CN114302931A

CN114302931A - Adhesive composition, adhesive tape, and method for producing electronic component

Info

Publication number: CN114302931A
Application number: CN202080061251.4A
Authority: CN
Inventors: 七里德重
Original assignee: Sekisui Chemical Co Ltd
Current assignee: Sekisui Chemical Co Ltd
Priority date: 2019-10-11
Filing date: 2020-09-24
Publication date: 2022-04-08
Also published as: KR20220081951A; WO2021070623A1; TW202120597A; JPWO2021070623A1

Abstract

The purpose of the present invention is to provide a pressure-sensitive adhesive composition that can be easily peeled off even after being subjected to a high-temperature processing treatment at 300 ℃ or higher in a state in which an adherend is fixed, a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition, and a method for producing an electronic component. The present invention is an adhesive composition comprising a polyimide resin (a) having a hydroxyl group and at least 1 (B) selected from a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups. The present invention also provides an adhesive composition comprising a polyimide resin (a) having a hydroxyl group and at least 1 (B') selected from a polyfunctional monomer having a plurality of double bonds in the molecule and a polyfunctional oligomer having a plurality of double bonds in the molecule, wherein the adhesive composition has a residual heating amount of 90% or more at 300 ℃ after ultraviolet irradiation.

Description

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

Technical Field

The invention relates to an adhesive composition, an adhesive tape and a method for manufacturing an electronic component.

Background

In the processing of electronic components such as semiconductors, in order to facilitate handling of the electronic components and prevent breakage thereof, 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. For example, when a thick film wafer cut out from high-purity single crystal silicon or the like is ground to a predetermined thickness to form a thin film wafer, the thick film wafer is bonded to the support plate via the 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 processing step (hereinafter, also referred to as "high adhesiveness and easy peelability").

As a 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 irradiation with ultraviolet rays, 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.

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 processes 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 ℃. However, if an electronic component protected with a conventional adhesive composition or adhesive tape is subjected to a high-temperature processing treatment of 300 ℃ or higher, adhesion is increased, and the adhesive force is not sufficiently reduced or adhesive residue is generated during peeling.

In view of the above-described situation, 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 high-temperature processing treatment at 300 ℃ or higher in a state in which an adherend is fixed, a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition, and a method for producing an electronic component.

Means for solving the problems

The present invention is an adhesive composition comprising a polyimide resin (a) having a hydroxyl group and at least 1 (B) selected from a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups (as "embodiment 1 of the present invention"). The present invention is also an adhesive composition containing a polyimide resin (a) having a hydroxyl group and at least 1 (B') selected from a polyfunctional monomer having a plurality of double bonds in the molecule and a polyfunctional oligomer having a plurality of double bonds in the molecule, the adhesive composition having a residual amount of 90% or more after heating at 300 ℃.

The present invention will be described in detail below.

First, embodiment 1 of the present invention will be explained.

The present inventors have studied an adhesive composition comprising a polyimide resin (a) having a hydroxyl group and at least 1 (B) selected from a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups. The present inventors have found that such an adhesive composition has initial adhesive force, but on the other hand, curing by both irradiation with light and heating increases the elastic modulus, and can suppress increase in adhesion by heating, and therefore, can be easily peeled off even after being subjected to a high-temperature processing treatment of 300 ℃.

The curing of the pressure-sensitive adhesive composition will be described in detail by way of an example in which the adherend is fixed, irradiated with light, and then heated. In this case, after the adherend is fixed, first, at least 1 kind of maleimide groups (B) selected from the group consisting of a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups are reacted with each other by irradiation with light. This causes uniform and rapid polymerization and crosslinking of the entire pressure-sensitive adhesive composition, which increases the elastic modulus and reduces the adhesive strength. Then, unreacted maleimide groups in the polymer of at least 1 (B) selected from the group consisting of a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups are reacted with hydroxyl groups of the polyimide resin (a) having hydroxyl groups by heating. This further increases the elastic modulus of the pressure-sensitive adhesive composition, and further decreases the adhesive strength. As described above, it is considered that the adhesive composition according to embodiment 1 of the present invention is cured by both irradiation with light and heating, and the elastic modulus is increased, so that the increase in adhesion due to heating can be sufficiently suppressed. The heating referred to herein may be heating performed when a high-temperature processing treatment of 300 ℃ or higher is performed in a state where an adherend is fixed, or may be a step of separately heating the pressure-sensitive adhesive composition from such a high-temperature processing treatment.

The adhesive composition according to embodiment 1 of the present invention contains a polyimide resin (a) having a hydroxyl group (hereinafter, also simply referred to as "polyimide resin (a)").

Since the polyimide resin (a) is a polyimide resin and has an imide skeleton in the main chain, it has extremely excellent heat resistance, and is less likely to undergo decomposition of the main chain even after being subjected to a high-temperature processing treatment at 300 ℃ or higher, and can prevent occurrence of adhesion promotion and generation of residual glue upon peeling.

In addition, the polyimide resin (a) has a hydroxyl group, and thus the hydroxyl group can react with unreacted maleimide groups in at least 1 kind (B) of polymers selected from a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups, which are obtained by irradiation with light, by heating.

The pressure-sensitive adhesive composition according to embodiment 1 of the present invention has initial adhesive force, but is cured by both irradiation with light and heating, increases the elastic modulus, and suppresses increase in adhesion due to heating, and therefore can be easily peeled off even after being subjected to a high-temperature processing treatment of 300 ℃.

The hydroxyl group of the polyimide resin (a) is not particularly limited, and may be an alcoholic hydroxyl group or a phenolic hydroxyl group. Among them, a phenolic hydroxyl group is preferable in view of high reactivity. Such a hydroxyl group-containing group (hydroxyl group-containing group) is not particularly limited, and examples of the hydroxyl group-containing group having an alcoholic hydroxyl group include aliphatic groups or aromatic groups having 3 to 18 carbon atoms and having an alcoholic hydroxyl group. 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, 2' -bis (4-hydroxyphenyl) hexafluoropropane, and the like. Among them, 2' -bis (4-hydroxyphenyl) hexafluoropropane is preferable from the viewpoint of good releasability after heating.

The polyimide resin (a) preferably has a hydroxyl group equivalent (weight average molecular weight/number of hydroxyl groups) of 5000 or less. When the functional group equivalent is 5000 or less, the increase in adhesion by heating can be further suppressed, and the releasability after heating can be improved. This is considered to be because the distance between crosslinks becomes shorter by having hydroxyl groups at a certain or higher density in the molecules of the polyimide resin (a). 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.

The polyimide resin (a) preferably has a functional group having a double bond in a side chain or a terminal.

By providing a functional group having a double bond in a side chain or a terminal of the polyimide resin (a), the functional groups having a double bond are reacted with each other by irradiation with light. Thus, the three-dimensional network formation by the light irradiation of the pressure-sensitive adhesive composition is more efficiently performed, and the solvent resistance is improved even in a state before heating, so that even in the case where the processing treatment using the solvent is performed in a state where the adherend is fixed, the processing treatment can be appropriately performed. Further, if the three-dimensional network formation of the pressure-sensitive adhesive composition by light irradiation is performed more efficiently, the elastic modulus is further increased, and the increase in adhesion by heating is further suppressed, and therefore, the peelability after heating is also improved.

Examples of the functional group having a double bond include a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, a (meth) acryloyl group, and a group containing these functional groups, which may be substituted. Among these, maleimide groups which may be substituted or groups containing allyl groups are preferable from the viewpoint of obtaining higher heat resistance, and in particular, tris (iso) cyanurate groups having 1 or more allyl groups are more preferable from the viewpoint of obtaining high adhesiveness.

