Adhesive film and wound body

Abstract

The purpose of the present invention is to provide: an adhesive film capable of preventing adhesive ooze even when stored in a roll shape; and a wound body of the adhesive film. The present invention pertains to an adhesive film which has an adhesive layer, and in which the adhesive layer satisfies the following first configuration and / or second configuration. First configuration: When the shear storage elastic modulus at T°C measured by dynamic viscoelasticity measurement is denoted as G'(T), mathematical formulae (A) and (B) are simultaneously satisfied. (A): 10≤G'(0) / G'(200)≤20000 (B): 105Pa≤G'(0)≤1010Pa Second configuration: When a load F (gf) is measured by a tack tester and the load after t seconds from contact with a probe is denoted as F(t), mathematical formula (C) is satisfied. (C): 0.60≤F(30) / F(1)≤0.96

Description

Adhesive films and wound bodies

[0001] This invention relates to adhesive films and wound bodies.

[0002] During the processing of electronic components such as semiconductors, in order to facilitate handling of the electronic components and prevent damage, they are often protected by fixing them to a support plate via an adhesive composition or by attaching adhesive tape to them. For example, when grinding a thick film wafer cut from a high-purity silicon single crystal to a predetermined thickness to produce a thin film wafer, the thick film wafer is bonded to a support plate via an adhesive composition.

[0003] Thus, adhesive compositions and adhesive tapes used for electronic components are required to have high adhesiveness sufficient to firmly fix electronic components during the processing process, as well as to be able to be peeled off without damaging the electronic components after the process is completed (hereinafter also referred to as "high adhesion and easy peeling"). As a means of achieving high adhesion and easy peeling, 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 the side chain or main chain of the polymer. By utilizing the fact that the polymer hardens when exposed to ultraviolet light due to the presence of a radiation-polymerizable functional group, the adhesive strength is reduced by irradiating with ultraviolet light during peeling, allowing for peeling without leaving any adhesive residue.

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

[0005] In recent years, the thinning and miniaturization of semiconductor products has led to the stacking of numerous semiconductor chips on wafers. Because wafers with such a large number of stacked semiconductor chips form large bumps, adhesive tapes applied to these bumpy surfaces require both the flexibility to conform to the unevenness and the thickness to fill in the bumps.

[0006] On the other hand, adhesive tapes are handled in roll form for convenience in transportation and storage. However, when conventional adhesive tapes are sold in roll form, the adhesive layer can sometimes flow and leak out from the edges. This is especially true for adhesive tapes that are applied to wafers with large bumps, as they are very soft at room temperature and have a large thickness, making adhesive leakage a common problem.

[0007] The present invention aims to provide an adhesive film that can suppress the leakage of adhesive even when stored in a roll, and a winding of the adhesive film.

[0008] Disclosure 1 is an adhesive film having an adhesive layer, wherein the adhesive layer satisfies at least one of the following first configuration or second configuration. First configuration: When the shear storage modulus at T°C measured by dynamic viscoelasticity measurement is G'(T), the following formulas (A) and (B) are simultaneously satisfied. 10 ≤ G'(0) / G'(200) ≤ 20000 ... (A) 10 ５ Pa ≤ G'(0) ≤ 10 １０ Pa...(B) Second configuration: When the load F(gf) is measured with a tack tester, and the load at t seconds after the probe contact is F(t), the following formula (C) is satisfied. 0.60 ≤ F(30) / F(1) ≤ 0.96...(C) The present disclosure 2 is that the G'(200) is 10 ８ The adhesive film according to Disclosure 1 is Pa or less. Disclosure 3 is an adhesive film according to Disclosure 3 in which the G'(200) is 10 ３The adhesive film according to Disclosure 1 or 2, wherein the adhesive layer has a pressure of Pa or higher. Disclosure 4 is the adhesive film according to any one of Disclosures 1 to 3, wherein the adhesive layer has a thickness of 20 μm or more and 200 μm or less. Disclosure 5 is the adhesive film according to any one of Disclosures 1 to 4, wherein the adhesive layer has a gel fraction of 0% or more and 90% or less. Disclosure 6 is the adhesive film according to any one of Disclosures 1 to 5, wherein the adhesive layer has a glass transition temperature of -5°C or more and 50°C or less. Disclosure 7 is the adhesive film according to any one of Disclosures 1 to 6, wherein the adhesive layer is formed using an adhesive composition, the adhesive composition contains an adhesive resin and a crosslinking agent, and the adhesive resin contains a base resin. Disclosure 8 is the adhesive film according to Disclosure 7, wherein the adhesive layer contains a crosslinked body having a structure derived from the base resin and a structure derived from the crosslinking agent. Disclosure 9 is an adhesive film according to Disclosure 7 or 8, wherein the base resin contains a resin having an imide skeleton as the repeating unit of the main chain. Disclosure 10 is an adhesive film according to Disclosure 9, wherein the resin having an imide skeleton as the repeating unit of the main chain has a polar functional group. Disclosure 11 is an adhesive film according to Disclosure 10, wherein the polar functional group contains a carboxyl group. Disclosure 12 is an adhesive film according to any one of Disclosures 9 to 11, wherein the resin having an imide skeleton as the repeating unit of the main chain has a weight-average molecular weight of 50,000 or more. Disclosure 13 is an adhesive film according to any one of Disclosures 7 to 12, wherein the adhesive resin contains a compound having a reactive carbon-carbon double bond. Disclosure 14 is an adhesive film according to any one of Disclosures 7 to 13, wherein the crosslinking agent contains a crosslinking agent having an epoxy group. Disclosure 15 is an adhesive film according to any one of Disclosures 7 to 14, wherein the crosslinking agent content is 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the base resin. Disclosure 16 is an adhesive film according to any one of Disclosures 7 to 15, wherein the adhesive composition contains an inorganic filler. Disclosure 17 is an adhesive film according to Disclosure 16, wherein the inorganic filler content is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the adhesive resin.Disclosure 18 is an adhesive film according to any one of Disclosures 1 to 17, wherein the adhesive film has a thickness of 20 μm or more and 200 μm or less. Disclosure 19 is an adhesive film according to any one of Disclosures 1 to 18, further comprising a substrate. Disclosure 20 is an adhesive film according to Disclosure 19, further comprising a second adhesive layer, wherein the adhesive layer, the substrate, and the second adhesive layer are in this order. Disclosure 21 is an adhesive film according to any one of Disclosures 1 to 20, used for temporary fixing. Disclosure 22 is an adhesive film according to any one of Disclosures 1 to 20, used for temporary fixing of electronic components. Disclosure 23 is a wound body in which an adhesive film according to any one of Disclosures 1 to 22 is wound. The present invention will be described in detail below.

[0009] The adhesive film of the present invention has an adhesive layer, the adhesive layer satisfies at least one of the following first configuration or second configuration described later. First configuration: When the shear storage modulus at T°C measured by dynamic viscoelasticity measurement is G'(T), the following formulas (A) and (B) are simultaneously satisfied. 10 ≤ G'(0) / G'(200) ≤ 20000 ... (A) 10 ５ Pa ≤ G'(0) ≤ 10 １０Pa... (B) By using an adhesive layer that simultaneously satisfies the above formulas (A) and (B), it is possible to sufficiently follow large unevenness and suppress the bleeding of the glue even when stored in a roll shape. Since the bleeding of the glue can be further suppressed, the above G'(0) / G'(200) is preferably greater than 10, more preferably 20 or more, still more preferably 30 or more, even more preferably 50 or more, preferably less than 20000, more preferably 17000 or less, still more preferably 15000 or less, and even more preferably 13000 or less. The above G'(0) and G'(200) can be adjusted, for example, by the type of adhesive resin constituting the adhesive layer, the content of the inorganic filler, the film forming process including UV irradiation on the film, etc. Also, by introducing a crosslinked structure by using a crosslinking agent or by using a resin having an imide skeleton as a repeating unit of the main chain in the base resin described later, the above formulas G'(0) and G'(200) can be easily adjusted within the ranges of the above formulas (A) and (B). Incidentally, the above G'(0) and G'(200) can be measured, for example, by using a viscoelastic spectrometer (manufactured by IT Measurement Control Co., Ltd., "DVA-200" or equivalent), and performing dynamic viscoelastic measurement under the conditions of a shear direction, a frequency of 10 Hz, a temperature rising rate of 10°C / min, and a temperature range from -50°C to 300°C. Also, in the measurement, after stacking the above adhesive layers so that the thickness becomes about 1 mm, the measurement of the shear storage modulus is performed.

[0010] The above G'(200) is 10 ８ Pa or less is preferable. When the above G'(200) is within the above range, the flexibility of the adhesive film can be further enhanced, and even when the adherend has large unevenness, the unevenness can be filled. The above G'(200) is 10 ７ Pa or less is more preferable, and 10 ６ Pa or less is still more preferable.

[0011] The above G'(200) is 10 ３It is preferable that it be Pa or higher. When G'(200) is within the above range, the leakage of adhesive can be further suppressed even when stored in roll form. G'(200) is 2 × 10 ３ It is more preferable that the pressure be Pa or higher, and 3 × 10 ３ It is even more preferable that the pressure be Pa or higher.

[0012] The above G'(0) is 10 １０ It is preferable that it is less than Pa. When G'(0) is within the above range, the flexibility of the adhesive film can be further increased and the adhesive film can be stored in a roll without breaking. G'(0) is 10 ９ It is more preferable that it be Pa or less, 10 ８ It is even more preferable that it be Pa or less.

[0013] The above G'(0) is 10 ５ It is preferable that it is greater than Pa. When G'(0) is within the above range, the leakage of adhesive can be further suppressed even when stored in roll form. G'(0) is 5 × 10 ５ It is more preferable that it be Pa or higher, 10 ６ It is even more preferable that the pressure be Pa or higher.

[0014] The adhesive layer satisfies at least one of the first configuration or the second configuration below. Second configuration: When the load F(gf) is measured with a tack tester, and the load at t seconds after the probe contact is F(t), the following formula (C) is satisfied. 0.60 ≤ F(30) / F(1) ≤ 0.96...(C) By using an adhesive layer that satisfies the above formula (C), it is possible to sufficiently follow the unevenness and to suppress the leakage of adhesive when stored in a roll. To further suppress the leakage of adhesive, it is preferable that F(30) / F(1) be 0.63 or more, more preferably 0.65 or more, even more preferably 0.69 or more, preferably 0.95 or less, more preferably 0.91 or less, even more preferably 0.87 or less, and even more preferably 0.83 or less. The above F(t) can be obtained, for example, by using a tack tester (RHESCA "TAC1000" tacking tester or equivalent) and pressing the probe against the sample for 30 seconds under the following conditions: probe and stage temperature of 25°C, probe diameter of 5 mm, probe indentation distance of 0.005 mm, probe pressing speed of 0.01 mm / s, pressing and holding time of 30 seconds, and touch detection level of 10 gf, and measuring the load t seconds after contact between the sample and the probe. Furthermore, the above F(t) is obtained by adopting the average value of three measurements.

