CN115066474A

CN115066474A - Adhesive composition, adhesive tape, and method for processing electronic component

Info

Publication number: CN115066474A
Application number: CN202180013198.5A
Authority: CN
Inventors: 七里德重; 高桥骏夫
Original assignee: Sekisui Chemical Co Ltd
Current assignee: Sekisui Chemical Co Ltd
Priority date: 2020-05-08
Filing date: 2021-05-07
Publication date: 2022-09-16
Also published as: KR20230008696A; JPWO2021225163A1; WO2021225163A1; TW202200748A

Abstract

The purpose of the present invention is to provide a pressure-sensitive adhesive composition that can be easily peeled off even after a high-temperature processing treatment at 250 ℃ or higher or 300 ℃ or higher in a state in which an adherend is fixed. Further, an object of the present invention is to provide an adhesive tape having an adhesive layer formed from the adhesive composition, and a method for processing an electronic component using the adhesive tape. The present invention relates to an adhesive composition containing an organosilicon-modified polyimide (a) and a curable resin (B) having a double bond.

Description

Adhesive composition, adhesive tape, and method for processing electronic component

Technical Field

The present invention relates to an adhesive composition that can be easily peeled off even after a high-temperature processing treatment at 250 ℃ or more or 300 ℃ or more is performed in a state where an adherend is fixed. The present invention also relates to an adhesive tape having an adhesive layer formed from the adhesive composition, and a method for processing an electronic component using the adhesive tape.

Background

In the processing of electronic components such as semiconductors, the electronic components are fixed to a support plate via an adhesive composition or an adhesive tape is attached to the electronic components for protection in order to facilitate handling of the electronic components and prevent breakage. For example, when a thick wafer cut out from high-purity single crystal silicon or the like is ground to a predetermined thickness to form a thin wafer, the thick wafer is bonded to a support plate via an adhesive composition.

The adhesive composition and the adhesive tape used for the electronic component are required to have high adhesiveness to firmly fix the electronic component in the processing step and to be peelable without damaging the electronic component after the completion of the processing step (hereinafter, also referred to as "high adhesiveness and easy peelability").

As means for 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 a side chain or a main chain of a polymer. By having a radiation-polymerizable functional group, the polymer is cured by ultraviolet irradiation, and by utilizing this, the adhesive force is reduced by irradiation with ultraviolet rays at the time of peeling, and peeling can be performed without adhesive residue.

As means for achieving high adhesion and easy peeling, there are also known: a method of blending a release agent such as silicone oil or silicone diacrylate in the pressure-sensitive adhesive composition or the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 5-32946

Disclosure of Invention

Problems to be solved by the invention

With the recent enhancement of electronic components in performance, various high-temperature processing steps have been performed on electronic components. For example, in the step of forming a metal thin film on the surface of an electronic component by sputtering, a metal thin film having more excellent conductivity can be formed by processing at a high temperature of about 300 to 350 ℃. In addition, when semiconductor wafers or chips are stacked in multiple layers, thermocompression bonding at high temperature is also required.

However, the conventional adhesive composition and adhesive tape have improved releasability by, for example, a method of blending a release agent, and if an electronic component protected with the adhesive composition and adhesive tape is subjected to a high-temperature processing treatment of 250 ℃ or more and a long time or a high-temperature processing treatment of 300 ℃ or more, adhesion is promoted, and the adhesive force cannot be sufficiently reduced at the time of release, or adhesive residue is generated due to thermal degradation of the adhesive.

The purpose of the present invention is to provide a pressure-sensitive adhesive composition that can be easily peeled off even after a high-temperature processing treatment at 250 ℃ or higher or 300 ℃ or higher in a state in which an adherend is fixed. Further, an object of the present invention is to provide an adhesive tape having an adhesive layer formed from the adhesive composition, and a method for processing an electronic component using the adhesive tape.

Means for solving the problems

The present invention relates to an adhesive composition containing an organosilicon-modified polyimide (a) and a curable resin having a double bond (B).

The present invention will be described in detail below.

The present inventors have studied an adhesive composition containing an organosilicon modified polyimide (a) and a curable resin having a double bond (B). The present inventors have found that such an adhesive composition has sufficient initial adhesive strength, and on the other hand, is suppressed in increased adhesion, and therefore can be easily peeled off even after a high-temperature processing treatment of 250 ℃ or more for a long time or 300 ℃ or more in a state in which an adherend is fixed, and have completed the present invention.

The adhesive composition of the present invention contains a silicone-modified polyimide (a).

When the silicone-modified polyimide (a) is not a main component of the adhesive composition, the silicone-modified polyimide (a) functions as a release agent, and bleeds out to the adherend interface, thereby facilitating peeling. When the silicone-modified polyimide (a) is a main component of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition has a silicone-derived structure at the adherend interface and has pressure-sensitive adhesiveness, and therefore can fix the adherend and can be easily peeled off even after a high-temperature processing treatment.

Further, the silicone-modified polyimide (a) has an imide skeleton and a silicone chain, and thus has extremely excellent heat resistance. Therefore, the silicone-modified polyimide (a) is less likely to undergo decomposition of the main chain even after being subjected to a high-temperature processing treatment at 250 ℃ or higher for a long time or at 300 ℃ or higher, and can prevent occurrence of adhesion promotion or generation of adhesive residue during peeling.

The number of repetitions of the siloxane unit (repeating unit having a siloxane skeleton) in the silicone chain of the silicone-modified polyimide (a) is not particularly limited, and a preferable lower limit is 10 and a preferable upper limit is 100. When the number of repeating siloxane units is 10 or more, the adhesive composition can exhibit more excellent releasability, and the heat resistance of the silicone-modified polyimide (a) is also improved. When the number of repeating siloxane units is 100 or less, excessive decrease in compatibility between the silicone-modified polyimide (a) and a solvent or other components can be suppressed. A more preferable lower limit of the number of repeating siloxane units is 20, a more preferable upper limit is 80, a further more preferable lower limit is 30, and a further more preferable upper limit is 60.

The weight average molecular weight of the silicone-modified polyimide (a) is not particularly limited, and when the silicone-modified polyimide (a) is not a main component of the adhesive composition, the lower limit is preferably 1000, and the upper limit is preferably 5 ten thousand. If the weight average molecular weight is 1000 or more, it is possible to prevent the adherend from being contaminated by an excessive amount of bleeding when the silicone-modified polyimide (a) functions as a release agent. If the weight average molecular weight is 5 ten thousand or less, the silicone-modified polyimide (a) can be sufficiently exuded to facilitate peeling. A more preferable lower limit of the weight average molecular weight is 3000, a more preferable upper limit is 3 ten thousand, a further more preferable lower limit is 5000, and a further more preferable upper limit is 2 ten thousand.

When the silicone-modified polyimide (a) is a main component of the adhesive composition, the weight average molecular weight of the silicone-modified polyimide (a) preferably has a lower limit of 5000 and an upper limit of 10 ten thousand. If the weight average molecular weight is 5000 or more, excessive flow can be suppressed when the silicone-modified polyimide (a) is the main component of the adhesive composition. If the weight average molecular weight is 10 ten thousand or less, the compatibility of the silicone-modified polyimide (a) with a solvent and other components can be improved. A more preferable lower limit of the weight average molecular weight is 6000, a still more preferable lower limit is 7000, a still more preferable lower limit is 8000, a still more preferable lower limit is 9000, and a particularly preferable lower limit is 1 ten thousand. A more preferable upper limit of the weight average molecular weight is 8 ten thousand, and a still more preferable upper limit is 5 ten thousand.

The weight average molecular weight is measured as a molecular weight in terms of polystyrene by a Gel Permeation Chromatography (GPC) method. As the column, HR-MB-M (manufactured by Waters) can be used, for example.

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, the functional group is introduced into the curable resin (B) having a double bond by chemical reaction with the curable resin (B) having a double bond directly or via a crosslinking agent or the like by irradiation with light, heating, or the like. Therefore, contamination due to adhesion of the silicone-modified polyimide (a) or the curable resin having a double bond (B) to an adherend can be suppressed.

