-2. The results are shown in Table 5.

[0200] (Example 2-17) The measurement of the laser processing depth after curing the temporary fixing material was performed using a laminate having the cured temporary fixing material and a support. The obtained temporary fixing material was heat-laminated at 100 °C with a speed memory of 3 using a thermal laminator (manufactured by Lami Corporation, "Leon13DX") on quartz. Thereafter, the temporary fixing material was cured in the same manner as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2. After irradiating the obtained laminate with laser light having a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm 2 from the quartz side, the laser processing depth was measured in the same manner as described above. Also, the laser processing depth when irradiated with laser light having an irradiation energy density of 400 mJ / cm 2 was measured in the same manner. Regarding the production of the temporary fixing material and the laminate, the measurement of the weight loss rate after curing the temporary fixing material, and the laser lift-off evaluation, the same methods as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2 were used. The results are shown in Table 6.

[0201] (Examples 2-18 to 2-28) In the above-mentioned "(laser processing depth after curing the temporary fixing material)", "(weight loss rate when heated at 290 °C for 30 minutes in a nitrogen atmosphere after curing the temporary fixing material)", and "(production of the laminate)", except that ultraviolet light with a wavelength of 405 nm was irradiated using an ultra-high pressure mercury lamp so that the integrated light amount was 20000 mJ / cm 2 the temporary fixing material and the laminate were produced and evaluated in the same manner as in Examples 2-1 to 2-2, 2-7 to 2-8, 2-10 to 2-16, and Comparative Examples 2-1 to 2-2. The results are shown in Tables 6 to 7.

[0202]

Table 5

[0203]

Table 6

[0204]

Table 7

[0205]

Table 8

Industrial Applicability

[0206] According to the present invention, even when irradiating with a low-energy laser beam, the support can be efficiently peeled off, and further, even when performing high-temperature processing, an adhesive film excellent in peelability with respect to an adherend can be provided. Further, according to the present invention, a cured product of the adhesive film can be provided. Furthermore, according to the present invention, a laminate having a support, the adhesive film, and a semiconductor in this order can be provided. Still further, according to the present invention, a method for manufacturing an electronic component having a step of efficiently peeling off the support even when irradiating with a low-energy laser beam and a step of easily peeling off the adherend even when performing high-temperature processing using the laminate can be provided. Also, according to the present invention, even when irradiating with a low-energy laser beam after curing, a temporary fixing material excellent in laser processing performance and capable of efficiently peeling off the support can be provided. Further, according to the present invention, a cured product of the temporary fixing material can be provided. Furthermore, according to the present invention, a laminate having the cured product can be provided. Still further, according to the present invention, a method for manufacturing an electronic component having a step of efficiently peeling off the support even when irradiating with a low-energy laser beam can be provided.

Claims

1. An adhesive film comprising an adhesive layer containing a curable adhesive, wherein the curable adhesive is a photocurable adhesive, The adhesive layer has a gel fraction of 65% by mass or more after being irradiated with light having a wavelength of 405 nm so that the integrated light amount is 20000 mJ / cm ２ and The adhesive layer has an attenuation coefficient of 1.0×10 or more with respect to light having a wavelength of 308 nm after being irradiated with light having a wavelength of 405 nm so that the integrated light quantity becomes 20000 mJ / cm ２ or more －４ ​ characterized by the adhesive film.

2. An adhesive film comprising an adhesive layer containing a curable adhesive, wherein the curable adhesive is a photocurable adhesive, wherein the adhesive layer has a gel fraction of 65% by mass or more after irradiation with light, The attenuation coefficient of the adhesive layer with respect to light having a wavelength of 308 nm after light irradiation is 1.0×10 －４ or more characterized by the adhesive film.

3. The adhesive film according to claim 1 or 2, wherein the curable adhesive contains a curable resin and a photoinitiator.

4. The adhesive film according to claim 3, wherein the curable resin contains a bismaleimide compound.

5. The adhesive film according to claim 3 or 4, wherein the extinction coefficient of the photoinitiator at a wavelength of 405 nm is 10 ml / (g·cm) or more.

6. The adhesive film according to claim 3, 4 or 5, wherein the content of the photoinitiator with respect to 100 parts by mass of the curable resin is 0.1 part by mass or more and 10 parts by mass or less.

7. The adhesive film according to claim 3, 4, 5 or 6, wherein the curable adhesive further contains an ultraviolet absorber.

8. The adhesive film according to claim 7, wherein the ultraviolet absorber contains a triazine-based ultraviolet absorber.

9. The adhesive film according to claim 7 or 8, wherein the content of the ultraviolet absorber with respect to 100 parts by mass of the curable resin is 1 part by mass or more and 30 parts by mass or less.