[0015] The above F(1) is preferably 10 gf or more and 1000 gf or less. When F(1) is within the above range, the flexibility of the adhesive film can be further increased, and even if the adherend has large irregularities, the irregularities can be filled in. The above F(1) is more preferably 20 gf or more, even more preferably 25 gf or more, even more preferably 500 gf or less, and even more preferably 490 gf or less.

[0016] The above F(30) is preferably 10 gf or more and 500 gf or less. When F(30) is within the above range, the leakage of adhesive can be further suppressed even when stored in roll form. The above F(30) is more preferably 20 gf or more, even more preferably 25 gf or more, even more preferably 400 gf or less, and even more preferably 390 gf or less.

[0017] The maximum value of F(t) above is F(t) ＭＡＸ It is preferable that the F(t) is between 10 gf and 1000 gf. ＭＡＸ Because it falls within the above range, even when stored in roll form, the leakage of adhesive can be further suppressed. The above F(t) ＭＡＸ It is more preferably 20 gf or more, even more preferably 25 gf or more, even more preferably 500 gf or less, and even more preferably 490 gf or less. ＭＡＸ Since t in this case is the time at which F is maximized, it does not need to be an integer.

[0018] Above F(30) / F(t) ＭＡＸ It is preferable that it is between 0.50 and 0.95. The above F(30) / F(t) ＭＡＸ Because the above range is maintained, even when stored in roll form, the leakage of adhesive can be further suppressed. The above F(30) / F(t) ＭＡＸ It is more preferably 0.55 or higher, even more preferably 0.60 or higher, even more preferably 0.90 or lower, and even more preferably 0.80 or lower.

[0019] The adhesive layer described above preferably has a thickness of 20 μm or more and 200 μm or less. If the thickness of the adhesive layer is greater than or equal to the lower limit, it can fill in any irregularities in the adherend, and if it is less than or equal to the upper limit, it can further suppress the leakage of adhesive even when stored in a roll. The thickness of the adhesive layer is more preferably 23 μm or more, even more preferably 25 μm or more, even more preferably 170 μm or less, and even more preferably 150 μm or less.

[0020] The above adhesive layer preferably has a gel fraction of 0% or more and 90% or less. Having the gel fraction of the adhesive layer within the above range makes it easier to satisfy the above formulas (A), (B), and (C). The gel fraction of the adhesive layer is more preferably 10% or more, even more preferably 20% or more, even more preferably 80% or less, and even more preferably 75% or less. The above gel fraction can be measured by the following method. Only the adhesive layer is removed from the obtained adhesive film. ０ (g) Remove, immerse in toluene, and shake in a shaker at a temperature of 23 degrees Celsius and 200 rpm for 24 hours. After shaking, use a metal mesh (mesh size #200, W １ (g)) is used to separate the toluene and the adhesive layer that has absorbed and swollen with toluene, and the separated adhesive layer is dried at 110°C for 1 hour. Mass W of the adhesive layer containing the metal mesh after drying. ２ Measure (g) and use the following formula to determine the gel fraction (%) of the adhesive layer: Gel fraction (%) = 100 × (W ２ -W １ ) / W ０ (W ０ : Mass of the initial adhesive layer, W １ Initial mass of the metal mesh, W ２ (Mass of the adhesive layer containing the metal mesh after drying)

[0021] The adhesive layer described above preferably has a glass transition temperature of -5°C or higher and 50°C or lower. Having the glass transition temperature of the adhesive layer within this range makes it easier to satisfy the above formulas (A), (B), and (C). The glass transition temperature of the adhesive layer is more preferably 0°C or higher, even more preferably 5°C or higher, even more preferably 40°C or lower, and even more preferably 35°C or lower. The glass transition temperature can be measured by the dynamic viscoelasticity measurement described above, and the temperature at which a maximum of loss tangent (tanδ) due to micro-Brownian motion appears among the maximums obtained by the dynamic viscoelasticity measurement is the glass transition temperature.

[0022] The above adhesive layer is formed using an adhesive composition, which preferably contains an adhesive resin and a crosslinking agent, and the adhesive resin preferably contains a base resin. By using an adhesive composition containing an adhesive resin containing a base resin and a crosslinking agent as the material for the above adhesive layer, and by ensuring that the formed adhesive layer contains a crosslinked body as described later, the above formulas (A), (B), and (C) can be more easily satisfied.

[0023] The adhesive layer preferably contains a crosslinked body having a structure derived from the base resin and a structure derived from the crosslinking agent. By containing a crosslinked body having a structure derived from the base resin and a structure derived from the crosslinking agent in the adhesive layer, the above formulas (A), (B), and (C) can be more easily satisfied.

[0024] Examples of the above-mentioned base resins include resins having an imide skeleton as the repeating unit of the main chain, and phenoxy resins. In particular, it is preferable that the above-mentioned base resin contains a resin having an imide skeleton as the repeating unit of the main chain, as this makes it easier to satisfy the above formulas (A), (B), and (C). The above-mentioned resin having an imide skeleton as the repeating unit of the main chain may contain multiple types of resins having imide skeletons as the repeating unit of the main chain.

[0025] The resin having the above-mentioned imide skeleton as the repeating unit of the main chain preferably has polar functional groups. The presence of polar functional groups in the resin having the above-mentioned imide skeleton as the repeating unit of the main chain makes it easier to crosslink with the above-mentioned crosslinking agent, and makes it easier to satisfy the above formulas (A), (B), and (C). The above-mentioned polar functional group may be one type or may contain multiple types. Examples of the above-mentioned polar functional group include carboxyl groups, amino groups, hydroxyl groups, etc. Among these, it is preferable that the above-mentioned polar functional group contains a carboxyl group because it makes it easier to satisfy the above formulas (A), (B), and (C).

[0026] The polar functional group is preferably located in at least one of the side chains and terminals of a resin having the imide skeleton as the repeating unit of the main chain. Because the side chains and terminals of the resin having the imide skeleton as the repeating unit of the main chain are highly reactive, having a crosslinkable functional group in the side chain or terminal makes it easier for the crosslinking agent to react with the polar functional group, resulting in a crosslinked product with a higher degree of crosslinking. In particular, since the reactivity is high at both terminals, it is more preferable for the polar functional group to be present at both terminals, and even more preferable for it to be present in the side chains in addition to both terminals. The presence of polar functional groups not only at both terminals but also in the side chains increases the number of crosslinking sites, resulting in a crosslinked product with a more complex crosslinking structure. As a result, it becomes easier to satisfy the above formulas (A), (B), and (C).

[0027] The resin having the above-mentioned imide skeleton as the repeating unit of the main chain preferably has a weight-average molecular weight of 50,000 or more. Having a weight-average molecular weight of 50,000 or more for the resin having the above-mentioned imide skeleton as the repeating unit of the main chain makes it easier to satisfy the above formulas (A), (B), and (C). From a similar viewpoint, the weight-average molecular weight of the resin having the above-mentioned imide skeleton as the repeating unit of the main chain is more preferably 60,000 or more, more preferably 200,000 or less, and more preferably 150,000 or less. In this specification, the weight-average molecular weight is measured as polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). As a column, for example, HR-MB-M (manufactured by Waters) can be used.

[0028] Specific examples of resins having the above-mentioned polar functional groups and the above-mentioned imide skeleton as the repeating unit of the main chain include resins having the constituent unit represented by the following formula (1) and having polar functional groups at least one of the terminal and side chains.

[0029]

[0030] In formula (1), P １ represents an aromatic group, Q １ This represents a linear, branched, or cyclic substituted or unsubstituted aliphatic group.

[0031] In the above formula (1), P１ The above P is preferably an aromatic group having 5 to 50 carbon atoms. １ The presence of an aromatic group with 5 to 50 carbon atoms results in superior heat resistance for the adhesive film of the present invention. That is, the adhesive film of the present invention can more effectively suppress outgassing, voids between the film and the adherend, and lifting during high-temperature processing, and can also more effectively suppress enhanced adhesion during high-temperature processing and adhesive residue during peeling. １ Specific examples include structures derived from aromatic acid anhydrides, which will be discussed later.

[0032] In the above formula (1), Q １ It is preferable that the aliphatic group is linear, branched, or cyclic, substituted or unsubstituted, having 2 to 100 carbon atoms. １ Because the aliphatic group is linear, branched, or cyclic substituted or unsubstituted with 2 to 100 carbon atoms, the adhesive layer has superior light transmittance, making it easier to cure the adhesive resin when it contains a compound having a reactive carbon-carbon double bond, as described later. Furthermore, the adhesive layer has superior flexibility, allowing the adhesive film of the present invention to conform well to substrates with uneven surfaces and to be more easily peeled off when no longer needed. １ Specific examples include structures derived from aliphatic diamine compounds, which will be discussed later.

[0033] A resin having a structural unit represented by the above formula (1) and having a polar functional group may have at least one structural unit selected from the group consisting of the structural unit represented by the following formula (2-1) and the structural unit represented by the following formula (2-2).

[0034]

[0035] In formula (2-1), P ２ represents an aromatic group, Q ２ P represents a group having a substituted or unsubstituted aromatic structure, and in formula (2-2), P ３ represents an aromatic group, S １represents a substituted or unsubstituted branched aliphatic group, or a substituted or unsubstituted aromatic group, and X represents a polar functional group.

[0036] P in equation (2-1) above ２ and P in formula (2-2) above ３ Each of these is preferably an aromatic group having 5 to 50 carbon atoms. ２ and P ３ Because the aromatic group has 5 to 50 carbon atoms, the adhesive film of the present invention exhibits superior heat resistance. That is, the adhesive film of the present invention can further suppress outgassing, voids between the film and the adherend, and lifting during high-temperature processing, and can further suppress enhanced adhesion and adhesive residue. ２ and P ３ Specific examples include structures derived from aromatic acid anhydrides, which will be discussed later.