The crosslinkable functional group is not particularly limited, and may be selected depending on the curable resin (B) having a double bond, and examples thereof include a carboxyl group, a hydroxyl group, an amide group, an isocyanate group, an epoxy group, and a double bond-containing functional group. Among them, a hydroxyl group or a double bond-containing functional group is preferable in view of obtaining higher heat resistance.

The double bond-containing functional group is not particularly limited, and examples thereof include: maleimide group, citraconimide group, vinyl ether group, allyl group, (meth) acryloyl group, etc., which may be substituted. Among them, preferred is a maleimide group which may be substituted, from the viewpoint of obtaining higher heat resistance.

The organic silicon-modified polyimide (a) is not particularly limited as long as it has both an imide skeleton and an organic silicon chain. The silicone chain may be present in the main chain or in the side chain of the silicone-modified polyimide (a).

Specific examples of the silicone-modified polyimide (A) include silicone-modified polyimides (A1) (wherein s 1. gtoreq.1, t 1. gtoreq.0, and u 1. gtoreq.0) each 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 (1 c).

[ chemical formula 1]

In the general formulae (1a) to (1c), P ¹ 、P ² And P ³ Each independently represents an alicyclic group or an aromatic group. Q ¹ Represents a silicone chain, 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. X ³ Represents a substituted or unsubstituted aliphatic group, aromatic group or double bond-containing functional group, X ³ _n1 N1 in (1) represents an integer of 1 or more.

In the above general formulae (1a) to (1c), P ¹ 、P ² And P ³ Each independently preferably an alicyclic group or aromatic group having 5 to 50 carbon atoms. By making P ¹ 、P ² And P ³ Each independently an alicyclic group or aromatic group having 5 to 50 carbon atoms, whereby the adhesive composition can exhibit particularly high heat resistance. P is above ¹ 、P ² And P ³ Preferred are structures derived from the following anhydrides.

In the above general formula (1a), Q ¹ The silicone chain is not particularly limited, and examples thereof include: and a silicone chain containing a siloxane unit having a repeating number within the above range (a repeating unit having a siloxane skeleton). Q above ¹ The structure derived from the following organosilicon compound having amino groups at both ends is preferred.

In the above general formula (1b), Q ² Preferably a substituted or unsubstituted aliphatic group or aromatic group having 2 to 100 carbon atoms. By making Q ² The adhesive sheet is a substituted or unsubstituted aliphatic group or aromatic group having 2 to 100 carbon atoms, particularly an aliphatic group, and thus can exhibit high flexibility, can exhibit high followability to an adherend having irregularities, and can improve peelability. Above Q ² The structure derived from the diamine compound described below is preferable, and the structure derived from the dimer diamine described below is more preferable.

In the general formula (1c), R is preferably a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms, a psa sheet produced using the psa composition can exhibit high flexibility, can exhibit high conformability to adherends having irregularities, and can also have improved peelability. The above R is preferably derived from the following diamine compound, and more preferably derived from the following diamine compound having a functional group.

In the silicone-modified polyimide (a1), both ends are not particularly limited, and examples thereof include: structures derived from acid anhydrides and diamine compounds which are raw materials of the above-mentioned silicone-modified polyimide (a1), and the like.

In the silicone-modified polyimide (A1), each of the two terminals may have X ¹ Q-and X ² -the structure represented. In this case, X ¹ Q-is bonded to the N atom in the structural unit represented by the above general formula (1a), the structural unit represented by the above general formula (1b), or the structural unit represented by the above general formula (1c) to form a terminal on the N atom side, and X ² The terminal opposite to the N atom. Q and Q ¹ Or Q ² Same as X ¹ And X ² Each independently represents a substituted or unsubstituted aliphatic group, aromatic group, or double bond-containing functional group.

In the above silicone-modified polyimide (A1), X is ¹ 、X ² And X ³ Examples of the "a" and "the" are, independently: aliphatic groups, alicyclic groups, aromatic groups, structures derived from acid anhydrides, structures derived from amine compounds, double bond-containing functional groups, and the like. Specifically, there may be mentioned: a structure derived from a single-terminal unreacted substance of an acid anhydride or a diamine compound which becomes a raw material of the above-mentioned silicone-modified polyimide (a 1).

Wherein, is selected from X ¹ 、X ² And X ³ At least one of them preferably contains a double bond-containing functional group. This further suppresses increase in adhesion of the pressure-sensitive adhesive composition, and improves releasability.

The double bond-containing functional group is not particularly limited, and examples thereof include: maleimide group, citraconimide group, vinyl ether group, allyl group, (meth) acryloyl group, etc., which may be substituted. Among them, a maleimide group which may be substituted is preferable in view of obtaining higher heat resistance.

In the above silicone-modified polyimide (A1), X ³ _n1 N1 in (b) is an integer of preferably 10 or less, more preferably 8 or less, further preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. In the silicone-modified polyimide (a1), a plurality of (n 1) xs contained in 1 structural unit ³ Each may be the same or may be different.

In the silicone-modified polyimide (a1), s1 is 1 or more, preferably 3 or more, preferably 10 or less, and more preferably 5 or less. t1 is 0 or 1 or more, preferably 1 or more, more preferably 3 or more, 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, preferably 10 or less, more preferably 5 or less. When s1, t1, and u1 are in the above range, the adhesive composition is more inhibited from becoming more strongly adhered, and the releasability is also improved.

The silicone-modified polyimide (a1) may be a block copolymer comprising a block component in which each of the structural units 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) are arranged in series. Alternatively, a random copolymer may be obtained by randomly arranging each of the structural units represented by the general formula (1a), the structural unit represented by the general formula (1b), and the structural unit represented by the general formula (1 c).

The organic silicon-modified polyimide (a) can be produced, for example, by reacting an organic silicon compound having amino groups at both ends with an acid anhydride (for example, an aromatic acid anhydride, an acid anhydride having an alicyclic group, or the like) to obtain an imide compound. Further, the diamine compounds may be reacted together as necessary.

Further, a diamine compound having a functional group is used as the diamine compound, and the functional group in the resulting imide compound is reacted with a compound having a functional group reactive with the functional group and a double bond-containing functional group (hereinafter referred to as a functional group-containing unsaturated compound), whereby a double bond-containing functional group can be introduced into a side chain.

Further, by adjusting the reaction ratio so that the terminal is a structure derived from the diamine compound, the resulting terminal amino group can be reacted with the functional group-containing unsaturated compound, thereby introducing a double bond-containing functional group to the terminal.

Examples of the organosilicon compound having amino groups at both ends include: and an organosilicon compound having amino groups at both ends and containing a siloxane unit having a repeating number within the above range (a repeating unit having a siloxane skeleton). Examples of commercially available products of such organosilicon compounds include KF-8010, X-22-161A, X-22-161B, KF-8012, and PAM-E (all manufactured by shin-Etsu chemical Co., Ltd.).

As the diamine compound, any of an aliphatic diamine compound and 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 irregularities, and can also have improved peelability. By using an aromatic diamine compound as the diamine compound, the heat resistance of the adhesive composition is further improved.

These aliphatic diamine compounds, aromatic diamine compounds and diamine compounds having functional groups may be used alone or in combination of two or more.

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' -diamino-N-methyldipropylamine, diaminomaleonitrile, 1, 3-diaminopentane, bis (4-amino-3-methylcyclohexyl) methane, 1, 2-bis (2-aminoethoxy) ethane, 3- (4), 8- (9) -bis (aminomethyl) tricyclo (5.2.1.02,6) decane, etc.

Among the aliphatic diamine compounds, dimer diamine is preferable from the viewpoint of improving flexibility and from the viewpoint of increasing compatibility of the silicone-modified polyimide (a) with a solvent and other components to facilitate production of an adhesive tape.

The dimer diamine refers to a diamine compound obtained by reducing and aminating a cyclic or acyclic dimer acid obtained as a dimer of an unsaturated fatty acid, and examples thereof include dimer diamines of a linear type, a monocyclic type, and a polycyclic type. The dimer diamine may contain a carbon-carbon unsaturated double bond or may be a hydride to which hydrogen is added. More specifically, the dimer diamine includes, for example: dimer diamine capable of constituting 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), and the like.

