Adhesive resin composition and temporary fixing material

Abstract

To provide an adhesive resin composition enabling clear observation of fine features of an adherend after bonding and allowing easy removal from an adherend having irregularities, and to provide a temporary fixing material including the adhesive resin composition.SOLUTION: This adhesive resin composition comprises a resin having an imide skeleton as a repeating unit in its main chain and a compound having a (meth)acryloyl group, wherein the compound having the (meth)acryloyl group has a molecular weight of 200,000 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an adhesive resin composition. The present invention also relates to a temporary fixing material containing the adhesive resin composition. [Background technology]

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

[0003] Thus, pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes used for electronic components are required to have high enough adhesion to firmly fix the electronic components during the processing step, and also to be able to be peeled off without damaging the electronic components after the processing step (hereinafter also referred to as "high adhesion and easy peeling"). As a means of achieving high adhesion and easy peeling, for example, Patent Document 1 discloses a pressure-sensitive adhesive sheet using a pressure-sensitive adhesive layer containing an adhesive polymer in which a polyfunctional monomer or oligomer having a radiation-polymerizable functional group is bonded to the side chain or main chain of the polymer. By utilizing the fact that the polymer has a radiation-polymerizable functional group, which hardens when irradiated with ultraviolet light, the adhesive strength is reduced by irradiating with ultraviolet light during peeling, allowing the sheet to be peeled off without leaving any adhesive residue. [Prior art documents] [Patent documents]

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

[0005] Since the surfaces of electronic components such as semiconductors have irregularities known as bumps, adhesive resin compositions and temporary fixing materials used in the manufacturing processes for semiconductors and other electronic components are required to have excellent peeling performance for electronic components with irregularities in order to prevent the occurrence of adhesive residues and damage to the electronic components when the adhesive resin composition or temporary fixing material is peeled off. Furthermore, the manufacturing process for electronic components such as semiconductors includes steps such as a step of forming a pattern circuit and a step of detecting foreign matter on the semiconductor, and in order to perform these steps accurately, it is necessary to be able to clearly recognize the details of electronic components such as semiconductors. Therefore, adhesive resin compositions and temporary fixing materials used in the manufacturing process for electronic components such as semiconductors are also required to have excellent recognition properties that allow the details of electronic components such as semiconductors that have been temporarily fixed using the adhesive resin composition or temporary fixing material to be clearly recognized.

[0006] An object of the present invention is to provide an adhesive resin composition that allows the details of the adhered adherend to be clearly recognized and that can be easily peeled from an adherend having unevenness, and a temporary fixing material containing the adhesive resin composition. [Means for solving the problem]

[0007] Disclosure 1 is an adhesive resin composition containing a resin having an imide skeleton in a repeating unit of its main chain and a compound having a (meth)acryloyl group, wherein the resin having an imide skeleton in a repeating unit of its main chain does not have a (meth)acryloyl group, and the compound having a (meth)acryloyl group has a molecular weight of 200,000 or less. Disclosure 2 is the adhesive resin composition of Disclosure 1, wherein the adhesive resin composition has a haze of 90% or less. Disclosure 3 is an adhesive resin composition according to Disclosure 1 or 2, in which the resin having an imide skeleton in a repeating unit of the main chain does not have a maleimide group and contains a resin having an imide skeleton in a repeating unit of the main chain. Disclosure 4 is the adhesive resin composition of Disclosure 3, which does not have a maleimide group and in which the resin having an imide skeleton in the repeating unit of the main chain has an aliphatic group derived from dimer diamine. Disclosure 5 is the adhesive resin composition according to Disclosure 1, 2, 3, or 4, which contains a compound having a maleimide group. Disclosure 6 is the adhesive resin composition of Disclosure 5, wherein the adhesive resin composition contains at least one selected from the group consisting of bismaleimide compounds and resins having a maleimide group and an imide skeleton in a repeating unit of the main chain. Disclosure 7 is the adhesive resin composition according to Disclosure 1, 2, 3, 4, 5, or 6, wherein the compound having a (meth)acryloyl group includes a monomer having a (meth)acryloyl group. Disclosure 8 is the adhesive resin composition according to Disclosure 1, 2, 3, 4, 5, 6, or 7, wherein the compound having a (meth)acryloyl group does not have an imide bond. Disclosure 9 is the adhesive resin composition according to Disclosure 1, 2, 3, 4, 5, 6, 7, or 8, wherein the compound having a (meth)acryloyl group has two or more (meth)acryloyl groups in one molecule. Disclosure 10 is the adhesive resin composition according to Disclosure 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the compound having a (meth)acryloyl group has a molecular weight of 50,000 or less. The present disclosure 11 is an adhesive resin composition according to the present disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, in which the content of the compound having the (meth)acryloyl group is 2 parts by mass or more and 70 parts by mass or less relative to 100 parts by mass of the resin having the imide skeleton in a repeating unit of the main chain. Disclosure 12 is the adhesive resin composition according to Disclosures 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the adhesive resin composition is photocurable or thermosetting. Disclosure 13 is the adhesive resin composition of Disclosures 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, wherein the adhesive resin composition has a 5% weight loss temperature of 350°C or higher. Disclosure 14 is a temporary fixing material containing the adhesive resin composition of Disclosure 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13. Disclosure 15 is the temporary fixing material of Disclosure 14, having an adhesive layer containing the adhesive resin composition. Disclosure 16 is the temporary fixing material of Disclosure 15, further comprising a substrate. Disclosure 17 is the temporary fixing material of Disclosure 16, wherein the haze of the substrate is 90% or less. Disclosure 18 is the temporary fixing material of Disclosure 15, 16, or 17, wherein the temporary fixing material is in the form of a tape. Disclosure 19 is the temporary fixing material of Disclosure 18, wherein the temporary fixing material has a haze of 90% or less. Disclosure 20 is the temporary fixing material of Disclosures 14, 15, 16, 17, 18, or 19 used for manufacturing electronic components. The present invention will be described in detail below.

[0008] Curable adhesives that have excellent heat resistance and can be used even in high-temperature processing as adhesive resin compositions or temporary fixing materials used in the manufacturing process of electronic components such as semiconductors, and that cure by heating or irradiation with energy rays, have been investigated. However, such curable adhesives with excellent heat resistance generally tend to be hard and difficult to stretch, which increases the peeling force when peeled off, causing damage to electronic components such as semiconductors, or causing parts of the curable adhesive to tear off and leaving residue. In particular, electronic components such as semiconductors are prone to damage and residue of the curable adhesive is likely to be left on uneven surfaces on which bumps (protruding electrodes) of semiconductor devices are formed. The present inventors have investigated the formulation of an adhesive resin composition containing a resin that does not contain a (meth)acryloyl group and has an imide skeleton in the repeating unit of its main chain, and a compound that has a relatively small molecular weight and contains a (meth)acryloyl group. As a result, they have found that an adhesive resin composition can be obtained that allows the details of the adhered adherend to be clearly recognized and that can be easily peeled from an adherend having irregularities, and have completed the present invention.

[0009] The adhesive resin composition of the present invention contains a resin having an imide skeleton in the repeating unit of its main chain and a compound having a (meth)acryloyl group. By containing a resin having an imide skeleton in the repeating unit of its main chain and a compound having a (meth)acryloyl group, the adhesive resin composition of the present invention allows the details of the adhered adherend to be clearly recognized and can be easily peeled from an adherend having unevenness. In this specification, the term "(meth)acryloyl" means acryloyl or methacryloyl.

[0010] The adhesive resin composition of the present invention may or may not be curable, but is preferably curable from the viewpoint of being more easily peeled from an adherend having unevenness. When the adhesive resin composition of the present invention is curable, it is preferably photocurable or thermosetting.

[0011] The adhesive resin composition of the present invention contains a resin having an imide skeleton in the repeating unit of its main chain. The resin having an imide skeleton in the repeating unit of its main chain does not have a (meth)acryloyl group. The resin having the imide skeleton in the repeating unit of the main chain has extremely excellent heat resistance due to the imide skeleton, and decomposition of the main chain is unlikely to occur even when subjected to high-temperature processing at or above 300° C. Therefore, by including the resin having the imide skeleton in the repeating unit of the main chain, the adhesive resin composition of the present invention can suppress the occurrence of voids and lifting between the adhesive resin composition and the support during high-temperature processing, and can also prevent increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend.