The functional group having a double bond may be located in either a side chain or a terminal of the polyimide resin (a), but is preferably located in a side chain. By having a functional group having a double bond in the side chain of the polyimide resin (a), solvent resistance in a state before heating is improved, and further increase in adhesion due to heating is suppressed, and releasability after heating is also improved. This is considered to be because the distance between crosslinks becomes short.

The polyimide resin (a) 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 solvent resistance before heating is improved, the increase in adhesion by heating is further suppressed, and the releasability after heating is also improved. This is considered to be because the distance between crosslinks becomes shorter by providing the polyimide resin (a) with functional groups having double bonds in the molecules at a density of a certain level or more. 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 is substantially about 600.

The weight average molecular weight of the polyimide resin (a) is preferably 5000 or more. By making the weight average molecular weight of the polyimide resin (a) 5000 or more, film formation is facilitated, and the obtained film exhibits a certain degree of flexibility, so that high conformability to an adherend having irregularities can be exhibited, and the peelability is also improved. The weight average molecular weight of the polyimide resin (a) is more preferably at most 5000, still more preferably at least 1 ten thousand, still more preferably at least 1.5 ten thousand, and particularly preferably at least 2 ten thousand. The upper limit of the weight average molecular weight of the polyimide resin (a) is not particularly limited, and is, for example, 30 ten thousand, particularly 10 ten thousand, from the viewpoint of solubility in a solvent.

The weight average molecular weight of the polyimide resin (a) is measured as a molecular weight in terms of polystyrene by a Gel Permeation Chromatography (GPC) method. More specifically, the measurement can be performed under the following conditions, for example.

A detector: differential refractometer (2414, made by Waters corporation)

Column: HR-MB-M (manufactured by Waters Co., Ltd.) or equivalent thereof

Mobile phase: THF (tetrahydrofuran)

Sample flow rate: 1mL/min

Column temperature: 40 deg.C

Specific examples of the polyimide resin (A) include a polyimide resin 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 s.gtoreq.0, t.gtoreq.0, and u.gtoreq.0), and both ends of which are X¹And X²The polyimide resin (A-1) shown.

[ chemical formula 1 ]

In the above general formulae (1a) to (1c), P¹、P²And P³Each independently represents an aromatic group, Q¹Represents a substituted or unsubstituted straight, branched or cyclic chainAliphatic radical of (2), Q²Represents a hydroxyl group-containing group, and R represents a substituted or unsubstituted branched aliphatic group or aromatic group. Is selected from X¹、X²And X³At least 1 of them represents a functional group having a double bond.

In the above general formulae (1a) to (1c), P¹、P²And P³Each independently preferably an aromatic group having 5 to 50 carbon atoms. By making P¹、P²And P³Each independently an aromatic group having 5 to 50 carbon atoms, so that the adhesive composition can exhibit particularly high heat resistance.

In the above general formulae (1a) to (1c), Q¹Preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. By making Q¹The adhesive tape produced using the adhesive composition 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 followability to an adherend having irregularities, and has improved peelability. In addition, Q¹Further, an aliphatic group derived from a diamine compound described later is preferable.

Among these, Q is a group having a function of improving flexibility, and also a function of increasing compatibility with the solvent and other components of the polyimide resin (a) and facilitating production of an adhesive tape¹Aliphatic groups derived from dimer diamines are preferred.

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

[ chemical formula 2 ]

In the above general formulae (4-1) to (4-4), R¹～R⁸And R¹³～R²⁰Each independently represents a linear or branched hydrocarbon group. Note that a represents a bonding position. Namely, the compound is bonded to N in the general formulae (1a) to (1 c).

In the above general formulae (4-1) to (4-4), R¹～R⁸And R¹³～R²⁰The hydrocarbon group is not particularly limited, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Wherein R is¹And R²、R³And R⁴、R⁵And R⁶、R⁷And R⁸、R¹³And R¹⁴、R¹⁵And R¹⁶、R¹⁷And R¹⁸And R¹⁹And R²⁰The total number of carbon atoms of (a) is preferably 7 or more and 50 or less. When the total number of carbon atoms is within the above range, a pressure-sensitive adhesive tape produced using the pressure-sensitive adhesive composition can exhibit higher flexibility, and the compatibility of the polyimide resin (a) with a solvent or 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 number of carbon atoms is more preferably 35 or less, still more preferably 25 or less, and still more preferably 18 or less.

The optical isomers 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) are not particularly limited, and any optical isomers are included.

In the above general formulae (1a) to (1c), Q²Represents a hydroxyl-containing group. As described above, Q²The hydroxyl group (b) may be an alcoholic hydroxyl group or a phenolic hydroxyl group, and a phenolic hydroxyl group is preferable from the viewpoint of high reactivity. Examples of the hydroxyl group-containing group include the above-mentioned hydroxyl group-containing group having an alcoholic hydroxyl group, and the above-mentioned hydroxyl group-containing group having a phenolic hydroxyl group.

In the general formulae (1a) to (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 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 have improved releasability.

In the general formulae (1a) to (1c), R is preferably 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 and X³And (4) bonding. Here, the "aromatic ester group" refers to a group in which an ester group is directly bonded to an aromatic ring, and the "aromatic ether group" refers to a group in which an ether group is directly bonded to an aromatic ring. By thus forming the portion bonded to the ester group or the ether group as an aromatic group, high heat resistance can be exhibited. On the other hand, by X³Bonded to R via an aromatic ester group or an aromatic ether group, whereby X³The double bonds in (B) are not conjugated and therefore do not interfere with the crosslinking of the polymer upon irradiation with light.

In the general formulae (1a) to (1c), the functional group having a double bond (crosslinkable unsaturated bond) is X¹、X²And X³At least 1 of (A), preferably at least X³Is a functional group having a double bond. By at least X³The functional group having a double bond improves the solvent resistance of the pressure-sensitive adhesive composition in a state before heating, further suppresses increase in adhesion by heating, and improves the releasability after heating.

In the above-mentioned X¹、X²And X³When any of the functional groups is a functional group other than the functional group having a double bond (a functional group having no double bond), examples of the functional group having no double bond include an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride, and an amine compound, each independently. Specifically, the unreacted single-terminal of the acid anhydride or diamine which is the raw material of the general formulae (1a) to (1c) may be mentioned.

In the general formulae (1a) to (1c), s, t, and u represent the content (mol%) of each of 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) in the polyimide resin (a).

The content of the structural unit represented by the general formula (1a) is 0 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, preferably 90 mol% or less, and more preferably 80 mol% or less. The content of the structural unit represented by the general formula (1b) is more than 0 mol%, preferably 10 mol% or more, more preferably 15 mol% or more, further preferably 20 mol% or more, preferably 100 mol% or less, and more preferably 50 mol% or less. The content of the structural unit represented by the general formula (1c) is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, preferably 50 mol% or less, and more preferably 30 mol% or less. When the content of each structural unit in the general formulae (1a) to (1c) is within the above range, the adhesive composition further suppresses increase in adhesion by heating, and improves the releasability after heating.

In the polyimide resin (a), the structural unit represented by the general formula (1b), and the structural unit represented by the general formula (1c) may be a block copolymer composed of a block component in which the respective structural units are continuously arranged, or may be a random copolymer in which the respective structural units are randomly arranged.

The polyimide resin (a) can be obtained, for example, by reacting a diamine compound with an aromatic acid anhydride, and further reacting, if necessary, a functional group of the obtained reactant with a compound having a functional group that reacts with the functional group and a functional group having a double bond (hereinafter referred to as a functional group-containing unsaturated compound).

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 have improved peelability. In addition, by using an aromatic diamine compound as the diamine compound, the heat resistance of the adhesive composition is further improved.

The diamine compound preferably contains a diamine compound having a hydroxyl group.

The polyimide resin (a) can have a hydroxyl group by including a diamine compound having a hydroxyl group in the diamine compound. The diamine compound having a hydroxyl group is not particularly limited, and may be a diamine compound having an alcoholic hydroxyl group or a diamine compound having a phenolic hydroxyl group.