Examples of the aromatic diamine compound include: 9, 10-diaminophenanthrene, 4 '-diaminooctafluorobiphenyl, 3, 7-diamino-2-methoxyfluorene, 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-diaminonaphthalene, 1, 2-diaminoanthraquinone, 2, 4-isopropylbenzene diamine, 1, 3-diaminotoluene, 1, 3-diaminomethylcyclohexane, 2-chloro-1, 4-diaminobenzene, 1, 4-diamino-2, 5-dichlorobenzene, 1, 4-diamino-2, 5-dimethylbenzene, 4 ' -diamino-2, 2 ' -bis (trifluoromethyl) biphenyl, bis (amino-3-chlorophenyl) ethane, bis (4-amino-3, 5-dimethylphenyl) methane, bis (4-amino-3, 5-diethylphenyl) methane, bis (4-amino-3-ethyldiaminofluorene, 2, 3-diaminonaphthalene, 2, 3-diaminophenol, -5-methylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, 4 ' -diaminophenylsulfone, methyl, ethyl, propyl, butyl, isobutyl, 3,3 ' -diaminophenylsulfone, 2-bis (4, (4 aminophenoxy) phenyl) sulfone, 2-bis (4- (3-aminophenoxy) phenyl) sulfone, 4 ' -oxydianiline, 4 ' -diaminodiphenyl sulfide, 3,4 ' -oxydianiline, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (4-aminophenoxy) benzene, 4 ' -bis (4-aminophenoxy) biphenyl, 4 ' -diamino-3, 3 ' -dihydroxybiphenyl, 4 ' -diamino-3, 3 ' -dimethylbiphenyl, 4 ' -diamino-3, 3 ' -dimethoxybiphenyl, dimethylbiphenyl, 4,3, 4 ' -diamino-3, 4 ' -diamino-3, 4 ' -diamino-3, 3 ' -diamino-4 ' -diamino-3, 3 ' -dimethoxy biphenyl, dimethylbiphenyl, dimethyl, Bisaniline M, Bisaniline P, 9-bis (4-aminophenyl) fluorene, tolidine sulfone, methylenebis (anthranilic acid), 1, 3-bis (4-aminophenoxy) -2, 2-dimethylpropane, 1, 3-bis (4-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) butane, 2,3,5, 6-tetramethyl-1, 4-phenylenediamine, 3 ', 5,5 ' -tetramethylbenzidine, 4 ' -diaminobenzanilide, 2-bis (4-aminophenyl) hexafluoropropane, polyoxyalkylene diamines (e.g., Jeffamine D-230, D400, D-2000 and D-4000 from Huntsman), 1, 3-cyclohexanedi (methylamine), m-xylylenediamine, p-xylylenediamine, and the like.

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, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the like. Examples of the diamine compound having a carboxyl group include 3, 5-diaminobenzoic acid and the like. Examples of the diamine compound having a halogen group include 2, 4-diaminochlorobenzene and the like.

Examples of the aromatic acid anhydride include: pyromellitic acid, 1,2,5, 6-naphthalene tetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 1,2,4, 5-naphthalene tetracarboxylic acid, 1,4,5, 8-naphthalene tetracarboxylic acid, 3,3 ', 4,4 ' -benzophenone tetracarboxylic acid, 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic acid, 3,3 ', 4,4 ' -biphenyl tetracarboxylic acid, 2,3,5, 6-pyridine tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, 4,4 ' -sulfonyl diphthalic acid, 1-trifluoromethyl-2, 3,5, 6-benzene tetracarboxylic acid, 2 ', 3,3 ' -biphenyl tetracarboxylic acid, 2-bis (3, 4-dicarboxyphenyl) propane, 2-bis (2, 3-dicarboxyphenyl) propane, 1, 1-bis (2, 3-dicarboxyphenyl) ethane, 1-bis (3, 4-dicarboxyphenyl) ethane, bis (2, 3-dicarboxyphenyl) methane, bis (3, 4-dicarboxyphenyl) sulfone, bis (3, 4-dicarboxyphenyl) ether, benzene-1, 2,3, 4-tetracarboxylic acid, 2,3,2 ', 3' -benzophenone tetracarboxylic acid, 2,3,3 ', 4' -benzophenone tetracarboxylic acid, phenanthrene-1, 8,9, 10-tetracarboxylic acid, pyrazine-2, 3,5, 6-tetracarboxylic acid, thiophene-2, 3,4, 5-tetracarboxylic acid, 2,3,3 ', 4' -biphenyl tetracarboxylic acid, 3,4,3 ', 4' -biphenyl tetracarboxylic acid, 2,3,2 ', 3 ' -biphenyltetracarboxylic acid, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide, 4 ' - (4,4 ' -isopropylidenediphenoxy) -bis (phthalic acid), and the like.

The unsaturated compound having a functional group is selected and used according to the functional group at the terminal or side chain of the imide compound.

For example, in the imide compound terminal or side chain functional groups for hydroxyl cases, can be cited with carboxyl maleimide compounds. Examples of the maleimide compound having a carboxyl group include: maleimide acetate, maleimide propionic acid, maleimide butyric acid, maleimide caproic acid, trans-4- (N-maleimidomethyl) cyclohexane-1-carboxylic acid, 19-maleimide-17-oxo-4, 7,10, 13-tetraoxa-16-azanonadecanoic acid, and the like. Further, there may be mentioned: 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 glycerol diallyl monoglycidyl ether. Further, there may be mentioned: glycidyl group-containing vinyl ether compounds such as glycidoxyethylvinyl ether, glycidoxybutylvinyl ether, glycidoxyhexylvinyl ether, glycidyldiethyleneglycol vinyl ether and glycidylcyclohexanedimethanol monovinyl ether, and the like. Further, there may be mentioned: and (meth) acryloyl compounds having an isocyanate group such as allyl isocyanate and 2- (meth) acryloyloxyethyl isocyanate.

In addition, for example, in the imide compound terminal or side chain of the functional group is carboxyl, can cite: and 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, there may be mentioned: allyl ether compounds having a glycidyl group such as allyl glycidyl ether and glycerol diallyl monoglycidyl ether. Further, there may be mentioned: glycidyl group-containing vinyl ether compounds such as glycidoxyethylvinyl ether, glycidoxybutylvinyl ether, glycidoxyhexylvinyl ether, glycidyldiethyleneglycol vinyl ether and glycidylcyclohexanedimethanol monovinyl ether, and the like.

Further, for example, in the imide compound terminal or side chain functional groups are amino, can cite maleic anhydride.

The content of the silicone-modified polyimide (a) is not particularly limited, and when the silicone-modified polyimide (a) is not the main component of the adhesive composition, the lower limit is preferably 0.5 parts by weight and the upper limit is preferably 100 parts by weight with respect to 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 more excellent releasability without staining an adherend. From the viewpoint of further improving the releasability while suppressing contamination of an adherend, the content of the silicone-modified polyimide (a) is preferably 1 part by weight at the lower limit, 50 parts by weight at the upper limit, 3 parts by weight at the lower limit, and 20 parts by weight at the upper limit.

Since the adhesive composition of the present invention has excellent heat resistance, sufficient effects can be exhibited even when the content of the silicone-modified polyimide (a) is small. Therefore, the possibility of contamination by the silicone-modified polyimide (a) can be further reduced.

When the silicone-modified polyimide (a) is the main component of the adhesive composition, the preferable lower limit of the content of the silicone-modified polyimide (a) is 100 parts by weight and the preferable upper limit is 400 parts by weight with respect to 100 parts by weight of the curable resin having a double bond (B). When the content of the silicone-modified polyimide (a) is within this range, the pressure-sensitive adhesive composition can exhibit more excellent releasability without staining an adherend. From the viewpoint of further improving the releasability while suppressing contamination of an adherend, the content of the silicone-modified polyimide (a) is preferably 150 parts by weight at the lower limit, 300 parts by weight at the upper limit, 200 parts by weight at the lower limit, and 250 parts by weight at the upper limit.