[0012] The resin having the imide skeleton in the repeating unit of the main chain preferably has a constitutional unit represented by the following formula (1).

[0013] [ka]

[0014] In formula (1), P 1 represents an aromatic group, and Q 1 represents a linear, branched, or cyclic substituted or unsubstituted aliphatic group.

[0015] In the above formula (1), P 1 is preferably an aromatic group having 5 to 50 carbon atoms. 1 When is an aromatic group having 5 to 50 carbon atoms, the adhesive resin composition obtained has better heat resistance. That is, outgassing during high-temperature processing, voids between the resin and the adherend, and lifting can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented.

[0016] In the above formula (1), Q 1 is preferably a linear, branched, or cyclic, substituted or unsubstituted aliphatic group having from 2 to 100 carbon atoms. 1 When is a linear, branched, or cyclic, substituted or unsubstituted aliphatic group having from 2 to 100 carbon atoms, the adhesive resin composition obtained has better light transmittance. In addition, the adhesive resin composition obtained has better flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off. Also, the above Q 1 is preferably an aliphatic group derived from a diamine compound. In particular, from the viewpoints of light transparency, flexibility, and compatibility with solvents and other components of the resin having the imide skeleton in the main chain repeating unit, the above Q is 1 is preferably an aliphatic group derived from dimer diamine. The dimer diamine is a diamine compound obtained by reducing and amminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples thereof include linear, monocyclic, and polycyclic dimer diamines. The dimer diamine may contain a carbon-carbon double bond or may be a hydrogenated product to which hydrogen has been added.

[0017] The aliphatic group derived from the dimer diamine is preferably at least one group selected from the group consisting of a group represented by the following formula (2-1), a group represented by the following formula (2-2), a group represented by the following formula (2-3), and a group represented by the following formula (2-4). Among these, the group represented by the following formula (2-2) is more preferred.

[0018] [ka]

[0019] In formulas (2-1) to (2-4), R 1 ~R 16 are each independently a linear or branched hydrocarbon group, and * represents a bond, which bonds to N in the above formula (1).

[0020] In the above formulas (2-1) to (2-4), R 1 ~R 16 The hydrocarbon group represented by R may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 9 and R 10 , R 11 and R 12 , R 13 and R 14 , and R 15 and R 16 The total number of carbon atoms in the above groups preferably has a lower limit of 7 and an upper limit of 50. When the total number of carbon atoms is within the above range, the resulting adhesive resin composition is superior in optical transparency, flexibility, and compatibility with solvents and other components of the resin having the imide skeleton in the main chain repeating unit. The total number of carbon atoms is more preferably 9 in lower limit, 35 in upper limit, 12 in even more preferred lower limit, 25 in even more preferred upper limit, 14 in even more preferred upper limit, and 18 in even more preferred upper limit.

[0021] The optical isomerism of the group represented by the above formula (2-1), the group represented by the above formula (2-2), the group represented by the above formula (2-3), and the group represented by the above formula (2-4) is not particularly limited, and includes any optical isomerism.

[0022] The resin having an imide skeleton in the repeating unit of the main chain preferably includes a resin having an imide skeleton in the repeating unit of the main chain but not having a maleimide group. The resin having an imide skeleton in the repeating unit of the main chain but not having a maleimide group may have a functional group having a carbon-carbon double bond other than the maleimide group (excluding a (meth)acryloyl group), but preferably does not have a functional group having a carbon-carbon double bond other than the maleimide group (hereinafter, the maleimide group and the functional group having a carbon-carbon double bond other than the maleimide group may be collectively referred to as a "functional group having a carbon-carbon double bond"). That is, the resin having an imide skeleton in the repeating unit of the main chain more preferably does not have a functional group having a carbon-carbon double bond and includes a resin having an imide skeleton in the repeating unit of the main chain.

[0023] The weight-average molecular weight of the resin having no maleimide group and an imide skeleton in the main chain repeating unit is preferably 20,000 (lower limit) and 2,000,000 (upper limit). When the weight-average molecular weight of the resin having no maleimide group and an imide skeleton in the main chain repeating unit is 20,000 or more, the resulting adhesive resin composition has better heat resistance. This means that outgassing and the formation of voids and lifting between the resin and the adherend during high-temperature processing can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented. When the weight-average molecular weight of the resin having no maleimide group and an imide skeleton in the main chain repeating unit is 2,000,000 or less, the resin having no maleimide group and an imide skeleton in the main chain repeating unit has better compatibility with solvents and other components. The weight average molecular weight of the resin that does not have a maleimide group and has an imide skeleton in the repeating unit of the main chain is more preferably 40,000 in lower limit and 600,000 in upper limit, still more preferably 50,000 in lower limit and still more preferably 300,000 in upper limit. In this specification, the weight-average molecular weight of the resin having the imide skeleton as a repeating unit in the main chain is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Specifically, for example, it can be measured using an APC system (Waters) under the following conditions: THF mobile phase, flow rate 1.0 mL / min, column temperature 40°C, sample concentration 0.2% by mass, and RI-PDA detector. The column that can be used is, for example, an HR-MB-M 6.0 x 150 mm (Waters).

[0024] Specific examples of the resin that does not have a maleimide group and has an imide skeleton in the repeating unit of the main chain include resins that have a constitutional unit represented by the above formula (1) and have functional groups at both ends that do not have maleimide groups.

[0025] The resin having a structural unit represented by the above formula (1) and functional groups at both ends that do not have maleimide groups may also have a structural unit represented by the following formula (3).

[0026] [ka]

[0027] In formula (3), P 2 represents an aromatic group, and Q 2 represents a group having a substituted or unsubstituted aromatic structure.

[0028] In the above formula (3), P 2 is preferably an aromatic group having 5 to 50 carbon atoms. 2 When is an aromatic group having 5 to 50 carbon atoms, the adhesive resin composition obtained has better heat resistance. That is, the occurrence of outgassing, voids, and lifting between the support and the resin composition during high-temperature processing can be further suppressed, and the occurrence of increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend can be further prevented.

[0029] In the above formula (3), Q 2 is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. 2 is a substituted or unsubstituted group having an aromatic structure having from 5 to 50 carbon atoms, the adhesive resin composition obtained has better heat resistance. That is, outgassing during high-temperature processing, voids between the resin and the adherend, and lifting can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented.

[0030] Examples of the functional group not having a maleimide group include an aliphatic group, an aromatic group, an acid anhydride group, an amino group, etc. Specific examples include an unreacted terminal group of an acid anhydride or diamine compound that is a raw material for a resin not having a maleimide group and having an imide skeleton in the repeating unit of the main chain. In a resin having a structural unit represented by the above formula (1) and having functional groups at both ends that do not have maleimide groups, the functional groups at both ends that do not have maleimide groups may be the same or different.

[0031] The content of the structural unit represented by formula (1) in a resin having a structural unit represented by formula (1) and functional groups at both ends that do not have maleimide groups is preferably 30 mol% at the lower limit, 90 mol% at the upper limit, 50 mol% at the more preferred lower limit, and 80 mol% at the more preferred upper limit. When a resin having a structural unit represented by the above formula (1) and having functional groups at both ends that do not have maleimide groups also has a structural unit represented by the above formula (3), the content of the structural unit represented by the above formula (3) preferably has a lower limit of 5 mol%, a preferred upper limit of 50 mol%, a more preferred lower limit of 10 mol%, a more preferred upper limit of 30 mol%, and an even more preferred lower limit of 20 mol%. In the structural unit represented by the above formula (1) and the structural unit represented by the above formula (3), when the content of each structural unit is within the above range, the adhesive resin composition obtained can further suppress the occurrence of outgassing, voids, and lifting between the adhesive resin composition and the support during high-temperature processing, and can be more easily peeled from the adherend. The structural unit represented by the above formula (1) and the structural unit represented by the above formula (3) may have a block structure consisting of block components in which the respective structural units are arranged consecutively, or may have a random structure in which the respective structural units are arranged randomly.

[0032] Examples of a method for producing the resin having no maleimide group and an imide skeleton in the repeating unit of the main chain include a method of reacting a diamine compound with an aromatic acid anhydride.

[0033] As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used. By using an aliphatic diamine compound as the diamine compound, the adhesive resin composition obtained has superior optical transparency, and also has superior flexibility, which allows it to exhibit high conformability to an adherend having irregularities and allows it to be more easily peeled off. Furthermore, by using an aromatic diamine compound as the diamine compound, the adhesive resin composition obtained will have better heat resistance. The diamine compounds may be used alone or in combination of two or more.

