Adhesive composition, adhesive tape, and method for treating electronic components

Abstract

An object of the present invention is to provide: an adhesive composition that can be easily peeled by light irradiation even after being subjected to high-temperature processing at 300 °C or higher in a state where an adherend is fixed; an adhesive tape having an adhesive layer formed of the adhesive composition; and a method for treating an electronic component. The adhesive composition of the present invention contains a reactive resin having a polyimide skeleton in the main chain and a functional group containing a double bond in the side chain or at the terminal, and a silicone compound or a fluorine compound.

Description

Technical Field

[0001] The present invention relates to an adhesive composition, an adhesive tape and a method for treating an electronic component. Background Art

[0002] When processing electronic components such as semiconductors, in order to facilitate the handling of the electronic components and prevent them from being damaged, the electronic components are fixed to a support plate with the aid of an adhesive composition, or an adhesive tape is attached to the electronic components for protection. For example, when a thick film wafer cut from high-purity single crystal silicon is ground to a predetermined thickness to form a thin film wafer, the thick film wafer is bonded to a support plate with the aid of an adhesive composition.

[0003] Such adhesive compositions and adhesive tapes for electronic components are required to have high adhesion to firmly fix the electronic components during the processing steps, and to be able to be peeled off without damaging the electronic components after the process is completed (hereinafter also referred to as "high adhesion and easy peeling").

[0004] As a means of achieving high adhesion and easy peeling, for example, Patent Document 1 discloses an adhesive sheet using an adhesive having a multifunctional monomer or oligomer having a radiation polymerizable functional group bonded to the side chain or main chain of the polymer. The polymer is cured by ultraviolet irradiation due to the radiation polymerizable functional group, and this is utilized to reduce the adhesive force by irradiating ultraviolet light during peeling, so that peeling can be performed without residual adhesive.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 5-32946 Summary of the invention

[0008] Problems to be solved by the invention

[0009] With the recent improvement in the performance of electronic components, various processes for processing electronic components have been carried out. For example, in the process of forming a metal film on the surface of an electronic component by sputtering, a metal film with better conductivity can be formed by processing at a high temperature of about 300 to 350°C. However, if an electronic component protected by a conventional adhesive composition or adhesive tape is subjected to a high temperature processing of more than 300°C, it sometimes causes hyperadhesion (Japanese: hyperadhesion), and the adhesive force is not sufficiently reduced during peeling, or residual adhesive is generated.

[0010] In view of the above situation, the object of the present invention is to provide: an adhesive composition that can be easily peeled by irradiating light even after being subjected to a high-temperature processing treatment of 300 °C or higher in a state where the adherend is fixed; an adhesive tape having an adhesive layer containing the adhesive composition; and a method for processing electronic components.

[0011] Means for solving the problem

[0012] The adhesive composition of the present invention contains a reactive resin and a silicone compound or a fluorine compound, and the reactive resin has an imide skeleton in the main chain and a functional group containing a double bond in the side chain or at the end.

[0013] Hereinafter, the present invention will be described in detail.

[0014] The adhesive composition according to an embodiment of the present invention contains: a reactive resin (hereinafter, also simply referred to as "reactive resin") having an imide skeleton in the main chain and a functional group containing a double bond in the side chain or at the end.

[0015] By having an imide skeleton in the main chain, the above-mentioned reactive resin has extremely excellent heat resistance. Even after being subjected to a high-temperature processing treatment of 300 °C or higher, the main chain is not easily decomposed, and it is possible to prevent the occurrence of enhanced adhesion or the generation of residual glue during peeling. In addition, by making the above-mentioned reactive resin have a functional group containing a double bond in the side chain or at the end, the entire adhesive composition can be uniformly and rapidly polymerized and crosslinked by irradiating light, the elastic modulus increases, and thus the adhesive force is greatly reduced, and it can be easily peeled.

[0016] Examples of the functional group containing a double bond present in the side chain or at the end of the above-mentioned reactive resin include: a maleimide group that can be substituted, a citraconimide group, a vinyl ether group, an allyl group, a (meth)acryloyl group, etc. Among them, from the aspect of obtaining higher heat resistance, a maleimide group that can be substituted is preferred.

[0017] The above-mentioned reactive resin preferably has a functional group equivalent weight (weight average molecular weight / number of functional groups containing a double bond) of 4000 or less. By making the above-mentioned functional group equivalent weight 4000 or less, the adhesive composition can exhibit higher heat resistance. It is considered that this is because: by having a functional group containing a double bond in the molecule of the reactive resin at a density of a certain level or more, the crosslinking distance becomes shorter, thereby further suppressing the enhanced adhesion caused by heating. The above-mentioned functional group equivalent weight is more preferably 3000 or less, and further preferably 2000 or less. The lower limit of the above-mentioned functional group equivalent weight is not particularly limited, and substantially, the lower limit is about 600.

[0018] The weight-average molecular weight of the above reactive resin is preferably 5000 or more. By making the weight-average molecular weight of the above reactive resin 5000 or more, film formation becomes easy, and the resulting film exhibits a certain degree of flexibility. Therefore, it can exhibit high followability to the adherend with unevenness and can be easily peeled off from the adherend. The weight-average molecular weight of the above reactive resin is more preferably 10000 or more, and further preferably 20000 or more. The upper limit of the weight-average molecular weight of the above reactive resin is not particularly limited, but since the solubility in the solvent decreases, it is, for example, 300000, especially 100000.

[0019] It should be noted that the weight-average molecular weight of the above reactive resin is measured by gel permeation chromatography (GPC) in terms of the molecular weight converted to polystyrene. As the column, for example, HR-MB-M (product name, manufactured by Waters Corporation) etc. can be used.

[0020] The above functional group containing a double bond can be located at either the side chain or the terminal of the above reactive resin. The above functional group containing a double bond is preferably present at both terminals of the above reactive resin, and more preferably further present at the side chain in addition to both terminals. The reactivity of the functional groups containing double bonds at both terminals of the above reactive resin is high, and the adhesive composition can be sufficiently cured by irradiation with light. As a result, adhesive enhancement can be further suppressed, and the adhesive composition can exhibit higher heat resistance.

[0021] In addition, by making the side chain of the above reactive resin have a functional group containing a double bond, the adhesive composition can exhibit higher heat resistance. It is considered that this is because by shortening the crosslinking distance, adhesive enhancement caused by heating can be further suppressed. In addition, by making the side chain of the above reactive resin have a functional group containing a double bond, it is easy to adjust the functional group equivalent to 4000 or less while making the weight-average molecular weight 5000 or more. Thereby, the adhesive composition has sufficient initial adhesiveness and excellent heat resistance, and there is little adhesive enhancement even during high-temperature processing at 300 °C or higher, and it can be more easily peeled off by irradiation with light.