[0037] In the above equation (2-1), Q ２ It is preferable that the group has an aromatic structure with 5 to 50 carbon atoms, either substituted or unsubstituted. ２ The presence of a group having an aromatic structure with 5 to 50 carbon atoms, whether substituted or unsubstituted, results in superior heat resistance for the adhesive film of the present invention. That is, the adhesive film of the present invention can more effectively suppress outgassing, voids between the film and the adherend, and lifting during high-temperature processing, as well as enhance adhesion during high-temperature processing and reduce adhesive residue during peeling. ２ Specific examples include structures derived from aromatic diamine compounds, which will be discussed later.

[0038] In the above formula (2-2), S １ It is preferable that the above S is a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. １ However, by being a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms, the adhesive layer becomes more flexible, allowing the adhesive film of the present invention to exhibit high conformability to adherends with uneven surfaces, and to be peeled off more easily when no longer needed.

[0039] In the above formula (2-2), S １ is an aromatic group having an aromatic ester group or an aromatic ether group, and the S １ In this invention, the aromatic ester group or aromatic ether group is preferably bonded to a polar functional group. Here, "aromatic ester group" means a group in which an ester group is directly bonded to an aromatic ring, and "aromatic ether group" means a group in which an ether group is directly bonded to an aromatic ring. By making the part bonded to the ester group or ether group an aromatic group in this way, the adhesive film of the present invention becomes more heat resistant. That is, the adhesive film of the present invention can more effectively suppress outgassing, voids between the film and the adherend, and lifting during high-temperature processing, and can also more effectively suppress enhanced adhesion during high-temperature processing and adhesive residue during peeling.

[0040] In a resin having a structural unit represented by formula (1) and having a polar functional group on at least one of its terminal and side chains, the preferred lower limit of the content of the structural unit represented by formula (1) is 30 mol%, the preferred upper limit is 90 mol%, the more preferred lower limit is 50 mol%, and the more preferred upper limit is 80 mol%. When a resin having a structural unit represented by formula (1) and having a polar functional group on at least one of its terminal and side chains also has a structural unit represented by formula (2-1), the preferred lower limit of the content of the structural unit represented by formula (2-1) is 5 mol%, the preferred upper limit is 50 mol%, the more preferred lower limit is 10 mol%, the more preferred upper limit is 30 mol%, and the still more preferred upper limit is 20 mol%. When a resin having a structural unit represented by formula (1) and having a polar functional group on at least one of its terminal and side chains also has a structural unit represented by formula (2-2), the preferred lower limit of the content of the structural unit represented by formula (2-2) is 10 mol%, the preferred upper limit is 50 mol%, the more preferred lower limit is 20 mol%, and the more preferred upper limit is 30 mol%. By having the content of each structural unit in the structural unit represented by formula (1), the structural unit represented by formula (2-1), and the structural unit represented by formula (2-2) within the above ranges, the adhesive film of the present invention can more effectively suppress outgassing, voids between the film and the adherend, and lifting during high-temperature processing, and can be more easily peeled off from the adherend after high-temperature processing. The constituent units represented by formula (1), formula (2-1), and formula (2-2) may have a block structure consisting of block components arranged in a continuous sequence, or they may have a random structure in which the constituent units are arranged randomly.

[0041] As a method for producing a resin having the above-mentioned polar functional group and having the above-mentioned imide skeleton as the repeating unit of the main chain, for example, a resin having the above-mentioned polar functional group and having the above-mentioned imide skeleton as the repeating unit of the main chain can be obtained by reacting a diamine compound with an aromatic acid anhydride. Alternatively, an imide compound can be prepared by reacting a diamine compound with an aromatic acid anhydride, and the functional group of the imide compound can be reacted with a compound having a functional group that reacts with the functional group and a polar functional group (hereinafter referred to as a functional group-polar functional group-containing compound).

[0042] The above-mentioned diamine compound can be either an aliphatic diamine compound or an aromatic diamine compound. By using an aliphatic diamine compound as the above-mentioned diamine compound, the adhesive film of the present invention will have superior light transmittance, and therefore, when the adhesive resin contains a compound having a reactive carbon-carbon double bond as described later, it will be easier to cure. Furthermore, the adhesive film of the present invention will have superior flexibility, exhibit high conformability to adherends with uneven surfaces, and will be easier to peel off when no longer needed. Furthermore, by using an aromatic diamine compound as the above-mentioned diamine compound, the adhesive film of the present invention will have superior heat resistance. The above-mentioned diamine compounds may be used individually or in combination of two or more types.

[0043] Examples of the above aliphatic diamine compounds include 1,10-diaminodecane, 1,12-diaminododecane, dimeramine, 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-diaminomentane, 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, 1,3-bisaminomethylcyclohexane, and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane.

[0044] Examples of the above aromatic diamine compounds 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-bisaminomethylbenzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino -3,5-diethylphenyl)methane, 9,9'-bis(4-amino-3-ethylphenyl)fluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenylsulfone, 3,3'-diaminophenylsulfone, 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-tolidine sulfone, 5,5'-methylenebis(anthranilic acid), 1,3-bis(4-aminophenoxy)-2,Examples include 2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylenediamines (e.g., Jeffamine D-230, D400, D-2000, and D-4000 from Huntsman), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, p-xylylenediamine, etc.

[0045] Examples of the above aromatic acid anhydrides include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and 2,3,5,6-pyridine. Tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyl diphthalic 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, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3, Examples of carboxylic acid anhydrides include 5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4'-oxydiphthalic acid, 4,4'-oxydiphthalic acid, 2,3',3,4'-tetracarboxydiphenyl oxide, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, and 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid).

[0046] The above functional group-polar functional group-containing compound is selected and used according to the functional group of the terminal or side chain of the imide compound. For example, if the functional group of the terminal or side chain of the imide compound is a hydroxyl group, the above functional group-polar functional group-containing compound may be a polar functional group-containing compound having a carboxyl group or an isocyanate group. Also, for example, if the functional group of the terminal or side chain of the imide compound is a carboxyl group, the above functional group-polar functional group-containing compound may be a polar functional group-containing compound having a hydroxyl group or a glycidyl group. Examples of polar functional group-containing compounds having a carboxyl group include terephthalic acid and adipic acid. Examples of polar functional group-containing compounds having an isocyanate group include toluene diisocyanate and hexamethylene diisocyanate.

[0047] The preferred lower limit for the content of the crosslinked material in 100 parts by mass of the adhesive resin is 10 parts by mass, and the preferred upper limit is 90 parts by mass. Having the crosslinked material content within this range makes it easier to satisfy the above formulas (A), (B), and (C). From a similar viewpoint, a more preferred lower limit for the crosslinked material content is 20 parts by mass, and a more preferred upper limit is 80 parts by mass.

[0048] The crosslinking agent that forms the basis of the crosslinked body only needs to be able to crosslink the base resin, and examples include crosslinking agents having epoxy groups and crosslinking agents having isocyanate groups. In particular, it is preferable that the crosslinking agent contains an epoxy group because it can easily form an adhesive layer that satisfies the above formulas (A), (B), and (C), and especially when the base resin is a resin having the above imide skeleton as the repeating unit of the main chain, it is preferable to use a crosslinking agent having epoxy groups.

[0049] The content of the crosslinking agent is preferably 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the base resin. Having the crosslinking agent content within this range makes it easier to satisfy the above formulas (A), (B), and (C). From a similar viewpoint, the crosslinking agent content is more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, even more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.

[0050] The above adhesive resin preferably contains a compound having a reactive carbon-carbon double bond. When the above adhesive resin contains a compound having a reactive carbon-carbon double bond, it can be cured by heat or light irradiation by incorporating a polymerization initiator into the adhesive layer (adhesive composition). When the compound having a reactive carbon-carbon double bond is cured, the heat resistance of the resulting adhesive film is improved and the tackiness is reduced, thereby further suppressing enhanced adhesion during high-temperature processing and adhesive residue during peeling.

[0051] Examples of compounds having the above-mentioned reactive carbon-carbon double bond include compounds having a radically reactive reactive carbon-carbon double bond. More specifically, examples include compounds having a maleimide group, a citracomide group, a vinyl ether group, an allyl group, a (meth)acryloyl group, and the like. Among these, from the viewpoint of the heat resistance of the adhesive film of the present invention, compounds having at least one group selected from the group consisting of a maleimide group and a (meth)acryloyl group are preferred, and compounds having a maleimide group are more preferred. In this specification, carbon-carbon double bonds contained in aromatic rings are not treated as the above-mentioned "reactive carbon-carbon double bond".

[0052] As the compound having the maleimide group described above, monomers or oligomers having a maleimide group are preferably used.

[0053] The monomer or oligomer having the maleimide group described above preferably has a group derived from a diamine compound. Either an aliphatic diamine compound or an aromatic diamine compound can be used as the diamine compound, but an aliphatic diamine compound is preferred. That is, the compound having the maleimide group is more preferably an aliphatic group derived from a diamine compound. By using an aliphatic diamine compound as the diamine compound, the adhesive layer becomes more light-transmitting, making it easier to cure compounds having reactive carbon-carbon double bonds. Furthermore, the adhesive layer becomes more flexible, allowing the adhesive film of the present invention to exhibit high conformability to substrates with uneven surfaces, and to be more easily peeled off when no longer needed.

[0054] Among the above aliphatic diamine compounds, dimer amines are preferred from the viewpoint of light transmittance, flexibility, and compatibility with solvents and other components. Dimer amines are diamine compounds obtained by reducing and aminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples include linear, monocyclic, and polycyclic dimer amines. Dimer amines may contain carbon-carbon double bonds or may be hydrogenated products with added hydrogen.

[0055] As the aliphatic group derived from the above dimer amine, at least one group selected from the group consisting of the group represented by formula (3-1), the group represented by formula (3-2), the group represented by formula (3-3), and the group represented by formula (3-4) is preferred. Among these, the group represented by formula (3-2) is more preferred.

[0056]

[0057] In formulas (3-1) to (3-4), R １ ~R １６ Each of the symbols independently represents a linear or branched hydrocarbon group, and * represents a bonding site. The bonding site * bonds to a nitrogen atom.

[0058] In the above equations (3-1) to (3-4), R １ ~R １６The hydrocarbon group represented by may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In particular, 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 １６ The preferred lower limit for the total number of carbon atoms is 7, and the preferred upper limit is 50. When the total number of carbon atoms is within the above range, the adhesive layer has excellent light transmittance and flexibility, and the resin having the imide skeleton as the repeating unit of the main chain, as described later, has better compatibility with other components and solvents in the adhesive layer. A more preferred lower limit for the total number of carbon atoms is 9, a more preferred upper limit is 35, an even more preferred lower limit is 12, an even more preferred upper limit is 25, an even more preferred lower limit is 14, and an even more preferred upper limit is 18.