[0034] Examples of the aliphatic diamine compound include 1,10-diaminodecane, 1,12-diaminododecane, dimer diamine, 1,2-diamino-2-methylpropane, 1,2-diaminocyclohexane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminomenthane, 1,8-diaminooctane, 1,9-diaminononane, 3,3'-diamino-N-methyldipropylamine, diaminomaleonitrile, 1,3-diaminopentane, bis(4-amino-3-methylcyclohexyl)methane, 1,2-bis(2-aminoethoxy)ethane, and 3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.02,6)decane.

[0035] Among the above aliphatic diamine compounds, dimer diamines are preferred from the viewpoints of light transparency, flexibility, and compatibility with solvents and other components of resins that do not have maleimide groups and have an imide skeleton in the main chain repeating unit. Specific examples of the above dimer diamines include dimer diamines that can constitute at least one group selected from the group consisting of the group represented by the above formula (2-1), the group represented by formula (2-2), the group represented by formula (2-3), and the group represented by formula (2-4).

[0036] Examples of the aromatic diamine compound include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-Diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane )methane, 9,9'-bis(4-amino-3-ethylphenyl)fluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, bis(4-amino-5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenylsulfone, 3,3'-diaminophenylsulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, 4,4'-oxydianiline, 4,4'- Diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene (Mitsui Chemicals Fine Co., Ltd., "Bisaniline M", etc.), 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene (Mitsui Chemicals Fine Co., Ltd., "Bisaniline P", etc.), 9,9-bis(4-aminophenyl)fluorene, o-tolidine sulfone, 5,5'-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, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylenediamines (e.g., Huntsman's Jeffamine Examples include cyclohexanebis(methylamine), m-xylylenediamine, and p-xylylenediamine.

[0037] Examples of the aromatic acid anhydride include pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4'-sulfonyldiphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxyphenyl)ethane ... (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 Examples of suitable carboxylic acid anhydrides include 2,10-tetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4'-oxydiphthalic acid, 4,4'-oxydiphthalic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, and 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid).

[0038] The content of the resin having no maleimide group and an imide skeleton in its main chain repeating unit per 100 parts by mass of the resin having an imide skeleton in its main chain repeating unit is preferably 10 parts by mass or less, and more preferably 90 parts by mass or less. When the content of the resin having no maleimide group and an imide skeleton in its main chain repeating unit is within this range, the adhesive resin composition obtained can be more easily peeled from an adherend. From the viewpoint of further improving peelability, the content of the resin having no maleimide group and an imide skeleton in its main chain repeating unit is more preferably 20 parts by mass or less, and more preferably 80 parts by mass or less.

[0039] The resin having an imide skeleton in the repeating unit of the main chain also preferably includes a resin having a maleimide group and an imide skeleton in the repeating unit of the main chain. By including the resin having a maleimide group and an imide skeleton in the repeating unit of the main chain, the adhesive resin composition obtained undergoes uniform and rapid polymerization and crosslinking throughout by irradiation with light or the like, and the elastic modulus increases, resulting in a significant decrease in adhesive strength. This makes it possible to more effectively prevent increased adhesion and the occurrence of adhesive residue upon peeling. When the resin having an imide skeleton in a repeating unit of its main chain includes a resin that does not have the maleimide group and has an imide skeleton in a repeating unit of its main chain, it preferably further includes a resin that has a functional group having a maleimide group and has an imide skeleton in a repeating unit of its main chain, in addition to the resin that does not have a maleimide group and has an imide skeleton in a repeating unit of its main chain.

[0040] The resin having the maleimide group and an imide skeleton in the repeating unit of the main chain may further have a functional group having a carbon-carbon double bond other than the maleimide group (excluding a (meth)acryloyl group). Examples of the other functional groups having a carbon-carbon double bond include a citraconic imide group, a vinyl ether group, and an allyl group. It should be noted that the carbon-carbon double bond contained in the aromatic ring is not considered to be the carbon-carbon double bond of the functional group having the carbon-carbon double bond.

[0041] In the resin having a maleimide group and an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond preferably has a functional group equivalent (weight average molecular weight / number of functional groups having a carbon-carbon double bond) of 4000 or less. When the functional group equivalent of the functional group having a carbon-carbon double bond is 4000 or less, the resulting adhesive resin composition has better heat resistance. This is thought to be because the presence of functional groups having a carbon-carbon double bond at a density above a certain level in the resin molecule shortens the inter-crosslink distance, thereby further suppressing adhesion enhancement. The functional group equivalent of the functional group having a carbon-carbon double bond is more preferably 3000 or less, and even more preferably 2000 or less. There is no particular preferred lower limit to the functional group equivalent weight of the functional group having a carbon-carbon double bond, but the substantial lower limit is about 600.

[0042] The resin having a maleimide group and an imide skeleton in the repeating unit of its main chain preferably has a weight-average molecular weight of 1,000 or more and 100,000 or less. Having a weight-average molecular weight of 1,000 or more for the resin having a maleimide group and an imide skeleton in the repeating unit of its main chain facilitates film formation of the adhesive layer, and the resulting adhesive resin composition exhibits a certain degree of flexibility, thereby enabling high conformability to an adherend having irregularities and facilitating peeling. Having a weight-average molecular weight of 100,000 or less for the resin having a maleimide group and an imide skeleton in the repeating unit of its main chain prevents the resin from becoming too soluble in a solvent. The weight-average molecular weight of the resin having a maleimide group and an imide skeleton in the repeating unit of its main chain is more preferably 1,500 or more and 50,000 or less, and even more preferably 2,000 or more and less than 20,000.

[0043] In the resin having a maleimide group and an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond may be present either in a side chain or at a terminal, but is preferably present at both terminals, and more preferably present in the side chain in addition to both terminals. The functional groups having carbon-carbon double bonds at both ends of the resin having the maleimide group and the imide skeleton in the repeating unit of the main chain are highly reactive, and can more fully cure the adhesive resin composition by irradiation with light, etc. As a result, it is possible to more effectively prevent the occurrence of increased adhesion and the occurrence of adhesive residue upon peeling. Furthermore, the presence of a functional group having a carbon-carbon double bond in the side chain of the resin having the maleimide group and an imide skeleton in the repeating unit of the main chain improves the heat resistance of the resulting adhesive resin composition. This is thought to be because the shorter inter-crosslink distance further suppresses adhesion enhancement. Furthermore, the presence of a functional group having a carbon-carbon double bond in the side chain of the resin having the maleimide group and an imide skeleton in the repeating unit of the main chain makes it easy to adjust the functional group equivalent to 4000 or less while maintaining the weight average molecular weight at 1000 or more. This allows the adhesive resin composition to have sufficient initial adhesive strength while also preventing adhesion enhancement and adhesive residue upon peeling.

[0044] As described above, in the resin having a maleimide group and an imide skeleton in the repeating unit of the main chain, the functional group having a carbon-carbon double bond may be located either in a side chain or at a terminal. When either the side chain or the terminal has a functional group other than a functional group having a carbon-carbon double bond (a functional group not having a carbon-carbon double bond), examples of the functional group not having a carbon-carbon double bond include an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride group, and an amino group. Specific examples include an unreacted terminal group of an acid anhydride or a diamine compound that is a raw material for the resin having a maleimide group and an imide skeleton in the repeating unit of the main chain. When the resin having a maleimide group and an imide skeleton in the repeating unit of the main chain has two or more functional groups not having a carbon-carbon double bond in the side chain or at the terminal, the functional groups not having a carbon-carbon double bond may be the same or different.

[0045] Specific examples of the resin having the maleimide group and an imide skeleton in the repeating unit of the main chain include resins having a constitutional unit represented by the above formula (1) and having a maleimide group at least at the end or in the side chain.

[0046] The resin having a structural unit represented by the above formula (1) and having a maleimide group at least at the end or at the side chain may have the above other functional group having a carbon-carbon double bond.

[0047] The resin having a structural unit represented by the above formula (1) and having a maleimide group at least at the end or at a side chain may have at least one structural unit selected from the group consisting of a structural unit represented by the following formula (4-1) and a structural unit represented by the following formula (4-2):

[0048] [ka]

[0049] In formula (4-1), P 3 represents an aromatic group, and Q3 represents a group having a substituted or unsubstituted aromatic structure and not having a functional group having a carbon-carbon double bond, and in formula (4-2), P 4 represents an aromatic group, R represents a substituted or unsubstituted aromatic group, and X represents a functional group having a carbon-carbon double bond.