[0022] Specific examples of the above reactive resin include, for example, a reactive resin (1) having a structural unit represented by the following general formula (1a), a structural unit represented by the following general formula (1b), and a structural unit represented by the following general formula (1c) (where s ≥ 1, t ≥ 0, u ≥ 0), and both terminals are represented by X 1 and X 2 respectively.

[0023] [Chemical formula 1]

[0024]

[0025] In the above general formulas (1a) to (1c), P 1 , P 2 and P 3 each independently represent an aromatic group, Q 1 represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, Q 2 represents a substituted or unsubstituted group having an aromatic structure, and R represents a substituted or unsubstituted branched aliphatic group or aromatic group. At least one selected from the group consisting of X 1 , X 2 and X 3 represents a functional group containing a double bond.

[0026] In the above general formulas (1a) to (1c), P 1 , P 2 , P 3 is preferably an aromatic group having 5 to 50 carbon atoms. By making P 1 , P 2 , P 3 be an aromatic group having 5 to 50 carbon atoms, the adhesive composition as one embodiment of the present invention can exhibit particularly high heat resistance.

[0027] In the above general formula (1a), Q 1 is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. By making Q 1 be a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, the adhesive tape manufactured using the adhesive composition as one embodiment of the present invention can exhibit high flexibility, can exhibit high followability to an adherend having irregularities, and the peelability is also improved.

[0028] In addition, Q 1 is preferably an aliphatic group derived from a diamine compound as described below. Among them, from the viewpoint of improving flexibility and the viewpoint that the compatibility with the solvent and other components of the above reactive resin (1) increases and the production of the adhesive tape becomes easy, Q 1 is preferably an aliphatic group derived from a dimer diamine.

[0029] The above aliphatic group derived from a dimer diamine is not particularly limited, and is preferably at least one selected from the group consisting of 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 them, the group represented by the following general formula (4-2) is more preferred.

[0030] [Chemical formula 2]

[0031]

[0032] In the above general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 each independently represent a linear or branched hydrocarbon group. It should be noted that * represents a bonding bond. That is, * is bonded to N in the above general formulas (1a) to (1c).

[0033] In the above general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 The hydrocarbon groups represented are not particularly limited and may be saturated hydrocarbon groups or unsaturated hydrocarbon groups. Among them, the sum of the carbon atom numbers of R 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 is preferably 7 or more and 50 or less. By making the sum of the carbon atom numbers within the above range, the adhesive tape manufactured using the adhesive composition as one embodiment of the present invention can exhibit higher flexibility, and in addition, the compatibility of the above reactive resin (1) with the solvent and other components is further increased. The sum of the carbon atom numbers is more preferably 9 or more, further preferably 12 or more, and even more preferably 14 or more. The sum of the carbon atom numbers is more preferably 35 or less, further preferably 25 or less, and even more preferably 18 or less.

[0034] 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), the optical isomers are not particularly limited and any optical isomers are also included.

[0035] In the above general formula (1b), Q 2 is preferably a group having an aromatic structure with 5 to 50 carbon atoms, which may be substituted or unsubstituted. By making Q 2is a substituted or unsubstituted aromatic group having 5 to 50 carbon atoms, so that the adhesive composition as an embodiment of the present invention can exhibit particularly high heat resistance.

[0036] In the above general formula (1c), R is preferably a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms. By making R a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms, the adhesive tape manufactured using the adhesive composition as an embodiment of the present invention can exhibit high flexibility, can exhibit high followability to an adherend having irregularities, and the peelability is also improved.

[0037] In the above general formula (1c), 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 3 bonded.

[0038] Here, the "aromatic ester group" means a group in which an ester group is directly bonded to an aromatic ring, and the "aromatic ether group" means a group in which an ether group is directly bonded to an aromatic ring. By making the part bonded to the ester group and the ether group an aromatic group in this way, the adhesive composition can exhibit high heat resistance. On the other hand, X 3 is bonded to R through an aromatic ester group or an aromatic ether group, whereby the double bond in X 3 does not conjugate with R, and thus does not hinder the polymerization crosslinking when irradiated with light.

[0039] In the above reactive resin (1), the functional group containing a double bond (crosslinkable unsaturated bond) is at least one selected from X 1 、X 2 and X 3 , and preferably at least X 3 is a functional group containing a double bond. By making at least X 3 a functional group containing a double bond, the adhesive composition can exhibit higher heat resistance.

[0040] In the case where any of the above X 1 , X 2 and X 3 is a functional group other than the functional group containing a double bond (functional group not having a double bond), examples of the functional group not having a double bond include, independently of each other, an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride, an amine compound, etc. Specifically, examples include acid anhydrides and mono-terminal unreacted products of diamine compounds that are raw materials for the above reactive resin (1).

[0041] In the above reactive resin (1), examples of the functional group containing a double bond include: a maleimide group which can be substituted, citraconimide group, vinyl ether group, allyl group, (meth)acryloyl group, etc. Among them, from the aspect of obtaining higher heat resistance, a maleimide group which can be substituted or an allyl group is preferred, and particularly from the aspect of obtaining high adhesiveness, a tris(isocyanuric acid) ester group having one or more allyl groups is more preferred.

[0042] In the above general formulas (1a) to (1c), s is 1 or more, preferably 3 or more, preferably 10 or less, and more preferably 5 or less. In the above general formulas (1a) to (1c), t is 0 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less. In the above general formulas (1a) to (1c), u is 0 or more, preferably 1 or more, more preferably 3 or more, preferably 10 or less, and more preferably 5 or less. In the above general formulas (1a) to (1c), if s, t, and u are within the above ranges, it can be easily peeled by curing.

[0043] It should be noted that in the above reactive resin (1), the structural unit represented by the above general formula (1a), the structural unit represented by the above general formula (1b), and the structural unit represented by the above general formula (1c) may be a block copolymer containing block components in which the respective structural units are continuously arranged, or a random copolymer in which the respective structural units are randomly arranged.

[0044] The above reactive resin can be obtained, for example, by reacting a diamine compound with an aromatic anhydride to prepare an imide compound, and further reacting a functional group of the imide compound with a compound having a functional group reactive with the functional group and a functional group containing a double bond (hereinafter referred to as a functional group-containing unsaturated compound).

[0045] As the above diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used.

