Pressure-sensitive adhesive composition, pressure-sensitive adhesive tape, and method for treating electronic components

Abstract

An objective of the present invention is to provide an adhesive composition that enables an adherend to be easily removed even after having spent an extended length of time at 250°C or higher, or having undergone a high-temperature machining process at a temperature of 300°C or higher in a state of being anchored. Another objective of the present invention is to provide an adhesive tape that includes an adhesive layer comprising the adhesive composition, and an electronic component processing method that uses said adhesive tape. The adhesive composition according to the present invention contains a silicone-modified polyimide (A) and a curable resin (B) having a double bond.

Description

[Technical Field]

[0001] The present invention relates to a pressure-sensitive adhesive composition that can be easily peeled off from an adherend even after prolonged processing at 250° C. or higher or high-temperature processing at 300° C. or higher while the adherend is fixed thereto. The present invention also relates to a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition, and a method for treating electronic components using the pressure-sensitive adhesive tape. [Background technology]

[0002] During processing of electronic components such as semiconductors, in order to facilitate handling of the electronic components and prevent breakage, the electronic components are protected by being fixed to a support plate via a pressure-sensitive adhesive composition or by being attached with a pressure-sensitive adhesive tape. For example, when a thick-film wafer cut from a high-purity silicon single crystal or the like is ground to a predetermined thickness to obtain a thin-film wafer, the thick-film wafer is adhered to a support plate via a pressure-sensitive adhesive composition.

[0003] Thus, pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes used for electronic components are required to have high enough adhesion to firmly fix the electronic components during the processing step, and also to be able to be peeled off without damaging the electronic components after the processing step (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 a pressure-sensitive adhesive sheet that uses a pressure-sensitive adhesive in which a polyfunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to the side chain or main chain of the polymer. By utilizing the fact that the polymer has a radiation-polymerizable functional group, which hardens when exposed to ultraviolet light, the adhesive strength is reduced by exposure to ultraviolet light during peeling, allowing the sheet to be peeled off without leaving any adhesive residue. Another known means for achieving high adhesion and easy peelability is to incorporate a release agent such as silicone oil or silicone diacrylate into the adhesive composition or the adhesive layer of the adhesive tape. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-32946 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, with the increasing performance of electronic components, various high-temperature processing steps have been performed on electronic components. For example, in a process of forming a metal thin film on the surface of an electronic component by sputtering, a metal thin film with superior conductivity can be formed by performing the processing at a high temperature of about 300 to 350°C. In addition, for example, when stacking semiconductor wafers or chips in multiple layers, thermocompression bonding at high temperatures is also required. However, when electronic components protected using conventional pressure-sensitive adhesive compositions or pressure-sensitive adhesive tapes that have been designed to improve peelability by, for example, blending a release agent are subjected to long-term high-temperature processing at 250°C or higher or high-temperature processing at 300°C or higher, the adhesion may increase, causing the adhesive strength to not decrease sufficiently upon peeling, or adhesive residue may be left behind due to thermal degradation of the pressure-sensitive adhesive.

[0006] An object of the present invention is to provide a pressure-sensitive adhesive composition that can be easily peeled off even after being subjected to a long-term processing treatment at 250° C. or higher or a high-temperature processing treatment at 300° C. or higher while the adherend is fixed thereto. Another object of the present invention is to provide a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition, and a method for treating electronic components using the pressure-sensitive adhesive tape. [Means for solving the problem]

[0007] The present invention is a pressure-sensitive adhesive composition containing a silicone-modified polyimide (A) and a curable resin (B) having a double bond. The present invention will be described in detail below.

[0008] The present inventors have investigated a pressure-sensitive adhesive composition containing a silicone-modified polyimide (A) and a curable resin (B) having a double bond. The inventors have found that such a pressure-sensitive adhesive composition has sufficient initial adhesive strength while suppressing adhesion enhancement, and therefore can be easily peeled off even after long periods of time at 250°C or higher or after high-temperature processing at 300°C or higher while the adherend is fixed thereto, thereby completing the present invention.

[0009] The pressure-sensitive adhesive composition of the present invention contains a silicone-modified polyimide (A). When the silicone-modified polyimide (A) is not the main component of the pressure-sensitive adhesive composition, the silicone-modified polyimide (A) acts as a release agent, bleeding out to the adherend interface and facilitating peeling. When the silicone-modified polyimide (A) is the main component of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition retains adhesiveness despite the presence of a silicone-derived structure at the adherend interface, so that the adherend can be fixed and easily peeled even after high-temperature processing. Furthermore, the silicone-modified polyimide (A) has an imide skeleton and silicone chains, which give it excellent heat resistance. Therefore, even after prolonged high-temperature processing at 250°C or higher or 300°C or higher, the silicone-modified polyimide (A) is resistant to main chain decomposition, preventing enhanced adhesion and adhesive residue upon peeling.

[0010] The silicone-modified polyimide (A) is not particularly limited by the number of repeating siloxane units (repeating units having a siloxane skeleton) in the silicone chain, but a preferred lower limit is 10 and a preferred upper limit is 100. If the number of repeating siloxane units is 10 or more, the pressure-sensitive adhesive composition can exhibit better releasability, and the heat resistance of the silicone-modified polyimide (A) can also be improved. If the number of repeating siloxane units is 100 or less, excessive deterioration in the compatibility of the silicone-modified polyimide (A) with solvents and other components can be prevented. The lower limit of the number of repeating siloxane units is more preferably 20, and the upper limit is more preferably 80, and the even more preferred lower limit is 30, and the even more preferred upper limit is 60.

[0011] The weight-average molecular weight of the silicone-modified polyimide (A) is not particularly limited, but when the silicone-modified polyimide (A) is not the main component of the pressure-sensitive adhesive composition, a preferred lower limit is 1,000 and a preferred upper limit is 50,000. If the weight-average molecular weight is 1,000 or more, it is possible to prevent the silicone-modified polyimide (A) from contaminating the adherend due to excessive bleed-out when it functions as a release agent. If the weight-average molecular weight is 50,000 or less, the silicone-modified polyimide (A) bleeds out sufficiently, making release easier. A more preferred lower limit of the weight-average molecular weight is 3,000, a more preferred upper limit is 30,000, an even more preferred lower limit is 5,000, and an even more preferred upper limit is 20,000.

[0012] When the silicone-modified polyimide (A) is the main component of a pressure-sensitive adhesive composition, the weight-average molecular weight of the silicone-modified polyimide (A) preferably has a lower limit of 5,000 and an upper limit of 100,000. A weight-average molecular weight of 5,000 or more can prevent excessive flow when the silicone-modified polyimide (A) is the main component of a pressure-sensitive adhesive composition. A weight-average molecular weight of 100,000 or less can improve the compatibility of the silicone-modified polyimide (A) with solvents and other components. A more preferred lower limit of the weight-average molecular weight is 6,000, an even more preferred lower limit is 7,000, an even more preferred lower limit is 8,000, an even more preferred lower limit is 9,000, and an especially preferred lower limit is 10,000. A more preferred upper limit of the weight-average molecular weight is 80,000, and an even more preferred upper limit is 50,000. The weight-average molecular weight is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). As the column, for example, HR-MB-M (manufactured by Waters Corporation) can be used.

[0013] The silicone-modified polyimide (A) preferably has a functional group capable of crosslinking with the curable resin (B) having a double bond. When the silicone-modified polyimide (A) has the crosslinkable functional group, it chemically reacts with the curable resin (B) having a double bond directly or via a crosslinking agent, etc., upon irradiation with light or heating, etc., and is incorporated into the curable resin (B) having a double bond. This prevents the silicone-modified polyimide (A) or the curable resin (B) having a double bond from adhering to and contaminating the adherend. The crosslinkable functional group is not particularly limited and is selected according to the curable resin (B) having a double bond, and examples thereof include a carboxy group, a hydroxyl group, an amide group, an isocyanate group, an epoxy group, a functional group having a double bond, etc. Among these, a hydroxyl group or a functional group having a double bond is preferred because higher heat resistance can be obtained.