[0059] The optical isomers of the group represented by formula (3-1), the group represented by formula (3-2), the group represented by formula (3-3), and the group represented by formula (3-4) are not particularly limited and include any optical isomer.

[0060] The monomer or oligomer having the maleimide group described above is preferably a bismaleimide compound from the viewpoint of heat resistance. Examples of the bismaleimide compound include BMI-689 (manufactured by Designer Molecules).

[0061] As the compound having the reactive carbon-carbon double bond described above, a resin having a functional group having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain can also be used. Examples of resins having a functional group having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain include resins having a maleimide group and an imide skeleton as the repeating unit of the main chain. In the case of the resin having a maleimide group and an imide skeleton as the repeating unit of the main chain described above, the maleimide group is the functional group having the reactive carbon-carbon double bond described above.

[0062] The resin having the above-mentioned functional groups having reactive carbon-carbon double bonds and an imide skeleton as the repeating unit of the main chain has a preferred upper limit of 4000 for the functional group equivalent (weight-average molecular weight / number of functional groups having reactive carbon-carbon double bonds) of the functional groups having reactive carbon-carbon double bonds. When the functional group equivalent of the above-mentioned functional groups having reactive carbon-carbon double bonds is 4000 or less, the adhesive film of the present invention exhibits superior heat resistance. This is thought to be because having functional groups having reactive carbon-carbon double bonds at a certain density or higher in the resin molecule shortens the crosslinking distance, thereby further suppressing increased adhesion during high-temperature processing. A more preferred upper limit for the functional group equivalent of the above-mentioned functional groups having reactive carbon-carbon double bonds is 3000, and an even more preferred upper limit is 2000. Furthermore, there is no particular preferred lower limit for the functional group equivalent of the above-mentioned functional groups having reactive carbon-carbon double bonds, but the practical lower limit is around 600.

[0063] The resin having the above-mentioned functional group having a reactive carbon-carbon double bond and having an imide skeleton as the repeating unit of the main chain has a preferred lower limit of weight-average molecular weight of 1,000 and a preferred upper limit of 100,000. A weight-average molecular weight of 1,000 or more for the above-mentioned functional group having a reactive carbon-carbon double bond and having an imide skeleton as the repeating unit of the main chain facilitates the formation of the adhesive layer, and the formed adhesive layer exhibits a certain degree of flexibility. Therefore, the adhesive film of the present invention exhibits high conformability to adherends with uneven surfaces and can be more easily peeled off when no longer needed. A weight-average molecular weight of 100,000 or less for the above-mentioned functional group having a reactive carbon-carbon double bond and having an imide skeleton as the repeating unit of the main chain prevents the solubility of the above-mentioned functional group having a reactive carbon-carbon double bond and having an imide skeleton as the repeating unit of the main chain from becoming too low in the solvent. The weight-average molecular weight of the resin having the above-mentioned functional group having a reactive carbon-carbon double bond and having an imide skeleton as the repeating unit of the main chain is more preferably 1,500 as the lower limit, more preferably 50,000 as the upper limit, and even more preferably 2,000 or more and less than 20,000.

[0064] In a resin having a functional group having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain, the functional group having a reactive carbon-carbon double bond may be located on either the side chain or the terminal, but it is preferable that it be present at both terminals, and more preferably that it be present on the side chain in addition to both terminals. The functional group having a reactive carbon-carbon double bond at both terminals of the resin having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain is highly reactive, and the adhesive layer can be cured more sufficiently by light irradiation or heating. As a result, enhanced adhesion during high-temperature processing and adhesive residue when peeling off the adhesive film can be further suppressed. Furthermore, the presence of a functional group having a reactive carbon-carbon double bond on the side chain of the resin having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain results in superior peelability of the adhesive film of the present invention. This is thought to be because the cross-linking distance is shortened, which further suppresses enhanced adhesion. Furthermore, by having a functional group having a reactive carbon-carbon double bond in the side chain of a resin having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain, it becomes easy to adjust the functional group equivalent to 4000 or less while maintaining a weight-average molecular weight of 1000 or more. As a result, the adhesive layer has sufficient initial adhesive strength, and at the same time, it is possible to further suppress the enhancement of adhesion during high-temperature processing of the adhesive film and the adhesive residue when peeling.

[0065] As described above, in a resin having the above-mentioned reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain, the functional group having the reactive carbon-carbon double bond may be located on either the side chain or the terminal. If either the side chain or the terminal does not have a reactive carbon-carbon double bond (i.e., if there is a functional group that does not have such a carbon-carbon double bond), examples of such functional groups that do not have a reactive carbon-carbon double bond include aliphatic groups, alicyclic groups, aromatic groups, acid anhydride groups, amino groups, etc. Specifically, examples include acid anhydrides that are raw materials for resins having the above-mentioned functional group having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain, and unreacted terminal components of diamine compounds. If a resin having the above-mentioned functional group having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain has two or more functional groups that do not have the above-mentioned carbon-carbon double bond on either the side chain or the terminal, each of the functional groups that do not have a carbon-carbon double bond may be the same or different.

[0066] Examples of resins having a functional group with a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain include, for example, a resin having a structural unit represented by formula (1) above and having a functional group with a reactive carbon-carbon double bond at least one of the terminal and side chains.

[0067] A resin having a functional group having the above-mentioned reactive carbon-carbon double bond and having an imide skeleton as the repeating unit of the main chain is, in formula (1) above, Q １ It is preferable that the aliphatic group is derived from a diamine compound. In particular, resins having a functional group having the reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain exhibit excellent compatibility with solvents and other components, and the resulting adhesive layer has higher light transmittance and flexibility, therefore, the above Q １It is preferably an aliphatic group derived from a dimer diamine. As the aliphatic group derived from the dimer diamine, for example, at least one group selected from the group consisting of the group represented by the above formula (3-1), the group represented by the above formula (3-2), the group represented by the above formula (3-3), and the group represented by the above formula (3-4) is preferable. Among them, the group represented by the above formula (3-2) is more preferable.

[0068] The resin having the structural unit represented by the above formula (1) and having a functional group having a reactive carbon-carbon double bond at at least one of the terminal and the side chain may have at least one structural unit selected from the group consisting of the structural unit represented by the following formula (4-1) and the structural unit represented by the following formula (4-2).

[0069]

[0070] In formula (4-1), P ４ represents an aromatic group, and Q ３ represents a group having a substituted or unsubstituted aromatic structure. In formula (4-2), P ５ represents an aromatic group, and S ２ represents a substituted or unsubstituted branched aliphatic group or a substituted or unsubstituted aromatic group, and Y represents a functional group having a carbon-carbon double bond.

[0071] P in the above formula (4-1) ４ and P in the above formula (4-2) ５ are preferably aromatic groups having 5 to 50 carbon atoms. When P ４ and P ５ are aromatic groups having 5 to 50 carbon atoms, the adhesive film of the present invention becomes more excellent in heat resistance. That is, the adhesive film of the present invention can further suppress the generation of outgas, voids between the adherend, and floating during high-temperature processing, and can also further suppress the promotion of adhesion to the adherend and the generation of glue residue when peeling from the adherend.

[0072] In the above formula (4-1), Q ３ is preferably a group having a substituted or unsubstituted aromatic structure having 5 to 50 carbon atoms. The above Q ３By being a group having an aromatic structure with 5 to 50 carbon atoms which may be substituted or unsubstituted, the adhesive film of the present invention becomes excellent in heat resistance. That is, the adhesive film of the present invention can further suppress the generation of outgas, voids between the adherend, and floating during high-temperature processing, and can also further suppress the enhancement of adhesion during high-temperature processing and the remaining glue during peeling.

[0073] In the above formula (4-2), S ２ is preferably a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. The above S ２ By being a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms, the above adhesive layer becomes excellent in flexibility, and the adhesive film of the present invention can exhibit high followability with respect to an adherend having irregularities, and can be peeled more easily when it becomes unnecessary.

[0074] In the above formula (4-2), S ２ 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 the S ２ is preferably bonded to a functional group having a reactive carbon-carbon double bond. Here, the "aromatic ester group" means a group in which an ester group is directly bonded to an aromatic ring, and the "aromatic ether group" means a group in which an ether group is directly bonded to an aromatic ring. By making the portion bonding to the ester group or the ether group an aromatic group in this way, the adhesive film of the present invention becomes excellent in heat resistance. That is, the adhesive film of the present invention can further suppress the generation of outgas, voids between the adherend, and floating during high-temperature processing, and can also further suppress the enhancement of adhesion during high-temperature processing and the remaining glue during peeling. On the other hand, by bonding a functional group having a reactive carbon-carbon double bond to S ２ via an aromatic ester group or an aromatic ether group, the carbon-carbon double bond in the functional group having a reactive carbon-carbon double bond does not conjugate with S ２ , so that the polymerization crosslinking when heated or irradiated with light is not hindered.

[0075] In a resin having a structural unit represented by formula (1) and a functional group having a reactive carbon-carbon double bond at least one of its terminal and side chains, the preferred lower limit of the structural unit represented by formula (1) is 30 mol%, the preferred upper limit is 90 mol%, the more preferred lower limit is 50 mol%, and the more preferred upper limit is 80 mol%. When a resin having a structural unit represented by formula (1) and a functional group having a reactive carbon-carbon double bond at least one of its terminal and side chains also has a structural unit represented by formula (4-1), the preferred lower limit of the structural unit represented by formula (4-1) is 5 mol%, the preferred upper limit is 50 mol%, the more preferred lower limit is 10 mol%, the more preferred upper limit is 30 mol%, and the still more preferred upper limit is 20 mol%. When a resin having a structural unit represented by formula (1) and a functional group having a reactive carbon-carbon double bond at least one of its terminal and side chains also has a structural unit represented by formula (4-2), the preferred lower limit of the content of the structural unit represented by formula (4-2) is 10 mol%, the preferred upper limit is 50 mol%, the more preferred lower limit is 20 mol%, and the more preferred upper limit is 30 mol%. By having the content of each structural unit in the structural unit represented by formula (1), the structural unit represented by formula (4-1), and the structural unit represented by formula (4-2) within the above ranges, the adhesive film of the present invention can more effectively suppress outgassing, voids between the film and the adherend, and lifting during high-temperature processing, and can be more easily peeled off from the adherend after high-temperature processing. Furthermore, the constituent units represented by formula (1), formula (4-1), and formula (4-2) may have a block structure consisting of block components in which each constituent unit is arranged in a continuous sequence, or they may have a random structure in which each constituent unit is arranged in a random sequence.