[0046] By using an aliphatic diamine compound as the above diamine compound, the adhesive tape manufactured using the adhesive composition as one embodiment of the present invention can exhibit high flexibility, can exhibit high followability to an adherend having irregularities, and the peelability is also improved.

[0047] By using an aromatic diamine compound as the above diamine compound, the heat resistance of the adhesive composition as one embodiment of the present invention is further improved.

[0048] In addition, by using a diamine compound having a functional group and reacting the functional group with the above functional group-containing unsaturated compound, a reactive resin having a functional group containing a double bond in the side chain can be manufactured.

[0049] These aliphatic diamine compounds, aromatic diamine compounds, and diamine compounds having functional groups may be used alone or in combination of two or more.

[0050] Examples of the 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, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, and the like.

[0051] Examples of the above aromatic diamine compounds include: 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bis(aminomethyl)benzene, 1,3-bis(aminomethyl)cyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, bis(3-chloro-4-aminophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-ethyl-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenyl sulfone, 3,3'-diaminophenyl sulfone, 2,2-bis(4-(4-aminophenoxy)phenyl)sulfone, 2,2-bis(4-(3-aminophenoxy)phenyl)sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, Bisaniline M, Bisaniline P, 9,9-bis(4-aminophenyl)fluorene, o-tolidine sulfone, methylenebis(o-aminobenzoic 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-benzenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylene diamines (e.g., Jeffamine D-230, D400, D-2000, and D-4000 of Huntsman), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, p-xylylenediamine, etc.

[0052] Among the above aliphatic diamine compounds, dimer diamine is preferred from the viewpoints of improving flexibility and increasing the compatibility of the above reactive resin with solvents and other components, thereby facilitating the production of the adhesive tape.

[0053] The above dimer diamine refers to a diamine compound obtained by reducing and aminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids. Examples thereof include linear, monocyclic, polycyclic and other dimer diamines. The above dimer diamine may contain carbon-carbon unsaturated double bonds or may be a hydride to which hydrogen has been added. More specifically, examples of the above dimer diamine include dimer diamines capable of forming the groups represented by the above general formula (4-1), general formula (4-2), general formula (4-3) and general formula (4-4).

[0054] Examples of the diamine compound having the above functional group include a diamine compound having a hydroxyl group, a diamine compound having a carboxyl group, a diamine compound having a halogen group, and the like.

[0055] Examples of the above 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, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and the like. Examples of the above diamine compound having a carboxyl group include 3,5-diaminobenzoic acid and the like. Examples of the above diamine compound having a halogen group include 2,4-diaminochlorobenzene and the like.

[0056] Examples of the above aromatic acid anhydrides include: pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3’,4,4’-benzophenonetetracarboxylic acid, 3,3’,4,4’-diphenylethertetracarboxylic acid, 3,3’,4,4’-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4’-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2’,3,3’-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 1,1-bis(3,4-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2’,3’-benzophenonetetracarboxylic acid, 2,3,3’,4’-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3’,4’-biphenyltetracarboxylic acid, 3,4,3’,4’-biphenyltetracarboxylic acid, 2,3,2’,3’-biphenyltetracarboxylic acid, 4,4’-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, 4,4’-(4,4’-isopropylidenediphenoxy)-bis(phthalic acid), etc.

[0057] As the above functional group-containing unsaturated compound, it is selected and used according to the functional group at the terminal or side chain of the above imide compound.

[0058] For example, in the case where the functional group at the terminal or side chain of the above imide compound is a hydroxyl group, maleimide compounds having a carboxyl group can be cited. As such maleimide compounds having a carboxyl group, for example, maleimide acetate, maleimide propionic acid, maleimide butyric acid, maleimide hexanoic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, 19-maleimide-17-oxo-4,7,10,13-tetraoxa-16-aza-nonadecanoic acid, etc. can be cited. In addition, vinyl compounds having an ether group such as butyl vinyl ether, allyl compounds having a glycidyl group such as diallyl monoglycidyl isocyanurate, allyl glycidyl ether, allyl ether compounds having a glycidyl group such as glycerol diallyl monoglycidyl ether, etc. can be cited. In addition, vinyl ether compounds having a glycidyl group such as glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, glycidyl cyclohexanedimethanol mono vinyl ether, etc. can be cited. In addition, allyl compounds having an isocyanate group such as allyl isocyanate, (meth)acryloyl compounds having an isocyanate group such as 2-(meth)acryloyloxyethyl isocyanate, etc. can be cited.

[0059] In addition, for example, in the case where the functional group at the terminal or side chain of the above imide compound is a carboxyl group, allyl compounds having a hydroxyl group such as trimethylolpropane diallyl ether, pentaerythritol triallyl ether, etc., allyl compounds having a glycidyl group such as diallyl monoglycidyl isocyanurate, etc. can be cited. In addition, allyl ether compounds having a glycidyl group such as allyl glycidyl ether, glycerol diallyl monoglycidyl ether, etc. can be cited. In addition, vinyl ether compounds having a glycidyl group such as glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, glycidyl cyclohexanedimethanol mono vinyl ether, etc. can be cited.

[0060] The adhesive composition according to one embodiment of the present invention contains a silicone compound or a fluorine compound.

[0061] The silicone compound and the fluorine compound have excellent heat resistance, so that even after a high-temperature processing step of 300 °C or higher, it is possible to prevent the adhesive composition from burning, and when peeling, it oozes to the adherend interface, making peeling easier.

[0062] The above silicone compound is not particularly limited, and for example, silicone oil, silicone diacrylate, silicone-based graft copolymer, etc. can be cited. The above fluorine compound is not particularly limited, and for example, hydrocarbon compounds having a fluorine atom, etc. can be cited.

[0063] The above silicone compound or fluorine compound preferably has a functional group capable of crosslinking with the above reactive resin. By making the above silicone compound or fluorine compound have a functional group capable of crosslinking with the above reactive resin, the above silicone compound or fluorine compound undergoes a chemical reaction with the above reactive resin and enters the above reactive resin through light irradiation during peeling or the like. Therefore, the situation where the above silicone compound or fluorine compound adheres to the adherend and causes contamination can be suppressed.

[0064] The functional group capable of crosslinking with the above reactive resin is not particularly limited, and examples thereof include: a carboxyl group, a free-radical polymerizable unsaturated bond (e.g., a vinyl group, a (meth)acryloyl group, a maleimide group that can be substituted), a hydroxyl group, an amide group, an isocyanate group, an epoxy group, etc.

[0065] Among them, from the viewpoints of environmental friendliness and easy disposal, a silicone compound having a functional group capable of crosslinking with the above reactive resin is preferred.