[0014] The functional group having a double bond is not particularly limited, and examples thereof include an optionally substituted maleimide group, a citraconic group, a vinyl ether group, an allyl group, a (meth)acrylic group, etc. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance.

[0015] The silicone-modified polyimide (A) is not particularly limited as long as it has an imide skeleton and a silicone chain, which may be present in the main chain or in a side chain of the silicone-modified polyimide (A). Specific examples of the silicone-modified polyimide (A) include silicone-modified polyimides (A1) having a structural unit represented by the following general formula (1a), a structural unit represented by the following general formula (1b), and a structural unit represented by the following general formula (1c) (where s1≧1, t1≧0, u1≧0).

[0016] [ka]

[0017] In general formulas (1a) to (1c), P 1 , P 2 and P 3 each independently represents an alicyclic group or an aromatic group. 1 represents the silicone chain, and Q 2 represents a substituted or unsubstituted aliphatic group or aromatic group, and R represents a substituted or unsubstituted branched aliphatic group or aromatic group. 3 represents a substituted or unsubstituted aliphatic group, aromatic group, or functional group having a double bond; X 3 n1 In the formula, n1 represents an integer of 1 or more.

[0018] In the above general formulas (1a) to (1c), P 1 , P 2 and P 3 are preferably each independently an alicyclic group or an aromatic group having 5 to 50 carbon atoms. 1 , P2 and P 3 are each independently an alicyclic group or an aromatic group having 5 to 50 carbon atoms, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance. 1 , P 2 and P 3 is preferably a structure derived from an acid anhydride, which will be described later.

[0019] In the above general formula (1a), Q 1 The silicone chain represented by the formula Q is not particularly limited, and examples thereof include silicone chains having a siloxane unit (a repeating unit having a siloxane skeleton) with a repeat number within the above range. 1 is preferably a structure derived from a silicone compound having amino groups at both ends, as described below.

[0020] In the above general formula (1b), Q 2 is preferably a substituted or unsubstituted aliphatic or aromatic group having 2 to 100 carbon atoms. 2 When Q is a substituted or unsubstituted aliphatic or aromatic group having 2 to 100 carbon atoms, especially an aliphatic group, the PSA sheet produced using the PSA composition can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and also has improved releasability. 2 is preferably a structure derived from a diamine compound described below, and more preferably a structure derived from a dimer diamine described below.

[0021] In the above general formula (1c), R is preferably a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms, a pressure-sensitive adhesive sheet produced using the pressure-sensitive adhesive composition can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and also has improved releasability. R is preferably a structure derived from a diamine compound described below, and more preferably a structure derived from a diamine compound having a functional group described below.

[0022] In the silicone-modified polyimide (A1), both ends are not particularly limited, and examples thereof include structures derived from the acid anhydride or diamine compound that are raw materials for the silicone-modified polyimide (A1). In the silicone-modified polyimide (A1), both ends are X 1 Q- and X 2 In this case, X 1 Q- is bonded to the N atom in the constitutional unit represented by the general formula (1a), the constitutional unit represented by the general formula (1b), or the constitutional unit represented by the general formula (1c) to form the terminal on the N atom side, and X 2 - is at the end opposite to the N atom. Q is Q 1 or Q 2 is the same as X 1 and X 2 each independently represents a substituted or unsubstituted aliphatic group, aromatic group, or functional group having a double bond.

[0023] In the silicone-modified polyimide (A1), X 1 , X 2 and X 3 The groups each independently include, for example, an aliphatic group, an alicyclic group, an aromatic group, a structure derived from an acid anhydride, a structure derived from an amine compound, a functional group having a double bond, etc. Specific examples include a structure derived from an unreacted end of an acid anhydride or diamine compound that is a raw material for the silicone-modified polyimide (A1). Among them, X 1 , X 2 and X 3 Preferably, at least one selected from the group consisting of contains a functional group having a double bond, which further suppresses increased adhesion of the pressure-sensitive adhesive composition and improves releasability. The functional group having a double bond is not particularly limited, and examples thereof include an optionally substituted maleimide group, a citraconic group, a vinyl ether group, an allyl group, a (meth)acrylic group, etc. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance. In the silicone-modified polyimide (A1), X 3 n1 In the above formula, n1 is preferably an integer of 10 or less, more preferably 8 or less, even more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. In the silicone-modified polyimide (A1), the plurality (n1) of X's contained in one structural unit 3 may be the same or different.

[0024] In the silicone-modified polyimide (A1), s1 is 1 or more, preferably 3 or more, and preferably 10 or less, more preferably 5 or less. t1 is 0 or 1 or more, preferably 1 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. u1 is 0 or 1 or more, preferably 1 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. When s1, t1, and u1 are within the above ranges, increased adhesion of the pressure-sensitive adhesive composition is further suppressed, and releasability is also improved. In the silicone-modified polyimide (A1), the structural unit represented by the general formula (1a), the structural unit represented by the general formula (1b), and the structural unit represented by the general formula (1c) may be a block copolymer consisting of block components in which the respective structural units are arranged consecutively. Alternatively, the structural unit represented by the general formula (1a), the structural unit represented by the general formula (1b), and the structural unit represented by the general formula (1c) may be a random copolymer in which the respective structural units are arranged randomly.

[0025] The silicone-modified polyimide (A) can be produced, for example, by reacting a silicone compound having amino groups at both ends with an acid anhydride (e.g., an aromatic acid anhydride, an acid anhydride having an alicyclic group, etc.) to obtain an imide compound. If necessary, a diamine compound may also be reacted. Furthermore, a diamine compound having a functional group is used as the diamine compound, and the functional group in the obtained imide compound is reacted with a compound having a functional group reactive with the functional group and a functional group having a double bond (hereinafter referred to as a functional group-containing unsaturated compound), thereby allowing a functional group having a double bond to be introduced into the side chain. Furthermore, by adjusting the reaction ratio, the terminal can be made to have a structure derived from the diamine compound, and then the functional group-containing unsaturated compound can be reacted with the resulting terminal amino group to introduce a functional group having a double bond at the terminal.

[0026] Examples of the silicone compound having amino groups at both ends include silicone compounds having amino groups at both ends and having a siloxane unit (a repeating unit having a siloxane skeleton) with a repeat number within the above range. Commercially available silicone compounds include KF-8010, X-22-161A, X-22-161B, KF-8012, and PAM-E (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0027] As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used. By using an aliphatic diamine compound as the diamine compound, a pressure-sensitive adhesive tape produced using the pressure-sensitive adhesive composition can exhibit high flexibility, can exhibit high conformability to an adherend having unevenness, and also has improved releasability.By using an aromatic diamine compound as the diamine compound, the heat resistance of the pressure-sensitive adhesive composition can be further improved. These aliphatic diamine compounds, aromatic diamine compounds and diamine compounds having a functional group may be used alone or in combination of two or more kinds.

[0028] Examples of the aliphatic diamine compound include 1,10-diaminodecane, 1,12-diaminododecane, dimer diamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane.

[0029] Among the above aliphatic diamine compounds, dimer diamine is preferred from the viewpoint of increasing flexibility and increasing the compatibility of the silicone-modified polyimide (A) with solvents and other components, thereby facilitating the production of the adhesive tape. The dimer diamine is a diamine compound obtained by reducing and amminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples thereof include linear, monocyclic, and polycyclic dimer diamines. The dimer diamine may contain a carbon-carbon unsaturated double bond or may be a hydrogenated product to which hydrogen has been added. More specific examples of the dimer diamine include dimer diamines capable of constituting the groups represented by general formula (4-1), (4-2), (4-3), and (4-4), as described below.