The diamine compound having an alcoholic hydroxyl group is not particularly limited, and examples thereof include 1, 3-diamino-2-propanol, 2, 4-diaminophenoxyethanol, 3, 5-diaminophenoxyethanol, and 2, 4-diaminobenzyl alcohol. These diamine compounds having an alcoholic hydroxyl group may be used alone, or 2 or more kinds thereof may be used in combination.

The diamine compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include 2, 4-diaminophenol, 3, 5-diaminophenol, 4, 6-diaminoresorcinol, 2 '-bis (3-amino-4-hydroxyphenyl) propane, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2 '-bis (3-amino-4-hydroxyphenyl) sulfone, 2' -bis (3-amino-4-hydroxyphenyl) methane, and 4,4 '-diamino-3, 3' -dihydroxybiphenyl. These diamine compounds having a phenolic hydroxyl group may be used alone, or 2 or more kinds thereof may be used in combination.

The diamine compound may contain a diamine compound having a functional group other than a hydroxyl group.

The functional group other than the hydroxyl group is not particularly limited, and examples thereof include a carboxyl group and the like. Examples of the diamine compound having a carboxyl group include 3, 5-diaminobenzoic acid and bis (4-amino-3-carboxyphenyl) methane. These diamine compounds having a functional group other than a hydroxyl group may be used alone, or 2 or more kinds thereof may be used in combination.

When the diamine compound contains the diamine compound having a hydroxyl group and/or the diamine compound having a functional group other than a hydroxyl group, if the diamine compound is reacted with the aromatic acid anhydride, the reactant has a hydroxyl group and/or a functional group other than a hydroxyl group. The polyimide resin (a) can have a functional group having a double bond in a side chain or a terminal thereof by reacting a compound having a functional group reactive with the hydroxyl group and/or a functional group other than the hydroxyl group and a functional group having a double bond (a functional group-containing unsaturated compound) with the hydroxyl group and/or the functional group other than the hydroxyl group.

If all of the hydroxyl groups react with the functional group-containing unsaturated compound, the polyimide resin (a) cannot have hydroxyl groups. Therefore, it is necessary to adjust the reactivity by appropriately adjusting the kind of the functional group-containing unsaturated compound, the reaction conditions, and the like.

The functional group-containing unsaturated compound is selected and used depending on the hydroxyl group and/or a functional group other than the hydroxyl group.

Examples of the functional group-containing unsaturated compound that reacts with a hydroxyl group include maleimide compounds having a carboxyl group, vinyl compounds having an ether group, allyl compounds having a glycidyl group, allyl ether compounds having a glycidyl group, vinyl ether compounds having a glycidyl group, allyl compounds having an isocyanate group, and (meth) acryloyl compounds having an isocyanate group. These functional group-containing unsaturated compounds may be used alone, or 2 or more kinds may be used in combination.

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. Examples of the vinyl compound having an ether group include butyl vinyl ether and the like. Examples of the allyl compound having a glycidyl group include diallyl monoglycidyl isocyanurate and the like. Examples of the allyl ether compound having a glycidyl group include allyl glycidyl ether and glycerol diallyl monoglycidyl ether. Examples of the glycidyl group-containing vinyl ether compound include glycidoxyethyl vinyl ether, glycidoxybutyl vinyl ether, glycidoxyhexyl vinyl ether, glycidyldiethylene glycol vinyl ether, and glycidylcyclohexanedimethanol monovinyl ether. Examples of the allyl compound having an isocyanate group include allyl isocyanate and the like. Examples of the (meth) acryloyl compound having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and the like.

Examples of the functional group-containing unsaturated compound that reacts with a carboxyl group include an allyl compound having a hydroxyl group, an allyl compound having a glycidyl group, an allyl ether compound having a glycidyl group, and a vinyl ether compound having a glycidyl group.

Examples of the allyl compound having a hydroxyl group include trimethylolpropane diallyl ether and pentaerythritol triallyl ether. Examples of the allyl compound having a glycidyl group include diallyl monoglycidyl isocyanurate and the like. Examples of the allyl ether compound having a glycidyl group include allyl glycidyl ether and glycerol diallyl monoglycidyl ether. Examples of the glycidyl group-containing vinyl ether compound include glycidoxyethyl vinyl ether, glycidoxybutyl vinyl ether, glycidoxyhexyl vinyl ether, glycidyldiethylene glycol vinyl ether, and glycidylcyclohexanedimethanol monovinyl ether.

The diamine compound may further contain another aliphatic diamine compound or another aromatic diamine compound in addition to the diamine compound having a hydroxyl group and the diamine compound having a functional group other than a hydroxyl group.

Examples of the other aliphatic diamine compounds 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, 1, 2-diaminododecane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 8-diaminoheptane, 1, 8-diaminomenthane, 1, 8-diaminooctane, 1, 9-diaminononane, 3' -diamino-N-methyldipropyramine, diaminomaleonitrile, 1, 3-diaminopentane, bis (4-amino-3-methylcyclohexyl) methane, 1, 2-bis (2-aminoethoxy) ethane, 1, 2-diaminododecane, 1, 2-diaminobutane, 1, 2-bis (2-aminoethoxy) ethane, 1, 2-diaminobutane, 1, 2-bis (2-one, or a) ethane, 2-one) ethane, and a mixture, 3(4),8(9) -bis (aminomethyl) tricyclo (5.2.1.02, 6) decane and the like. These other aliphatic diamine compounds may be used alone, or 2 or more thereof may be used in combination.

Among the other aliphatic diamine compounds, dimer diamine is preferable from the viewpoint of improving flexibility, increasing compatibility with the solvent and other components of the polyimide resin (a), and facilitating 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 a hydride to which hydrogen is added.

More specifically, the dimer diamine includes, for example, dimer diamines which constitute 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).

Examples of the other aromatic diamine compounds 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-isopropylbenzenediamine, 1, 3-bisaminomethylbenzene, 1, 3-bisaminomethylcyclohexane, and the like, 2-chloro-1, 4-diaminobenzene, 1, 4-diamino-2, 5-dichlorobenzene, 1, 4-diamino-2, 5-dimethylbenzene, 4 ' -diamino-2, 2 ' -bistrifluoromethylbiphenyl, 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, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3-ethylphenyl) methane, 4 ' -diaminophenylsulfone, methyl ether, ethyl ether, methyl ether, ethyl ether, 3,3 ' -diaminophenylsulfone, 2-bis (4- (4-aminophenoxy) phenyl) sulfone, 2-bis (4- (3-aminophenoxy) phenyl) sulfone, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl sulfide, 3,4 ' -diaminodiphenyl ether, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (4-aminophenoxy) benzene, 4 ' -bis (4-aminophenoxy) biphenyl, 4 ' -diamino-3, 3 ' -dimethylbiphenyl, 4 ' -diamino-3, 3 ' -dimethoxybiphenyl, Bisaniline M, Bisaniline P, 9-bis (4-aminophenyl) fluorene, and mixtures thereof, O-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. These other aromatic diamine compounds may be used alone, or 2 or more thereof may be used in combination.

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 ' -biphenyl 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-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 ' -biphenyltetracarboxylic acid, 2,3,2 ', 3 ' -biphenyltetracarboxylic acid, 4 ' -bis (3, 4-dicarboxyphenoxy) diphenyl sulfide, 4 ' - (4,4 ' -isopropylidenediphenoxy) -bis (phthalic acid), and the like. These aromatic acid anhydrides may be used alone, or 2 or more of them may be used in combination.

The adhesive composition as the 1 st embodiment of the invention contains at least 1 (B) (hereinafter, also simply referred to as "polyfunctional maleimide compound (B)") selected from a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups.