[0066] As the silicone compound having a functional group capable of crosslinking with the above reactive resin, a silicone compound having a siloxane skeleton in the main chain and a functional group containing a double bond in the side chain or at the end is preferred.

[0067] The above silicone compound having a siloxane skeleton in the main chain and a functional group containing a double bond in the side chain or at the end is not particularly limited, and preferably contains at least one selected from the silicone compound represented by the following general formula (I), the silicone compound represented by the following general formula (II), and the silicone compound represented by the following general formula (III). These silicone compounds have particularly high heat resistance and high polarity, and thus are likely to exude from the adhesive composition.

[0068] [Chemical formula 3]

[0069]

[0070] In the above general formula (I), general formula (II), and general formula (III), X and Y each independently represent an integer of 0 to 1200, and R represents a functional group containing a double bond.

[0071] In the above general formula (I), general formula (II), and general formula (III), examples of the functional group containing a double bond represented by R include: a maleimide group that can be substituted, a citraconimide group, a vinyl ether group, an allyl group, a (meth)acryloyl group, etc. Among them, from the aspect of obtaining higher heat resistance, a maleimide group that can be substituted is preferred. It should be noted that in the above general formula (I), general formula (II), and general formula (III), when there are multiple Rs, the multiple Rs can be the same or different.

[0072] Commercially available products of the silicone compounds having (meth)acryloyl groups on the siloxane backbone represented by the above general formula (I), general formula (II), and general formula (III) include, for example, EBECRYL 350, EBECRYL 1360 (both manufactured by Daicel-Cytec), and the like. In addition, BYK-UV3500 (manufactured by BYK-Chemie), TEGO RAD2250 (manufactured by Evonik) (R is acryloyl group in both cases), and the like can be mentioned.

[0073] The content of the above silicone compound or fluorine compound in the adhesive composition as an embodiment of the present invention is not particularly limited. The preferable lower limit is 0.1 part by weight, and the preferable upper limit is 20 parts by weight with respect to 100 parts by weight of the above reactive resin. If the content of the above silicone compound or fluorine compound is within this range, the adhesive composition can exhibit excellent peelability without contaminating the adherend. From the viewpoint of further improving the peelability while suppressing contamination, the more preferable lower limit of the content of the above silicone compound or fluorine compound is 0.3 part by weight, and the more preferable upper limit is 10 parts by weight.

[0074] It should be noted that the adhesive composition as an embodiment of the present invention has excellent heat resistance. Therefore, even if the content of the above silicone compound or fluorine compound is small, sufficient effects can be exhibited. Therefore, the possibility of contamination caused by the above silicone compound or fluorine compound can be further reduced.

[0075] The adhesive composition as an embodiment of the present invention preferably further contains: a polyfunctional monomer or polyfunctional oligomer (hereinafter, also simply referred to as "polyfunctional monomer or polyfunctional oligomer") having two or more functional groups containing double bonds in the molecule and a molecular weight of 5000 or less. By containing such a polyfunctional monomer or polyfunctional oligomer, the adhesive composition undergoes three-dimensional crosslinking based on light irradiation more efficiently and can be peeled off more easily.

[0076] Examples of the functional groups containing double bonds in the above polyfunctional monomer or polyfunctional oligomer include a maleimide group which may be substituted, a citraconimide group, a vinyl ether group, an allyl group, a (meth)acryloyl group, and the like. Among them, from the aspect of obtaining higher heat resistance, a maleimide group which may be substituted is preferable.

[0077] The content of the above-mentioned polyfunctional monomer or polyfunctional oligomer in the adhesive composition as an embodiment of the present invention is not particularly limited. The preferable lower limit in the total 100 parts by weight of the above-mentioned reactive resin and the above-mentioned polyfunctional monomer or polyfunctional oligomer is 5 parts by weight, and the preferable upper limit is 100 parts by weight. If the content of the above-mentioned polyfunctional monomer or polyfunctional oligomer is within this range, the adhesive composition can exhibit particularly excellent peelability. From the viewpoint of further improving the peelability, the more preferable lower limit of the content of the above-mentioned polyfunctional monomer or polyfunctional oligomer is 10 parts by weight, and the more preferable upper limit is 50 parts by weight.

[0078] The adhesive composition as an embodiment of the present invention preferably further contains a photoinitiator.

[0079] As the above-mentioned photoinitiator, for example, a photoinitiator activated by irradiating light with a wavelength of 250 to 800 nm can be cited.

[0080] As the above-mentioned photoinitiator, for example, the following can be cited: acetophenone derivative compounds such as methoxyacetophenone, benzoin ether-based compounds such as benzoin propyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzil dimethyl ketal and acetophenone diethyl ketal, phosphine oxide derivative compounds, etc. In addition, the following can be cited: bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenyl propane and other photo radical polymerization initiators. These photoinitiators can be used alone or in combination of two or more.

[0081] The content of the above-mentioned photoinitiator in the adhesive composition as an embodiment of the present invention is not particularly limited. The preferable lower limit relative to 100 parts by weight of the above-mentioned reactive resin is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. If the content of the above-mentioned photoinitiator is within this range, by irradiating light, the whole of the adhesive composition polymerizes and crosslinks uniformly and rapidly, the elastic modulus increases, and thus the adhesive force is greatly reduced, and the adherend can be easily peeled off. The more preferable lower limit of the content of the above-mentioned photoinitiator is 0.3 part by weight, and the more preferable upper limit is 3 parts by weight.

[0082] The adhesive composition as an embodiment of the present invention may further contain a gas generator that generates gas by irradiating light. By containing the above-mentioned gas generator, even after being processed at a high temperature of 300 °C or higher, the gas generated by irradiating light is released to the interface with the adherend, so that the adherend can be peeled off more easily and without residual glue.

[0083] As the above-described gas generant, for example, tetrazole compounds or their salts, triazole compounds or their salts, azo compounds, azide compounds, xanthone acetic acid, carbonates, etc. can be cited. These gas generants can be used alone or in combination of two or more. Among them, tetrazole compounds or their salts are preferred from the viewpoint of particularly excellent heat resistance.

[0084] The content of the above-described gas generant in the adhesive composition according to an embodiment of the present invention is not particularly limited, and the lower limit of the preferred amount is 5 parts by weight and the upper limit of the preferred amount is 50 parts by weight with respect to 100 parts by weight of the above-described reactive resin. If the content of the above-described gas generant is within this range, the adhesive composition can exhibit particularly excellent peelability. The more preferred lower limit of the content of the above-described gas generant is 8 parts by weight, and the more preferred upper limit is 30 parts by weight.