[0030] Examples of the aromatic diamine compound include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, and 1,5 -Diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)ethane )methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-ethyldiaminofluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, -5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenyl sulfone, 3,3'-diaminophenyl sulfone, 2,2-bis(4,(4-aminophenoxy)phenyl)sulfone, 2,2-bis(4-(3-aminophenoxy)phenyl)sulfone (oxy)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, methylenebis(anthranilic acid), 1,3-bis(4-aminophenoxy)-2,Examples of suitable alkyl ethers 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., Huntsman's Jeffamine D-230, D400, D-2000, and D-4000), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, and p-xylylenediamine.

[0031] Examples of the diamine compound having a functional group include a diamine compound having a hydroxyl group, a diamine compound having a carboxyl group, and a diamine compound having a halogen group. Examples of the diamine compound having a hydroxyl group include 1,3-diamino-2-propanol, 2,4-diaminophenoxyethanol, 3,5-diaminophenoxyethanol, 2,4-diaminophenol, 3,5-diaminophenol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol dihydrochloride, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. Examples of the diamine compound having a carboxyl group include 3,5-diaminobenzoic acid. Examples of the diamine compound having a halogen group include 2,4-diaminochlorobenzene.

[0032] Examples of the aromatic acid anhydride include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6 -pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)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 Examples of suitable carboxylic acids include carboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4,3',4'-biphenyltetracarboxylic acid, 2,3,2',3'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, and 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid).

[0033] The functional group-containing unsaturated compound is selected depending on the functional group at the end or side chain of the imide compound. For example, when the functional group at the terminal or side chain of the imide compound is a hydroxyl group, a maleimide compound having a carboxyl group can be used. Examples of the maleimide compound having a 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. Further examples include vinyl compounds having an ether group such as butyl vinyl ether, allyl compounds having a glycidyl group such as diallyl monoglycidyl isocyanurate, and allyl ether compounds having a glycidyl group such as allyl glycidyl ether and glycerin diallyl monoglycidyl ether. Further examples include vinyl ether compounds having a glycidyl group, such as glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, and glycidyl cyclohexanedimethanol monovinyl ether. Further examples include allyl compounds having an isocyanate group, such as allyl isocyanate, and (meth)acryloyl compounds having an isocyanate group, such as 2-(meth)acryloyloxyethyl isocyanate. Furthermore, for example, when the functional group at the terminal or side chain of the imide compound is a carboxyl group, examples of the usable compound include allyl compounds having a hydroxyl group, such as trimethylolpropane diallyl ether and pentaerythritol triallyl ether, and allyl compounds having a glycidyl group, such as diallyl monoglycidyl isocyanurate. Further examples include allyl ether compounds having a glycidyl group, such as allyl glycidyl ether and glycerin diallyl monoglycidyl ether. Further examples include vinyl ether compounds having a glycidyl group, such as glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, and glycidyl cyclohexanedimethanol monovinyl ether. Furthermore, for example, when the functional group at the end or side chain of the imide compound is an amino group, examples of the suitable amine include maleic anhydride.

[0034] The content of the silicone-modified polyimide (A) is not particularly limited, but when the silicone-modified polyimide (A) is not the main component of the pressure-sensitive adhesive composition, a preferred lower limit is 0.5 parts by weight and a preferred upper limit is 100 parts by weight per 100 parts by weight of the curable resin (B) having a double bond. When the content of the silicone-modified polyimide (A) is within this range, the pressure-sensitive adhesive composition can exhibit better releasability without contaminating the adherend. From the viewpoint of further improving releasability while suppressing contamination of the adherend, a more preferred lower limit of the content of the silicone-modified polyimide (A) is 1 part by weight and a more preferred upper limit is 50 parts by weight, an even more preferred lower limit is 3 parts by weight, and an even more preferred upper limit is 20 parts by weight. Furthermore, since the pressure-sensitive adhesive composition of the present invention has excellent heat resistance, it can exert a sufficient effect even when the content of the silicone-modified polyimide (A) is relatively small, which further reduces the possibility of contamination by the silicone-modified polyimide (A).

[0035] When the silicone-modified polyimide (A) is the main component of the pressure-sensitive adhesive composition, the content of the silicone-modified polyimide (A) is preferably 100 parts by weight at the lower limit and 400 parts by weight at the upper limit per 100 parts by weight of the curable resin (B) having a double bond. When the content of the silicone-modified polyimide (A) is within this range, the pressure-sensitive adhesive composition can exhibit superior releasability without contaminating the adherend. From the viewpoint of further improving releasability while suppressing contamination of the adherend, the content of the silicone-modified polyimide (A) is more preferably 150 parts by weight at the lower limit and 300 parts by weight at the upper limit, and even more preferably 200 parts by weight at the lower limit and 250 parts by weight at the upper limit. The silicone-modified polyimide (A) being the main component of the pressure-sensitive adhesive composition means that the content of the silicone-modified polyimide (A) is, for example, 50% by weight or more, preferably more than 50% by weight, of the total amount of resin components constituting the pressure-sensitive adhesive composition (e.g., the silicone-modified polyimide (A), curable resin (B) having a double bond, etc.). The content of the silicone-modified polyimide (A) is usually less than 100% by weight, preferably 90% by weight or less, more preferably 80% by weight or less of the total amount of resin components constituting the pressure-sensitive adhesive composition.

[0036] The pressure-sensitive adhesive composition of the present invention contains a curable resin (B) having a double bond. By including the curable resin (B), the entire pressure-sensitive adhesive composition is polymerized and crosslinked uniformly and quickly upon irradiation with light or heating, and the elastic modulus is increased, resulting in a significant decrease in adhesive strength. This prevents adhesion enhancement, allowing the composition to be easily peeled off from an adherend even after prolonged treatment at 250°C or higher or high-temperature treatment at 300°C or higher while the composition is fixed to the adherend.

[0037] The curable resin (B) is not particularly limited as long as it has a functional group having a double bond. The functional group having a double bond is not particularly limited, and examples thereof include an optionally substituted maleimide group, a citraconic imide group, a vinyl ether group, an allyl group, and a (meth)acrylic group. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance.

[0038] The content of the curable resin (B) is not particularly limited, but when the silicone-modified polyimide (A) is not the main component of the pressure-sensitive adhesive composition, it is, for example, 50% by weight or more, preferably more than 50% by weight, of the total amount of resin components constituting the pressure-sensitive adhesive composition (e.g., the silicone-modified polyimide (A), the curable resin (B) having a double bond, etc.). The content of the curable resin (B) is usually less than 100% by weight, preferably 90% by weight or less, of the total amount of resin components constituting the pressure-sensitive adhesive composition. When the silicone-modified polyimide (A) is the main component of the pressure-sensitive adhesive composition, the content of the curable resin (B) is preferably 20% by weight or more, more preferably 25% by weight or more, and even more preferably 30% by weight or more of the total amount of resin components constituting the pressure-sensitive adhesive composition (e.g., the silicone-modified polyimide (A), the curable resin (B) having a double bond, etc.). The content of the curable resin (B) is preferably 50% by weight or less, more preferably 40% by weight or less, and even more preferably 35% by weight or less of the total amount of resin components constituting the pressure-sensitive adhesive composition.

[0039] Specific examples of the curable resin (B) include polyimide resins having double bonds, acrylic resins having double bonds, etc. Among these, polyimide resins having double bonds are preferred. The curable resin (B) is a polyimide resin having an imide skeleton, which allows the pressure-sensitive adhesive composition to exhibit particularly high heat resistance, thereby further suppressing the generation of residues due to thermal degradation and improving releasability. In particular, the curable resin (B) preferably contains a curable resin (B1) having an imide skeleton in the main chain and a functional group having a double bond in the side chain or at the terminal.