The silicone-modified polyimide (a) as a main component of the adhesive composition means: 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 the resin components constituting the adhesive composition (for example, the silicone-modified polyimide (a), the curable resin having a double bond (B), and the like). The content of the silicone-modified polyimide (a) is usually less than 100% by weight, preferably 90% by weight or less, and more preferably 80% by weight or less of the total amount of the resin components constituting the adhesive composition.

The adhesive composition of the present invention contains a curable resin (B) having a double bond.

By containing the curable resin (B), the entire pressure-sensitive adhesive composition is polymerized and crosslinked uniformly and rapidly by irradiation with light, heating, or the like, and the elastic modulus is increased, whereby the adhesive strength is significantly reduced. This suppresses increase in adhesion, and therefore, the adhesive can be easily peeled off even after a long-time processing at 250 ℃ or higher or a high-temperature processing at 300 ℃ or higher in a state in which the adherend is fixed.

The curable resin (B) is not particularly limited as long as it has a double bond-containing functional group. The double bond-containing functional group is not particularly limited, and examples thereof include a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, and a (meth) acryloyl group, which may be substituted. Among them, maleimide groups which may be substituted are preferable from the viewpoint of obtaining higher heat resistance.

The content of the curable resin (B) is not particularly limited, and when the silicone-modified polyimide (a) is not the main component of the adhesive composition, the content is, for example, 50% by weight or more, preferably more than 50% by weight of the total amount of the resin components constituting the adhesive composition (for example, the silicone-modified polyimide (a), the curable resin (B) having a double bond, and the like). 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 the resin components constituting the adhesive composition.

When the silicone-modified polyimide (a) is the main component of the adhesive composition, the content of the curable resin (B) is preferably 20% by weight or more, more preferably 25% by weight or more, and still more preferably 30% by weight or more of the total amount of the resin components constituting the adhesive composition (for example, the silicone-modified polyimide (a), the curable resin (B) having a double bond, and the like). The content of the curable resin (B) is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 35% by weight or less of the total amount of resin components constituting the adhesive composition.

Specific examples of the curable resin (B) include polyimide resins having double bonds, acrylic resins having double bonds, and the like. Among them, polyimide resins having a double bond are preferable.

The curable resin (B) is a polyimide resin, and the adhesive composition can exhibit particularly high heat resistance by providing the curable resin (B) with an imide skeleton, and therefore generation of residue due to thermal deterioration is further suppressed, and releasability is also improved. Among them, 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 a side chain or a terminal.

The curable resin (B1) preferably has a double bond-containing functional group equivalent (weight average molecular weight/number of double bond-containing functional groups) of 4000 or less. When the functional group equivalent is 4000 or less, the adhesive composition can exhibit higher heat resistance. This is considered to be because: by having a double bond-containing functional group at a certain or higher density in the molecule of the curable resin (B1), the distance between crosslinks becomes shorter, and the adhesion promotion is further suppressed. The functional group equivalent is more preferably 3000 or less, and still more preferably 2000 or less. The lower limit of the functional group equivalent is not particularly limited, and the lower limit is substantially about 600.

The weight average molecular weight of the curable resin (B1) is preferably 5000 or more. By setting the weight average molecular weight of the curable resin (B1) to 5000 or more, film formation is facilitated, and the obtained film exhibits a certain degree of flexibility, and therefore, high conformability to an adherend having irregularities can be exhibited, and peeling from the adherend can be facilitated. The weight average molecular weight of the curable resin (B1) is more preferably 10000 or more, and still more preferably 20000 or more. The upper limit of the weight average molecular weight of the curable resin (B1) is not particularly limited, but is, for example, 300000, particularly 100000, since the solubility in a solvent is low.

The double bond-containing functional group may be located at any of a side chain or a terminal of the curable resin (B1). The double bond-containing functional groups are preferably present at both ends of the curable resin (B1), and more preferably further present in side chains in addition to both ends. The double bond-containing functional groups at both ends of the curable resin (B1) have high reactivity, and the adhesive composition can be cured more sufficiently by irradiation with light, heating, or the like. As a result, the adhesion promotion can be further suppressed, and the pressure-sensitive adhesive composition can exhibit higher heat resistance.

Further, the adhesive composition can exhibit higher heat resistance by the presence of a functional group having a double bond in the side chain of the curable resin (B1). This is believed to be because: the distance between crosslinks becomes shorter, and thus the adhesion promotion is more suppressed. Further, by having a functional group containing a double bond in a side chain of the curable resin (B1), the weight average molecular weight and the functional group equivalent can be easily adjusted to the above ranges.

The curable resin (B1) preferably further has a hydroxyl group.

When the curable resin (B1) has the hydroxyl group, the hydroxyl group reacts with, for example, a maleimide group or the like of another component by heating or the like, and the elastic modulus of the pressure-sensitive adhesive composition is further increased, and the adhesive force is further decreased. This further suppresses increase in adhesion of the pressure-sensitive adhesive composition, and improves releasability.

The hydroxyl group-containing group is not particularly limited, and may have an alcoholic hydroxyl group or a phenolic hydroxyl group. Among them, those having a phenolic hydroxyl group are preferable in view of high reactivity.

Examples of the hydroxyl group-containing group having an alcoholic hydroxyl group include aliphatic groups or aromatic groups having an alcoholic hydroxyl group with 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 having 6 to 24 carbon atoms, and more specifically, examples thereof include phenol, bisphenol a, bisphenol F, biphenol, and 2, 2' -bis (4-hydroxyphenyl) hexafluoropropane. Among them, 2' -bis (4-hydroxyphenyl) hexafluoropropane is preferable from the viewpoint of good releasability.

In the curable resin (B1), the functional group equivalent (weight average molecular weight/number of hydroxyl-containing groups) of the hydroxyl-containing groups is preferably 5000 or less. When the functional group equivalent is 5000 or less, the adhesive composition is more inhibited from increasing adhesion and the releasability is also improved. This is considered to be because: the curable resin (B1) has hydroxyl-containing groups in a certain or higher density in the molecule, and thereby the crosslinking distance is shortened. The functional group equivalent is more preferably 3000 or less, and still more preferably 1000 or less. The lower limit of the functional group equivalent is not particularly limited, and is substantially about 500.

More specifically, the curable resin (B1) preferably has a structural unit represented by the following general formula (1d), a structural unit represented by the following general formula (1e), and a structural unit represented by the following general formula (1f) (wherein s 2. gtoreq.1, t 2. gtoreq.0, and u 2. gtoreq.0), and both ends are each represented by X ⁴ -and X ⁵ A curable resin (B1-1) represented by (A).

[ chemical formula 2]

In the general formulae (1d) to (1f), P ⁴ 、P ⁵ And P ⁶ Each independently represents an alicyclic group or an aromatic group. Q 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 group or aromatic group. Is selected from X ⁴ 、X ⁵ And X ⁶ At least one of them represents a double bond-containing functional group, X ⁶ _n2 N2 in (1) represents an integer of 1 or more.

In the above general formulae (1d) to (1f), P ⁴ 、P ⁵ And P ⁶ Each independently preferably an alicyclic group or aromatic group having 5 to 50 carbon atoms. By making P ⁴ 、P ⁵ And P ⁶ Each independently an alicyclic group or aromatic group having 5 to 50 carbon atoms, whereby the adhesive composition can exhibit particularly high heat resistance.

In the above general formula (1d), Q ³ Preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. By making Q ³ The pressure-sensitive adhesive sheet is a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, and therefore can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and can also have improved peelability.

In addition, Q ³ The aliphatic group derived from the diamine compound as described above is preferable. Among these, Q is a group of compounds which can improve flexibility and facilitate the production of an adhesive tape by increasing the compatibility of the curable resin (B1-1) with a solvent and other components ³ Preferably an aliphatic group derived from dimer diamine.