[0085] The adhesive composition according to an embodiment of the present invention may contain, for example, known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, resins, surfactants, waxes, and particulate fillers.

[0086] Examples of the above-described particulate filler include inorganic fillers containing at least one selected from oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconium, and their composites. Among them, silicon-aluminum-boron composite oxides, silicon-titanium composite oxides, and silica-titania composite oxides are preferred because they have physical properties similar to those of silica commonly used as an inorganic filler.

[0087] The average particle diameter of the above-described inorganic filler is not particularly limited, and the lower limit of the preferred amount is 0.1 μm, and the upper limit of the preferred amount is 30 μm.

[0088] The content of the above-described inorganic filler is not particularly limited, and the lower limit of the preferred amount is 30 parts by weight and the upper limit of the preferred amount is 150 parts by weight with respect to 100 parts by weight of the above-described reactive resin. The more preferred lower limit of the content of the above-described inorganic filler is 60 parts by weight, and the more preferred upper limit is 120 parts by weight.

[0089] The method for producing the adhesive composition according to an embodiment of the present invention is not particularly limited, and examples thereof include a method of mixing the above-described reactive resin, silicone compound or fluorine compound, and additives as required using a bead mill, ultrasonic dispersion, homogenizer, high-output disperser, roll mill, etc.

[0090] An adhesive tape having an adhesive layer formed of the adhesive composition according to an embodiment of the present invention is also one of the present inventions.

[0091] The adhesive tape as one embodiment of the present invention may be a support tape having an adhesive layer formed of an adhesive composition as one embodiment of the present invention on one or both surfaces of a substrate, or may be a non-support tape without a substrate.

[0092] Examples of the above-mentioned substrate include: sheets formed of transparent resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, and polyimide. In addition, sheets having a mesh-like structure, sheets with holes, etc. may also be used.

[0093] The adhesive composition and the adhesive tape as one embodiment of the present invention have an initial adhesive force. On the other hand, they have excellent heat resistance. Even after high-temperature processing at 300°C or higher, there is little increase in adhesion, and they can be easily peeled by irradiating light. The adhesive composition and the adhesive tape as one embodiment of the present invention have particularly excellent heat resistance, and thus can be suitably used for: protecting adherends subjected to high-temperature processing at 300°C or higher, and temporary fixing. In particular, during the processing of electronic components such as semiconductors, in order to facilitate the processing of electronic components and prevent breakage, it can be suitably used for: fixing electronic components to a support plate by means of an adhesive composition or an adhesive tape, or attaching an adhesive tape to an electronic component for protection.

[0094] Specifically, for example, there is provided a method for processing an electronic component, which includes: a step of temporarily fixing an electronic component on an adhesive tape as one embodiment of the present invention, a step of irradiating light on the adhesive tape, a step of heat-treating the electronic component, and a step of peeling the adhesive tape from the electronic component. Such a method for processing an electronic component is also one of the present inventions.

[0095] The step of irradiating light on the above-mentioned adhesive tape may be performed immediately before the step of peeling the adhesive tape from the above-mentioned electronic component, but is preferably performed after the step of temporarily fixing the electronic component on the above-mentioned adhesive tape and before the step of heat-treating the above-mentioned electronic component. By performing the step of irradiating light on the above-mentioned adhesive tape before the step of heat-treating the above-mentioned electronic component, the adhesive tape can exhibit more excellent heat resistance.

[0096] Effects of the Invention

[0097] According to the present invention, it is possible to provide: an adhesive composition that can be easily peeled by irradiating light even after high-temperature processing at 300°C or higher in a state where an adherend is fixed; an adhesive tape having an adhesive layer formed of the adhesive composition; and a method for processing an electronic component. Detailed Embodiments

[0098] Hereinafter, embodiments will be listed to illustrate the embodiments of the present invention in more detail, but the present invention is not limited to these embodiments.

[0099] (Preparation of Reactive Resin)

[0100] (1) Preparation of Reactive Resin 1

[0101] 250 mL of toluene was put into a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 56 g (0.1 mol) of a dimer diamine (manufactured by Croda, Priamine 1075) and 19.1 g (0.09 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark separator and a condenser were installed on the flask, and the mixture was refluxed for 2 hours to form an amine-terminated diimide. After cooling the reaction product to below room temperature, 12.8 g (0.13 mol) of maleic anhydride was added, and then 5 g (0.05 mol) of methanesulfonic anhydride was added. After further refluxing the mixture for 12 hours, it was cooled to room temperature, 300 mL 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, and the solvent was removed under vacuum to obtain a reactive resin 1 shown by the following formula (1-1) which was amber-colored and waxy, having an imide skeleton in the main chain and maleimide groups at both ends.

[0102] For the obtained reactive resin 1, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters) as a column, and as a result, the weight-average molecular weight was 5000.

[0103] [Chemical Formula 4]

[0104]

[0105] (2) Preparation of Reactive Resin 2

[0106] Into a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar, 250 mL of toluene was added. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 28 g (0.05 mol) of a dimer diamine (manufactured by Croda, Priamine 1075), 4.5 g (0.05 mol) of 1,3-diamino-2-propanol, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were installed on the flask, and the mixture was refluxed for 2 hours to synthesize a hydroxyl-containing polyimide. After cooling the reaction mixture to room temperature, 10.5 g (0.05 mol) of maleimide hexanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further refluxed for 12 hours. After cooling to room temperature, 300 mL of toluene was added to the flask, and the impurities were precipitated and removed by standing. The resulting solution was filtered through a fritted glass funnel filled with silica gel, and the solvent was removed under vacuum to obtain a reactive resin 2 shown by the following formula (1-2) which was amber-colored and waxy and had an imide skeleton in the main chain and a maleimide group in the side chain.

[0107] For the obtained reactive resin 2, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters) as a column, and as a result, the weight-average molecular weight was 30,000.

[0108] [Chemical formula 5]

[0109]

[0110] (3) Preparation of reactive resin 3

[0111] 250 mL of toluene was charged into a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 28 g (0.05 mol) of a dimer diamine (manufactured by Croda, Priamine 1075), 4.5 g (0.05 mol) of 1,3-diamino-2-propanol, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were installed on the flask, and the mixture was refluxed for 2 hours to synthesize a hydroxyl group-containing polyimide. After cooling the reaction mixture to room temperature, 200 g of a greatly excessive amount of butyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.1 g of a palladium acetate phenanthroline complex were added to the flask, and the mixture was refluxed at 60 °C for 14 hours. The excessive butyl vinyl ether was removed by distillation using an evaporator. After cooling to room temperature, 300 mL of toluene was added to the flask, and the impurities were precipitated and removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel, and the solvent was removed under vacuum to obtain a reactive resin 3 shown by the following formula (1-3) which was amber-colored and waxy and had an imide skeleton in the main chain and a vinyl ether group in the side chain.