[0040] The curable resin (B1) preferably has a double bond functional group equivalent (weight average molecular weight / number of double bond functional groups) of 4000 or less. Having a functional group equivalent of 4000 or less allows the pressure-sensitive adhesive composition to exhibit higher heat resistance. This is thought to be because the presence of double bond functional groups at a density above a certain level in the molecules of the curable resin (B1) shortens the inter-crosslink distance, thereby further suppressing adhesion enhancement. The functional group equivalent is more preferably 3000 or less, and even more preferably 2000 or less. There is no particular restriction on the lower limit of the functional group equivalent, but the lower limit is substantially about 600.

[0041] The curable resin (B1) preferably has a weight-average molecular weight of 5,000 or more. When the curable resin (B1) has a weight-average molecular weight of 5,000 or more, film formation becomes easy, and the resulting film exhibits a certain degree of flexibility, allowing it to exhibit high conformability to an adherend having irregularities and to be easily peeled off from the adherend. The weight-average molecular weight of the curable resin (B1) is more preferably 10,000 or more, and even more preferably 20,000 or more. The upper limit of the weight-average molecular weight of the curable resin (B1) is not particularly limited, but is, for example, 300,000, particularly 100,000, since the solubility in solvents becomes low.

[0042] The double bond-containing functional group may be present either in a side chain or at a terminal of the curable resin (B1). The double bond-containing functional group is preferably present at both terminals of the curable resin (B1), and more preferably present at both terminals and also in a side chain. The double bond-containing functional groups at both terminals of the curable resin (B1) are highly reactive, allowing the pressure-sensitive adhesive composition to be cured more sufficiently by irradiation with light or heating. As a result, adhesion enhancement can be further suppressed, and the pressure-sensitive adhesive composition can exhibit higher heat resistance. Furthermore, the presence of a functional group having a double bond in the side chain of the curable resin (B1) allows the pressure-sensitive adhesive composition to exhibit higher heat resistance. This is thought to be because the shorter inter-crosslink distance further suppresses adhesion enhancement. Furthermore, the presence of a functional group having a double bond in the side chain of the curable resin (B1) makes it easier to adjust the weight-average molecular weight and the functional group equivalent within the above ranges.

[0043] The curable resin (B1) preferably further contains a hydroxyl group-containing group. When the curable resin (B1) has the hydroxyl group-containing group, the hydroxyl group reacts with, for example, a maleimide group of another component upon heating, thereby further increasing the elastic modulus of the pressure-sensitive adhesive composition and further decreasing the adhesive strength, thereby further suppressing the adhesion of the pressure-sensitive adhesive composition and improving the releasability.

[0044] The hydroxyl group-containing group is not particularly limited, and may have an alcoholic hydroxyl group or a phenolic hydroxyl group, with the phenolic hydroxyl group being preferred due to its high reactivity. Examples of the hydroxyl group-containing group having an alcoholic hydroxyl group include aliphatic or aromatic groups having an alcoholic hydroxyl group and having 3 to 18 carbon atoms. Examples of the hydroxyl group-containing group having a phenolic hydroxyl group include aromatic groups having a phenolic hydroxyl group and having 6 to 24 carbon atoms, more specific examples include phenol, bisphenol A, bisphenol F, biphenol, and 2,2'-bis(4-hydroxyphenyl)hexafluoropropane. Of these, 2,2'-bis(4-hydroxyphenyl)hexafluoropropane is preferred because it provides good releasability.

[0045] The curable resin (B1) preferably has a functional group equivalent (weight average molecular weight / number of hydroxyl-containing groups) of 5,000 or less. Having a functional group equivalent of 5,000 or less further suppresses increased adhesion of the pressure-sensitive adhesive composition, improving peelability. This is thought to be because the presence of hydroxyl-containing groups at a certain density or higher in the molecules of the curable resin (B1) shortens the inter-crosslink distance. The functional group equivalent is more preferably 3,000 or less, and even more preferably 1,000 or less. There is no particular restriction on the lower limit of the functional group equivalent, but the lower limit is substantially about 500.

[0046] More specifically, the curable resin (B1) has a constitutional unit represented by the following general formula (1d), a constitutional unit represented by the following general formula (1e), and a constitutional unit represented by the following general formula (1f) (where s2≧1, t2≧0, u2≧0), and both ends of the constitutional unit are each represented by X 4 - and X 5 Preferably, the curable resin (B1-1) is represented by the formula:

[0047] [ka]

[0048] In general formulas (1d) to (1f), P 4 , P 5 and P 6 each independently represents an alicyclic group or an aromatic group. 3 represents a substituted or unsubstituted linear, branched or cyclic aliphatic group; Q 4 represents a substituted or unsubstituted aromatic group, and R represents a substituted or unsubstituted branched aliphatic or aromatic group. 4 , X 5 and X 6 At least one selected from the group consisting of represents a functional group having a double bond, and X 6 n2 In the formula, n2 represents an integer of 1 or more.

[0049] In the above general formulas (1d) to (1f), P 4 , P 5 and P 6 are preferably each independently an alicyclic group or an aromatic group having 5 to 50 carbon atoms. 4 , P 5 and P 6 are each independently an alicyclic group or aromatic group having 5 to 50 carbon atoms, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance.

[0050] In the above general formula (1d), Q 3 is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. 3 is a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, the pressure-sensitive adhesive sheet produced using the pressure-sensitive adhesive composition can exhibit high flexibility and can exhibit high conformability to an adherend having irregularities, and the releasability is also improved. Also, Q 3 is preferably an aliphatic group derived from the diamine compound described above. Among these, from the viewpoint of enhancing flexibility and increasing compatibility with the solvent and other components of the curable resin (B1-1), thereby facilitating production of the adhesive tape, Q is preferably an aliphatic group derived from the diamine compound described above. 3is preferably an aliphatic group derived from dimer diamine.

[0051] The aliphatic group derived from the dimer diamine is not particularly limited, but is preferably at least one selected from the group consisting of a group represented by the following general formula (4-1), a group represented by the following general formula (4-2), a group represented by the following general formula (4-3), and a group represented by the following general formula (4-4). Among these, the group represented by the following general formula (4-2) is more preferred.

[0052] [ka]

[0053] In the above general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 are each independently a linear or branched hydrocarbon group. Note that * represents a bond. That is, * is bonded to N in the above general formulae (1d) to (1f).

[0054] In the above general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 The hydrocarbon group represented by R is not particularly limited, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 , and R 19 and R 20The total number of carbon atoms is preferably 7 or more and 50 or less. When the total number of carbon atoms is within the above range, the pressure-sensitive adhesive tape produced using the pressure-sensitive adhesive composition can exhibit higher flexibility, and the compatibility with the solvent and other components of the curable resin (B1-1) can also be further improved. The total number of carbon atoms is more preferably 9 or more, even more preferably 12 or more, and even more preferably 14 or more. The total number of carbon atoms is more preferably 35 or less, even more preferably 25 or less, and even more preferably 18 or less.

[0055] The optical isomerism of the group represented by the general formula (4-1), the group represented by the general formula (4-2), the group represented by the general formula (4-3), and the group represented by the general formula (4-4) is not particularly limited, and includes any optical isomerism.

[0056] In the above general formula (1e), Q 4 is preferably a substituted or unsubstituted aromatic group having 5 to 50 carbon atoms. 4 When Q is a substituted or unsubstituted aromatic group having 5 to 50 carbon atoms, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance. 4 is preferably the above hydroxyl group-containing group.

[0057] In the above general formula (1f), R is preferably a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms, a pressure-sensitive adhesive sheet produced using the pressure-sensitive adhesive composition can exhibit high flexibility and can exhibit high conformability to an adherend having unevenness, and also has improved releasability.