The polyfunctional maleimide compound (B) has a plurality of maleimide groups, and the maleimide groups react with each other by irradiation with light. In addition, unreacted maleimide groups in the polymer of the polyfunctional maleimide compound (B) react with hydroxyl groups of the polyimide resin (a) by heating. The pressure-sensitive adhesive composition according to embodiment 1 of the present invention has initial adhesive force, but is cured by both irradiation with light and heating, and the elastic modulus thereof increases, and the increase in adhesion due to heating can be suppressed, and therefore, the pressure-sensitive adhesive composition can be easily peeled off even after being subjected to a high-temperature processing treatment of 300 ℃.

In addition, by providing the above-mentioned polyfunctional maleimide compound (B) with a maleimide group, the pressure-sensitive adhesive composition according to embodiment 1 of the present invention can exhibit particularly high heat resistance as compared with the case of having other functional groups.

The number of maleimide groups in the polyfunctional maleimide compound (B) is not particularly limited as long as it is plural, and is, for example, 2 or more, 3 or more, or 4 or more. The upper limit of the number of maleimide groups in the polyfunctional maleimide compound (B) is not particularly limited, and is, for example, 20 or less, 15 or less, or 10 or less.

The polyfunctional maleimide compound (B) is not particularly limited, and a polyfunctional monomer or a polyfunctional oligomer having a plurality of maleimide groups and a molecular weight of 5000 or less is preferable. Specific examples thereof include 4,4 ' -diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol a diphenyl ether 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 ' -diphenyl ether bismaleimide, and 4,4 ' -diphenylsulfone bismaleimide. These polyfunctional maleimide compounds (B) may be used alone or in combination of 2 or more.

The content of the polyfunctional maleimide compound (B) in the adhesive composition according to embodiment 1 of the present invention is not particularly limited, and the preferable lower limit is 5 parts by weight and the preferable upper limit is 500 parts by weight with respect to 100 parts by weight of the polyimide resin (a). When the content of the polyfunctional maleimide compound (B) is within this range, particularly excellent releasability can be exhibited. From the viewpoint of further improving the peelability, the content of the polyfunctional maleimide compound (B) is preferably 10 parts by weight at the lower limit, more preferably 15 parts by weight at the lower limit, more preferably 400 parts by weight at the upper limit, more preferably 200 parts by weight at the upper limit, still more preferably 50 parts by weight at the upper limit, and particularly preferably 40 parts by weight at the upper limit.

The adhesive composition according to embodiment 1 of the present invention may further contain at least 1 kind (C) (hereinafter, also simply referred to as "polyfunctional vinyl ether compound or polyfunctional allyl compound (C)") selected from a polyfunctional monomer having at least 2 or more vinyl ether groups or allyl groups and a polyfunctional oligomer having at least 2 or more vinyl ether groups or allyl groups.

By containing the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C), the pressure-sensitive adhesive tape produced using the pressure-sensitive adhesive composition according to embodiment 1 of the present invention can exhibit high flexibility, can exhibit high conformability to adherends having irregularities, and can also have improved peelability.

The polyfunctional vinyl ether compound or polyfunctional allyl compound (C) is not particularly limited, and is preferably a polyfunctional monomer or polyfunctional oligomer having at least 2 vinyl ether groups or allyl groups and a weight average molecular weight of 10000 or less. Specific examples thereof 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 vinyl ether compounds and polyfunctional allyl compounds (C) may be used alone or in combination of 2 or more.

The content of the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C) in the adhesive composition according to embodiment 1 of the present invention is not particularly limited. The content of the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C) is preferably 5 parts by weight in the lower limit and 30 parts by weight in the total 100 parts by weight of the polyimide resin (a), the polyfunctional maleimide compound (B) and the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C). When the content of the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C) is within this range, particularly excellent flexibility can be exhibited. From the viewpoint of further improving flexibility, the content of the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C) is preferably 10 parts by weight at the lower limit, more preferably 20 parts by weight at the upper limit, and still more preferably 15 parts by weight at the upper limit.

The adhesive composition according to embodiment 1 of the present invention preferably further contains 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, benzoin ether-based compounds, ketal derivative compounds, phosphine oxide derivative compounds, and the like.

Examples of the acetophenone derivative compound include methoxyacetophenone and the like. Examples of the benzoin ether-based compound include benzoin propyl ether and benzoin isobutyl ether. Examples of the ketal derivative compound include benzildimethylketal and acetophenone diethylketal. These photopolymerization initiators may be used alone, or 2 or more of them may be used in combination.

As the photopolymerization initiator, a photo radical polymerization initiator may be used. Examples of the photo radical polymerization initiator include bis (. eta.5-cyclopentadienyl) titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone,. alpha. -hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone, or 2 or more of them may be used in combination.

The content of the photopolymerization initiator in the adhesive composition according to embodiment 1 of the present invention is not particularly limited, and a preferable lower limit is 0.1 part by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total of the polyimide resin (a), the polyfunctional maleimide compound (B), and the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C). 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 according to embodiment 1 of the present invention preferably further contains a thermosetting agent.

The heat-curing agent is not particularly limited, and examples thereof include amine compounds, modified amines, acid anhydrides, and compounds having a phenolic hydroxyl group.

The heat-curing agent is preferably a heat-curing agent having fluxant properties, and examples of such a heat-curing agent include acid anhydrides and compounds having phenolic hydroxyl groups.

The acid anhydride is not particularly limited, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. Among them, methyl nadic anhydride or trialkyl tetrahydrophthalic anhydride is preferable because it is hydrophobized. These acid anhydrides may be used alone, or 2 or more kinds may be used in combination.

As the acid anhydride, acid anhydride particles having 3 or more functions can be used. The above-mentioned acid anhydride particles having 3 or more functions are not particularly limited, and examples thereof include particles containing acid anhydride having 3 or more functions such as trimellitic anhydride and particles containing acid anhydride having 4 or more functions such as pyromellitic anhydride, benzophenone tetracarboxylic anhydride, methylcyclohexene tetracarboxylic anhydride and polyazelaic anhydride.

The compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include bisphenol a, bisphenol F, phenol novolac, cresol novolac, dicyclopentadiene phenol, aralkyl phenol, triphenol, tetraphenol, resol-type phenol, biphenyl dimethylene-type phenol, phenol resin-silica mixture, and derivatives and modifications thereof. Among them, phenol novolak, cresol novolak, dicyclopentadiene phenol, biphenyl dimethylene phenol, phenol resin-silica mixture, and derivatives and modifications thereof are preferable.

Examples of commercially available products of the heat-curing agent include allyl phenol resins such as 2, 2' -diallylbisphenol a, allyl phenols (manufactured by macrochemical chemical industry co., kryol chemical industry co., ltd.) such as acrylpolymethylene resin and allyl ether phenol resin.

The content of the thermosetting agent in the adhesive composition according to embodiment 1 of the present invention is not particularly limited, and a preferable lower limit is 0.1 part by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total of the polyimide resin (a), the polyfunctional maleimide compound (B), and the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C). When the content of the thermosetting agent is within this range, particularly excellent releasability can be exhibited. The lower limit of the content of the thermosetting agent is more preferably 0.5 part by weight, and the upper limit is more preferably 5 parts by weight.

The adhesive composition according to embodiment 1 of the present invention may further contain a thermosetting accelerator.

The above-mentioned thermosetting accelerator is not particularly limited, and examples of commercially available products include 2MZ, 2MZ-P, 2PZ-PW, 2P4MZ, C11Z-CNS, 2PZ-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2MZ-OK, 2PHZ-PW, 2P4MHZ-PW, 2E4 MZ. BIS, VT-OK, MAVT-OK (manufactured by four nations chemical industries, above). Among these thermal curing accelerators, those which are stable up to 130 ℃ and activated at 135 to 200 ℃ are particularly preferable, and examples of such thermal curing accelerators include 2MA-OK and 2 MAOK-PW.