[0112] For the obtained reactive resin 3, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters Co., Ltd.) as a column, and as a result, the weight-average molecular weight was 30,000.

[0113] [Chemical formula 6]

[0114]

[0115] (4) Preparation of reactive resin 4

[0116] 250 mL of toluene was charged into a 500-mL round-bottomed flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 28 g (0.05 mol) of a dimer diamine (manufactured by Croda, Priamine 1075), 7.6 g (0.05 mol) of 3,5-diaminobenzoic acid, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to synthesize a carboxylic acid-containing polyimide. After cooling the reaction mixture to room temperature, 300 mL of toluene was added to the flask, and the impurities were precipitated and removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel, and then 13.3 g (0.05 mol) of diallyl monoglycidyl isocyanurate (manufactured by Shikoku Kasei) and 3 g (0.3 mol) of triethylamine were added, and the mixture was further heated for 3 hours. After cooling to room temperature, the solvent was removed under vacuum to obtain a reactive resin 4 shown by the following formula (1-4) in the form of an amber wax, having an imide skeleton in the main chain and a diallyl isocyanurate group in the side chain.

[0117] For the obtained reactive resin 4, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters) as a column, and as a result, the weight-average molecular weight was 35,000.

[0118] [Chemical formula 7]

[0119]

[0120] (5) Preparation of reactive resin 5

[0121] Into a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar, 250 mL of toluene was added. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 47.8 g (0.09 mol) of a dimer diamine (manufactured by Croda, Priamine 1075), 3.7 g (0.01 mol) of Bis-AP-AF, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were installed on the flask, and the mixture was refluxed for 2 hours to synthesize a carboxylic acid-containing polyimide. After cooling the reaction mixture to room temperature, 300 mL of toluene was added to the flask, and the impurities were precipitated and removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel, and then 4.2 g (0.02 mol) of maleimide hexanoic acid and 3 g (0.03 mol) of triethylamine were added, and the mixture was further heated for 3 hours. After cooling to room temperature, the solvent was removed under vacuum to obtain a reactive resin 5 shown by the following formula (1-5) which was amber-colored and waxy and had an imide skeleton in the main chain and a maleimide group in the side chain.

[0122] For the obtained reactive resin 5, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters) as a column, and as a result, the weight average molecular weight was 35,000.

[0123] [Chemical formula 8]

[0124]

[0125] (6) Preparation of reactive resin 6

[0126] 250 mL of toluene was charged into a 500 mL round-bottomed flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 31.9 g (0.06 mol) of a dimer diamine (Priamine 1075, manufactured by Croda), 14.7 g (0.04 mol) of Bis-AP-AF, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were installed on the flask, and the mixture was refluxed for 2 hours to synthesize a carboxylic acid-containing polyimide. After cooling the reaction mixture to room temperature, 300 mL 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, and then 16.9 g (0.08 mol) of maleimide hexanoic acid and 3 g (0.03 mol) of triethylamine were added, and the mixture was further heated for 3 hours. After cooling to room temperature, the solvent was removed under vacuum to obtain the reactive resin 6 shown in the above formula (1-5) which was amber wax-like and had an imide skeleton in the main chain and a maleimide group in the side chain.

[0127] For the obtained reactive resin 6, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters) as a column, and as a result, the weight average molecular weight was 35,000.

[0128] (7) Preparation of reactive resin 7

[0129] 250 mL of toluene was charged into a 500 mL round-bottomed flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 42.5 g (0.08 mol) of a dimer diamine (Priamine 1075, manufactured by Croda), 7.3 g (0.02 mol) of Bis-AP-AF, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were installed on the flask, and the mixture was refluxed for 2 hours to synthesize a carboxylic acid-containing polyimide. After cooling the reaction mixture to room temperature, 300 mL 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, and then 8.6 g (0.04 mol) of GO-BVE (glycidoxybutyl vinyl ether, manufactured by NIPPON CARBIDE) and 3 g (0.03 mol) of triethylamine were added, and the mixture was further heated for 3 hours. After cooling to room temperature, the solvent was removed under vacuum to obtain the reactive resin 7 shown in the following formula (1-6) which was amber wax-like and had an imide skeleton in the main chain and a vinyl ether group in the side chain.

[0130] For the obtained reactive resin 7, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters Corporation) as a column, and as a result, the weight average molecular weight was 35,000.

[0131] [Chemical formula 9]

[0132]

[0133] (8) Preparation of reactive resin 8

[0134] 250 mL of toluene was put into a 500 mL round-bottomed flask equipped with a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 42.5 g (0.08 mol) of a dimer diamine (manufactured by Croda Corporation, Priamine 1075), 7.3 g (0.02 mol) of Bis-AP-AF, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to synthesize a carboxylic acid-containing polyimide. After cooling the reaction mixture to room temperature, 300 mL of toluene was added to the flask, and impurities were precipitated and removed by standing. After filtering the obtained solution through a glass frit funnel filled with silica gel, 10.6 g (0.04 mol) of DA-MGIC (diamino monoglycidyl isocyanurate, manufactured by Shikoku Kasei Co., Ltd.) and 3 g (0.3 mol) of triethylamine were added, and further heated for 3 hours. After cooling to room temperature, the solvent was removed under vacuum to obtain a reactive resin 8 shown by the following formula (1-7) which was amber-colored waxy and had an imide skeleton in the main chain and an allyl group in the side chain.

[0135] For the obtained reactive resin 8, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters Corporation) as a column, and as a result, the weight average molecular weight was 35,000.

[0136] [Chemical formula 10]

[0137]

[0138] (9) Preparation of reactive resin 9

[0139] 250 mL of toluene was charged into a 500 mL round-bottomed flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 21.2 g (0.04 mol) of a dimer diamine (manufactured by Croda, Priamine 1075), 12.3 g (0.03 mol) of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 11.0 g (0.03 mol) of Bis-AP-AF, and 21.8 g (0.1 mol) of pyromellitic dianhydride were added in sequence. A Dean-Stark tube and a condenser were attached to the flask, and the mixture was refluxed for 2 hours to synthesize a carboxylic acid-containing polyimide. After cooling the reaction mixture to room temperature, 300 mL of toluene was added to the flask, and impurities were precipitated and removed by standing. The resulting solution was filtered through a fritted glass funnel filled with silica gel, and then 15.9 g (0.06 mol) of DA-MGIC (diamino monoglycidyl isocyanurate, manufactured by Shikoku Kasei Co., Ltd.) and 3 g (0.03 mol) of triethylamine were added, and the mixture was further heated for 3 hours. After cooling to room temperature, the solvent was removed under vacuum to obtain a reactive resin 9 shown by the following formula (1-8) as an amber solid, having an imide skeleton in the main chain and an allyl group in the side chain.