[0076] A resin having a functional group with a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain can be produced by, for example, the following method. Specifically, first, an imide compound is prepared by reacting a diamine compound with an aromatic acid anhydride. Next, the functional group of the imide compound is reacted with 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") to obtain a resin having a functional group with a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain. Alternatively, a resin having a functional group with a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain can also be obtained by reacting a diamine compound with an aromatic acid anhydride to prepare an imide compound, and then reacting the terminal end of the imide compound with, for example, maleic anhydride.

[0077] The above-mentioned diamine compound can be either an aliphatic diamine compound or an aromatic diamine compound. By using an aliphatic diamine compound as the above-mentioned diamine compound, the adhesive film of the present invention will have superior light transmittance, making it easier to cure compounds having a reactive carbon-carbon double bond. Furthermore, the adhesive film of the present invention will have superior flexibility, exhibiting high conformability to adherends with uneven surfaces, and will be easier to peel off when no longer needed. Furthermore, by using an aromatic diamine compound as the above-mentioned diamine compound, the adhesive film of the present invention will have superior heat resistance. The above-mentioned diamine compounds may be used individually or in combination of two or more types.

[0078] Examples of the above aliphatic diamine compounds include 1,10-diaminodecane, 1,12-diaminododecane, dimeramine, 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-diaminomentane, 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, 1,3-bisaminomethylcyclohexane, and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane.

[0079] Among the aliphatic diamine compounds described above, dimer amines are preferred because they have a functional group having the reactive carbon-carbon double bond described above, and an imide skeleton as the repeating unit of the main chain, exhibiting excellent compatibility with the resin, solvent and other components, and resulting in higher light transmittance and flexibility of the resulting adhesive layer. Specifically, examples of dimer amines include dimer amines that can constitute at least one group selected from the group consisting of the group represented by formula (3-1), the group represented by formula (3-2), the group represented by formula (3-3), and the group represented by formula (3-4).

[0080] Examples of the above aromatic diamine compounds 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-bisaminomethylbenzene, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino -3,5-diethylphenyl)methane, 9,9'-bis(4-amino-3-ethylphenyl)fluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenylsulfone, 3,3'-diaminophenylsulfone, 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-tolidine sulfone, 5,5'-methylenebis(anthranilic acid), 1,3-bis(4-aminophenoxy)-2,Examples include 2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylenediamines (e.g., Jeffamine D-230, D400, D-2000, and D-4000 from Huntsman), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, p-xylylenediamine, etc.

[0081] Examples of the above aromatic acid anhydrides include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and 2,3,5,6-pyridine. Tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyl diphthalic 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, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3, Examples of carboxylic acid anhydrides include 5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4'-oxydiphthalic acid, 4,4'-oxydiphthalic acid, 2,3',3,4'-tetracarboxydiphenyl oxide, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, and 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid).

[0082] The above-mentioned functional group-containing unsaturated compound is selected and used according to the functional group of the terminal or side chain of the imide compound. For example, if the functional group of the terminal or side chain of the imide compound is a hydroxyl group, the above-mentioned functional group-containing unsaturated compound can be a maleimide compound having a carboxyl group, a vinyl compound having an ether group, an allyl compound having a glycidyl group, an allyl ether compound having a glycidyl group, a vinyl ether compound having a glycidyl group, an allyl compound having an isocyanate group, or a (meth)acryloyl compound having an isocyanate group. Also, for example, if the functional group of the terminal or side chain of the imide compound is a carboxyl group, the above-mentioned functional group-containing unsaturated compound can be an allyl compound having a hydroxyl group, an allyl compound having a glycidyl group, an allyl ether compound having a glycidyl group, or a vinyl ether compound having a glycidyl group. Examples of maleimide compounds having the carboxyl group include maleimide acetate, maleimidopropionic acid, maleimidobutyric acid, maleimidohexanoic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, and 19-maleimido-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid. Examples of vinyl compounds having the ether group include butyl vinyl ether. Examples of allyl compounds having the glycidyl group include diallyl monoglycidyl isocyanurate. Examples of allyl ether compounds having the glycidyl group include allyl glycidyl ether and glycerin diallyl monoglycidyl ether. Examples of vinyl ether compounds having the glycidyl group include glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, and glycidylcyclohexanedimethanol monovinyl ether. Examples of allyl compounds having the above-mentioned isocyanate group include allyl isocyanate. Examples of (meth)acryloyl compounds having the above-mentioned isocyanate group include 2-(meth)acryloyloxyethyl isocyanate.Examples of allyl compounds having the hydroxyl group mentioned above include trimethylolpropanediallyl ether and pentaerythritol triallyl ether.

[0083] In 100 parts by mass of the compound having the reactive carbon-carbon double bond, the preferred lower limit of the content of the compound having the maleimide group is 10 parts by mass, and the preferred upper limit is 90 parts by mass. By having a content of 10 parts by mass or more of the compound having the maleimide group, the adhesive film of the present invention can further suppress the enhancement of adhesion during high-temperature processing. By having a content of 90 parts by mass or less of the compound having the maleimide group, the adhesive film of the present invention can further improve the peelability from an uneven substrate after high-temperature processing. A more preferred lower limit of the content of the compound having the maleimide group is 20 parts by mass, a more preferred upper limit is 80 parts by mass, an even more preferred lower limit is 30 parts by mass, and an even more preferred upper limit is 70 parts by mass.

[0084] Examples of compounds having a (meth)acryloyl group include monomers having a (meth)acryloyl group. Among these, monomers having a (meth)acryloyl group are preferred from the viewpoint of exfoliation.

[0085] The monomer having the (meth)acryloyl group preferably does not have an imide bond. Because the monomer having the (meth)acryloyl group does not have an imide bond, the resulting adhesive film can be easily peeled off from an uneven substrate.

[0086] The monomer having the (meth)acryloyl group preferably has two or more (meth)acryloyl groups in one molecule. Having two or more (meth)acryloyl groups in one molecule of the monomer allows the entire adhesive layer to cure uniformly and sufficiently, thus increasing the elastic modulus and significantly reducing the adhesive strength. As a result, the adhesive film of the present invention can suppress increased adhesion during high-temperature processing and the generation of adhesive residue when peeled off after high-temperature processing.

[0087] Examples of monomers having two or more (meth)acryloyl groups in one molecule include ABE-300 (total number of (meth)acryloyl groups: 2), A-BPE-4 (total number of (meth)acryloyl groups: 2), A-BPE-10 (total number of (meth)acryloyl groups: 2), A-BPE-30 (total number of (meth)acryloyl groups: 2), A-DCP (total number of (meth)acryloyl groups: 2), and A-9300S (total number of (meth)acryloyl groups: 2 or 3) (all manufactured by Shin Nakamura Chemical Co., Ltd.).

[0088] In 100 parts by mass of the above-mentioned compound having a reactive carbon-carbon double bond, the preferred lower limit of the content of the compound having the (meth)acryloyl group is 2 parts by mass, and the preferred upper limit is 70 parts by mass. By having a content of 2 parts by mass or more of the compound having the (meth)acryloyl group, the adhesive film of the present invention can further suppress the enhancement of adhesion during high-temperature processing. By having a content of 70 parts by mass or less of the compound having the (meth)acryloyl group, the adhesive film of the present invention can further improve the peelability from an uneven substrate after high-temperature processing. A more preferred lower limit for the content of the compound having the (meth)acryloyl group is 3 parts by mass, a more preferred upper limit is 60 parts by mass, an even more preferred lower limit is 5 parts by mass, and an even more preferred upper limit is 50 parts by mass.

[0089] The preferred lower limit for the content of the compound having a reactive carbon-carbon double bond in 100 parts by mass of the adhesive resin is 10 parts by mass, and the preferred upper limit is 90 parts by mass. By having the content of the compound having a reactive carbon-carbon double bond within this range, the adhesive film of the present invention can be peeled more easily. From the viewpoint of further improving peelability, a more preferred lower limit for the content of the compound having a reactive carbon-carbon double bond is 20 parts by mass, a more preferred upper limit is 80 parts by mass, an even more preferred lower limit is 30 parts by mass, an even more preferred upper limit is 70 parts by mass, an even more preferred lower limit is 40 parts by mass, and an even more preferred upper limit is 60 parts by mass.

[0090] The above adhesive resin may contain resins other than the crosslinked material and the compound having the reactive carbon-carbon double bond, provided that it satisfies formulas (A) and (B), or formula (C).

[0091] The above adhesive composition preferably contains an inorganic filler. The presence of an inorganic filler in the adhesive composition, i.e., the resulting adhesive layer, makes it easier to satisfy the above formulas (A), (B), and (C). Examples of the inorganic filler include at least one selected from the group consisting of oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconia, and composites thereof. Among these, silica and talc are preferred because they make it easier to satisfy the above formulas (A), (B), and (C), and are readily available and inexpensive commercially.

[0092] The inorganic filler described above may be surface-modified. Examples of modifying functional groups for surface-modifying the inorganic filler include alkylsilane groups, methacryloyl groups, and dimethylsiloxane groups. Among these, dimethylsiloxane groups are preferred because they have appropriate hydrophobicity.

[0093] The preferred lower limit for the average particle size of the inorganic filler is 5 nm, and the preferred upper limit is 30 μm. Having the average particle size of the inorganic filler within this range helps to further suppress unintended peeling during high-temperature processing, and allows for easy peeling by peel treatment when peeling occurs. A more preferred lower limit for the average particle size of the inorganic filler is 10 nm, a more preferred upper limit is 20 μm, an even more preferred lower limit is 15 nm, and an even more preferred upper limit is 15 μm. The average particle size can be determined, for example, by observing 50 arbitrary inorganic fillers with an electron microscope or optical microscope and calculating the average particle size of each inorganic filler, or by performing laser diffraction particle size distribution measurement.

[0094] The content of the inorganic filler is preferably 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the adhesive resin. By setting the content of the inorganic filler relative to the adhesive resin within the above range, it becomes easier to satisfy the above formulas (A), (B), and (C). From a similar viewpoint, the content of the inorganic filler is more preferably 3 parts by mass or more, even more preferably 7 parts by mass or more, even more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.