[0050] P in the above formula (4-1) 3 and P in the above formula (4-2) 4 is preferably an aromatic group having 5 to 50 carbon atoms. 3 and P 4 When is an aromatic group having 5 to 50 carbon atoms, the adhesive resin composition obtained has better heat resistance. That is, outgassing during high-temperature processing, voids between the resin and the adherend, and lifting can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented.

[0051] In the above formula (4-1), Q 3 is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. 3 When is a substituted or unsubstituted group having an aromatic structure of 5 to 50 carbon atoms, the adhesive resin composition obtained has better heat resistance. That is, it is possible to further suppress outgassing during high-temperature processing, voids between the resin and the adherend, and lifting, and it is also possible to further prevent increased adhesion to the adherend and adhesive residue when peeled from the adherend.

[0052] In the above formula (4-2), R is preferably a substituted or unsubstituted aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted aromatic group having 2 to 100 carbon atoms, the adhesive resin composition obtained has excellent flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off.

[0053] In the above formula (4-2), R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or aromatic ether group in R is preferably bonded to X. Here, "aromatic ester group" refers to a group in which an ester group is directly bonded to an aromatic ring, and "aromatic ether group" refers to a group in which an ether group is directly bonded to an aromatic ring. When the aromatic group has a moiety that bonds to an ester group or an ether group, the resulting adhesive resin composition has better heat resistance. That is, outgassing during high-temperature processing, voids between the resin and the adherend, and lifting can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented. Meanwhile, when X is bonded to R via an aromatic ester group or an aromatic ether group, the carbon-carbon double bond in X is not conjugated with R, and therefore polymerization and crosslinking upon heating or light irradiation are not hindered.

[0054] The content of the structural unit represented by formula (1) in a resin having a maleimide group at least at an end or at a side chain is preferably 30 mol% or less, more preferably 50 mol%, and more preferably 90 mol% or less, and more preferably 80 mol% or less. When a resin having a structural unit represented by the above formula (1) and having a maleimide group at least at either its terminal or its side chain also has a structural unit represented by the above formula (4-1), the content of the structural unit represented by the above formula (4-1) is preferably 5 mol% at its lower limit, more preferably 10 mol% at its lower limit, even more preferably 20 mol% at its upper limit, and more preferably 50 mol% at its upper limit, and even more preferably 30 mol% at its upper limit. When a resin having a structural unit represented by the above formula (1) and having a maleimide group at least at either the end or the side chain also has a structural unit represented by the above formula (4-2), the content of the structural unit represented by the above formula (4-2) is preferably 10 mol% at its lower limit, more preferably 20 mol%, and more preferably 50 mol% and more preferably 30 mol% at its upper limit. When the content of each of the structural units represented by the above formula (1), the structural unit represented by the above formula (4-1), and the structural unit represented by the above formula (4-2) is within the above range, the adhesive resin composition obtained can further suppress outgassing during high-temperature processing, voids between the composition and the adherend, and lifting, and can be more easily peeled from the adherend. The structural unit represented by the above formula (1), the structural unit represented by the above formula (4-1), and the structural unit represented by the above formula (4-2) may have a block structure consisting of block components in which the respective structural units are arranged consecutively, or may have a random structure in which the respective structural units are arranged randomly.

[0055] Examples of methods for producing the resin having the maleimide group and an imide skeleton in the repeating unit of the main chain include the following methods. That is, a resin having the maleimide group and an imide skeleton in the repeating unit of the main chain can also be obtained by reacting a diamine compound with an aromatic acid anhydride to prepare an imide compound, and then reacting the terminal of the imide compound with, for example, maleic anhydride. Alternatively, a diamine compound is reacted with an aromatic acid anhydride to prepare an imide compound, and then a compound having a functional group reactive with the functional group of the imide compound and a functional group having a carbon-carbon double bond (hereinafter also referred to as a "functional group-containing unsaturated compound") is reacted with the functional group of the imide compound to obtain a resin having the maleimide group and an imide skeleton in the repeating unit of the main chain.

[0056] The diamine compound and aromatic acid anhydride used in the method for producing a resin having a maleimide group and an imide skeleton in the repeating unit of the main chain may be the same as those used in the method for producing a resin having no maleimide group and an imide skeleton in the repeating unit of the main chain.

[0057] The functional group-containing unsaturated compound is selected depending on the functional group at the end or side chain of the imide compound. For example, when the functional group at the end or side chain of the imide compound is a hydroxyl group, examples of the functional group-containing unsaturated compound 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, (meth)acryloyl compounds having an isocyanate group, and allyl compounds having a hydroxyl group. Furthermore, for example, when the functional group at the end or side chain of the imide compound is a carboxy group, examples of the functional group-containing unsaturated compound 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 maleimide compound having a carboxy group include maleimide acetate, maleimidopropionic acid, maleimidobutyric acid, maleimidohexanoic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, and 19-maleimido-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid. Examples of the vinyl compound having an ether group include butyl vinyl ether. The allyl compound having a glycidyl group includes, for example, diallyl monoglycidyl isocyanurate. Examples of the allyl ether compound having a glycidyl group include allyl glycidyl ether and glycerin diallyl monoglycidyl ether. Examples of the vinyl ether compound having a glycidyl group include glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, and glycidyl cyclohexanedimethanol monovinyl ether. The allyl compound having an isocyanate group includes, for example, allyl isocyanate. Examples of the (meth)acryloyl compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate. Examples of the allyl compound having a hydroxyl group include trimethylolpropane diallyl ether and pentaerythritol triallyl ether.

[0058] The content of the resin having a maleimide group and an imide skeleton in its main chain repeating unit per 100 parts by mass of the resin having an imide skeleton in its main chain repeating unit is preferably 10 parts by mass or less, and preferably 100 parts by mass or less. When the content of the resin having a maleimide group and an imide skeleton in its main chain repeating unit per 100 parts by mass of the resin having an imide skeleton in its main chain repeating unit is within this range, the adhesive resin composition can be more easily peeled off. From the viewpoint of further improving peelability, the content of the resin having a maleimide group and an imide skeleton in its main chain repeating unit per 100 parts by mass of the resin having an imide skeleton in its main chain repeating unit is more preferably 20 parts by mass or less, even more preferably 30 parts by mass or less, and more preferably 90 parts by mass or less, even more preferably 80 parts by mass or even more preferably 70 parts by mass or less.

[0059] The content of the resin having an imide skeleton in the main chain repeating unit in the adhesive resin composition of the present invention is preferably up to 99% by mass. By having the content of the resin having an imide skeleton in the main chain repeating unit of 99% by mass or less, the releasability from an adherend having irregularities during heating can be further improved. The content of the resin having an imide skeleton in the main chain repeating unit is more preferably up to 98% by mass, even more preferably up to 96% by mass, and even more preferably up to 90% by mass. Furthermore, the content of the resin having an imide skeleton in the repeating unit of the main chain is preferably 5% by mass or less. By having the content of the resin having an imide skeleton in the repeating unit of the main chain of 5% by mass or more, it is possible to further suppress the increase in adhesion during high-temperature processing. The content of the resin having an imide skeleton in the repeating unit of the main chain is more preferably 10% by mass or less, and even more preferably 20% by mass or less.

[0060] The adhesive resin composition of the present invention preferably contains a compound having a maleimide group. By including a compound having a maleimide group in the adhesive resin composition of the present invention, three-dimensional reticulation by irradiation with light or the like becomes more efficient, and it is possible to more effectively prevent enhanced adhesion and the occurrence of adhesive residue upon peeling. In addition, the resulting adhesive resin composition has better heat resistance.

[0061] The compound having a maleimide group is not particularly limited as long as it has a maleimide group, and may be a resin having the maleimide group and an imide skeleton in the repeating unit of its main chain. The adhesive resin composition preferably contains at least one selected from the group consisting of bismaleimide compounds and resins having a maleimide group and an imide skeleton in the repeating unit of its main chain.

[0062] Examples of the bismaleimide compound include monomers having a bismaleimide structure, such as BMI-689 (manufactured by Designer Molecules). In this specification, a resin having the above-mentioned maleimide group and an imide skeleton in the repeating unit of the main chain, and having a bismaleimide structure, will be treated as the above-mentioned "resin having a maleimide group and an imide skeleton in the repeating unit of the main chain."