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

[ chemical formula 3]

In the above general formulae (4-1) to (4-4), R ¹ ～R ⁸ And R ¹³ ～R ²⁰ Each independently represents a linear or branched hydrocarbon group. In addition, denotes a bond. Namely, the compound is bonded to N in the general formulae (1d) to (1 f).

In the above general formulae (4-1) to (4-4), R ¹ ～R ⁸ And R ¹³ ～R ²⁰ The hydrocarbon group is not particularly limited, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Wherein R is 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 ²⁰ The total number of carbon atoms in each group is preferably 7 to 50. When the total number of carbon atoms is within the above range, the adhesive tape produced using the adhesive composition can exhibit higher flexibility, and the compatibility of the curable resin (B1-1) with a solvent and other components is further increased. The total number of carbon atoms is more preferably 9 or more, still more preferably 12 or more, and still more preferably 14 or more. The total of the carbon numbers is more preferably 35 or less, still more preferably 25 or less, and still more preferably 18 or less.

The optical isomers in the group represented by the above general formula (4-1), the group represented by the above general formula (4-2), the group represented by the above general formula (4-3) and the group represented by the above general formula (4-4) are not particularly limited, and include arbitrary optical isomers.

In the above general formula (1e), Q ⁴ Preferably a substituted or unsubstituted aromatic group having 5 to 50 carbon atoms. By making Q ⁴ The adhesive composition can exhibit particularly high heat resistance by virtue of the aromatic group having 5 to 50 carbon atoms being substituted or unsubstituted. When the curable resin (B1) has the hydroxyl group-containing group, Q ⁴ Preferably the above-mentioned hydroxyl groupRadical of (a).

In the general formula (1f), R is preferably a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms, the pressure-sensitive adhesive tape produced using the pressure-sensitive adhesive composition can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and can also have improved peelability.

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 preferably bonded to X ⁶ And (6) bonding.

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 thus making the portion bonded to the ester group or the ether group an aromatic group, the adhesive composition can exhibit high heat resistance. On the other hand, X ⁶ Bonded to R via an aromatic ester group or an aromatic ether group, whereby X ⁶ The double bond in (B) does not conjugate with R, and therefore does not inhibit the crosslinking of the polymer upon irradiation with light.

In the curable resin (B1-1), the double bond-containing functional group (crosslinkable unsaturated bond) is selected from X ⁴ 、X ⁵ And X ⁶ At least one of (1), preferably at least X ⁶ Is a functional group containing a double bond. By at least X ⁶ The adhesive composition can exhibit higher heat resistance because of the double bond-containing functional group.

In the above-mentioned X ⁴ 、X ⁵ And X ⁶ When any of the functional groups is a functional group other than the double bond-containing functional group (a functional group not containing a double bond), examples of the functional group not containing a double bond include, independently, an aliphatic group, an alicyclic group, an aromatic group, a structure derived from an acid anhydride, a structure derived from an amine compound, and the like. Specifically, there may be mentioned: a structure derived from a single-terminal unreacted product of an acid anhydride or diamine compound which is a raw material of the curable resin (B1-1).

The above curable resin (B1-1) In, X ⁶ _n2 N2 in (b) is an integer of preferably 10 or less, more preferably 8 or less, further preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. In the curable resin (B1-1), a plurality of (n 2) X's are contained in one structural unit ⁶ The respective may be the same or different.

In the curable resin (B1-1), s2 is 1 or more, preferably 3 or more, preferably 10 or less, and more preferably 5 or less. t2 is 0 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, more preferably 5 or less. u2 is 0 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, more preferably 5 or less. When s2, t2, and u2 are in the above range, the adhesive composition is more inhibited from becoming more strongly adhered, and the 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 composed of a block component in which the structural units are arranged in series, or a random copolymer in which the structural units are arranged randomly.

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. In this case, a diamine compound having a functional group is used as the diamine compound, and the functional group in the resulting imide compound is reacted with a compound having a functional group reactive with the functional group and a double bond-containing functional group (the functional group-containing unsaturated compound), whereby the double bond-containing functional group can be introduced into the side chain.

The diamine compound, the aromatic acid anhydride and the 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 for obtaining the silicone-modified polyimide (a) are used.

The content of the curable resin (B1) in the entire curable resin (B) is not particularly limited, and the preferred lower limit is 30% by weight. When the content of the curable resin (B1) is 30 wt% or more, the adhesive composition is more inhibited from increasing in adhesiveness and also improved in releasability. A more preferable lower limit of the content of the curable resin (B1) is 50 wt%.

The upper limit of the content of the curable resin (B1) in the entire curable resin (B) is not particularly limited, and may be 100% by weight.

Examples of the curable resin (B) include: a polyfunctional monomer or a polyfunctional oligomer having at least 2 or more maleimide groups (B2), a polyfunctional monomer or a polyfunctional oligomer having at least 2 or more vinyl ether groups or allyl groups (B3), and the like. These polyfunctional monomers or polyfunctional oligomers are preferably used in combination with the curable resin (B1). By using these polyfunctional monomers or polyfunctional oligomers in combination with the curable resin (B1), the three-dimensional network formation of the pressure-sensitive adhesive composition by irradiation with light, heating, or the like is more efficiently performed, the adhesive composition is more inhibited from becoming too strong, and the releasability is improved.

The polyfunctional monomer or polyfunctional oligomer (B2) is not particularly limited, and is preferably a polyfunctional monomer or polyfunctional oligomer having a molecular weight of 5000 or less and having at least 2 maleimide groups. Specifically, examples thereof include: 4,4 ' -diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol a diphenylether bismaleimide, 3 ' -dimethyl-5, 5 ' -diethyl-4, 4 ' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6 ' -bismaleimide- (2,2, 4-trimethyl) hexane, 4 ' -diphenylether bismaleimide, 4 ' -diphenylsulfone bismaleimide, bismaleimide having a structure derived from a diamine, and the like.

The bismaleimide having a structure derived from a dimer diamine preferably has a structure derived from a dimer diamine, at least one selected from 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). Among these, the group represented by the above general formula (4-2) is more preferable.

These polyfunctional monomers or polyfunctional oligomers (B2) may be used alone or in combination of 2 or more.

By including the above-mentioned 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 irregularities, and can also improve peelability.

The polyfunctional monomer or polyfunctional oligomer (B3) is not particularly limited, and is preferably a polyfunctional monomer or polyfunctional oligomer having a molecular weight of 10000 or less and having at least 2 vinyl ether groups or allyl groups. Specifically, examples thereof include: triallyl isocyanurate, cyclohexane divinyl ether, polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, Crossmer-U (trade name, vinyl ether-terminated polyester), and the like. These polyfunctional monomers or polyfunctional oligomers (B3) may be used alone or in combination of 2 or more.

The total content of the curable resin (B2) and the curable resin (B3) in the entire curable resin (B) is not particularly limited, and a preferable lower limit is 20 wt%. If the total content of the curable resin (B2) and the curable resin (B3) is 20 wt% or more, the adhesive composition is more inhibited from increasing in adhesiveness and also improved in releasability. A more preferable 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) in the entire curable resin (B) is not particularly limited, and may be 100% by weight. Only one of the curable resin (B2) and the curable resin (B3) may be contained in the adhesive composition, or both of them may be contained in the adhesive composition.

The adhesive composition of the present invention preferably further comprises a photopolymerization initiator.

Examples of the photopolymerization initiator include those 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 benzildimethylketal and acetophenone diethylketal, and phosphine oxide derivative compounds. Further, there may be mentioned: a photo radical polymerization initiator such as bis (. eta.5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, alpha-hydroxycyclohexylphenyl ketone, 2-hydroxymethylphenylpropane, etc. These photopolymerization initiators may be used alone, or 2 or more of them may be used in combination.

The content of the photopolymerization initiator is not particularly limited, and the lower limit is preferably 0.1 part by weight and the upper limit is preferably 10 parts by weight with respect to 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 uniformly and rapidly polymerized and crosslinked by irradiation with light, and the elastic modulus is increased, whereby the adhesive strength is greatly reduced and the pressure-sensitive adhesive composition can be easily peeled. A more preferable lower limit of the content of the photopolymerization initiator is 0.3 parts by weight, and a more preferable upper limit is 3 parts by weight.