[0140] For the obtained reactive resin 9, measurement was carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters) as a column, and as a result, the weight average molecular weight was 35,000.

[0141] [Chemical formula 11]

[0142]

[0143] (Preparation of acrylic reactive resin)

[0144] Prepare a reactor equipped with a thermometer, a stirrer, and a condenser. After adding 94 parts by weight of 2-ethylhexyl acrylate as an (alkyl) acrylate, 6 parts by weight of 2-hydroxyethyl methacrylate as a functional group-containing monomer, 0.01 part by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate to the reactor, heat the reactor to start refluxing. Next, add 0.01 part by weight of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator to the above reactor, and initiate polymerization under reflux. Next, 0.01 part by weight of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane is added also 1 hour and 2 hours after the start of polymerization. In addition, 0.05 part by weight of tert-hexyl perpivalate is added 4 hours after the start of polymerization, and the polymerization reaction is continued. Then, 8 hours after the start of 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 500,000 is obtained.

[0145] To 100 parts by weight of the resin solid content of the obtained ethyl acetate solution containing the functional group-containing (meth)acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound is added, and reacted to obtain an acrylic reactive resin.

[0146] For the obtained acrylic reactive resin, measurement is carried out by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (product name, manufactured by Waters Corporation) as a column, and as a result, the weight average molecular weight is 550,000.

[0147] (Preparation of polyfunctional monomer)

[0148] (1) Preparation of polyfunctional monomer 1

[0149] Put 250 mL of toluene into a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stir bar. Add 56 g (0.1 mol) of dimer diamine (manufactured by Croda, Priamine 1075) and 19.6 g (0.2 mol) of maleic anhydride. Next, add 5 g of methanesulfonic anhydride. After refluxing the solution for 12 hours, cool it to room temperature, add 300 mL of toluene to the flask, and precipitate and remove the salt by standing. After filtering the obtained solution through a glass frit funnel filled with silica gel, remove the solvent under vacuum to obtain a brown liquid polyfunctional monomer 1 represented by the following formula (2-1).

[0150] [Chemical formula 12]

[0151]

[0152] (2) Purchase of polyfunctional monomer 2

[0153] Purchase the trifunctional acrylate shown in the following formula (2-2), i.e., SR-387 (manufactured by Arkema, Tris(2-acryloxyethyl)Isocyanulate), and use it as the polyfunctional monomer 2.

[0154] [Chemical formula 13]

[0155]

[0156] (Preparation of silicone bismaleimide)

[0157] Put 100 mL of toluene into a 300 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer, add 10.5 g (0.05 mol) of maleimide hexanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., reagent), 25 g (0.025 mol) of silicone resin X-21-5841 (manufactured by Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups at both ends, and 1 g (mol) of p-toluenesulfonic acid monohydrate. Next, heat and stir at 100 °C for 3 hours. After cooling to room temperature, add 5 g of triethylamine and stir for 1 hour, then wash with 100 g of water and evaporate the solvent to obtain the silicone bismaleimide shown in the following formula (3) (m = 11, n = 5).

[0158] [Chemical formula 14]

[0159]

[0160] (Example 1)

[0161] Add 100 parts by weight of the reactive resin 1, 0.3 part by weight of a bifunctional silicone acrylate (DAICEL-ALLNEX Co., Ltd., EBECRYL350) as a silicone compound, and 1 part by weight of Irgacure 369 (manufactured by BASF Co., Ltd.) as a photoinitiator to 150 mL of toluene to prepare a toluene solution of the adhesive composition.

[0162] Coat the toluene solution of the obtained adhesive composition on the corona-treated surface of a 25-μm-thick polyimide film (manufactured by Ube Industries, Ltd., Kapton) that has been corona-treated on one side with a doctor blade so that the thickness of the dry film becomes 40 μm, and heat at 110 °C for 1 minute to dry the coating solution. Then, leave it standing for curing at 40 °C for 3 days to obtain an adhesive tape.

[0163] (Examples 2 to 20, Comparative Examples 1 to 3)

[0164] The types and compounding amounts of the reactive resin, polyfunctional monomer, silicone compound or fluorine compound, and photopolymerization initiator were as shown in Tables 1 and 2. Other than that, the operation was the same as in Example 1 to obtain an adhesive composition and an adhesive tape.

[0165] In Example 8, as the silicone compound, a 6-functional silicone acrylate (manufactured by DAICEL-ALLNEX, EBECRYL 1360) was used.

[0166] In Example 9 and Comparative Example 1, as the fluorine compound, a photoreactive fluorine compound (manufactured by DIC, MEGAFACE RS-56) was used.

[0167] In Example 15, 5-phenyl-1H-tetrazole (manufactured by Masuda Chemical Co., Ltd.) was used as the gas generator, and 9,10-diglycidoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.) was used as the photosensitizer.

[0168] (Evaluation)

[0169] The adhesive tapes obtained in the examples and comparative examples were evaluated by the following methods.

[0170] The results are shown in Tables 1 and 2.

[0171] (1) Evaluation of peelability

[0172] After cutting the obtained adhesive tape into a width of 1 inch, it was heat-laminated onto 1-mm-thick glass using a laminator at 100°C. After lamination, using an ultra-high pressure mercury lamp, ultraviolet light with a wavelength of 365 nm was irradiated from the glass side at an intensity of 20 mW / cm 2 for 150 seconds. After ultraviolet irradiation, it was heated on a hot plate at 300°C for 10 minutes from the glass side.

[0173] For the test pieces after lamination, after ultraviolet irradiation, and after heating at 300°C, a 180° peel test was conducted at 25°C and a tensile speed of 30 mm / second to measure the adhesive strength (N / inch).

[0174] (2) Evaluation of the appearance of the adhesive tape after heating at 300°C

[0175] In the above evaluation of peelability, the appearance of the adhesive tape after heating at 300°C was visually observed and evaluated according to the following criteria.

[0176] 〇: No peeling or foaming from the glass was confirmed.

[0177] △: Fine bubbles were confirmed between the glass and the tape.

[0178] ×: Partial peeling occurred between the glass and the tape.