[0063] Furthermore, when only a resin that does not have the above-mentioned maleimide group and has an imide skeleton in a repeating unit of its main chain is used as the resin having an imide skeleton in a repeating unit of its main chain, it is preferable to contain a bismaleimide compound in the adhesive resin composition of the present invention in order to impart more excellent curability to the resin having an imide skeleton in a repeating unit of its main chain.

[0064] The compound having a maleimide group preferably has a group derived from a diamine compound. As the diamine compound, either an aliphatic diamine compound or an aromatic diamine compound can be used, but an aliphatic diamine compound is preferred. That is, the compound having a maleimide group more preferably has an aliphatic group derived from a diamine compound. By using an aliphatic diamine compound as the diamine compound, the adhesive resin composition obtained has superior light transmittance. Furthermore, the adhesive resin composition obtained has superior flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off.

[0065] Among the above aliphatic diamine compounds, the above-mentioned dimer diamines are preferred from the viewpoints of light transparency, flexibility, and compatibility with the solvent of the compound having a maleimide group and other components.

[0066] When the compound having a maleimide group includes a bismaleimide compound, the content of the bismaleimide compound relative to 100 parts by mass of the resin having an imide skeleton in the main chain repeating unit is preferably 5 parts by mass at the lower limit and 90 parts by mass at the upper limit. By ensuring that the content of the bismaleimide compound is within this range, the adhesive resin composition can be more easily peeled off. From the viewpoint of further improving peelability, the content of the bismaleimide compound is more preferably 10 parts by mass at the lower limit and 50 parts by mass at the upper limit.

[0067] The adhesive resin composition of the present invention contains a compound having a (meth)acryloyl group. By containing a compound having a (meth)acryloyl group, the adhesive resin composition of the present invention can be easily peeled from an adherend having unevenness.

[0068] The compound having a (meth)acryloyl group is not particularly limited as long as it has a (meth)acryloyl group and satisfies the molecular weight range described below, and may be a monomer or a multimer such as an oligomer or polymer. Among them, from the viewpoint of easily adjusting the molecular weight of the compound having a (meth)acryloyl group within the range described below and having better compatibility with the resin having the imide skeleton in the repeating unit of the main chain, it is preferable that the compound having a (meth)acryloyl group contains the monomer having a (meth)acryloyl group.

[0069] The upper limit of the molecular weight of the compound having a (meth)acryloyl group is 200,000. When the molecular weight of the compound having a (meth)acryloyl group is 200,000 or less, it has excellent compatibility with the resin having the imide skeleton in the main chain repeating unit, and therefore, the details of the adherend adhered using the adhesive resin composition of the present invention can be clearly recognized. The upper limit of the molecular weight of the compound having a (meth)acryloyl group is preferably 100,000, more preferably 50,000, even more preferably 40,000, even more preferably 10,000, particularly preferably 3,000, and especially more preferably 2,000. Furthermore, as described below, the compound having the (meth)acryloyl group preferably has two or more (meth)acryloyl groups in one molecule, and from the viewpoint that the sum of the molecular weights of the two acryloyl groups is 142, the lower limit of the molecular weight of the compound having the (meth)acryloyl group is preferably 150, and more preferably 200.

[0070] In this specification, the molecular weight of the compound having a (meth)acryloyl group can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent molecular weight. Specifically, for example, measurements can be performed using an APC system (Waters) under the following conditions: THF mobile phase, flow rate 1.0 mL / min, column temperature 40°C, sample concentration 0.2% by mass, and RI-PDA detector. The column used can be an HR-MB-M 6.0 x 150 mm (Waters).

[0071] The weight molecular weight of the compound having a (meth)acryloyl group may be measured by gas chromatography mass spectrometry (GC / MS). Specifically, for example, measurement can be performed using a gas chromatograph mass spectrometer (gas chromatography (GC): manufactured by Agilent Technologies, Inc., "78906B" or the like; mass spectrometer (MS): manufactured by JEOL Ltd., "JMS Q1500" or the like) under the following conditions. <Gas chromatography mass spectrometry conditions> Ionization voltage: 70eV Carrier gas: He ·Flow rate: 1.0mL / min Column temperature: After holding at 40°C for 4 minutes, increase the temperature to 350°C at a rate of 10°C / min and hold at 350°C for 10 minutes.

[0072] The structure of the compound having a (meth)acryloyl group is not particularly limited, and examples thereof include structures derived from a substituted or unsubstituted aromatic skeleton, a substituted or unsubstituted alicyclic skeleton, or a substituted or unsubstituted aliphatic skeleton. Specific examples thereof include compounds having a structure derived from a skeleton such as an ethylene skeleton, a propylene skeleton, a bisphenol skeleton, a tricyclodecane dimethanol skeleton, or an isocyanurate skeleton, and having a (meth)acryloyl group.

[0073] The compound having a (meth)acryloyl group preferably does not have an imide bond, which makes it easier to peel from an adherend having irregularities.

[0074] The compound having a (meth)acryloyl group preferably has two or more (meth)acryloyl groups in one molecule. When the compound having a (meth)acryloyl group has two or more (meth)acryloyl groups in one molecule, the adhesive resin composition as a whole forms a uniform and sufficient crosslinked body, and the elastic modulus increases, resulting in a significant decrease in adhesive strength, making it possible to prevent increased adhesion and the occurrence of adhesive residue upon peeling. The upper limit of the number of (meth)acryloyl groups in one molecule of the (meth)acryloyl group-containing compound is not particularly limited, but is preferably 150, more preferably 135, and even more preferably 120.

[0075] Examples of monomers having two or more (meth)acryloyl groups in one molecule include ABE-300 (molecular weight: 132, total number of (meth)acryloyl groups: 2), A-BPE-4 (molecular weight: 176, total number of (meth)acryloyl groups: 2), A-BPE-10 (molecular weight: 440, total number of (meth)acryloyl groups: 2), A-BPE-30 (molecular weight: 1656, total number of (meth)acryloyl groups: 2), A-DCP (molecular weight: 151, total number of (meth)acryloyl groups: 2), and A-9300S (molecular weight: 225, total number of (meth)acryloyl groups: 2 or 3) (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0076] Examples of polymers having two or more (meth)acryloyl groups in one molecule include Artcure (registered trademark) RA-3953MP (molecular weight: 40,000, total number of (meth)acryloyl groups: 114), RA-3602MI (molecular weight: 20,000, total number of (meth)acryloyl groups: 67), and OAP-5000 (molecular weight: 15,000, total number of (meth)acryloyl groups: 8) (all manufactured by Negami Chemical Industrial Co., Ltd.).

[0077] The content of the compound having a (meth)acryloyl group relative to 100 parts by mass of the resin having an imide skeleton in the main chain repeating unit is preferably 2 parts by mass at the lower limit and 70 parts by mass at the upper limit. When the content of the compound having a (meth)acryloyl group is within the above range, the adhesive resin composition of the present invention can be more easily peeled from an adherend having irregularities, and because of its excellent compatibility with the resin having an imide skeleton in the main chain repeating unit, the details of the adherend adhered using the adhesive resin composition of the present invention can be clearly recognized. The content of the compound having a (meth)acryloyl group is more preferably 3 parts by mass at the lower limit and 60 parts by mass at the upper limit, and even more preferably 5 parts by mass at the lower limit and 50 parts by mass at the upper limit.

[0078] The adhesive resin composition of the present invention preferably contains a polymerization initiator. By containing a polymerization initiator, the adhesive resin composition of the present invention is more easily cured, and the adhesion of the resulting adhesive resin composition to an adherend can be more effectively suppressed during high-temperature processing, so that the adhesive resin composition can be more easily peeled from the adherend.

[0079] The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, of which a photopolymerization initiator is preferred from the viewpoint of storage stability.

[0080] Examples of the photopolymerization initiator include those that are activated by irradiation with light having a wavelength of 250 to 800 nm. Among these, the photopolymerization initiator has a molar absorption coefficient at 405 nm of preferably 10 ml / (g cm), more preferably 200 ml / (g cm), and even more preferably 405 ml / (g cm), which is less likely to overlap with the absorption wavelength of the resin having the imide skeleton in the main chain repeating unit, and is sufficiently activated when the adhesive resin composition is irradiated with light. There is no particular upper limit to the molar absorption coefficient at 405 nm, but it is 1.0 × 10 6 The practical upper limit is about ml / (g·cm).