The adhesive composition of the present invention may further comprise a gas generating agent that generates gas by irradiating light. By containing the gas generating agent, even after a long time at 250 ℃ or more or a high temperature processing treatment at 300 ℃ or more, the gas generated by irradiation with light is released to the interface with the adherend, and therefore the adherend can be peeled off more easily without adhesive residue.

Examples of the gas generating agent include tetrazole compounds and salts thereof, triazole compounds and salts thereof, azo compounds, azide compounds, xanthone acetic acid, and carbonate salts.

The tetrazole compound or a salt thereof is not particularly limited, and examples thereof include a mono-tetrazole compound, a bistetrazole compound, an azobistetrazole compound, and salts thereof.

Specific examples of the mono-tetrazole 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-benzamide) -5-mercaptotetrazole, 5-tolyltetrazole, 5-phenyltetrazole, 5-aminotetrazole monohydrate, 5- (m-aminophenyl) tetrazole, 5-acetamidotetrazole, N- (1H-tetrazol-5-yl) -N-octanoylamide, 1-cyclohexyl-5-chlorobutyltetrazole, 1- (m-acetamidophenyl) -5-mercaptotetrazole, 1-methyl-5-mercaptotetrazole, 1- (4-carboxyphenyl) -5-mercaptotetrazole, 1-methyl-5-ethyltetrazole, 5-aminomethyl-1H-tetrazole, 4, 5-bis (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' -bistetrazole disodium salt, and 5,5 '-bistetrazole dipiperazinium salt (Japanese: 5, 5' - ビステトラゾールジピペラジウム salt).

Specific examples of the azobistetrazole compound include 5, 5-azobis-1H-tetrazole, a compound of 5, 5-azobis-1H-tetrazole with guanidine, and a compound of 5, 5-1H-azobistetrazole with methylguanidine.

These gas generating agents may be used alone, or 2 or more kinds thereof may be used in combination. Among them, from the viewpoint of particularly excellent heat resistance, a bitetrazole compound or a salt thereof is preferable.

The content of the gas generating agent is not particularly limited, and a preferable lower limit is 5 parts by weight and a preferable upper limit is 50 parts by weight with respect 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 preferable lower limit of the content of the gas generating agent is 8 parts by weight, and a more preferable upper limit is 30 parts by weight.

The adhesive composition of the present invention may contain known additives such as a photosensitizer, a heat stabilizer, an antioxidant, an antistatic agent, a plasticizer, a resin, a surfactant, a wax, and a particulate filler.

Examples of the fine particle filler include: an inorganic filler comprising at least 1 selected from the group consisting of oxides of silicon, titanium, aluminum, calcium, boron, magnesium, cerium, and zirconia, talc, mica, and a composite thereof. Among them, silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, silica-titania composite oxide, or talc is preferable.

The average particle diameter of the inorganic filler is not particularly limited, but the lower limit is preferably 0.1 μm and the upper limit is preferably 30 μm.

The content of the inorganic filler is not particularly limited, and a preferable lower limit is 5 parts by weight and a preferable upper limit is 100 parts by weight with respect to 100 parts by weight of the total of the silicone-modified polyimide (a) and the curable resin (B). A more preferable lower limit of the content of the inorganic filler is 10 parts by weight, and a more preferable upper limit is 50 parts by weight.

The adhesive composition of the present invention preferably has a weight loss rate after heating at 300 ℃ of 5% by weight or less, and more preferably 3% by weight or less, as measured at a temperature rise rate of 10 ℃/minute after curing. When the weight loss ratio is within the above range, the adhesive composition can exhibit particularly high heat resistance, and therefore, the adhesion promotion is further suppressed, and the releasability is also improved.

Note that the weight and weight loss rate after heating at 300 ℃ can be measured as follows: 10mg of a sample cured by ultraviolet irradiation was collected and placed in an aluminum cup, and measured at a temperature increase rate of 10 ℃ per minute using, for example, a thermogravimetric measuring apparatus STA7200 (manufactured by Hitachi High-TechScience). As the ultraviolet ray irradiation, an ultra-high pressure mercury lamp was used at 20mW/cm ² The ultraviolet ray of 365nm was irradiated at the intensity of (2) for 150 seconds.

The method for adjusting the weight loss rate to 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) having higher heat resistance. Examples of the method for improving the heat resistance of the silicone-modified polyimide (a) include: a method of increasing the content of aromatic groups, a method of decreasing the molecular weight of silicone chains in the structural unit, and the like.

The method for producing the adhesive composition of the present invention is not particularly limited, and examples thereof include the following methods: the silicone-modified polyimide (a), the curable resin (B), and additives that are blended as necessary are mixed using a bead mill, ultrasonic dispersion, homogenizer, high-output disperser, roll mill, or the like.

An adhesive tape having an adhesive layer formed of the adhesive composition of the present invention is also one aspect of the present invention.

The adhesive tape of the present invention may be a supporting tape having an adhesive layer formed of the adhesive composition of the present invention on one or both sides of a substrate, or may be a non-supporting tape having no substrate.

Examples of the substrate include: acrylic (japanese: アクリル), olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, and other transparent resins. Further, a sheet having a mesh structure, a sheet having holes, or the like may be used.

The pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape of the present invention have initial pressure-sensitive adhesive force, and are suppressed in adhesion promotion, and can be easily peeled off even after a high-temperature processing treatment at 250 ℃ or more for a long time or 300 ℃ or more in a state in which an adherend is fixed. Therefore, the adhesive composition and the adhesive tape of the present invention can be suitably used for: protecting and temporarily fixing an adherend subjected to a high-temperature processing at 250 ℃ or higher for a long time or at 300 ℃ or higher. In particular, in the processing of electronic components such as semiconductors, in order to facilitate handling of the electronic components and prevent breakage thereof, it is preferable to use: the electronic component is fixed to the support plate via the adhesive composition or the adhesive tape, or the adhesive tape is attached to the electronic component for protection.

Specifically, for example, there is a method for processing an electronic component, which includes: the step (1) of temporarily fixing an electronic component on the adhesive tape of the present invention, the step (2) of curing the adhesive layer of the adhesive tape of the present invention, the step (3) of heat-treating the electronic component, and the step (4) of peeling the adhesive tape of the present invention from the electronic component. Such a method for processing an electronic component is also one of the present invention.

The step (2) of curing the adhesive layer of the adhesive tape of the present invention may be performed immediately before the step (4) of peeling the adhesive tape of the present invention from the electronic component, but is preferably performed after the step (1) of temporarily fixing the electronic component on the adhesive tape of the present invention and before the step (3) of heat-treating the electronic component. Thus, the adhesive tape of the present invention can exhibit more excellent heat resistance.

Effects of the invention

The present invention can provide a pressure-sensitive adhesive composition that can be easily peeled off even after a high-temperature processing treatment at 250 ℃ or more or 300 ℃ or more is performed in a state where an adherend is fixed. Further, according to the present invention, an adhesive tape having an adhesive layer formed from the adhesive composition and a method for processing an electronic component using the adhesive tape can be provided.

Detailed Description

The mode 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.

(preparation of Silicone-modified polyimide (A))

The procedure of the following synthesis examples 1 to 11 was followed to prepare silicone-modified polyimides (a) having the structures shown in table 1 (synthesis examples 1 to 11).

(1) Synthesis example 1

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Then, 34.4g (0.04 mol) of an organosilicon compound having amino groups at both terminals (KF-8010, manufactured by shin-Etsu chemical Co., Ltd., repeat number of siloxane unit: 11, weight average molecular weight: 860) and 31.2g (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 an organosilicon modified polyimide (a) (synthesis example 1).

The silicone-modified polyimide (A) (Synthesis example 1) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 6000.

(2) Synthesis example 2

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Then, 88g (0.02 mol) of an organosilicon compound having amino groups at both terminals (KF-8012, manufactured by shin-Etsu chemical Co., Ltd., repeat number of siloxane unit: 60, weight average molecular weight 4400) and 15.6g (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 an organosilicon modified polyimide (a) (synthesis example 2).