[0058] In the general formula (1f), R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or the aromatic ether group in R is X 6 It is preferred that the compound is bonded to Here, the term "aromatic ester group" refers to a group in which an ester group is directly bonded to an aromatic ring, and the term "aromatic ether group" refers to a group in which an ether group is directly bonded to an aromatic ring. By converting the moiety bonded to the ester group or ether group into an aromatic group, the pressure-sensitive adhesive composition can exhibit high heat resistance. On the other hand, X 6 is bonded to R via an aromatic ester group or an aromatic ether group, whereby X 6 Since the double bond in the middle is not conjugated with R, it does not interfere with polymerization and cross-linking when irradiated with light.

[0059] In the curable resin (B1-1), the functional group having a double bond (crosslinkable unsaturated bond) is X 4 , X 5 and X 6 At least one selected from the group consisting of 6 is preferably a functional group having a double bond. 6 When is a functional group having a double bond, the pressure-sensitive adhesive composition can exhibit higher heat resistance. Above X 4 , X 5 and X 6 When any of the above is a functional group other than a functional group having a double bond (a functional group having no double bond), the functional group having no double bond can each independently be, for example, an aliphatic group, an alicyclic group, an aromatic group, a structure derived from an acid anhydride, a structure derived from an amine compound, etc. Specific examples include a structure derived from an unreacted end of an acid anhydride or diamine compound that is a raw material for the curable resin (B1-1). In the curable resin (B1-1), X 6 n2 In the formula, n2 is preferably an integer of 10 or less, more preferably 8 or less, even more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. In the curable resin (B1-1), the plurality (n2) of X's contained in one structural unit 6 may be the same or different.

[0060] In the curable resin (B1-1), s2 is 1 or more, preferably 3 or more, and preferably 10 or less, more preferably 5 or less. t2 is 0 or more, preferably 1 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. u2 is 0 or more, preferably 1 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less. When s2, t2, and u2 are within the above ranges, increased adhesion of the pressure-sensitive adhesive composition is further suppressed, and releasability is also improved. In the curable resin (B1-1), the structural unit represented by the general formula (1d), the structural unit represented by the general formula (1e), and the structural unit represented by the general formula (1f) may be a block copolymer consisting of block components in which the respective structural units are arranged consecutively, or may be a random copolymer in which the respective structural units are arranged randomly.

[0061] The curable resin (B1-1) can be produced, for example, by reacting a diamine compound with an aromatic acid anhydride to obtain an imide compound. At this time, a diamine compound having a functional group is used as the diamine compound, and the functional group in the obtained imide compound is reacted with a compound having a functional group reactive with the functional group and a functional group having a double bond (the above-mentioned functional group-containing unsaturated compound), thereby introducing a functional group having a double bond into the side chain. The diamine compound, aromatic acid anhydride, and functional group-containing unsaturated compound are not particularly limited, and examples thereof include the same diamine compound, aromatic acid anhydride, and functional group-containing unsaturated compound as those used in obtaining the silicone-modified polyimide (A) described above.

[0062] The content of the curable resin (B1) relative to the total curable resin (B) is not particularly limited, but a preferred lower limit is 30% by weight. If the content of the curable resin (B1) is 30% by weight or more, the adhesion of the pressure-sensitive adhesive composition is further suppressed and the peelability is improved. A more preferred lower limit of the content of the curable resin (B1) is 50% by weight. The upper limit of the content of the curable resin (B1) relative to the total amount of the curable resin (B) is not particularly limited, and may be 100% by weight.

[0063] Examples of the curable resin (B) include a polyfunctional monomer or oligomer (B2) having at least two maleimide groups, and a polyfunctional monomer or oligomer (B3) having at least two vinyl ether groups or allyl groups. These polyfunctional monomers or oligomers are preferably used in combination with the curable resin (B1). By using these polyfunctional monomers or oligomers in combination with the curable resin (B1), the three-dimensional network formation of the pressure-sensitive adhesive composition by light irradiation or heating can be more efficiently achieved, thereby further suppressing increased adhesion of the pressure-sensitive adhesive composition and improving releasability.

[0064] The polyfunctional monomer or polyfunctional oligomer (B2) is not particularly limited, but is preferably a polyfunctional monomer or polyfunctional oligomer having at least two maleimide groups and a molecular weight of not more than 5000. Specific examples include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, and bismaleimides having a structure derived from dimer diamine. The bismaleimide having a structure derived from dimer diamine preferably has at least one structure derived from dimer diamine selected from the group consisting of a group represented by the general formula (4-1), a group represented by the general formula (4-2), a group represented by the general formula (4-3), and a group represented by the general formula (4-4). Among these, the group represented by the general formula (4-2) is more preferred. These polyfunctional monomers or polyfunctional oligomers (B2) may be used alone or in combination of two or more kinds.

[0065] By including the polyfunctional monomer or polyfunctional oligomer (B3), a pressure-sensitive adhesive sheet produced using the pressure-sensitive adhesive composition can exhibit high flexibility, can exhibit high conformability to an adherend having unevenness, and also has improved releasability. The polyfunctional monomer or oligomer (B3) is not particularly limited, but is preferably a polyfunctional monomer or oligomer having at least two vinyl ether groups or allyl groups with a molecular weight of 10,000 or less. Specific examples include triallyl isocyanurate, cyclohexane divinyl ether, polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, and Crossmer U (trade name, vinyl ether-terminated polyester). These polyfunctional monomers or oligomers (B3) may be used alone or in combination of two or more.

[0066] The total content of the curable resin (B2) and the curable resin (B3) in the entire curable resin (B) is not particularly limited, but a preferred lower limit is 20% by weight. If the total content of the curable resin (B2) and the curable resin (B3) is 20% by weight or more, the adhesion of the pressure-sensitive adhesive composition is further suppressed and the releasability is improved. A more preferred lower limit of the total content of the curable resin (B2) and the curable resin (B3) is 50% by weight. The upper limit of the total content of the curable resins (B2) and (B3) relative to the total content of the curable resin (B) is not particularly limited and may be 100% by weight. Note that the pressure-sensitive adhesive composition may contain only one of the curable resins (B2) and (B3), or both of them.

[0067] The pressure-sensitive adhesive composition of the present invention preferably further contains a photopolymerization initiator. The photopolymerization initiator may be, for example, one that is activated by irradiation with light having a wavelength of 250 to 800 nm. Examples of the photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone, benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal, and phosphine oxide derivative compounds. Further examples include photoradical polymerization initiators such as bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone or in combination of two or more.

[0068] The content of the photopolymerization initiator is not particularly limited, but a preferred lower limit is 0.1 parts by weight and a preferred upper limit is 10 parts by weight per 100 parts by weight of the curable resin (B). When the content of the photopolymerization initiator is within this range, the entire pressure-sensitive adhesive composition is polymerized and crosslinked uniformly and quickly upon irradiation with light, and the elastic modulus increases, resulting in a significant decrease in adhesive strength and easy peeling. A more preferred lower limit of the content of the photopolymerization initiator is 0.3 parts by weight and a more preferred upper limit is 3 parts by weight.

[0069] The pressure-sensitive adhesive composition of the present invention may further contain a gas-generating agent that generates gas upon irradiation with light. By containing the gas-generating agent, even after prolonged high-temperature processing at 250°C or higher or high-temperature processing at 300°C or higher, the gas generated upon irradiation with light is released at the interface with the adherend, making it possible to peel the adherend more easily and without leaving any adhesive residue.

[0070] Examples of the gas generating agent include tetrazole compounds or salts thereof, triazole compounds or salts thereof, azo compounds, azide compounds, xanthone acetate, carbonates, and the like.