[0095] When the adhesive layer contains the compound having the reactive carbon-carbon double bond, it is preferable that the adhesive composition contains a polymerization initiator. By containing a polymerization initiator in the adhesive composition (the resulting adhesive layer), the compound having the reactive carbon-carbon double bond becomes easier to cure. As a result, the adhesive film of the present invention can suppress the increased adhesion of the adhesive layer to the adherend even when high-temperature processing is performed during application, and can be peeled off more easily from the adherend after high-temperature processing.

[0096] The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, but a photopolymerization initiator is preferred from the viewpoint of storage stability.

[0097] Examples of the above-mentioned photopolymerization initiators include those that are activated by irradiation with light of a wavelength of 250 to 800 nm. In particular, it is preferable that the above-mentioned photopolymerization initiator be activated by light of a wavelength of 405 nm, as this does not overlap much with the absorption wavelength of the above-mentioned crosslinked material and the compound having the reactive carbon-carbon double bond, and is sufficiently activated even when the adhesive layer is irradiated with long-wavelength light such as visible light. Specifically, it is preferable that the molar extinction coefficient for light of a wavelength of 405 nm is high, with a preferred lower limit of 10 ml / (g·cm), a more preferred lower limit of 50 ml / (g·cm), and an even more preferred lower limit of 100 ml / (g·cm). Furthermore, there is no particular upper limit to the molar extinction coefficient for light of a wavelength of 405 nm, but 1.0 × 10⁻⁶ is preferable. ５ The practical upper limit is approximately ml / (g·cm).

[0098] Examples of the above-mentioned photopolymerization initiators include acetophenone compounds, benzoin ether compounds, ketal compounds, phosphine oxide compounds, and oxime ester compounds. Among these, oxime ester compounds are preferred because they are sufficiently activated even by long-wavelength light such as visible light. Examples of the above-mentioned acetophenone compounds include methoxyacetophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one. Examples of the above-mentioned benzoin ether compounds include benzoin propyl ether and benzoin isobutyl ether. Examples of the above-mentioned ketal compounds include benzyldimethyl ketal and acetophenone diethyl ketal. Examples of the above-mentioned phosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Examples of the above oxime ester compounds include 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)-1,2-octadione, Irgacure OXE03 (manufactured by BASF), Irgacure OXE04 (manufactured by BASF), Nikkacure TKG-01 (manufactured by Nippon Chemical Industries, Ltd.), etc. Examples of the above photopolymerization initiators include bis(η5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, 2-hydroxymethylphenylpropane, etc. These photopolymerization initiators may be used individually or in combination of two or more.

[0099] Examples of the above-mentioned thermal polymerization initiators include organic peroxide-based thermal polymerization initiators. Examples of commercially available organic peroxide-based thermal polymerization initiators include perbutyl H and permil H (both manufactured by NOF Corporation).

[0100] The content of the polymerization initiator is preferably 0.1 parts by mass and preferably 10 parts by mass per 100 parts by mass of the adhesive resin. When the content of the polymerization initiator is within this range, the entire adhesive layer polymerizes and crosslinks uniformly and rapidly, and the elastic modulus increases, which significantly reduces the adhesive strength. This suppresses increased adhesion during high-temperature processing of the resulting adhesive film and prevents adhesive residue during peeling. A more preferable lower limit for the content of the polymerization initiator is 0.3 parts by mass and a more preferable upper limit is 5.0 parts by mass.

[0101] The above adhesive composition preferably contains a surface modifier. The presence of a surface modifier in the adhesive composition (the resulting adhesive layer) allows the surface modifier to bleed out to the substrate interface during peeling of the adhesive film of the present invention, making peeling easier. Examples of the surface modifier include silicone compounds and fluorine compounds. Silicone compounds and fluorine compounds used as surface modifiers can suppress charring of the adhesive layer even after high-temperature processing at 300°C or higher, and furthermore, they bleed out to the substrate interface during peeling of the adhesive film of the present invention, making peeling easier. Among these, silicone compounds are preferred from the viewpoint of being environmentally friendly and easy to dispose of.

[0102] The surface modifier described above may have functional groups that can crosslink with the crosslinked material and the compound having a reactive carbon-carbon double bond. Because the surface modifier has functional groups that can crosslink with the crosslinked material and the compound having a reactive carbon-carbon double bond, the surface modifier is incorporated through a chemical reaction with the crosslinked material and the compound having a reactive carbon-carbon double bond upon irradiation with light or reaction with a crosslinking agent. Therefore, contamination of the adherend by silicone compounds or fluorine compounds can be suppressed. Examples of functional groups that can crosslink with the crosslinked material and the compound having a reactive carbon-carbon double bond include carboxyl groups, functional groups having radically polymerizable unsaturated bonds (e.g., vinyl groups, (meth)acryloyl groups, optionally substituted maleimide groups), hydroxyl groups, amide groups, isocyanate groups, epoxy groups, and the like.

[0103] Examples of the above-mentioned silicone or fluorine compounds include silicone oil, silicone diacrylate, and silicone-based graft copolymer. Specifically, silicone compounds having a siloxane skeleton in the main chain and a functional group having a carbon-carbon double bond in the side chain or terminal are preferred. As for 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 terminal, at least one selected from the group consisting of the silicone compound represented by the following formula (5-1), the silicone compound represented by the following formula (5-2), and the silicone compound represented by the following formula (5-3) is preferred. These silicone compounds have particularly excellent heat resistance and high polarity, making it easy to bleed out from the adhesive layer.

[0104]

[0105] In formulas (5-1) to (5-3) above, m and n in formulas (5-1) and (5-3) above each independently represent an integer between 0 and 1200, and in formulas (5-1) to (5-3) above, Z represents a functional group having a carbon-carbon double bond.

[0106] In formulas (5-1) to (5-3) above, examples of functional groups having a carbon-carbon double bond represented by Z include optionally substituted maleimide groups, citraconimide groups, vinyl ether groups, allyl groups, (meth)acryloyl groups, etc. Among these, optionally substituted maleimide groups are preferred because they result in superior heat resistance for the adhesive film of the present invention. In formulas (5-1) to (5-3) above, if there are multiple Zs, each Z may be the same or different.

[0107] Among the silicone compounds represented by the above formulas (5-1) to (5-3), commercially available examples include EBECRYL350 and EBECRYL1360 (both manufactured by Daicel Ornex Co., Ltd.). Other examples include BYK-UV3500 (manufactured by Bic Chemie Co., Ltd.) and TEGO ZAD2250 (manufactured by Evonik Corporation) (in both cases, Z is an acryloyl group).

[0108] Examples of the fluorine compounds mentioned above include hydrocarbon compounds containing fluorine atoms.

[0109] The preferred lower limit of the content of the surface modifier is 0.1 parts by mass and the preferred upper limit is 20 parts by mass per 100 parts by mass of the adhesive resin. By having the surface modifier content within this range, the adhesive film of the present invention exhibits superior peelability without contaminating the adherend. From the viewpoint of further improving peelability while suppressing contamination, a more preferred lower limit for the surface modifier content is 0.3 parts by mass and a more preferred upper limit is 10 parts by mass. Furthermore, since the adhesive layer has excellent heat resistance, it can exhibit sufficient effect even with a relatively small amount of the surface modifier, further reducing the possibility of contamination by the surface modifier.

[0110] The above adhesive composition may further contain a gas generating agent. By including the gas generating agent, even after high-temperature processing at 300°C or higher, the gas generated by irradiation with light or heating is released at the interface with the adherend, making it easier to peel the adhesive film from the adherend without leaving any adhesive residue. Furthermore, even when peeling the adhesive film from a thin adherend after high-temperature processing at 300°C or higher, damage to the adherend can be suppressed.

[0111] Preferably, the above-mentioned gas generating agent has a weight loss rate of 5% or less at 300°C when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere, as measured by TG-DTA (thermogravimetric differential thermal analysis). If the weight loss rate of the above-mentioned gas generating agent is 5% or less, decomposition of the gas generating agent is less likely to occur even when high-temperature processing treatment is performed at 300°C or higher, and the resulting adhesive film will have superior heat resistance. In other words, the resulting adhesive film can suppress unintended peeling during high-temperature processing treatment, and can also suppress enhanced adhesion and adhesive residue when peeling. The above-mentioned TG-DTA (thermogravimetric differential thermal analysis) measurement can be performed using, for example, a TG-DTA device (Hitachi High-Tech Science Corporation, "STA7200RV"), etc.

[0112] Examples of the gas generating agents mentioned above include gas generating agents that generate gas by heating, and gas generating agents that generate gas by irradiation with light. These gas generating agents may be used individually or in combination of two or more. In particular, from the viewpoint of preventing the decomposition of the gas generating agent during high-temperature processing, gas generating agents that generate gas by irradiation with light are preferred, and gas generating agents that generate gas by irradiation with ultraviolet light are more preferred. Examples of the gas generating agents mentioned above include tetrazole compounds or their salts, triazole compounds or their salts, azo compounds, azide compounds, xanthone acetate, carbonates, etc. These gas generating agents may be used individually or in combination of two or more. In particular, tetrazole compounds or their salts are preferred because they have excellent heat resistance.

[0113] The preferred lower limit of the content of the gas generating agent is 5.0 parts by mass and the preferred upper limit is 50 parts by mass per 100 parts by mass of the adhesive resin. Having the gas generating agent content within this range results in particularly excellent peelability of the adhesive film of the present invention. A more preferred lower limit for the gas generating agent content is 8.0 parts by mass and a more preferred upper limit is 30 parts by mass.

[0114] The above adhesive composition (the resulting adhesive layer) may contain known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, surfactants, and waxes, as long as they do not impair the effects of the present invention.

[0115] The adhesive film of the present invention preferably further has a base material. The adhesive film of the present invention can be further improved in terms of handling by having a base material. Examples of the base material include resin films such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, polyetheretherketone (PEEK), and polyamide (PA). In particular, from the viewpoint of high heat resistance, a film containing a resin having repeating units in the main chain skeleton that include at least one selected from the group consisting of ether bonds, ketone groups, ester bonds, amide bonds, and imide bonds is preferred, and it is more preferable to include at least one selected from the group consisting of polyetheretherketone (PEEK) film, polyamide film, and polyimide film, with polyetheretherketone (PEEK) film being even more preferred. In addition, films having a mesh structure, films with holes, glass, etc. can also be used as the base material.

[0116] The thickness of the above substrate has a preferred lower limit of 5 μm and a preferred upper limit of 150 μm. Having the substrate thickness within this range makes it easier to adjust the light transmittance at a wavelength of 405 nm and the flexibility of the adhesive film of the present invention, as described later, to appropriate levels. A more preferred lower limit for the substrate thickness is 10 μm, and a more preferred upper limit is 100 μm.