The silicone-modified polyimide (A) (Synthesis example 2) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 10000.

(3) Synthesis example 3

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 60g (0.02 mol) of an organosilicon compound having amino groups at both ends (X-22-161B, product of shin-Etsu chemical Co., Ltd., number of repeating siloxane units: 40, weight average molecular weight 3000) was added. Further, 5610.7g (0.02 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 31.2g (0.06 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were sequentially added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an organosilicon modified polyimide (a) (synthesis example 3).

The silicone-modified polyimide (A) (Synthesis example 3) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 15000.

(4) Synthesis example 4

250mL of toluene was put into a 500mL round-bottom flask containing a Teflon (registered trademark) stirrer. Next, 48g (0.03 mol) of an organosilicon compound having amino groups at both ends (X-22-161A, manufactured by shin-Etsu chemical Co., Ltd., the number of repeating siloxane units: 21, and a weight average molecular weight of 1600) and 31.2g (0.06 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were sequentially added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an organosilicon modified polyimide (a) (synthesis example 4).

The silicone-modified polyimide (A) (Synthesis example 4) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 3000.

(5) Synthesis example 5

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 80g (0.05 mol) of an organosilicon compound having amino groups at both ends (X-22-161A, product of shin-Etsu chemical Co., Ltd., the number of repeating siloxane units: 21, weight average molecular weight 1600) and 26g (0.05 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were sequentially added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an organosilicon modified polyimide (a) (synthesis example 5).

The silicone-modified polyimide (A) (Synthesis example 5) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 50000.

(6) Synthesis example 6 (organosilicon modified polyimide (A) having terminal Maleimide group)

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 96g (0.06 mol) of an organosilicon compound having amino groups at both ends (X-22-161A, manufactured by shin-Etsu chemical Co., Ltd., the number of repeating siloxane units: 21, and a weight average molecular weight of 1600) and 20.8g (0.04 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were added in this order. A Dean-Stark tube and a condenser were installed in the flask, and the mixture was refluxed for 2 hours to synthesize a polyimide having an amine at the end. After the reaction mixture was cooled to room temperature or lower, 2.0g (0.02 mol) of maleic anhydride was added, and then 35g (0.35 mol) of methanesulfonic anhydride was added. The reaction mixture was further refluxed for 12 hours, and after the reaction mixture was cooled to room temperature, it was filtered through a glass frit funnel filled with silica gel to obtain an organosilicon modified polyimide (a) (synthesis example 6).

The silicone-modified polyimide (A) (Synthesis example 6) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 7000.

(7) Synthesis example 7 (organosilicon modified polyimide (A) having allyl group in side chain)

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 64g (0.04 mol) of an organosilicon compound having amino groups at both ends (X-22-161A, product of shin-Etsu chemical Co., Ltd., number of repeating siloxane units: 21, weight average molecular weight 1600) was added. Further, 5.2g (0.02 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) propane and 20.8g (0.04 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were successively added thereto. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours, then 5.7G (0.05 mol) of NEOALLYL G (allyl glycidyl ether, manufactured by Osakacaoda Co., Ltd.) and 0.2G (2 mmol) of triethylamine were added, and the mixture was further heated for 3 hours. After cooling to room temperature, an organosilicon modified polyimide (a) (synthesis example 7) was obtained.

The silicone-modified polyimide (A) (Synthesis example 7) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 8000.

(8) Synthesis example 8 (Silicone-modified polyimide (A) having hydroxyl group)

250mL of toluene was put into a 500mL round-bottom flask containing a Teflon (registered trademark) stirrer. Next, 64g (0.04 mol) of an organosilicon compound having amino groups at both ends (X-22-161A, product of shin-Etsu chemical Co., Ltd., number of repeating siloxane units: 21, weight average molecular weight 1600) was added. Further, 5.2g (0.02 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) propane and 20.8g (0.04 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were successively added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an organosilicon modified polyimide (a) (synthesis example 8).

The silicone-modified polyimide (A) (Synthesis example 8) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 6000.

(9) Synthesis example 9

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 20.8g (0.08 mol) of an organosilicon compound having amino groups at both ends (PAM-E, the number of repeating siloxane units is 3, and the weight average molecular weight is 260, manufactured by shin-Etsu chemical Co., Ltd.) and 62.4g (0.12 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were sequentially added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an organosilicon modified polyimide (a) (synthesis example 9).

The silicone-modified polyimide (A) (Synthesis example 9) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 5000.

(10) Synthesis example 10

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 114g (0.01 mol) of an organosilicon compound having amino groups at both terminals (KF-8008, manufactured by shin-Etsu chemical Co., Ltd., the number of repeating siloxane units: 150, and a weight average molecular weight of 11400) and 10.4g (0.02 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were sequentially added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an organosilicon modified polyimide (a) (synthesis example 10).

The silicone-modified polyimide (A) (Synthesis example 10) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 50000.

(11) Synthesis example 11

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 88g (0.02 mol) of an organosilicon compound having amino groups at both ends (KF-8012, product of shin-Etsu chemical Co., Ltd., number of repeating siloxane units: 60, weight average molecular weight 4400) was added. Further, 16g (0.03 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 26g (0.05 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were sequentially added. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain an organosilicon modified polyimide (a) (synthesis example 11).

The silicone-modified polyimide (A) (Synthesis example 11) thus obtained was measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (Waters corporation) as a column, and found to have a weight average molecular weight of 100000.

[ Table 1]

(preparation of curable resin (B))

(1) Synthesis of 2-functional Maleimide represented by the following formula (11)

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. Next, 35g (0.35 mol) of triethylamine and 35g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 56g (0.1 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 19.1g (0.09 mol) of pyromellitic 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 synthesize polyimide. After the reaction mixture was cooled to room temperature, 12.8g (0.13 mol) of maleic anhydride was added, followed by 5g (0.05 mol) of methanesulfonic anhydride. After the reaction mixture was further refluxed for 12 hours, cooled to room temperature, and 300mL of toluene was added to the flask, and impurities were precipitated and removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel to obtain 2-functional maleimide represented by the following formula (11).

The obtained 2-functional maleimide was measured by a Gel Permeation Chromatography (GPC) method using THF as an eluent and HR-MB-M (Waters corporation) as a column, and the weight average molecular weight was 15000.

[ chemical formula 4]

(2) Synthesis of 2-functional Maleimide represented by the following formula (12)

250mL of toluene was put into a 500mL round-bottomed flask containing a Teflon (registered trademark) stirrer. 56g (0.1 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 19.6g (0.2 mol) of maleic anhydride were added, and then 5g of methanesulfonic anhydride was added. After the solution was refluxed for 12 hours, cooled to room temperature, and 300mL of toluene was added to the flask, and the salt was precipitated and removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel to obtain a 2-functional maleimide represented by the following formula (12).

[ chemical formula 5]

(Synthesis of acrylic resin)

A reactor equipped with a stirrer and a condenser was prepared, and 94 parts by weight of 2-ethylhexyl acrylate as an alkyl (meth) acrylate, 6 parts by weight of hydroxyethyl methacrylate as a functional group-containing monomer, 0.01 part by weight of lauryl mercaptan and 80 parts by weight of ethyl acetate were added to the reactor, and then the reactor was heated to start reflux. Next, 0.01 part 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. Then, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane in an amount of 0.01 part by weight was added 1 hour and 2 hours after the start of the polymerization, and tert-hexyl peroxypivalate in an amount of 0.05 part by weight was added 4 hours after the start of the polymerization, and the polymerization reaction was continued. Then, 8 hours after the start of the polymerization, an ethyl acetate solution of a functional group-containing (meth) acrylic polymer having a solid content of 55% by weight and a weight average molecular weight of 60 ten thousand was obtained.

To 100 parts by weight of the resin solid content of the obtained ethyl acetate solution containing the functional group-containing (meth) acrylic polymer was added 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound, and the mixture was reacted to obtain an acrylic resin.