[0081] Examples of the photopolymerization initiator include acetophenone derivatives, benzoin ether compounds, ketal derivatives, phosphine oxide derivatives, and oxime ester compounds. Examples of the acetophenone derivatives include methoxyacetophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and the like. Examples of the benzoin ether compounds include benzoin propyl ether and benzoin isobutyl ether. Examples of the ketal derivatives include benzyl dimethyl ketal and acetophenone diethyl ketal. Examples of the phosphine oxide derivatives include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Examples of the oxime ester compound include 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)-1,2-octadione, and the like. Further, examples of the photopolymerization initiator include bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone or in combination of two or more.

[0082] Examples of the thermal polymerization initiator include Perbutyl H and Percumyl H (both manufactured by NOF Corporation).

[0083] The content of the polymerization initiator is preferably 0.1 parts by mass or less and 10 parts by mass or less per 100 parts by mass of the resin having an imide skeleton as a repeating unit in the main chain. By using the polymerization initiator within this range, the adhesive resin composition is uniformly and quickly polymerized and crosslinked throughout, and the elastic modulus increases, significantly reducing the adhesive strength. This prevents increased adhesion and the occurrence of adhesive residue upon peeling. The lower limit of the polymerization initiator content is more preferably 0.3 parts by mass, and the upper limit is more preferably 5 parts by mass.

[0084] The adhesive resin composition of the present invention preferably further contains a silicone compound or a fluorine compound. By containing a silicone compound or a fluorine compound, the adhesive resin composition of the present invention can be prevented from burning during high-temperature processing at 300°C or higher, and further, when the resulting adhesive resin composition is peeled off, the silicone compound or the fluorine compound bleeds out to the interface with the adherend, making peeling easier. Among these, silicone compounds are preferred from the viewpoint of being environmentally friendly and easy to dispose of.

[0085] The silicone compound or fluorine compound may have a functional group capable of crosslinking with the resin having the imide skeleton in its main chain repeating unit. When the silicone compound or fluorine compound has a functional group capable of crosslinking with the resin having the imide skeleton in its main chain repeating unit, the silicone compound or fluorine compound is chemically reacted with the resin having the imide skeleton in its main chain repeating unit or the compound having the maleimide group upon irradiation with light or reaction with a crosslinking agent, etc., and is incorporated into the resin. This prevents the silicone compound or fluorine compound from adhering to and contaminating the adherend. Examples of functional groups capable of crosslinking with the resin having the imide skeleton in its main chain repeating unit or the compound having the maleimide group include a carboxy group, a functional group having a radically polymerizable unsaturated bond (e.g., a vinyl group, a (meth)acryloyl group, or an optionally substituted maleimide group), a hydroxy group, an amide group, an isocyanate group, and an epoxy group.

[0086] Examples of the silicone compound include silicone oil, silicone diacrylate, silicone graft copolymer, etc. Specifically, a silicone compound having a siloxane skeleton in the main chain and a functional group having a carbon-carbon double bond in the side chain or at the terminal is preferred. The silicone compound having a siloxane skeleton in its main chain and a functional group having a carbon-carbon double bond in its side chain or at its terminal is preferably at least one selected from the group consisting of silicone compounds represented by the following formula (5-1), silicone compounds represented by the following formula (5-2), and silicone compounds represented by the following formula (5-3): These silicone compounds are particularly excellent in heat resistance and, due to their high polarity, tend to bleed out easily from the adhesive layer.

[0087] [ka]

[0088] X in the above formulas (5-1) to (5-3) and Y in the above formulas (5-1) and (5-3) each independently represent an integer of 0 or more and 1200 or less, and R in the above formulas (5-1) to (5-3) represents a functional group having a carbon-carbon double bond.

[0089] In the above formulas (5-1) to (5-3), examples of the functional group having a carbon-carbon double bond represented by R include an optionally substituted maleimide group, a citraconic imide group, a vinyl ether group, an allyl group, and a (meth)acryloyl group. Among these, an optionally substituted maleimide group is preferred because the resulting adhesive resin composition has better heat resistance. In addition, when there are multiple Rs in the above formulas (5-1) to (5-3), the respective Rs may be the same or different.

[0090] Among the silicone compounds represented by the above formulas (5-1) to (5-3), commercially available examples include EBECRYL350 and EBECRYL1360 (both manufactured by Daicel-Allnex Co., Ltd.), etc. Other examples include BYK-UV3500 (manufactured by BYK-Chemie KK) and TEGO RAD2250 (manufactured by Evonik AG) (in both cases, R is an acryloyl group).

[0091] Examples of the fluorine compound include hydrocarbon compounds having fluorine atoms.

[0092] The content of the silicone compound or fluorine compound is preferably 0.1 parts by mass at the lower limit and 20 parts by mass at the upper limit relative to 100 parts by mass of the resin having an imide skeleton as a repeating unit in the main chain. When the content of the silicone compound or fluorine compound is within this range, the resulting adhesive resin composition does not contaminate the adherend and has excellent releasability. From the viewpoint of further improving releasability while suppressing contamination, the lower limit of the content of the silicone compound or fluorine compound is more preferably 0.3 parts by mass, and the upper limit is more preferably 10 parts by mass. Since the adhesive resin composition of the present invention contains a resin having an imide skeleton in the main chain repeating unit and has relatively excellent heat resistance, it can exert a sufficient effect even if the content of the silicone compound or fluorine compound is relatively small, thereby further reducing the possibility of contamination by the silicone compound or fluorine compound.

[0093] The adhesive resin composition of the present invention preferably further contains an inorganic filler, which can prevent the adhesive resin composition from decreasing in elastic modulus at high temperatures and can further prevent peeling during high-temperature processing, even when the composition is subjected to high-temperature processing at 300°C or higher.

[0094] Examples of the inorganic filler include at least one inorganic filler selected from the group consisting of oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconia, silica, talc, and composites thereof. Among these, silica and talc are preferred because they are commercially available at low cost and easily available.

[0095] The inorganic filler may be surface-modified. Examples of the functional group that may be used to modify the surface of the inorganic filler include an alkylsilane group, a methacryloyl group, and a dimethylsiloxane group. Among these, a dimethylsiloxane group is preferred because it has appropriate hydrophobicity.

[0096] The preferred lower limit of the average particle size of the inorganic filler is 5 nm, and the preferred upper limit is 30 μm. By having the average particle size of the inorganic filler within this range, the resulting adhesive resin composition can be more effectively prevented from peeling during high-temperature processing, and can be easily peeled by peel treatment. The more preferred lower limit of the average particle size of the inorganic filler is 10 nm, and the more preferred upper limit is 20 μm, and the even more preferred lower limit is 15 nm, and the even more preferred upper limit is 15 μm. The average particle size can be determined, for example, by observing 50 particles of any inorganic filler under an electron microscope or an optical microscope and calculating the average particle size of each inorganic filler, or by performing laser diffraction particle size distribution measurement.

[0097] The content of the inorganic filler is preferably 1 part by mass at the lower limit and 20 parts by mass at the upper limit relative to 100 parts by mass of the resin having an imide skeleton as a main chain repeating unit. By setting the content of the inorganic filler within this range, the adhesive resin composition obtained can be more effectively prevented from peeling during high-temperature processing, and can be easily peeled by peel treatment. The lower limit of the inorganic filler content is more preferably 3 parts by mass, and the upper limit is more preferably 15 parts by mass, and even more preferably 5 parts by mass, and even more preferably 10 parts by mass.

[0098] The adhesive resin composition of the present invention may further contain a gas-generating agent. By containing the gas-generating agent, even after high-temperature processing at 300°C or higher, the gas generated by irradiation with light or the like is released at the interface with the adherend, making it possible to peel the adhesive resin composition from the adherend more easily and without leaving any adhesive residue. Furthermore, even when the adhesive resin composition is peeled from a thin adherend after high-temperature processing at 300°C or higher, damage to the adherend can be prevented.

[0099] The gas generating agent preferably has a weight loss rate of 5% or less at 300°C when heated from 30°C to 300°C at a temperature increase rate of 10°C / min in a nitrogen atmosphere as measured by TG-DTA (thermogravimetry-differential thermal analysis). If the weight loss rate is 5% or less, decomposition of the gas generating agent is unlikely to occur even when high-temperature processing is performed at 300°C or higher, and the adhesive resin composition has better heat resistance. In other words, peeling can be further suppressed during high-temperature processing, and enhanced adhesion and the generation of adhesive residue upon peeling can be further prevented. The TG-DTA (thermogravimetry-differential thermal analysis) measurement can be carried out using, for example, a TG-DTA device (manufactured by Hitachi High-Tech Science Corporation, "STA7200RV") or the like.