[0117] The adhesive film of the present invention further comprises a second adhesive layer, and preferably has the adhesive layer, the substrate, and the second adhesive layer in this order. Since the adhesive film of the present invention is a double-sided tape having an adhesive layer, a substrate, and a second adhesive layer, it can be used for applications such as fixing an object to a support substrate via the adhesive film. The second adhesive layer may be the same as the adhesive layer, or a different one may be used.

[0118] The method for producing the adhesive film of the present invention is not particularly limited. For example, first, the base resin, the crosslinking agent, and optionally additives such as the reactive carbon-carbon double bond compound or the inorganic filler are mixed using a bead mill, ultrasonic dispersion, homogenizer, high-power disperser, roll mill, etc., to obtain a solution of the adhesive composition. Next, the obtained adhesive composition solution is applied to the release-treated surface of a PET film that has been treated on one side using an applicator, etc., and dried to form an adhesive layer. After that, an adhesive film having a substrate and an adhesive layer on one side of the substrate can be obtained by stacking the substrate and the adhesive layer facing each other. Alternatively, after forming a second adhesive layer in the same manner as described above, an adhesive film having a substrate and adhesive layers on both sides of the substrate can be obtained by stacking the adhesive layer on one side of the substrate and the second adhesive layer on the other side of the substrate facing each other. Note that during the formation of the adhesive layer, the base resin is crosslinked by the crosslinking agent to form the crosslinked body.

[0119] The adhesive film of the present invention preferably has a thickness of 20 μm or more and 200 μm or less. When the thickness of the adhesive film of the present invention is above the lower limit, it can adequately follow even large irregularities and can further suppress the leakage of adhesive when stored in a roll, and when it is below the upper limit, it can further improve handling. From a similar viewpoint, the thickness of the adhesive film of the present invention is more preferably 25 μm or more, even more preferably 30 μm or more, even more preferably 190 μm or less, and even more preferably 180 μm or less.

[0120] The adhesive film of the present invention has no particular limitations on its applications, but because it has excellent release properties, it can be suitably used for temporary fixing. Furthermore, because the adhesive film of the present invention has excellent heat resistance and can suppress increased adhesion during high-temperature processing and adhesive residue when peeled off, it can be suitably used for temporary fixing of adherends that undergo high-temperature heat treatment, such as electronic components. Specifically, for example, it can be used to temporarily fix electronic components to a support plate via the adhesive film of the present invention, or to protect electronic components by attaching the adhesive film of the present invention to them, in order to facilitate handling of electronic components such as semiconductors during processing and to prevent damage to the electronic components.

[0121] The adhesive film of the present invention improves handling because it suppresses the leakage of adhesive even when stored as a wound (roll) body. A wound body in which such an adhesive film of the present invention is wound is also one of the present inventions.

[0122] The winding body of the present invention may have an adhesive film portion thickness of 300 μm or more ((diameter of the winding body - diameter of the winding core) / 2). In a winding body of adhesive film, as the thickness of the adhesive film portion increases, that is, as the number of turns increases, force is applied toward the winding core due to winding pressure and the weight of the adhesive film itself, so the adhesive film closer to the winding core is more prone to adhesive leakage. The winding body of the present invention suppresses adhesive leakage of the adhesive film, so adhesive leakage is less likely to occur even when the winding body is made beyond the above range. The thickness of the adhesive film portion of the above winding body may be 1 cm or more, or 1.5 cm or more. There is no particular upper limit to the thickness of the adhesive film portion of the above winding body, but from the viewpoint of handling, it is about 15 cm.

[0123] The diameter of the core of the winding body of the present invention may be 30 cm or less. When an adhesive film is used as a winding body, reducing the diameter of the core reduces the volume of the winding body, but the number of turns increases, making it easier for the adhesive to overflow. In the winding body of the present invention, overflow of adhesive can be suppressed, so even if the core is small, the problem of overflow of adhesive is less likely to occur, and the adhesive film can be stored in a more space-saving manner. The diameter of the core of the winding body of the present invention may be 20 cm or less, or 15 cm or less. There is no particular lower limit to the diameter of the core of the above-mentioned winding body, but from the viewpoint of handling, it is about 7 cm.

[0124] The length of the adhesive film in the winding direction of the present invention can be the same as that of conventional adhesive film windings, but for example, it can be between 1 m and 100 m.

[0125] The width of the winding body of the present invention (length in the elongation direction of the winding body) is appropriately adjusted according to the size of the adherend, but examples include 100 mm or more and 500 mm or less. The width of the adhesive film in the winding body of the present invention (length in the direction perpendicular to the winding direction) is also approximately the same as the width of the winding body, so the length can be within the above range.

[0126] According to the present invention, it is possible to provide an adhesive film that can suppress the leakage of adhesive even when stored in a roll, and a winding of the adhesive film.

[0127] The embodiments of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0128] (Synthesis of Polyimide Compound A) 250 mL of toluene was added to a 500 mL round-bottom flask containing a Teflon® stirrer. 39.9 g (0.075 mol) of dimeramine (Croda, "Priamine 1075") and 23.3 g (0.075 mol) of 4,4'-oxydiphthalic anhydride were added in that order. A Dean-Stark tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A toluene solution of a brown solid resin (polyimide compound A) having a repeating imide skeleton as the main chain unit, represented by the following formula (6), was obtained. Polyimide compound A has either a carboxyl group or an amino group at its terminal end. The obtained polyimide compound A was measured using gel permeation chromatography (GPC, instrument name: Acquity APC system (Waters)) with THF as the eluent and an HR-MB-M 6.0 × 150 mm column (Waters), and its weight-average molecular weight was found to be 70,000.

[0129]

[0130] (Preparation of Acrylic Polymer) A reactor equipped with a thermometer, stirrer, and condenser was prepared. 94 parts by mass of 2-ethylhexyl acrylate as an alkyl (meth)acrylate, 6.0 parts by mass of 2-hydroxyethyl methacrylate as a functional group-containing monomer, 0.01 parts by mass of lauryl mercaptan, and 80 parts by mass of ethyl acetate were added to the reactor, and the reactor was heated and reflux was started. Subsequently, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added to the reactor as a polymerization initiator, and polymerization was started under reflux. Next, 0.01 parts by mass of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added 1 hour and 2 hours after the start of polymerization, and then 0.05 parts by mass of t-hexylperoxypivalate was added 4 hours after the start of polymerization to continue the polymerization reaction. Eight hours after the start of polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% and a weight-average molecular weight of 600,000 was obtained. To 100 parts by mass of the resin solids of the obtained ethyl acetate solution containing the functional group-containing (meth)acrylic polymer, 3.5 parts by mass of 2-isocyanatoethyl methacrylate was added as a functional group-containing unsaturated compound and reacted to obtain an acrylic polymer. The obtained acrylic polymer was measured by gel permeation chromatography (GPC) using THF as the eluent and an HR-MB-M 6.0 × 150 mm column (Waters), and the weight-average molecular weight was found to be 600,000.

[0131] (Example 1) A toluene solution of the adhesive composition was prepared by adding 70 parts by mass of polyimide compound A, 30 parts by mass of BMI-689 (a resin having a reactive carbon-carbon double bond and an imide skeleton as repeating units in the main chain, manufactured by Designer Molecules) as a compound having a reactive carbon-carbon double bond, 2 parts by mass of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819, manufactured by IGM Resins) as a photopolymerization initiator, 0.04 parts by mass of TETRAD-X (a crosslinking agent having an epoxy group, manufactured by Mitsubishi Gas Chemical Company) as a crosslinking agent, and 1.0 part by mass of BYK-UV3500 (manufactured by Bic Chemie) as a surface modifier, and mixing them together in 150 mL of toluene. A toluene solution of the obtained adhesive composition was applied using a doctor knife to the release-treated surface of a 50 μm thick PET film that had been treated on one side, so that the dry film thickness was 30 μm. The coating solution was dried by heating at 110°C for 5 minutes to obtain an adhesive film consisting only of the adhesive layer. The obtained adhesive film was then protected by laminating the PET film onto the side of the adhesive layer where no PET film was placed, with the release-treated surface facing the adhesive layer.

[0132] (Examples 3-5, 8-13, 15-25, Comparative Examples 1, 3) Adhesive films were obtained in the same manner as in Example 1, except that the composition of the adhesive layer was as shown in Tables 1-4. Details of the materials in the table are as follows. Polyimide compound B: PIAD152H, a resin having either a carboxyl group or an amino group at either the terminal or side chain and an imide skeleton as the repeating unit of the main chain, manufactured by Arakawa Chemical Co., Ltd. BMI-3000Gel: A resin having a reactive carbon-carbon double bond and an imide skeleton as the repeating unit of the main chain, manufactured by Designer Molecules, Inc. TETRAD-C: Crosslinking agent having epoxy groups, manufactured by Mitsubishi Gas Chemical Co., Ltd. MT-10-MEK: Silica filler, manufactured by Tokuyama Corporation UN-5500: Urethane acrylate, manufactured by Negami Kogyo Co., Ltd. Omnirad 379EG: Photopolymerization initiator, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one, manufactured by IGM Resins, Inc. Coronate L45K: Isocyanate-based crosslinking agent, manufactured by Tosoh Corporation EBECRYL 350: Silicone diacrylate, manufactured by Daicel Ornex.

[0133] (Example 2) A toluene solution of the adhesive composition was prepared by adding 70 parts by mass of polyimide compound A as the base resin, 30 parts by mass of BMI-689 (a resin having a reactive carbon-carbon double bond and an imide skeleton as repeating units in the main chain, manufactured by Designer Molecules) as a compound having a reactive carbon-carbon double bond, 2 parts by mass of Omnirad 819 (manufactured by IGM Resins) as a photopolymerization initiator, 0.1 parts by mass of TETRAD-X (a crosslinking agent having an epoxy group, manufactured by Mitsubishi Gas Chemical Company) as a crosslinking agent, and 1.0 part by mass of BYK-UV3500 (manufactured by Bic Chemie) as a surface modifier to 150 mL of toluene and mixing. A toluene solution of the obtained adhesive composition was applied using a doctor knife to the release-treated surface of a 50 μm thick PET film that had been treated on one side, so that the dry film thickness was 130 μm. The coating solution was dried by heating at 110°C for 5 minutes to form an adhesive layer. Next, a second adhesive layer with a thickness of 20 μm was formed in the same manner as the first adhesive layer. Subsequently, the adhesive layer was superimposed on one side of a polyether ether ketone (PEEK) film (EXPEEK, manufactured by Kurabo Industries Ltd.), and the second adhesive layer was superimposed on the other side, thereby laminating and integrating the layers to obtain an adhesive film having an adhesive layer and a second adhesive layer on both sides of the substrate.