(example 1)

300mL of toluene was prepared. To this, 10 parts by weight of an organosilicon-modified polyimide (A) (Synthesis example 1), 60 parts by weight of a 2-functional maleimide represented by the above formula (11), 30 parts by weight of a 2-functional maleimide represented by the above formula (12), 3 parts by weight of Omnirad 819 (manufactured by IGM Resins Co.) as a photopolymerization initiator, and 10 parts by weight of silica (REOLOSIL MT-10, manufactured by Tokuyama) as an inorganic filler were added. Thus, a toluene solution of the adhesive composition was prepared.

The obtained toluene solution of the adhesive composition was applied to a corona-treated surface of a polyimide film (Kapton, manufactured by yu seiko) having a thickness of 25 μm, on one surface of which corona treatment was performed, by a doctor blade so that the thickness of the dried film became 40 μm, and the applied solution was dried by heating at 110 ℃ for 1 minute. Then, the adhesive tape was left to stand and cured at 40 ℃ for 3 days to obtain an adhesive tape.

Using an ultra-high pressure mercury lamp at 20mW/cm ² The adhesive tape thus obtained was irradiated with 365nm ultraviolet rays for 150 seconds. 10mg of the adhesive tape cured by ultraviolet irradiation was collected and put in an aluminum cup, and the weight ratio after heating at 300 ℃ was measured at a temperature increase rate of 10 ℃ per minute by a thermogravimetric apparatus STA7200 (manufactured by Hitachi High-TechScience).

(examples 2 to 19 and comparative examples 1 to 2)

Adhesive tapes were obtained in the same manner as in example 1, except that the compounding ingredients were changed as shown in table 2. Details of the materials shown in table 2 are shown below.

NK ESTER A-9300 (ethoxylated isocyanuric acid triacrylate, manufactured by Xinzhongcun chemical Co., Ltd.)

Bistetrazole-disodium salt (manufactured by Zeta chemical Co., Ltd.)

< evaluation >

The adhesive tapes obtained in examples and comparative examples were evaluated by the following methods. The results are shown in Table 2.

(1) Evaluation of releasability (measurement of adhesive Strength)

The resulting adhesive tape was cut into 1 inch widths and then heat laminated to 1mm thick glass by a 100 ℃ laminator. After lamination, an extra-high pressure mercury lamp was used from the glass side at 20mW/cm ² The ultraviolet ray of 365nm was irradiated at the intensity of (2) for 150 seconds. After the irradiation with ultraviolet rays, the glass was heated for 10 minutes by passing through a hot plate at 300 ℃.

The test pieces after the irradiation with ultraviolet rays and after the heating at 300 ℃ were subjected to a 180 DEG peel test at 25 ℃ and a tensile rate of 30 mm/sec, and the adhesive strength (N/inch) was measured.

(2) Evaluation of protrusion and residue after 30 minutes heating at 250 ℃ C

The resulting adhesive tape was cut into 1 inch widths and then heat laminated to 1mm thick glass by a 100 ℃ laminator. After lamination, an extra-high pressure mercury lamp was used from the glass side at 20mW/cm ² Ultraviolet ray 15 of 365nm intensityFor 0 second. After the irradiation with ultraviolet rays, the glass was heated for 30 minutes by passing through a hot plate at 250 ℃.

The test piece heated at 250 ℃ for 30 minutes was visually observed for the protrusion of the adhesive tape from the glass.

Good: no bulge is generated

And (delta): the area of the bump is less than one tenth of the whole

X: the area of the bump is more than one tenth of the whole

Further, the test piece after heating at 250 ℃ for 30 minutes was subjected to a 180 DEG peel test under conditions of 25 ℃ and a tensile rate of 30 mm/sec. The surface of the glass from which the adhesive tape was peeled was visually observed and evaluated by the following criteria.

Good: no residual gum was confirmed

And (delta): although no residual adhesive was present, blurring was observed on the peeled surface

X: the residual gum is confirmed

[ Table 2]

Industrial applicability

The present invention can provide a pressure-sensitive adhesive composition that can be easily peeled off even after a high-temperature processing treatment at 250 ℃ or more or 300 ℃ or more is performed in a state where an adherend is fixed. Further, the present invention can provide an adhesive tape having an adhesive layer formed from the adhesive composition, and a method for processing an electronic component using the adhesive tape.

Claims

1. An adhesive composition characterized by containing an organosilicon-modified polyimide A and a curable resin B having a double bond.

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

3. The adhesive composition according to claim 1 or 2, wherein the silicone-modified polyimide A is a silicone-modified polyimide 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), wherein s1 is not less than 1, t1 is not less than 0, and u1 is not less than 0,

in the general formulae (1a) to (1c), P ¹ 、P ² And P ³ Each independently represents an alicyclic group or an aromatic group; q ¹ Represents a silicone chain, 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; x ³ Represents a substituted or unsubstituted aliphatic group, aromatic group or double bond-containing functional group, X ³ _n1 N1 in (1) represents an integer of 1 or more.

4. The adhesive composition according to claim 1,2 or 3, wherein the number of repeating siloxane units in the silicone chain of the silicone-modified polyimide A is 10 or more and 100 or less.

5. The adhesive composition according to claim 1,2,3, or 4, wherein the silicone-modified polyimide A has a weight average molecular weight of 1000 or more and 5 ten thousand or less.

6. The adhesive composition according to claim 1,2,3 or 4, wherein the silicone-modified polyimide A has a weight average molecular weight of 5000 or more and 10 ten thousand or less.

7. The adhesive composition according to claim 1,2,3,4, 5, or 6, wherein the silicone-modified polyimide a has a functional group capable of crosslinking with the curable resin B having a double bond.

8. The adhesive composition according to claim 1,2,3,4, 5,6, or 7, wherein the content of the silicone-modified polyimide a is 0.5 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the curable resin B having a double bond.

9. The adhesive composition according to claim 1,2,3,4, 5,6, or 7, wherein the content of the silicone-modified polyimide a is 100 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the curable resin B having a double bond.

10. The adhesive composition according to claim 1,2,3,4, 5,6, 7, 8 or 9, wherein the curable resin B having a double bond contains a polyimide resin having a double bond.

11. The adhesive composition according to claim 10, wherein the curable resin B having a double bond contains a curable resin B1 having an imide skeleton in a main chain and a functional group having a double bond in a side chain or a terminal.

12. The adhesive composition according to claim 11, wherein the curable resin B1 having an imide skeleton in its main chain and a functional group having a double bond in its side chain or terminal has a hydroxyl group.

13. The adhesive composition according to claim 11 or 12, wherein the curable resin B1 having an imide skeleton in its main chain and a functional group having a double bond in its side chain or terminal is a curable resin B1-1, and the curable resin B1-1 has a structural unit represented by the following general formula (1d) and a junction represented by the following general formula (1e)A structural unit represented by the following general formula (1f), and X is attached to each of both ends ⁴ -and X ⁵ -represents, wherein s 2. gtoreq.1, t 2. gtoreq.0, u 2. gtoreq.0,

in the general formulae (1d) to (1f), P ⁴ 、P ⁵ And P ⁶ Each independently represents an alicyclic group or an aromatic group; q 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 group or aromatic group; is selected from X ⁴ 、X ⁵ And X ⁶ At least one of them represents a double bond-containing functional group, X ⁶ _n2 N2 in (1) represents an integer of 1 or more.

14. The adhesive composition according to claim 1,2,3,4, 5,6, 7, 8,9,10, 11, 12 or 13, wherein the curable resin B having a double bond contains a polyfunctional monomer or a polyfunctional oligomer B2 having at least 2 or more maleimide groups.

15. An adhesive tape characterized by having an adhesive layer formed from the adhesive composition of claim 1,2,3,4, 5,6, 7, 8,9,10, 11, 12, 13 or 14.

16. A method of processing electronic components, comprising: step 1 of temporarily fixing an electronic component to the adhesive tape according to claim 15; a step 2 of curing the adhesive layer of the adhesive tape; a step 3 of heat-treating the electronic component; and a step 4 of peeling the adhesive tape from the electronic component.