[0100] Examples of the gas generating agent include a gas generating agent that generates gas by heating and a gas generating agent that generates gas by irradiating with light. Among them, from the viewpoint of preventing decomposition of the gas generating agent during high-temperature processing, a gas generating agent that generates gas by irradiating with light is preferred, and a gas generating agent that generates gas by irradiating with ultraviolet light is more preferred. These gas generating agents may be used alone or in combination of two or more. Examples of the gas generating agent include tetrazole compounds or salts thereof, triazole compounds or salts thereof, azo compounds, azide compounds, xanthone acetate, carbonates, etc. Among these, tetrazole compounds or salts thereof are preferred because of their particularly excellent heat resistance. These gas generating agents may be used alone or in combination of two or more.

[0101] The content of the gas generating agent is preferably 5 parts by mass or less and 50 parts by mass or less per 100 parts by mass of the resin having an imide skeleton as a repeating unit in the main chain. When the content of the gas generating agent is within this range, the resulting adhesive resin composition has particularly excellent releasability. The more preferred lower limit of the content of the gas generating agent is 8 parts by mass, and the more preferred upper limit is 30 parts by mass.

[0102] The adhesive resin composition of the present invention may contain known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, surfactants, and waxes, as long as the effects of the present invention are not impaired.

[0103] The method for producing the adhesive resin composition of the present invention is not particularly limited, and examples thereof include a method of mixing a resin having the above-mentioned imide skeleton in a repeating unit of the main chain, a compound having a (meth)acryloyl group, and, if necessary, a maleimide compound and additives using a bead mill, ultrasonic dispersion, a homogenizer, a high-power disperser, a roll mill, or the like.

[0104] The adhesive resin composition of the present invention preferably has a haze upper limit of 90%. When the adhesive resin composition of the present invention has a haze of 90% or less, the adhesive resin composition of the present invention becomes more uniform, and the details of the adherend bonded using the adhesive resin composition of the present invention can be more clearly recognized. The adhesive resin composition of the present invention more preferably has a haze upper limit of 80%, and even more preferably 50%. There is no particular lower limit to the haze of the adhesive resin composition of the present invention, and 0% is the most preferred. In this specification, the haze is measured in accordance with JIS K 7136. Specifically, the haze of the adhesive resin composition of the present invention can be obtained by preparing a sample of the adhesive resin composition so as to have a thickness of 50 μm and measuring the haze.

[0105] Examples of methods for adjusting the haze of the adhesive resin composition of the present invention include a method of changing the type of resin having the imide skeleton in the repeating unit of the main chain or the type of compound having the (meth)acryloyl group to a type with high transparency, and a method of improving the compatibility between the components in the adhesive resin composition (for example, a method of using the monomer having the (meth)acryloyl group as the compound having the (meth)acryloyl group).

[0106] The adhesive resin composition of the present invention preferably has a lower limit of 350°C for the 5% weight loss temperature. By having an adhesive resin composition of the present invention with a 5% weight loss temperature of 350°C or higher, it can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the adhesive resin composition and the support during high-temperature processing can be more effectively suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be more effectively prevented. The adhesive resin composition of the present invention more preferably has a lower limit of 360°C, and even more preferably has a lower limit of 370°C for the 5% weight loss temperature. Furthermore, the upper limit of the 5% weight loss temperature of the adhesive resin composition of the present invention is not particularly limited, but is substantially about 600°C.

[0107] The adhesive resin composition of the present invention preferably has a lower limit of 230°C for the 1% weight loss temperature. By having an adhesive resin composition of the present invention with a 1% weight loss temperature of 230°C or higher, it can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the adhesive resin composition and the support during high-temperature processing can be more effectively suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be more effectively prevented. The adhesive resin composition of the present invention more preferably has a lower limit of 240°C, and even more preferably has a lower limit of 250°C for the 1% weight loss temperature. Furthermore, the upper limit of the 1% weight loss temperature of the adhesive resin composition of the present invention is not particularly limited, but is substantially about 600°C.

[0108] The adhesive resin composition of the present invention preferably has a lower limit of 400°C for the 10% weight loss temperature. By having an adhesive resin composition of the present invention have a 10% weight loss temperature of 400°C or higher, it can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the adhesive resin composition and the support during high-temperature processing can be more effectively suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be more effectively prevented. The adhesive resin composition of the present invention more preferably has a lower limit of 410°C, and even more preferably has a lower limit of 420°C for the 10% weight loss temperature. Furthermore, the upper limit of the 10% weight loss temperature of the adhesive resin composition of the present invention is not particularly limited, but is substantially about 600°C.

[0109] The weight loss temperature of the adhesive resin composition of the present invention can be measured as follows. That is, the adhesive resin composition is weighed into an aluminum pan, and the aluminum pan is set in the apparatus. Under a nitrogen atmosphere, the measurement sample is heated from 25°C to 500°C at a heating rate of 10°C / min using a thermogravimetric analyzer (STA7200 (manufactured by Hitachi High-Tech Science Corporation) or its equivalent), and the temperatures at which the weight of the adhesive resin composition decreases by 1%, 5%, or 10% are measured. When measuring the weight loss temperature of the adhesive resin composition, the adhesive resin composition may be cured or uncured. When the adhesive resin composition is a photocurable adhesive resin composition, the curing conditions for curing the adhesive resin composition are, for example, a wavelength of 405 nm and an irradiation intensity of 480 mW / cm. 2 For example, the adhesive resin composition can be cured by irradiating it with light for 60 seconds, and if the adhesive resin composition is a thermosetting type, it can be cured by heating it in an oven at 200°C for 30 minutes.

[0110] Examples of methods for adjusting the weight loss temperature of the adhesive resin composition of the present invention include a method of changing the type of resin having the imide skeleton in the repeating unit of the main chain or the type of compound having the (meth)acryloyl group to a type with higher heat resistance.

[0111] A temporary fixing material containing the adhesive resin composition of the present invention also constitutes the present invention. The form of the temporary fixing material of the present invention is not particularly limited, and may be in the form of a liquid, a paste, or the like, or may be in the form of having an adhesive layer containing the adhesive resin composition of the present invention. Among these, a temporary fixing material having an adhesive layer containing the resin composition of the present invention is preferred, and a tape-shaped temporary fixing material is more preferred.

[0112] In the case of the temporary fixing material having an adhesive layer, it may or may not have a substrate. If the temporary fixing material does not have a substrate, there is no need to select a substrate, and it can have a cheaper and simpler configuration. If the temporary fixing material has a substrate, it is easier to handle. In particular, it is preferable that the temporary fixing material has a substrate. Furthermore, when the temporary fixing material has a substrate, the adhesive layer may be provided on only one surface of the substrate, or on both surfaces of the substrate.

[0113] The adhesive layer preferably has a haze upper limit of 90%. When the adhesive layer has a haze of 90% or less, the details of the adherend bonded using the temporary fixing material of the present invention can be clearly recognized. The adhesive layer's haze upper limit is more preferably 80%, and even more preferably 50%. There is no particular lower limit to the haze of the adhesive layer, and 0% is the most preferable.

[0114] Methods for adjusting the haze of the adhesive layer include, for example, using an adhesive resin composition with low haze as the adhesive resin composition contained in the adhesive layer, and adjusting the thickness of the adhesive layer.

[0115] When the temporary fixing material has a base material, examples of the base material include resin sheets such as acrylic, olefin, polycarbonate, vinyl chloride, ABS resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, polyether ether ketone (PEEK), and polyamide (PA). Among these, resin sheets of polyimide and polyether ether ketone (PEEK), which have high heat resistance, are preferably used. Furthermore, sheets with a mesh structure, sheets with holes, glass, etc. can also be used.

[0116] The upper limit of the haze of the substrate is preferably 90%. When the haze of the substrate is 90% or less, the details of the adherend bonded using the temporary fixing material of the present invention can be clearly recognized. The upper limit of the haze of the substrate is more preferably 80%, and even more preferably 50%. There is no particular lower limit to the haze of the substrate, and 0% is the most preferable.