The content of the thermosetting accelerator in the adhesive composition according to embodiment 1 of the present invention is not particularly limited, and a preferable lower limit is 0.1 part by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the total of the polyimide resin (a), the polyfunctional maleimide compound (B), and the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C). When the content of the thermosetting accelerator is within this range, particularly excellent releasability can be exhibited. A more preferable lower limit of the content of the above heat curing accelerator is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.

The adhesive composition according to embodiment 1 of the present invention preferably further contains an organosilicon compound or a fluorine compound.

Since the silicone compound and the fluorine compound have excellent heat resistance, the pressure-sensitive adhesive composition can be prevented from scorching even after being subjected to a high-temperature processing treatment of 300 ℃ or higher, and can be exuded to the adherend interface during peeling, thereby facilitating peeling.

The organic silicon compound is not particularly limited, and examples thereof include silicone oil, silicon diacrylate, and organic silicon graft copolymer. The fluorine compound is not particularly limited, and examples thereof include hydrocarbon compounds having a fluorine atom.

The organic silicon compound or the fluorine compound is preferably an organic silicon compound or a fluorine compound having a functional group capable of crosslinking with the polyimide resin (a). When the organic silicon compound and the fluorine compound have a functional group capable of crosslinking with the polyimide resin (a), the organic silicon compound and the fluorine compound chemically react with the polyimide resin (a) by irradiation with light, a reaction with a crosslinking agent, or the like and enter the polyimide resin (a), and therefore adhesion of the organic silicon compound or the fluorine compound to an adherend and contamination can be further suppressed. Among them, an organic silicon compound having a functional group capable of crosslinking with the polyimide resin (a) is preferable from the viewpoint of environmental friendliness and easy disposal.

Examples of the functional group capable of crosslinking with the polyimide resin (a) include a radical-polymerizable unsaturated bond (e.g., a vinyl group, (meth) acryloyl group, and optionally substituted maleimide group), a carboxyl group, a hydroxyl group, an amide group, an isocyanate group, and an epoxy group.

The organic silicon compound having a functional group capable of crosslinking with the polyimide resin (a) is preferably an organic silicon compound represented by the following general formula (I), general formula (II), or general formula (III), which has a siloxane skeleton in the main chain and a functional group having a double bond in a side chain or a terminal. These organosilicon compounds have particularly high heat resistance and high polarity, and therefore easily bleed out from the adhesive composition.

[ chemical formula 3 ]

In the general formula (I), the general formula (II) and the general formula (III), X and Y independently represent an integer of 0 to 1200, and R represents a functional group having a double bond.

In the general formulae (I), (II) and (III), examples of the double-bond-containing functional group represented by R include a maleimide group, a citraconimide group, a vinyl ether group, an allyl group, a (meth) acryloyl group, and the like, which may be substituted. Among them, maleimide groups which may be substituted are preferable from the viewpoint of obtaining higher heat resistance. In the general formula (I), the general formula (II), and the general formula (III), when a plurality of R are present, the plurality of R may be the same or different.

Examples of commercially available products of the organosilicon compounds having a (meth) acryloyl group in the siloxane skeleton represented by the general formulae (I), (II) and (III) include EBECRYL350 and EBECRYL1360 (both R are acryloyl groups) manufactured by Daicel-Cytec, BYK-UV3500 manufactured by BYK Chemie, TEGO RAD2250(R is an acryloyl group) manufactured by Evonik, and the like.

The content of the organic silicon compound or the fluorine compound in the adhesive composition according to embodiment 1 of the present invention is not particularly limited, and a preferable lower limit is 0.1 part by weight and a preferable upper limit is 20 parts by weight with respect to 100 parts by weight of the total of the polyimide resin (a), the polyfunctional maleimide compound (B), and the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C). When the content of the organosilicon compound or the fluorine compound is within this range, excellent releasability can be exhibited without staining an adherend. From the viewpoint of further improving the releasability while suppressing contamination of the adherend, the content of the above-mentioned organosilicon compound or fluorine compound has a more preferable lower limit of 0.3 parts by weight and a more preferable upper limit of 10 parts by weight.

The pressure-sensitive adhesive composition according to embodiment 1 of the present invention has excellent heat resistance, and therefore can exhibit sufficient effects even when the content of the organic silicon compound or the fluorine compound is small. Therefore, the possibility of contamination by the above-mentioned organosilicon compound or fluorine compound can be further reduced.

The adhesive composition according to embodiment 1 of the present invention may further include a gas generating agent that generates a gas by irradiation with light. By containing the gas generating agent, 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. These gas generating agents may be used alone, or 2 or more of them may be used in combination. Among them, a tetrazole compound or a salt thereof is preferable because it is particularly excellent in heat resistance.

The content of the gas generating agent in the pressure-sensitive adhesive composition according to embodiment 1 of the present invention 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 polyimide resin (a), the polyfunctional maleimide compound (B), and the polyfunctional vinyl ether compound or polyfunctional allyl compound (C). When the content of the gas generating agent is within this range, particularly excellent releasability can be exhibited. 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 pressure-sensitive adhesive composition according to embodiment 1 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.

The fine particle filler preferably contains at least 1 inorganic filler selected from oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconia, and composites thereof. Among them, silicon-aluminum-boron composite oxide, silicon-titanium composite oxide, and silica-titania composite oxide are more preferable because they have physical properties similar to those of silica which is generally used as an inorganic filler.

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 amount of the inorganic filler is not particularly limited, and is preferably 30 parts by weight at the lower limit and 150 parts by weight at the upper limit, based on 100 parts by weight of the total of the polyimide resin (a), the polyfunctional maleimide compound (B), and the polyfunctional vinyl ether compound or polyfunctional allyl compound (C). A more preferable lower limit of the amount of the inorganic filler is 60 parts by weight, and a more preferable upper limit is 120 parts by weight.

The adhesive composition according to embodiment 1 of the present invention preferably has a residual heating amount of 90% or more at 300 ℃ after ultraviolet irradiation. When the residual heating amount at 300 ℃ is 90% or more, the heat resistance of the adhesive composition is improved and the adhesive composition is less likely to be decomposed even at high temperatures. As a result, the pressure-sensitive adhesive composition is less likely to decompose even after being subjected to a high-temperature processing treatment at 300 ℃ or higher, and can further prevent the occurrence of increased adhesion or the occurrence of adhesive residue during peeling. A more preferable lower limit of the amount of the residual heat at 300 ℃ is 93%, and a still more preferable lower limit is 95%. The upper limit of the amount of the heating residue at 300 ℃ is not particularly limited, but is preferably as high as possible, and the upper limit is substantially 100% or 99%, for example.

The residual heating amount at 300 ℃ can be measured by the following method.

For the sample of the adhesive composition, an ultra-high pressure mercury lamp was used at 20mW/cm²The ultraviolet ray of 365nm was irradiated at the intensity of (2) for 150 seconds. A sample of the adhesive composition after uv irradiation was weighed and placed in an aluminum cup. The measurement sample was heated from 25 ℃ to 300 ℃ at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere using a thermogravimetric apparatus (STA7200 (manufactured by Hitachi High-Tech Science Co., Ltd.) or the like, and the heating residue at 300 ℃ was measured.

The method for adjusting the residual heating amount at 300 ℃ to the above range is not particularly limited, and a method using the polyfunctional maleimide compound (B) and the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C) in the same type or in different contents is preferred.

The method for producing the adhesive composition according to embodiment 1 of the present invention is not particularly limited, and examples thereof include a method of mixing the polyimide resin (a), the polyfunctional maleimide compound (B), and the components blended as necessary as described above using a bead mill, ultrasonic dispersion, homogenizer, high power disperser, roll mill, or the like.

Next, embodiment 2 of the present invention will be explained.