[0071] The tetrazole compound or salt thereof is not particularly limited, and examples thereof include monotetrazole compounds, bistetrazole compounds, azobistetrazole compounds, and salts thereof. Specific examples of the monotetrazole compound or a salt thereof include 1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 1-methyl-5-mercaptotetrazole, 1-methyl-5-ethyl-tetrazole, 1-(dimethylaminoethyl)-5-mercaptotetrazole, 1H-5-hydroxy-tetrazole, 1-methyl-5-ethyltetrazole, 1-propyl-5-methyl-tetrazole, 1-phenyl-5-hydroxytetrazole, 1-phenyl-5-mercaptotetrazole, 1-(p-ethoxyphenyl)-5-mercaptotetrazole, 1-(4 -benzamido)-5-mercaptotetrazole, 5-tolyltetrazole, 5-phenyltetrazole, 5-aminotetrazole monohydrate, 5-(m-aminophenyl)tetrazole, 5-acetamidotetrazole, N-(1H-tetrazol-5-yl)-n-octanamide, 1-cyclohexyl-5-chlorobutyltetrazole, 1-(m-acetaminophenyl)-5-mercaptotetrazole, 1-methyl-5-mercaptotetrazole, 1-(4-carboxyphenyl)-5-mercaptotetrazole, 1-methyl-5-ethyltetrazole, 5-aminomethyl-1-H-tetrazole, 4,5-di(-tetrazolyl)-[1,2,3]triazole, and the like. Specific examples of the bistetrazole compound or a salt thereof include 5,5'-bistetrazole diammonium salt, 5,5'-bistetrazole disodium salt, 5,5'-bistetrazole dipiperadium salt, and the like. Specific examples of the azobistetrazole compound include 5,5-azobis-1H-tetrazole, a compound of 5,5-azobis-1H-tetrazole and guanidine, and a compound of 5,5-1H-azobistetrazole and methylguanidine. These gas generating agents may be used alone or in combination of two or more. Among them, bistetrazole compounds or salts thereof are preferred because of their excellent heat resistance.

[0072] The content of the gas generating agent is not particularly limited, but a preferred lower limit is 5 parts by weight and a preferred upper limit is 50 parts by weight relative to 100 parts by weight of the total of the silicone-modified polyimide (A) and the curable resin (B). When the content of the gas generating agent is within this range, the pressure-sensitive adhesive composition can exhibit particularly excellent releasability. A more preferred lower limit of the content of the gas generating agent is 8 parts by weight and a more preferred upper limit is 30 parts by weight.

[0073] The pressure-sensitive adhesive composition of the present invention may contain known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, resins, surfactants, waxes, and fine particle fillers.

[0074] Examples of the particulate filler include inorganic fillers made of at least one selected from the group consisting of oxides of silicon, titanium, aluminum, calcium, boron, magnesium, cerium, and zirconia, talc, mica, and composites thereof, among which silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, silica-titania composite oxide, and talc are preferred.

[0075] The average particle size of the inorganic filler is not particularly limited, but the preferred lower limit is 0.1 μm and the preferred upper limit is 30 μm. The content of the inorganic filler is not particularly limited, but a preferred lower limit is 5 parts by weight and a preferred upper limit is 100 parts by weight, based on 100 parts by weight of the total of the silicone-modified polyimide (A) and the curable resin (B). A more preferred lower limit of the content of the inorganic filler is 10 parts by weight and a more preferred upper limit is 50 parts by weight.

[0076] The pressure-sensitive adhesive composition of the present invention preferably has a weight loss rate of 5% by weight or less, more preferably 3% by weight or less, after curing and heating at 300°C, measured at a heating rate of 10°C / min. When the weight loss rate is within the above range, the pressure-sensitive adhesive composition can exhibit particularly high heat resistance, thereby further suppressing adhesion enhancement and improving releasability. The weight and weight loss rate after heating at 300°C can be measured by taking 10 mg of a sample after UV irradiation and curing, placing it in an aluminum cup, and using, for example, a thermogravimetric analyzer STA7200 (manufactured by Hitachi High-Tech Science Corporation) at a heating rate of 10°C / min. UV irradiation was performed using an ultra-high pressure mercury lamp, irradiating 365 nm UV light at 20 mW / cm. 2 The irradiation is carried out for 150 seconds at an intensity of .

[0077] The method for adjusting the weight loss rate within the above range is not particularly limited, and examples thereof include a method of selecting and using the silicone-modified polyimide (A) or the curable resin (B) that have higher heat resistance. Examples of methods for improving the heat resistance of the silicone-modified polyimide (A) include a method of increasing the content of aromatic groups and a method of reducing the molecular weight of the silicone chain in the constituent unit.

[0078] The method for producing the pressure-sensitive adhesive composition of the present invention is not particularly limited, and examples thereof include a method in which the silicone-modified polyimide (A), the curable resin (B), and additives to be blended as necessary are mixed using a bead mill, ultrasonic dispersion, homogenizer, high-power disperser, roll mill, etc.

[0079] The present invention also includes a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present invention. The pressure-sensitive adhesive tape of the present invention may be a support tape having a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of the present invention on one or both surfaces of a substrate, or may be a non-support tape having no substrate.

[0080] Examples of the substrate include sheets made of transparent resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, etc. Sheets having a mesh structure, sheets with holes, etc. can also be used.

[0081] The pressure-sensitive adhesive composition and pressure-sensitive adhesive tape of the present invention have initial adhesive strength while suppressing adhesion enhancement, and can be easily peeled off even after undergoing high-temperature processing at 250°C or higher for a long period of time or at 300°C or higher while the adherend is fixed thereto. Therefore, the pressure-sensitive adhesive composition and pressure-sensitive adhesive tape of the present invention can be suitably used for protecting or temporarily fixing an adherend that will undergo high-temperature processing at 250°C or higher for a long period of time or at 300°C or higher. In particular, the pressure-sensitive adhesive composition and pressure-sensitive adhesive tape can be suitably used for protecting electronic components such as semiconductors by fixing the electronic components to a support plate via the pressure-sensitive adhesive composition or pressure-sensitive adhesive tape or by attaching the pressure-sensitive adhesive tape to the electronic components, in order to facilitate handling of the electronic components and prevent damage during processing of the electronic components.

[0082] Specifically, for example, the method for treating an electronic component includes the steps of (1) temporarily fixing an electronic component on the pressure-sensitive adhesive tape of the present invention, (2) curing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape of the present invention, (3) heat-treating the electronic component, and (4) peeling the pressure-sensitive adhesive tape of the present invention from the electronic component. Such a method for treating an electronic component also constitutes one aspect of the present invention. Although step (2) of curing the adhesive layer of the pressure-sensitive adhesive tape of the present invention may be carried out immediately before step (4) of peeling the pressure-sensitive adhesive tape of the present invention from the electronic component, it is preferably carried out after step (1) of temporarily fixing the electronic component on the pressure-sensitive adhesive tape of the present invention and before step (3) of heat-treating the electronic component, which allows the pressure-sensitive adhesive tape of the present invention to exhibit better heat resistance. [Effects of the Invention]

[0083] According to the present invention, it is possible to provide a pressure-sensitive adhesive composition that can be easily peeled off even after being subjected to a long-term high-temperature processing treatment at 250° C. or higher or 300° C. or higher while the adherend is fixed thereto. Furthermore, according to the present invention, it is possible to provide a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition, and a method for treating electronic components using the pressure-sensitive adhesive tape. DETAILED DESCRIPTION OF THE INVENTION

[0084] The following examples further illustrate aspects of the present invention, but the present invention is not limited to these examples.

[0085] (Preparation of Silicone-Modified Polyimide (A)) According to the procedures of the following Synthesis Examples 1 to 11, silicone-modified polyimides (A) (Synthesis Examples 1 to 11) having the structures shown in Table 1 were prepared.