[0179] (3) Evaluation of the peeled surface after heating at 300°C and peeling

[0180] In the above evaluation of peelability, heat is applied at 300°C, and then the surface of the glass after peeling the adhesive tape is visually observed and evaluated according to the following criteria.

[0181] 〇: No residual adhesive was confirmed.

[0182] △: Although there is no residual adhesive, blurring was confirmed on the peeled surface.

[0183] ×: Residual adhesive was confirmed.

[0184] [Table 1]

[0185]

[0186] [Table 2]

[0187]

[0188] Industrial applicability

[0189] According to the present invention, it is possible to provide: an adhesive composition that can be easily peeled by irradiating light even after being subjected to a high-temperature processing treatment of 300°C or higher in a state where an adherend is fixed; an adhesive tape having an adhesive layer formed of the adhesive composition; and a method for treating an electronic component.

Claims

1. An adhesive composition comprising a reactive resin and a silicone compound, wherein the reactive resin has an imide skeleton in the main chain and a functional group containing a double bond in the side chain or at the terminal. Among them, the silicone compound has a functional group capable of crosslinking with the reactive resin. The weight average molecular weight of the reactive resin is 5000 or more.

2. An adhesive composition comprising a reactive resin and a silicone compound, wherein the reactive resin has an imide skeleton in the main chain and a functional group containing a double bond in the side chain or at the terminal. Among them, the silicone compound has a functional group capable of crosslinking with the reactive resin. The reactive resin 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 the two terminals are respectively X 1 and X 2 denote the reactive resin 1, In the general formulas (1a) to (1c), s ≥ 1, t ≥ 0, u ≥ 0, P 1 , P 2 and P 3 each independently represent an aromatic group, Q 1 represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, Q 2 represents a substituted or unsubstituted group having an aromatic structure, R represents a substituted or unsubstituted branched aliphatic group or aromatic group, and at least one selected from the group consisting of X 1 , X 2 and X 3 represents a functional group containing a double bond. When any one of X 1 , X 2 and X 3 is a functional group other than the functional group containing a double bond, that is, a functional group having no double bond, the functional group having no double bond is selected from an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride, and an amine compound.

3. The adhesive composition according to claim 1 or 2, Among them, the functional group containing a double bond is an optionally substituted maleimide group, citraconimide group, vinyl ether group, allyl group, or (meth)acryloyl group.

4. The adhesive composition according to claim 1 or 2, Among them, the functional group containing a double bond is located in the side chain of the reactive resin.

5. The adhesive composition according to claim 1 or 2, Among them, the functional group equivalent of the reactive resin containing a double bond, that is, the weight average molecular weight / the number of functional groups containing a double bond, is 4000 or less.

6. The adhesive composition according to claim 1 or 2, Among them, the weight average molecular weight of the reactive resin is 300000 or less.

7. The adhesive composition according to claim 1, Among them, The reactive resin 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 the two terminals are respectively X 1 and X 2 representing the reactive resin 1, In the general formulas (1a) to (1c), s ≥ 1, t ≥ 0, u ≥ 0, P 1 , P 2 and P 3 each independently represents an aromatic group, Q 1 represents a substituted or unsubstituted linear, branched or cyclic aliphatic group, Q 2 represents a substituted or unsubstituted group having an aromatic structure, R represents a substituted or unsubstituted branched aliphatic group or aromatic group, and at least one selected from the group consisting of X 1 , X 2 and X 3 represents a functional group containing a double bond. When any one of X 1 , X 2 and X 3 is a functional group other than the functional group containing a double bond, that is, a functional group having no double bond, the functional group having no double bond is selected from an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride, and an amine compound.

8. The adhesive composition according to claim 2 or 7, Among them, In the general formulas (1a) to (1c), P 1 , P 2 and P 3 are each independently an aromatic group having 5 to 50 carbon atoms, Q 1 is a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, Q 2 is a substituted or unsubstituted aromatic structure-containing group having 5 to 50 carbon atoms, and R is a substituted or unsubstituted branched aliphatic group or aromatic group having 2 to 100 carbon atoms.

9. The adhesive composition according to claim 2 or 7, Among them, In the general formula (1c), X 3 is a functional group containing a double bond.

10. The adhesive composition according to claim 2 or 7, Among them, In the general formula (1c), 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 bonded to X 3 bonded.

11. The adhesive composition according to claim 2 or 7, Among them, In the general formula (1a), Q 1 is an aliphatic group derived from a dimer diamine, and the aliphatic group derived from a dimer diamine is at least one selected from the group consisting of 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). In the general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 each independently represents a linear or branched hydrocarbon group.

12. The adhesive composition according to claim 2, Among them, the silicone compound having a functional group capable of crosslinking with the reactive resin is a silicone compound having a siloxane skeleton in the main chain and a functional group containing a double bond in the side chain or at the terminal. The silicone compound having a siloxane skeleton in the main chain and a functional group containing a double bond in the side chain or at the terminal contains at least one selected from the group consisting of the silicone compound represented by the following general formula (I), the silicone compound represented by the following general formula (II), and the silicone compound represented by the following general formula (III). In the general formula (I), X represents an integer of 0 to 1200, Y represents an integer greater than 0 and 1200 or less. In the general formula (II) or general formula (III), X and Y each independently represent an integer of 0 to 1200. In the general formula (I), general formula (II) or general formula (III), R represents a functional group containing a double bond.

13. The adhesive composition according to claim 1 or 2, further comprising a polyfunctional monomer or polyfunctional oligomer having two or more functional groups containing a double bond in the molecule and a molecular weight of 5000 or less.

14. The adhesive composition according to claim 13, Among them, In a total of 100 parts by weight of the reactive resin and the polyfunctional monomer or polyfunctional oligomer, the content of the polyfunctional monomer or polyfunctional oligomer is 5 parts by weight or more and 50 parts by weight or less.

15. The adhesive composition according to claim 1 or 2, further comprising a photoinitiator.

16. The adhesive composition according to claim 15, wherein, the content of the photoinitiator is 0.1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the reactive resin.

17. The adhesive composition according to claim 1 or 2, further comprising a gas generating agent that generates gas upon irradiation with light.

18. The adhesive composition according to claim 17, wherein, the content of the gas generating agent is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the reactive resin.

19. An adhesive tape having an adhesive layer formed of the adhesive composition according to any one of claims 1 to 18.

20. A method for processing an electronic component, comprising a step of temporarily fixing the electronic component on the adhesive tape according to claim 19, a step of irradiating the adhesive tape with light, a step of performing heat treatment on the electronic component, and a step of peeling the adhesive tape from the electronic component.

Images