10. The adhesive film according to claim 3, 4, 5, 6, 7, 8 or 9, wherein the curable adhesive further contains a release agent.

11. The adhesive film according to claim 10, wherein the release agent contains at least one selected from the group consisting of a silicone-based release agent and an acrylic-based release agent.

12. The adhesive film according to claim 10 or 11, wherein the content of the release agent with respect to 100 parts by mass of the curable resin is 0.1 part by mass or more and 20 parts by mass or less.

13. The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein the gel fraction of the adhesive layer before irradiation with light is 60% by mass or less.

14. The adhesive layer has an attenuation coefficient of 1.0×10 with respect to light having a wavelength of 308 nm before irradiation with light. －４ The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein the adhesive layer has an attenuation coefficient of 1.0×10 or more with respect to light having a wavelength of 308 nm before irradiation with light.

15. The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, which has a substrate.

16. The 5% weight loss temperature when heated at a heating rate of 10 °C / min in a nitrogen atmosphere after irradiation with light having a wavelength of 405 nm so that the integrated light quantity becomes 20000 mJ / cm ２ is 300 °C or higher, and the adhesive film according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15.

17. The adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, which is used for temporarily fixing electronic components.

18. A cured product obtained by curing the adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, A cured product in which the laser processing depth is 0.10 μm or more when laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm² is pulse-irradiated. ２ ​

19. A laminate having a support, the adhesive film according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, and a semiconductor device in this order.

20. Using the laminate according to claim 19, A light irradiation step of irradiating the laminate with light from the support side, A high-temperature processing step of subjecting the laminate to heat treatment or a process involving heat generation, A support peeling step of irradiating the laminate with laser light having a wavelength of 200 nm or more and 355 nm or less from the support side to peel the support from the adhesive film, and An adhesive film peeling step of peeling the adhesive film from the semiconductor device A method for manufacturing an electronic component having.

21. A temporary fixing material containing a curable adhesive, The curable adhesive is a photo-curable adhesive, After curing by irradiating light with a wavelength of 365 nm so that the integrated light quantity becomes 20000 mJ / cm ２ when laser light with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm ２ is pulse-irradiated, the laser processing depth is 0.10 μm or more A temporary fixing material characterized by this.

22. A temporary fixing material containing a curable adhesive, When the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm² after hardening is pulse-irradiated, the laser processing depth is 0.10 µm or more ２ ​ A temporary fixing material characterized by this.

23. The laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 300 mJ / cm after hardening is pulse-irradiated is 1.0 µm or less. The temporary fixing material according to claim 21 or 22. ２ ​

24. The laser processing depth when the laser beam with a wavelength of 308 nm, a pulse width of 10 nsec, and an irradiation energy density of 400 mJ / cm ２ is irradiated with pulsed light is 1.0 μm or less, the temporary fixing material according to claim 21, 22, or 23.

25. The curable adhesive contains a curable resin, and the curable resin contains a resin having an imide skeleton as a repeating unit of the main chain. The temporary fixing material according to claim 21, 22, 23 or 24.

26. The temporary fixing material according to claim 25, wherein the content of the resin having an imide skeleton as a repeating unit of the main chain is 65 parts by mass or more in 100 parts by mass of the curable resin.

27. The curable adhesive contains an ultraviolet absorber or an ultraviolet scattering agent. The temporary fixing material according to claim 21, 22, 23, 24, 25 or 26.

28. The ultraviolet absorber or the ultraviolet scattering agent contains a triazine-based ultraviolet absorber or titanium oxide. The temporary fixing material according to claim 27.

29. The curable adhesive contains a photoinitiator. The temporary fixing material according to claim 21, 22, 23, 24, 25, 26, 27 or 28.

30. The temporary fixing material according to claim 21, 22, 23, 24, 25, 26, 27, 28 or 29, wherein the weight loss rate when heated at 290 ° C for 30 minutes in a nitrogen atmosphere after curing is 7% or less.

31. A cured product obtained by curing the temporary fixing material according to claim 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

32. Having a support, the cured product according to claim 31, and a semiconductor device in this order, The support has a light transmittance of 50% or more at a wavelength of 300 nm or more and 400 nm or less. A laminate. **Claim 33** A method for manufacturing an electronic component, characterized in that a laminate including a support, a cured product of a temporary fixing material, and a semiconductor device in this order is provided. Laser light having a wavelength of 308 nm or more and 355 nm or less, a pulse width of 100 nsec or less, and an irradiation energy density of 500 mJ / cm ２ is pulse-irradiated from the support side to have a support peeling step of peeling the support from the laminate ​

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