[0086] (1) Synthesis Example 1 A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 34.4 g (0.04 mol) of a silicone compound having amino groups at both ends (KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 11, weight-average molecular weight 860) and 31.2 g (0.06 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 1). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 1) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 6,000.

[0087] (2) Synthesis Example 2 A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 88 g (0.02 mol) of a silicone compound having amino groups at both ends (KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 60, weight-average molecular weight 4400) and 15.6 g (0.03 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 2). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 2) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 10,000.

[0088] (3) Synthesis Example 3 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon stirrer. Next, 60 g (0.02 mol) of a silicone compound having amino groups at both ends (X-22-161B, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 40, weight-average molecular weight 3000) was added. Furthermore, 5610.7 g (0.02 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 31.2 g (0.06 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 3). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 3) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 15,000.

[0089] (4) Synthesis Example 4 A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 48 g (0.03 mol) of a silicone compound having amino groups at both ends (X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 21, weight-average molecular weight 1600) and 31.2 g (0.06 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 4). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 4) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 3,000.

[0090] (5) Synthesis Example 5 A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 80 g (0.05 mol) of a silicone compound having amino groups at both ends (X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 21, weight-average molecular weight 1600) and 26 g (0.05 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 5). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 5) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 50,000.

[0091] (6) Synthesis Example 6 (Silicone-modified polyimide (A) having terminal maleimide groups) A 500 mL round-bottom flask equipped with a Teflon® stirrer was charged with 250 mL of toluene. Next, 96 g (0.06 mol) of a silicone compound bearing amino groups at both ends (X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 21, weight-average molecular weight 1600) and 20.8 g (0.04 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added, in this order. A Dean-Stark tube and condenser were attached to the flask, and the mixture was refluxed for 2 hours to synthesize an amine-terminated polyimide. After cooling the reaction mixture below room temperature, 2.0 g (0.02 mol) of maleic anhydride was added, followed by 35 g (0.35 mol) of methanesulfonic anhydride. The reaction mixture was refluxed for an additional 12 hours, cooled to room temperature, and then filtered through a glass fritted funnel filled with silica gel to obtain silicone-modified polyimide (A) (Synthesis Example 6). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 6) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 7,000.

[0092] (7) Synthesis Example 7 (Silicone-modified polyimide (A) having an allyl group in the side chain) A 500 mL round-bottom flask equipped with a Teflon® stirrer was charged with 250 mL of toluene. Next, 64 g (0.04 mol) of a silicone compound bearing amino groups at both ends (X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 21, weight-average molecular weight 1600) was added. 5.2 g (0.02 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane and 20.8 g (0.04 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added, in that order. A Dean-Stark tube and condenser were attached to the flask, and the mixture was refluxed for 2 hours. After that, 5.7 g (0.05 mol) of Neoallyl G (allyl glycidyl ether, manufactured by Osaka Soda Co., Ltd.) and 0.2 g (2 mmol) of triethylamine were added, and the mixture was heated for an additional 3 hours. The mixture was cooled to room temperature to obtain a silicone-modified polyimide (A) (Synthesis Example 7). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 7) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 8,000.

[0093] (8) Synthesis Example 8 (Hydroxyl Group-Containing Silicone-Modified Polyimide (A)) A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 64 g (0.04 mol) of a silicone compound having amino groups at both ends (X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 21, weight-average molecular weight 1600) was added. 5.2 g (0.02 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane and 20.8 g (0.04 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added, in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 8). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 8) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 6,000.

[0094] (9) Synthesis Example 9 A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 20.8 g (0.08 mol) of a silicone compound having amino groups at both ends (PAM-E, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 3, weight-average molecular weight 260) and 62.4 g (0.12 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 9). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 9) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 5,000.

[0095] (10) Synthesis Example 10 A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 114 g (0.01 mol) of a silicone compound having amino groups at both ends (KF-8008, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 150, weight-average molecular weight 11,400) and 10.4 g (0.02 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 10). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 10) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 50,000.

[0096] (11) Synthesis Example 11 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon stirrer. Next, 88 g (0.02 mol) of a silicone compound having amino groups at both ends (KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 60, weight-average molecular weight 4400) was added. Furthermore, 16 g (0.03 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 26 g (0.05 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain silicone-modified polyimide (A) (Synthesis Example 11). The weight average molecular weight of the obtained silicone-modified polyimide (A) (Synthesis Example 11) was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (Waters Corporation) column, and was found to be 100,000.

[0097] [Table 1]

[0098] (Preparation of Curable Resin (B)) (1) Synthesis of bifunctional maleimide represented by the following formula (11): 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon stirrer. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 56 g (0.1 mol) of dimer diamine (Croda, Priamine 1075) and 19.1 g (0.09 mol) of pyromellitic anhydride were added, in that order. A Dean-Stark tube and condenser were attached to the flask, and the mixture was refluxed for 2 hours to synthesize polyimide. After cooling the reaction mixture to room temperature, 12.8 g (0.13 mol) of maleic anhydride was added, followed by 5 g (0.05 mol) of methanesulfonic anhydride. The reaction mixture was refluxed for an additional 12 hours, cooled to room temperature, and 300 mL of toluene was added to the flask. Impurities were precipitated and removed by standing. The resulting solution was filtered through a glass fritted funnel filled with silica gel to obtain a bifunctional maleimide represented by the following formula (11). The weight-average molecular weight of the obtained bifunctional maleimide was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (manufactured by Waters Corporation) as a column, and was found to be 15,000.

[0099] [ka]

[0100] (2) Synthesis of bifunctional maleimide represented by the following formula (12) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 56 g (0.1 mol) of dimer diamine (Croda, Priamine 1075) and 19.6 g (0.2 mol) of maleic anhydride were added, followed by 5 g of methanesulfonic anhydride. The solution was refluxed for 12 hours, cooled to room temperature, and 300 mL of toluene was added to the flask. The salt was allowed to settle and removed. The resulting solution was filtered through a glass-fritted funnel filled with silica gel to obtain a bifunctional maleimide represented by the following formula (12).

[0101] [ka]

[0102] (Synthesis of acrylic resin) A reactor equipped with a stirrer and a condenser was prepared. 94 parts by weight of 2-ethylhexyl acrylate as a (meth)acrylic acid alkyl ester, 6 parts by weight of hydroxyethyl methacrylate as a functional group-containing monomer, 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate were added to the reactor. The reactor was then heated to initiate reflux. Subsequently, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator was added to the reactor, and polymerization was initiated under reflux. Next, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added at 1 hour and 2 hours after the start of polymerization. Furthermore, 0.05 parts by weight of t-hexylperoxypivalate was added 4 hours after the start of polymerization to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% by weight and a weight-average molecular weight of 600,000 was obtained. 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound was added to 100 parts by weight of the resin solid content of the obtained ethyl acetate solution containing the functional group-containing (meth)acrylic polymer, and the mixture was reacted to obtain an acrylic resin.

[0103] Example 1 300 mL of toluene was prepared. To this was added 10 parts by weight of silicone-modified polyimide (A) (Synthesis Example 1), 60 parts by weight of the bifunctional maleimide represented by the above formula (11), 30 parts by weight of the bifunctional maleimide represented by the above formula (12), 3 parts by weight of Omnirad 819 (manufactured by IGM Resins) as a photopolymerization initiator, and 10 parts by weight of silica (Reolosil MT-10, manufactured by Tokuyama Corporation) as an inorganic filler. This prepared a toluene solution of the pressure-sensitive adhesive composition. The obtained toluene solution of the pressure-sensitive adhesive composition was applied to the corona-treated surface of a 25 μm-thick polyimide film (Kapton, manufactured by Ube Industries, Ltd.) that had been corona-treated on one side, using a doctor knife to give a dried film thickness of 40 μm, and the coating solution was dried by heating at 110° C. for 1 minute. Thereafter, the film was left to stand and aged at 40° C. for 3 days to obtain a pressure-sensitive adhesive tape. The adhesive tape was then irradiated with 365 nm ultraviolet light at 20 mW / cm using an ultra-high pressure mercury lamp. 2 After curing by UV irradiation, 10 mg of the adhesive tape was sampled and placed in an aluminum cup, and the weight fraction after heating to 300°C at a heating rate of 10°C / min was measured using a thermogravimetric analyzer STA7200 (Hitachi High-Tech Science Corporation).