The present inventors have studied the reason why the pressure-sensitive adhesive composition of embodiment 1 of the present invention can be easily peeled off even after being subjected to a high-temperature processing treatment of 300 ℃ or more in a state in which an adherend is fixed, and as a result, have found that the residual heating amount at 300 ℃ after ultraviolet irradiation of the pressure-sensitive adhesive composition affects. Then, as a result of further studies, it was found that the same effects as those of the pressure-sensitive adhesive composition according to embodiment 1 of the present invention are exhibited by setting the residual heating amount at 300 ℃ after the ultraviolet irradiation of the pressure-sensitive adhesive composition to a specific range, not only in the case of using the above polyfunctional maleimide compound (B), but also in the case of using a specific polyfunctional unsaturated compound (B').

That is, the present inventors have studied an adhesive composition which comprises a polyimide resin (a) having a hydroxyl group and at least 1 (B') selected from a polyfunctional monomer having a plurality of double bonds in the molecule and a polyfunctional oligomer having a plurality of double bonds in the molecule and has a residual amount of 90% or more after ultraviolet irradiation after heating at 300 ℃. The present inventors have found that such a pressure-sensitive adhesive composition can be easily peeled off even after being subjected to a high-temperature processing treatment of 300 ℃ or higher in a state in which an adherend is fixed, and have completed the present invention.

The adhesive composition according to embodiment 2 of the present invention contains the same polyimide resin (a) as that contained in the adhesive composition according to embodiment 1 of the present invention.

The adhesive composition according to embodiment 2 of the present invention contains at least 1 (B ') selected from a polyfunctional monomer having a plurality of double bonds in the molecule and a polyfunctional oligomer having a plurality of double bonds in the molecule (hereinafter, simply referred to as "polyfunctional unsaturated compound (B')").

For example, when the adherend is fixed and then heated after irradiation with light, the polyfunctional unsaturated compound (B') has a plurality of double bonds, and thus the double bonds react with each other by irradiation with light. Further, the unreacted double bond in the polymer of the polyfunctional unsaturated compound (B') reacts with the hydroxyl group of the polyimide resin (a) by heating. The pressure-sensitive adhesive composition according to embodiment 2 of the present invention has initial adhesive force, but is cured by both irradiation with light and heating, and the elastic modulus thereof increases, and the increase in adhesion due to heating can be suppressed, and therefore, the pressure-sensitive adhesive composition can be easily peeled off even after being subjected to a high-temperature processing treatment of 300 ℃.

Examples of the functional group having a double bond in the polyfunctional unsaturated compound (B') include a maleimide group, a citraconimide group, (meth) acryloyl group, vinyl ether group, and allyl group. These functional groups may be substituted. Among them, from the viewpoint of reactivity, a maleimide group and a (meth) acryloyl group are preferable, and from the viewpoint of obtaining higher heat resistance, a maleimide group which may be substituted is more preferable. These double bond-containing functional groups may be used alone or in combination of 2 or more in the above polyfunctional unsaturated compound (B').

The number of double bonds (the number of functional groups having a double bond) in the polyfunctional unsaturated compound (B') is not particularly limited as long as it is plural, and is, for example, 2 or more, 3 or more, or 4 or more. The upper limit of the number of double bonds in the polyfunctional unsaturated compound (B') is not particularly limited, and is, for example, 20 or less, 15 or less, or 10 or less.

The polyfunctional unsaturated compound (B') may be the polyfunctional maleimide compound (B) or the polyfunctional vinyl ether compound or the polyfunctional allyl compound (C). In addition, other polyfunctional monomers or polyfunctional oligomers than the above polyfunctional maleimide compound (B) and the above polyfunctional vinyl ether compound or polyfunctional allyl compound (C) may also be used.

The other polyfunctional monomer or polyfunctional oligomer is preferably a polyfunctional monomer or polyfunctional oligomer having a molecular weight of 1 ten thousand or less, and more preferably a polyfunctional monomer or polyfunctional oligomer having a molecular weight of 5000 or less and a number of double bonds in the molecule of 2 to 20, in order to efficiently perform three-dimensional reticulation of the adhesive composition by heating or irradiation with light.

As the other polyfunctional monomer or polyfunctional oligomer, specifically, for example, at least 1 (C) selected from a polyfunctional monomer having a plurality of acrylate groups and a polyfunctional oligomer having a plurality of acrylate groups (hereinafter, also simply referred to as "polyfunctional acrylate compound (C)") is preferable. Examples of the polyfunctional acrylate compound (C) include trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (2-acryloyloxyethyl) isocyanurate, and commercially available oligoester (meth) acrylates. These polyfunctional acrylate compounds (C) may be used alone or in combination of 2 or more.

The content of the polyfunctional unsaturated compound (B') in the pressure-sensitive adhesive composition according to embodiment 2 of the present invention is not particularly limited as long as the residual amount of the pressure-sensitive adhesive composition after ultraviolet irradiation at 300 ℃ satisfies a specific range, and may be the same as the content of the polyfunctional maleimide compound (B) in the pressure-sensitive adhesive composition according to embodiment 1 of the present invention.

The adhesive composition according to embodiment 2 of the present invention has a residual heating amount at 300 ℃ of 90% or more after ultraviolet irradiation. When the residual heating amount at 300 ℃ is 90% or more, the heat resistance of the adhesive composition is improved and the adhesive composition is less likely to be decomposed even at high temperatures. As a result, the pressure-sensitive adhesive composition is less likely to decompose even after being subjected to a high-temperature processing treatment at 300 ℃ or higher, and can further prevent the occurrence of increased adhesion or the occurrence of adhesive residue during peeling. The preferable lower limit of the amount of the residual heat at 300 ℃ is 93%, and the more preferable lower limit is 95%. The upper limit of the amount of the heating residue at 300 ℃ is not particularly limited, but is preferably as high as possible, and the upper limit is substantially 100% or 99%, for example.

The method for adjusting the residual heating amount at 300 ℃ to the above range is not particularly limited, and a method for adjusting the kind or content of the polyfunctional unsaturated compound (B') is preferably used. The polyfunctional maleimide compound (B) can be preferably used as the polyfunctional unsaturated compound (B') having high heat resistance.

The adhesive composition according to embodiment 2 of the present invention may contain a photopolymerization initiator, a thermosetting agent, a thermosetting accelerator, an organosilicon compound or a fluorine compound, a gas generating agent, an inorganic filler, and the like, as in the adhesive composition according to embodiment 1 of the present invention. These components and other configurations can be made the same as in the case of the pressure-sensitive adhesive composition according to embodiment 1 of the present invention.

An adhesive tape having an adhesive layer containing the adhesive composition according to embodiment 1 or the adhesive composition according to embodiment 2 (according to embodiment 3 of the present invention) is also one of the present invention.

The adhesive tape according to embodiment 3 of the present invention may be a supporting tape having an adhesive layer containing the adhesive composition on one or both surfaces of a substrate, or may be an unsupported tape having no substrate.

Examples of the substrate include a sheet containing a transparent resin such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, and polyimide. 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 adhesive strength, but are cured by both irradiation with light and heating, increase in elastic modulus, and increase in adhesion due to heating can be suppressed, and therefore, even after being subjected to a high-temperature processing treatment of 300 ℃ or more in a state in which an adherend is fixed, they can be easily peeled off. Therefore, the pressure-sensitive adhesive composition and the pressure-sensitive adhesive tape of the present invention can be suitably used for the protection and temporary fixation of an adherend subjected to a high-temperature processing treatment at 300 ℃ or higher. In particular, when an electronic component such as a semiconductor is processed, the adhesive tape can be suitably used for fixing the electronic component to a support plate with an adhesive composition or an adhesive tape or attaching the adhesive tape to the electronic component for protection in order to facilitate handling of the electronic component and prevent the electronic component from being damaged.