[0134] (Examples 6, 7, Comparative Example 2) Adhesive films were obtained in the same manner as in Example 2, except that the composition and thickness of the adhesive layer were as shown in Tables 1 and 4.

[0135] (Example 14) A toluene solution of the adhesive composition was prepared by adding 70 parts by mass of polyimide compound A as the base resin, 30 parts by mass of BMI-689 (a resin having a reactive carbon-carbon double bond and an imide skeleton as repeating units in the main chain, manufactured by Designer Molecules) as a compound having a reactive carbon-carbon double bond, 2 parts by mass of Omnirad 819 (manufactured by IGM Resins) as a photopolymerization initiator, and 1.0 part by mass of BYK-UV3500 (manufactured by Bic Chemie) as a surface modifier and mixing the mixture. The obtained toluene solution of the adhesive composition was applied with a doctor knife to the release-treated surface of a 50 μm thick PET film that had been treated on one side, so that the dry film thickness was 30 μm, and the coating solution was dried by heating at 110°C for 5 minutes to form an adhesive layer. Next, the resulting adhesive layer was treated with a UV LED at a wavelength of 405 nm and an irradiation intensity of 460 J / cm². ２ By irradiating the compound having a reactive carbon-carbon double bond with light for 10 seconds, an adhesive film consisting only of an adhesive layer was obtained by semi-curing the compound. For the obtained adhesive film, the PET film was laminated onto the surface of the adhesive layer where no PET film was placed, with the release-treated surface facing the adhesive layer, to protect the adhesive layer.

[0136] (Example 26) An adhesive film was obtained in the same manner as in Example 14, except that the composition and thickness of the adhesive layer were as shown in Table 3.

[0137] <Physical Properties> The following measurements were performed on the obtained adhesive film. The results are shown in Tables 5 to 8.

[0138] (Measurement of Shear Storage Modulus G'(T)) A 1 mm thick measurement sample was prepared by stacking the adhesive layers of the obtained adhesive film. Dynamic viscoelasticity measurements were performed on the obtained measurement sample using a viscoelastic spectrometer (IT Measurement Control Co., Ltd., "DVA-200") under the conditions of shear direction, frequency of 10 Hz, heating rate of 10 °C / min, and temperature range from -50 °C to 300 °C. From the obtained measurement results, the shear storage modulus G' at 0 °C, 25 °C, 100 °C, and 200 °C was recorded, and G'(0) / G'(200) was calculated based on the shear storage moduli G'(0) and G'(200) at 0 °C and 200 °C. For Examples 2, 6, 7 and Comparative Example 2, in which the adhesive film has a substrate, a measurement sample was prepared by forming only the adhesive layer using the above method, and measurements were performed.

[0139] (Measurement of load using a tack tester) For the adhesive layer of the obtained adhesive film, a tack tester (RHESCA, tacking tester TAC1000) was used to press the probe against the sample for 30 seconds under the following conditions: probe and stage temperature 25°C, probe diameter 5 mm, probe indentation distance 0.005 mm, probe pressing speed 0.01 mm / s, pressing hold time 30 seconds, and touch detection level 10 gf. The load during pressing was measured at time intervals, and the loads at contact (0 seconds), 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 10 seconds, 15 seconds, 20 seconds, and 30 seconds after contact were obtained. Then, the same measurement was repeated twice, and the average load at each time was calculated to obtain F(0), F(1), F(2), F(3), F(4), F(5), F(10), F(15), F(20), and F(30). Furthermore, F(t) is calculated from the average of the maximum loads during measurement. ＭＡＸ We obtained the following based on the obtained load: F(30) / F(t) ＭＡＸ And F(30) / F(1) was calculated. For Examples 2, 6, 7 and Comparative Example 2, in which the adhesive film is a substrate, measurement samples were prepared by forming only the adhesive layer using the method described above, and measurements were taken.

[0140] (Measurement of glass transition temperature Tg) The glass transition temperature was defined as the temperature at which a maximum of loss loss tangent (tanδ) caused by micro-Brownian motion appeared, obtained from the dynamic viscoelasticity measurement performed during the measurement of the shear storage modulus described above.

[0141] (Measurement of Gel Fraction) 50 mg of the adhesive layer was taken from the obtained adhesive film, immersed in toluene, and shaken for 24 hours at a temperature of 23°C and 200 rpm. After shaking, the toluene and the toluene-absorbing and swollen adhesive layer were separated using a metal mesh (mesh size #200), and the separated adhesive layer was dried for 1 hour at 110°C. The mass of the adhesive layer including the metal mesh after drying was measured, and the gel fraction (%) of the adhesive layer was measured using the following formula: Gel fraction (%) = 100 × (W ２ -W １ ) / W ０ (W ０ : Mass of the initial adhesive layer (g), W １ : Initial mass of metal mesh (g), W ２ : Mass of the adhesive layer containing the metal mesh after drying (g)

[0142] <Evaluation> The adhesive films obtained in the examples and comparative examples were evaluated using the following method. The results are shown in Tables 5 to 8.

[0143] (Evaluation of adhesive leakage) A 5 cm square piece was cut from the adhesive film with the PET film (release film) still attached to obtain a test specimen. The obtained test specimen was placed on a stainless steel plate, and a 1.5 kg copper plate was then placed on top of the test specimen. Next, the test specimen sandwiched between the stainless steel plate and the copper plate was left to stand in a 40°C oven for 72 hours, and the adhesive film was visually inspected to check for any leakage of adhesive from the sides. Subsequently, the same procedure as above was performed on another test specimen, except that it was left to stand in the oven for 150 hours, and the presence or absence of adhesive leakage from the sides was checked. If there was adhesive leakage after 72 hours, it was marked as "×", if there was no adhesive leakage after 72 hours but there was adhesive leakage after 150 hours, it was marked as "△", and if there was no adhesive leakage even after 150 hours, it was marked as "〇".

[0144] (Evaluation of Embedding Ability for Irregularities) A ​​silicon wafer (Φ8 inch, 725 μm thick) was prepared by making grooves with a depth of 10 μm, a width of 30 μm, and a spacing of 100 μm using a dicing device (DISCO Corporation, "DFD6360") to create a wafer with irregularities of 10 μm. Next, a wafer with irregularities of 3 μm was prepared using the same method except that the groove depth was 3 μm. Subsequently, the adhesive layer of the obtained adhesive film was attached to the irregular surfaces of the prepared wafers with 10 μm and 3 μm irregularities under vacuum conditions at 80°C. The unevenness was observed using a microscope (Keyence Corporation, Digital Microscope VHX-970F), and the ability to embed unevenness was evaluated as follows: "○" if the adhesive layer could embed a wafer with unevenness of 10 μm depth, "△" if it could embed a wafer with unevenness of 3 μm depth, and "×" if it could not embed a wafer with unevenness of 3 μm depth.

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153] According to the present invention, it is possible to provide an adhesive film that can suppress the leakage of adhesive even when stored in a roll, and a winding of the adhesive film.

Claims

1. An adhesive film having an adhesive layer, wherein the adhesive layer satisfies at least one of the following first configuration or second configuration. First configuration: When the shear storage modulus at T°C measured by dynamic viscoelasticity measurement is G'(T), the following formulas (A) and (B) are simultaneously satisfied. 10 ≤ G'(0) / G'(200) ≤ 20000 ... (A) 10 ５ Pa ≤ G'(0) ≤ 10 １０ Pa... (B) Second configuration: When the load F(gf) is measured with a tack tester, and the load at t seconds after the probe contact is F(t), the following equation (C) is satisfied: 0.60 ≤ F(30) / F(1) ≤ 0.96... (C) 2. The above G'(200) is 10 ８ The adhesive film according to claim 1, wherein the hardness is Pa or less.

3. The above G'(200) is 10 ３ The adhesive film according to claim 1 or 2, wherein the hardness is Pa or greater.

4. The adhesive film according to any one of claims 1 to 3, wherein the adhesive layer has a thickness of 20 μm or more and 200 μm or less.

5. The adhesive film according to any one of claims 1 to 4, wherein the adhesive layer has a gel fraction of 0% or more and 90% or less.

6. The adhesive film according to any one of claims 1 to 5, wherein the adhesive layer has a glass transition temperature of -5°C or higher and 50°C or lower.

7. The adhesive film according to any one of claims 1 to 6, wherein the adhesive layer is formed using an adhesive composition, the adhesive composition contains an adhesive resin and a crosslinking agent, and the adhesive resin contains a base resin.

8. The adhesive film according to claim 7, wherein the adhesive layer contains a crosslinked body having a structure derived from the base resin and a structure derived from the crosslinking agent.

9. The adhesive film according to claim 7 or 8, wherein the base resin contains a resin having an imide skeleton as the repeating unit of the main chain.

10. The adhesive film according to claim 9, wherein the resin having the imide skeleton as the repeating unit of the main chain has polar functional groups.

11. The adhesive film according to claim 10, wherein the polar functional group includes a carboxyl group.

12. The adhesive film according to any one of claims 9 to 11, wherein the resin having the imide skeleton as the repeating unit of the main chain has a weight-average molecular weight of 50,000 or more.

13. The adhesive film according to any one of claims 7 to 12, wherein the adhesive resin contains a compound having a reactive carbon-carbon double bond.

14. The adhesive film according to any one of claims 7 to 13, wherein the crosslinking agent contains a crosslinking agent having an epoxy group.

15. The adhesive film according to any one of claims 7 to 14, wherein the content of the crosslinking agent is 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the base resin.

16. The adhesive film according to any one of claims 7 to 15, wherein the adhesive composition contains an inorganic filler.

17. The adhesive film according to claim 16, wherein the content of the inorganic filler is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the adhesive resin.

18. The adhesive film according to any one of claims 1 to 17, wherein the adhesive film has a thickness of 20 μm or more and 200 μm or less.

19. Furthermore, an adhesive film according to any one of claims 1 to 18, comprising a base material.

20. The adhesive film according to claim 19, further comprising a second adhesive layer, wherein the adhesive layer, the substrate, and the second adhesive layer are arranged in this order.

21. An adhesive film according to any one of claims 1 to 20, for use in temporary fixing.

22. An adhesive film according to any one of claims 1 to 20, used for temporary fixing of electronic components.

23. A winding body in which the adhesive film according to any one of claims 1 to 22 is wound.

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