[0104] (Examples 2 to 1 0, 13~19, Reference Examples 11~12, Comparative Examples 1-2) An adhesive tape was obtained in the same manner as in Example 1, except that the ingredients were changed as shown in Table 2. Details of the materials shown in Table 2 are described below. NK Ester A-9300 (ethoxylated isocyanuric acid triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) Bistetrazole disodium salt (Masuda Chemical Co., Ltd.)

[0105] <Evaluation> Example , Reference Examples, The adhesive tapes obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Table 2.

[0106] (1) Evaluation of peelability (measurement of adhesive strength) The obtained adhesive tape was cut into a width of 1 inch and then heat-laminated onto a 1 mm thick glass sheet using a laminator at 100°C. After lamination, 365 nm ultraviolet light was applied from the glass side at 20 mW / cm using an ultra-high pressure mercury lamp. 2 After the ultraviolet irradiation, the glass side was heated on a hot plate at 300°C for 10 minutes. After UV irradiation and heating at 300°C, the test pieces were subjected to a 180° peel test at 25°C and a pulling speed of 30 mm / sec to measure the adhesive strength (N / inch).

[0107] (2) Evaluation of lifting and residue after heating at 250°C for 30 minutes The obtained adhesive tape was cut into a width of 1 inch and then heat-laminated onto a 1 mm thick glass sheet using a laminator at 100°C. After lamination, 365 nm ultraviolet light was applied from the glass side at 20 mW / cm using an ultra-high pressure mercury lamp. 2 After the ultraviolet irradiation, the glass side was heated on a hot plate at 250°C for 30 minutes. After heating at 250°C for 30 minutes, the test piece was visually inspected for any separation of the adhesive tape from the glass. 〇: No floating occurred △: The area of the float was less than one-tenth of the total area ×: The area of the float was more than one-tenth of the total area

[0108] Furthermore, a 180° peel test was performed on the test piece after heating at 250°C for 30 minutes at 25°C and a pulling speed of 30 mm / sec. After peeling the adhesive tape, the glass surface was visually observed and evaluated according to the following criteria. 〇: No adhesive residue was observed △: No adhesive residue was found, but cloudiness was observed on the peeled surface. ×: Adhesive residue was observed

[0109] [Table 2] [Industrial Applicability]

[0110] According to the present invention, it is possible to provide a pressure-sensitive adhesive composition that can be easily peeled off even after being subjected to a long-term high-temperature processing treatment at 250° C. or higher or 300° C. or higher while the adherend is fixed thereto. Furthermore, according to the present invention, it is possible to provide a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition, and a method for treating electronic components using the pressure-sensitive adhesive tape.

Claims

1. The composition contains a silicone-modified polyimide (A) and a curable resin (B) having a double bond and having a structure other than that of the silicone-modified polyimide (A), The silicone-modified polyimide (A) has a silicone chain having a repeating number of siloxane units of 10 or more and 100 or less, the curable resin (B) having a double bond contains at least one selected from the group consisting of a curable resin (B1) having an imide skeleton in its main chain and functional groups having double bonds at both ends, and a polyfunctional monomer or polyfunctional oligomer (B2) having a structure other than the curable resin (B1) having an imide skeleton in its main chain and functional groups having double bonds at both ends, and having at least two maleimide groups; The curable resin (B1) having an imide skeleton in its main chain and functional groups having double bonds at both ends is a curable resin (B1-1) having a structural unit represented by the following general formula (1d) and a structural unit represented by the following general formula (1e) (where s2≧1 and t2≧0), and having functional groups having double bonds at both ends, The polyfunctional monomer or polyfunctional oligomer (B2) having at least two maleimide groups has a structure derived from dimer diamine, The content of the silicone-modified polyimide (A) is 0.5 parts by weight or more and 400 parts by weight or less per 100 parts by weight of the curable resin (B) having a double bond. A pressure-sensitive adhesive composition characterized by: 【Chemical 1】 In general formulas (1d) to (1e), P 4 and P 5 each independently represent a cyclic aliphatic group or an aromatic group, Q 3 represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group, and Q 4 represents a substituted or unsubstituted aromatic group.

2. 2. The pressure-sensitive adhesive composition according to claim 1, wherein the weight loss rate after curing at 300°C measured at a heating rate of 10°C / min is 5% by weight or less.

3. 3. The pressure-sensitive adhesive composition according to claim 1, wherein the silicone-modified polyimide (A) is a silicone-modified polyimide having a structural unit represented by the following general formula (1a) and a structural unit represented by the following general formula (1b) (where s1≧1, t1≧0): 【Chemistry 2】 In general formulas (1a) to (1b), P １ and P2 each independently represent a cyclic aliphatic group or an aromatic group. １ represents a silicone chain, and Q ２ represents a substituted or unsubstituted aliphatic or aromatic group.

4. The pressure-sensitive adhesive composition according to claim 1 or 2, characterized in that the silicone-modified polyimide (A) is a silicone-modified polyimide having a constituent unit represented by the following general formula (1a) and a constituent unit represented by the following general formula (1c) (where s1≧1, u1≧0): 【Chemistry 3】 In general formulas (1a) and (1c), P1 and P3 each independently represent a cyclic aliphatic group or an aromatic group. Q1 represents a silicone chain, R represents a substituted or unsubstituted branched aliphatic group or an aromatic group. X3 represents a substituted or unsubstituted aliphatic group or an aromatic group, and n1 in X3n1 represents an integer of 1 or greater.

5. The pressure-sensitive adhesive composition according to claim 1 or 2, characterized in that the silicone-modified polyimide (A) is a silicone-modified polyimide having a constituent unit represented by the following general formula (1a) and a constituent unit represented by the following general formula (1c) (where s1≧1, u1≧0): 【Chemistry 4】 In general formulas (1a) and (1c), P1 and P3 each independently represent a cyclic aliphatic group or an aromatic group. Q1 represents a silicone chain, R represents a substituted or unsubstituted branched aliphatic group or an aromatic group. X3 represents a functional group having a double bond, and n1 in X3n1 represents an integer of 1 or greater.

6. 6. The pressure-sensitive adhesive composition according to claim 1, wherein the silicone-modified polyimide (A) has a weight-average molecular weight of 1,000 or more and 50,000 or less.

7. 6. The pressure-sensitive adhesive composition according to claim 1, wherein the silicone-modified polyimide (A) has a weight-average molecular weight of 5,000 or more and 100,000 or less.

8. 8. The pressure-sensitive adhesive composition according to claim 1, wherein the silicone-modified polyimide (A) has a functional group capable of crosslinking with the curable resin (B) having a double bond.

9. 9. The pressure-sensitive adhesive composition according to claim 1, 2, 3, 4, 5, 6, 7, or 8, wherein the curable resin (B1) having an imide skeleton in its main chain and functional groups having double bonds at both ends further has a hydroxyl group-containing group.

10. 10. An adhesive tape comprising an adhesive layer comprising the adhesive composition according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9.

11. 11. A method for processing electronic components, comprising the steps of: (1) temporarily fixing an electronic component on the adhesive tape according to claim 10; (2) curing the adhesive layer of the adhesive tape; (3) heat treating the electronic component; and (4) peeling the adhesive tape from the electronic component.

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