Specifically, for example, there is a method for manufacturing an electronic component, which includes: a step (1) of temporarily fixing an electronic component on the adhesive tape according to embodiment 3 of the present invention, a step (2) of irradiating the adhesive tape according to embodiment 3 of the present invention with light, a step (3) of heat-treating the electronic component, and a step (4) of peeling the adhesive tape according to embodiment 3 of the present invention from the electronic component. Such a method for manufacturing an electronic component (embodiment 4 of the present invention) is also one aspect of the present invention.

The step (3) may be a step of subjecting the electronic component to a high-temperature processing treatment at 300 ℃ or higher. In the step (3), the adhesive tape according to embodiment 3 of the present invention is heated and cured in addition to the electronic components, and the elastic modulus is increased. Alternatively, the step of heating the adhesive tape according to embodiment 3 of the present invention may be performed separately from step (3) before or after step (3).

Effects of the invention

The present invention can provide an adhesive composition that can be easily peeled off even after being subjected to a high-temperature processing treatment of 300 ℃ or higher in a state in which an adherend is fixed, an adhesive tape having an adhesive layer containing the adhesive composition, and a method for producing an electronic component.

Detailed Description

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

(preparation of polyimide resin)

(1) Preparation of polyimide resin 1

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 42.5g (0.08 mol) of dimer diamine (Priamine 1075, manufactured by Croda), 1.8g (0.02 mol) of 1, 3-diamino-2-propanol, and 52.0g (0.1 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 synthesize a hydroxyl group-containing polyimide. After the reaction mixture was cooled to room temperature, 300mL of toluene was added to the flask, and the mixture was allowed to stand to precipitate and remove impurities. The obtained solution was filtered through a glass frit funnel filled with silica gel, to obtain polyimide resin 1 represented by formula (1-1) (structural unit(s) represented by general formula (1a) was 80 mol%, structural unit (t) represented by general formula (1b) was 20 mol%, and functional group equivalent of hydroxyl group 4600).

The weight average molecular weight of the polyimide resin 1 thus obtained was 25000 as measured by a Gel Permeation Chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters corporation) as a column.

[ chemical formula 4 ]

(2) Preparation of polyimide resin 2

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 42.5g (0.08 mol) of dimer diamine (Priamine 1075, manufactured by Croda), 7.3g (0.02 mol) of Bis-AP-AF (manufactured by Central Glass) and 52.0g (0.1 mol) of 4,4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride were added in this order. In addition, Bis-AP-AF means 2, 2-Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane. A dean stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to synthesize a hydroxyl group-containing polyimide. After the reaction mixture was cooled to room temperature, 300mL of toluene was added to the flask, and the mixture was allowed to stand to precipitate and remove impurities. The obtained solution was filtered through a glass frit funnel filled with silica gel, to obtain a polyimide resin 2 represented by the following formula (1-2) (structural unit(s) represented by general formula (1a) was 80 mol%, structural unit (t) represented by general formula (1b) was 20 mol%, and functional group equivalent of hydroxyl group was 2400).

The weight average molecular weight of the polyimide resin 2 thus obtained was 26000 as measured by a Gel Permeation Chromatography (GPC) method using THF as an eluent and HR-MB-M (Waters corporation) as a column.

[ chemical formula 5 ]

(3) Preparation of polyimide resin 3

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 31.9g (0.06 mol) of dimer diamine (Priamine 1075, manufactured by Croda), 14.7g (0.04 mol) of Bis-AP-AF, and 52.0g (0.1 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 synthesize a hydroxyl group-containing polyimide. After the reaction mixture was cooled to room temperature, 300mL of toluene was added to the flask, and the mixture was allowed to stand to precipitate and remove impurities. The obtained solution was filtered through a glass frit funnel filled with silica gel, to obtain polyimide resin 3 represented by formula (1-2) (structural unit(s) represented by general formula (1a) was 60 mol%, structural unit (t) represented by general formula (1b) was 40 mol%, functional group equivalent of hydroxyl group 1200).

The weight average molecular weight of the polyimide resin 3 thus obtained was 25000 as a result of measurement by a Gel Permeation Chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters corporation) as a column.

(4) Preparation of polyimide resin 4

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 42.5g (0.08 mol) of dimer diamine (Priamine 1075, manufactured by Croda), 4.3g (0.02 mol) of 4,4 '-diamino-3, 3' -dihydroxybiphenyl, and 52.0g (0.1 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 synthesize a hydroxyl group-containing polyimide. After the reaction mixture was cooled to room temperature, 300mL of toluene was added to the flask, and the mixture was allowed to stand to precipitate and remove impurities. The obtained solution was filtered through a glass frit funnel filled with silica gel, to obtain polyimide resin 4 represented by formula (1-3) (structural unit(s) represented by general formula (1a) was 80 mol%, structural unit (t) represented by general formula (1b) was 20 mol%, functional group equivalent of hydroxyl group was 2300).

The weight average molecular weight of the polyimide resin 4 thus obtained was 28000 as measured by Gel Permeation Chromatography (GPC) using THF as an eluent and HR-MB-M (manufactured by Waters corporation) as a column.

[ chemical formula 6 ]

(5) Preparation of polyimide resin 5 (polyimide resin having allyl group in side chain)

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 37.3g (0.07 mol) of dimer diamine (Priamine 1075, manufactured by Croda), 3.7g (0.01 mol) of Bis-AP-AF3, 5-diaminobenzoic acid, 3.0g (0.02 mol) and 52.0g (0.1 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 synthesize a polyimide containing a hydroxyl group and a carboxylic acid. After the reaction mixture was cooled to room temperature, 300mL of toluene was added to the flask, and the mixture was allowed to stand to precipitate and remove impurities. The resulting solution was filtered through a glass sand funnel filled with silica gel to obtain a polyimide containing hydroxyl and carboxylic acid.

The resulting solution was filtered through a glass funnel filled with silica gel, 5.3g (0.02 mol) of DA-MGIC (diaminomonoglycidyl isocyanurate, manufactured by Sikko chemical Co., Ltd.) and 3g (0.3 mol) of triethylamine were added thereto, and the mixture was further heated for 3 hours. After cooling to room temperature, the solvent was removed in vacuo to obtain a polyimide resin 5 represented by the following formula (1-4) (structural unit(s) represented by general formula (1a) was 70 mol%, structural unit (t) represented by general formula (1b) was 10 mol%, structural unit (u) represented by general formula (1c) was 20 mol%, functional group equivalent of hydroxyl group 4800) which was amber wax-like and had an allyl group in a side chain.

The weight average molecular weight of the polyimide resin 5 thus obtained was 46000 as a result of measurement by a Gel Permeation Chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters corporation) as a column.

[ chemical formula 7 ]

(6) Preparation of polyimide resin 6 (polyimide resin having maleimide group at the terminal)

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 42.5g (0.08 mol) of dimer diamine (Priamine 1075, manufactured by Croda), 7.3g (0.02 mol) of Bis-AP-AF, and 46.8g (0.09 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 synthesize a hydroxyl group-containing polyimide.

To the resulting hydroxyl group-containing polyimide solution were added 2.0g (0.02 mol) of maleic anhydride and 5g of methanesulfonic anhydride. After the solution was refluxed for 12 hours, cooled to room temperature, 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 sand funnel filled with silica gel. Then, the solvent was removed in vacuo to obtain a brown liquid polyimide resin 6 represented by the following formula (1-5) having a maleimide group (not shown in formula (1-5)) at the terminal (structural unit(s) represented by general formula (1a) was 80 mol%, structural unit (t) represented by general formula (1b) was 20 mol%, functional group equivalent of hydroxyl group 2300).

The weight average molecular weight of the polyimide resin 6 thus obtained was 24000 as measured by a Gel Permeation Chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters corporation) as a column.

[ chemical formula 8 ]

(7) Preparation of polyimide resin 7 (polyimide resin having no hydroxyl group)

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 53.1g (0.1 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 52.0g (0.1 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 synthesize a hydroxyl group-containing polyimide. After the reaction mixture was cooled to room temperature, 300mL of toluene was added to the flask, and the mixture was allowed to stand to precipitate and remove impurities. The obtained solution was filtered through a glass frit funnel filled with silica gel, to obtain a polyimide resin 7 represented by the following formula (1-6) having no hydroxyl group (the structural unit(s) represented by the general formula (1a) was 100 mol%, and the structural unit (t) represented by the general formula (1b) was 0 mol%).

The weight average molecular weight of the polyimide resin 7 thus obtained was 20000 as measured by a Gel Permeation Chromatography (GPC) method using THF as an eluent and HR-MB-M (manufactured by Waters corporation) as a column.

[ chemical formula 9 ]

(preparation of Maleimide)

(1) Preparation of 2-functional Maleimide (polyfunctional Maleimide Compound (B))

250mL of toluene was put into a 500mL round-bottom flask equipped with 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, 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 sand funnel filled with silica gel, and then the solvent was removed in vacuo to obtain a brown liquid 2-functional maleimide represented by the following formula (2-1).

[ chemical formula 10 ]

(2) Preparation of monofunctional maleimides

250mL of toluene was put into a 500mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. Oleylamine (reagent) 53g (0.2 mol) and maleic anhydride 19.6g (0.2 mol) were added, followed by methanesulfonic anhydride 5 g. After the solution was refluxed for 12 hours, cooled to room temperature, 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 sand funnel filled with silica gel, and then the solvent was removed in vacuo to obtain a brown liquid monofunctional maleimide represented by the following formula (3-1).

[ chemical formula 11 ]

(example 1)

To 300mL of toluene were added 70 parts by weight of the polyimide resin 1 obtained above, 30 parts by weight of 2-functional maleimide and 3 parts by weight of Irgacure 365 (manufactured by BASF) as a photopolymerization initiator to prepare a toluene solution of the adhesive composition.

The obtained toluene solution of the adhesive composition was applied with a doctor blade to a corona-treated surface of a polyimide film (Kapton, manufactured by yu xiong corporation) having a thickness of 25 μm, which was corona-treated on one surface thereof, 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 aged at 40 ℃ for 3 days to obtain an adhesive tape.

(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 as shown in tables 1 to 2. The details of the materials shown in tables 1 to 2 are as follows.

Vinyl ether (vinyl ether-terminated polyester, Crossmer U001, manufactured by NIPPON CARBIDE Co., Ltd.)

Acrylate (Dicyclodecane dimethanol diacrylate, IRR-241K, manufactured by DAICEL-ALLNEX Co., Ltd.)

2-functional acrylate (tris (2-acryloyloxyethyl) isocyanurate, A-9300, manufactured by Xinzhongcun chemical Co., Ltd.)

Organosilicon Compound (2-functional Silicone acrylate, EBECRYL350, manufactured by DAICEL-ALLNEX Co., Ltd.)

Fluorine Compound (fluorine surfactant, Megafac RS-56, DIC Co., Ltd.)

Heat-curing agent (2, 2' -diallylbisphenol A, RESITOP APG-1, manufactured by GROUR CHEMICAL Co., Ltd.)

(evaluation)

The pressure-sensitive adhesive tapes obtained in examples and comparative examples were evaluated by the following methods.

The results are shown in tables 1 to 2.

(1) Evaluation of solvent resistance in the Pre-heating State (measurement of gel fraction)

Using an ultra-high pressure mercury lamp at 20mW/cm²The obtained adhesive tape was irradiated with 365nm ultraviolet rays for 150 seconds.

The pressure-sensitive adhesive tape after ultraviolet irradiation was cut into a flat rectangular shape of 40mm × 30mm to prepare a test piece, and the weight (weight before toluene immersion) was measured. Next, the test piece was immersed in toluene at 25 ℃ for 24 hours, and then taken out of the toluene and dried at 25 ℃ for 1 hour. The weight of the dried test piece (weight after toluene immersion) was measured, and the gel fraction (═ weight after toluene immersion/weight before toluene immersion × 100) was calculated.

(2) Evaluation of Heat resistance (measurement of residual Heat at 300 ℃ C.)

10mg of the adhesive tape irradiated with ultraviolet rays was collected and placed in an aluminum cup, and the residual heating amount at 300 ℃ was measured at a temperature rise of 10 ℃/min by a thermogravimetric apparatus STA7200 (manufactured by Hitachi High-Tech Science Co.).

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

The resulting adhesive tape was cut into a width of 1 inch, and then heat laminated with 1mm thick glass using a 100 ℃ laminator. After lamination, an ultra-high pressure mercury lamp was used at 20mW/cm from the glass side²The ultraviolet ray of 365nm was irradiated at the intensity of (2) for 150 seconds. After the irradiation with ultraviolet rays, the glass was heated on a hot plate at 300 ℃ for 10 minutes.

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

[ TABLE 1 ]

[ TABLE 2 ]

Industrial applicability

Claims

1. An adhesive composition comprising a polyimide resin (A) having a hydroxyl group and at least 1 (B) selected from a polyfunctional monomer having a plurality of maleimide groups and a polyfunctional oligomer having a plurality of maleimide groups.

2. An adhesive composition comprising a polyimide resin (A) having a hydroxyl group and at least 1 (B') selected from a polyfunctional monomer having a plurality of double bonds in the molecule and a polyfunctional oligomer having a plurality of double bonds in the molecule, said adhesive composition having a residual amount of 90% or more after being heated at 300 ℃ after being irradiated with ultraviolet light.

3. The adhesive composition according to claim 1 or 2, wherein the hydroxyl group of the polyimide resin (a) is a phenolic hydroxyl group.

4. The adhesive composition according to any one of claims 1 to 3, wherein the polyimide resin (A) has a functional group having a double bond in a side chain or a terminal.

5. The adhesive composition of claim 1, further comprising at least 1 (C) selected from the group consisting of a polyfunctional monomer having at least 2 or more vinyl ether groups or allyl groups and a polyfunctional oligomer having at least 2 or more vinyl ether groups or allyl groups.

6. The adhesive composition according to claim 4, wherein the polyimide resin (A) has 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), and both ends of the polyimide resin (A) are respectively represented by X¹And X²The polyimide resin (A-1) is represented by the formula, wherein s is not less than 0, t is not less than 0, and u is not less than 0,

in the general formulae (1a) to (1c), P¹、P²And P³Each independently represents an aromatic group, Q¹Represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, Q²Represents a hydroxyl-containing group, R represents a substituted or unsubstituted branched aliphatic group or aromatic group, and is selected from X¹、X²And X³At least 1 of them represents a functional group having a double bond.

7. The adhesive composition according to claim 6, wherein in the general formula (1a), Q¹Is an aliphatic group derived from a dimer diamine, which is at least 1 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),

in the general formulae (4-1) to (4-4), R¹～R⁸And R¹³～R²⁰Each independently represents a linear or branched hydrocarbon group.

8. The adhesive composition according to any one of claims 1 to 7, further comprising a thermal curing agent.

9. The adhesive composition according to any one of claims 1 to 8, further comprising an organosilicon compound or a fluorine compound.

10. The adhesive composition according to any one of claims 1 to 9, further comprising a gas generating agent that generates a gas.

11. An adhesive tape having an adhesive layer comprising the adhesive composition of any one of claims 1 to 10.

12. A method of manufacturing an electronic component, comprising: a step (1) of temporarily fixing an electronic component on the adhesive tape according to claim 11, a step (2) of irradiating the adhesive tape with light, a step (3) of performing heat treatment on the electronic component, and a step (4) of peeling the adhesive tape from the electronic component.