[0117] Examples of methods for adjusting the haze of the substrate include using a highly transparent substrate (e.g., glass), adjusting the thickness of the substrate, and adjusting the crystallinity of the resin constituting the substrate by annealing or the like.

[0118] The substrate preferably has a thickness of 5 μm at its lower limit and 100 μm at its upper limit. By ensuring that the thickness of the substrate is within the above range, the optical transparency and flexibility of the temporary fixing material can be improved. The substrate more preferably has a thickness of 10 μm at its lower limit and 100 μm at its upper limit.

[0119] The method for producing the temporary fixing material of the present invention is not particularly limited. For example, the adhesive resin composition obtained by the method described above is applied with an applicator or the like to the release-treated surface of a PET film that has been subjected to a release treatment on one side, and then dried to form an adhesive layer containing the adhesive resin composition. Thereafter, another PET film that has been subjected to a release treatment on one side is overlaid so that the release-treated surface faces the adhesive layer, thereby obtaining a temporary fixing material that does not have a substrate, as a temporary fixing material in a form that has an adhesive layer. Furthermore, after forming the adhesive layer by the above-mentioned method, a temporary fixing material having a substrate can be obtained by stacking the substrate and the adhesive layer so that they face each other.

[0120] The temporary fixing material of the present invention preferably has a lower limit of 230°C for the 1% weight loss temperature. By having a 1% weight loss temperature of 230°C or higher, the temporary fixing material of the present invention can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the material and the support can be further suppressed during high-temperature processing, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented. The temporary fixing material of the present invention more preferably has a lower limit of 240°C, and even more preferably has a lower limit of 250°C for the 1% weight loss temperature. Furthermore, the upper limit of the 1% weight loss temperature of the temporary fixing material of the present invention is not particularly limited, but is substantially about 600°C.

[0121] The temporary fixing material of the present invention preferably has a lower limit of 350°C for a 5% weight loss temperature. By having a 5% weight loss temperature of 350°C or higher, the temporary fixing material of the present invention can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the material and the support during high-temperature processing can be further suppressed, and enhanced adhesion to the adherend and adhesive residue upon peeling from the adherend can be further prevented. The temporary fixing material of the present invention more preferably has a lower limit of 360°C, and even more preferably has a lower limit of 370°C for a 5% weight loss temperature. Furthermore, although there is no particular upper limit to the 5% weight loss temperature of the temporary fixing material of the present invention, the upper limit is substantially about 600°C.

[0122] The temporary fixing material of the present invention preferably has a lower limit of 10% weight loss temperature of 400°C. When the temporary fixing material of the present invention has a 10% weight loss temperature of 400°C or higher, it can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the material and the support during high-temperature processing can be more effectively suppressed, and it can also be more effectively prevented from causing increased adhesion to the adherend or leaving adhesive residue when peeled from the adherend. A more preferable lower limit of the 10% weight loss temperature of the temporary fixing material of the present invention is 410°C, and an even more preferable lower limit is 420°C. Furthermore, the upper limit of the 10% weight loss temperature of the temporary fixing material of the present invention is not particularly limited, but is substantially about 600°C.

[0123] The weight loss temperature of the temporary fixing material of the present invention can be measured as follows. Specifically, the temporary fixing material is weighed into an aluminum pan, and the aluminum pan is placed in the apparatus. In a nitrogen atmosphere, the measurement sample is heated from 25°C at a heating rate of 10°C / min using a thermogravimetric measuring device (STA7200 (Hitachi High-Tech Science Corporation) or equivalent), and the temperatures at which the weight of the temporary fixing material decreases by 1%, 5%, or 10% are measured. When measuring the weight loss temperature of a temporary fixing material, the temporary fixing material may be cured or uncured. As the curing conditions when curing the temporary fixing material, the same method as used to measure the weight loss temperature of the adhesive resin composition described above can be used. Furthermore, in the case of a temporary fixing material having a substrate, the weight loss temperature of the temporary fixing material including the substrate is measured.

[0124] Examples of methods for adjusting the weight loss temperature of the temporary fixing material of the present invention include a method for adjusting the weight loss temperature of the adhesive resin composition contained in the adhesive layer, and a method for using a substrate with high heat resistance as the substrate.

[0125] When the temporary fixing material of the present invention has the adhesive layer, the preferred lower limit of the thickness of the entire temporary fixing material of the present invention is 5 μm, and the preferred upper limit is 550 μm. When the total thickness of the temporary fixing material is 5 μm or more, the entire temporary fixing material can initially have sufficient pressure-sensitive or heat-sensitive adhesive strength. When the total thickness of the temporary fixing material is 550 μm or less, the entire temporary fixing material can exhibit high flexibility, exhibit high conformability to an adherend having irregularities, and can be more easily peeled off. The more preferred lower limit of the total thickness of the temporary fixing material is 10 μm, and the more preferred upper limit is 400 μm, and the even more preferred lower limit is 20 μm, and the even more preferred upper limit is 300 μm, and the even more preferred lower limit is 30 μm, and the even more preferred upper limit is 250 μm, and the particularly preferred upper limit is 200 μm.

[0126] When the temporary fixing material of the present invention is in the form of a tape, the upper limit of the haze of the temporary fixing material of the present invention is preferably 90%. When the haze of the temporary fixing material of the present invention is 90% or less, the details of the adherend bonded using the temporary fixing material of the present invention can be more clearly recognized. The upper limit of the haze of the temporary fixing material of the present invention is more preferably 80%, and even more preferably 50%. Furthermore, there is no particular lower limit to the haze of the temporary fixing material of the present invention, and 0% is the most preferable.

[0127] Examples of methods for adjusting the haze of the temporary fixing material of the present invention include methods for adjusting the haze and thickness of each layer (for example, adhesive layer, substrate, etc.) that constitutes the temporary fixing material.

[0128] The adhesive resin composition and temporary fixing material of the present invention can prevent increased adhesion to an adherend after high-temperature heat treatment or the generation of adhesive residue upon peeling, and can be easily peeled off from an adherend. Therefore, the adhesive resin composition and temporary fixing material of the present invention can be suitably used for protecting and temporarily fixing an adherend that undergoes high-temperature heat treatment. The adhesive resin composition and temporary fixing material of the present invention allow the details of the adhered adherend to be clearly recognized, and can be easily peeled off from an adherend having unevenness, making them particularly suitable for use in the manufacture of electronic components such as semiconductors. Specifically, for example, during the processing of electronic components such as semiconductors, the adhesive resin composition or temporary fixing material of the present invention can be used to fix electronic components to a support plate or to protect electronic components by attaching the adhesive resin composition or temporary fixing material of the present invention to the electronic components, thereby facilitating handling of the electronic components and preventing damage. [Effects of the Invention]

[0129] According to the present invention, it is possible to provide an adhesive resin composition that allows the details of the adhered adherend to be clearly recognized and that can be easily peeled from an adherend having unevenness. Furthermore, according to the present invention, it is possible to provide a temporary fixing material containing the adhesive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0130] The following examples will explain the present invention in more detail, but the present invention is not limited to these examples.

[0131] (Synthesis of Polyimide Compound A) A 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer was charged with 250 mL of toluene. 39.9 g (0.075 mol) of dimer diamine (Croda, "Priamine 1075") and 39 g (0.075 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added, in that order. A Dean-Stark tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A brown solid toluene solution of a resin (polyimide compound A) having a structural unit represented by the following formula (6), no maleimide group, and an imide skeleton in the main chain repeating unit was obtained. The weight-average molecular weight of the obtained polyimide compound A was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M 6.0 × 150 mm (manufactured by Waters Corporation) as a column, and was found to be 90,000.

[0132] [ka]

[0133] (Synthesis of Polyimide Compound B) A 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer was charged with 250 mL of toluene. 39.9 g (0.075 mol) of dimer diamine (Croda, "Priamine 1075") and 23.3 g (0.075 mol) of 4,4'-oxydiphthalic anhydride were added, in that order. A Dean-Stark tube and a condenser were attached to the flask, and the resulting mixture was refluxed for 6 hours and cooled to room temperature. A brown solid toluene solution of a resin (polyimide compound B) having a structural unit represented by the following formula (7), no maleimide group, and an imide skeleton in the main chain repeating unit was obtained. The weight-average molecular weight of the obtained polyimide compound B was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) as a column, and was found to be 70,000.

[0134] [ka]

[0135] (Synthesis of polyimide compound C) A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 88 g (0.02 mol) of a silicone compound having amino groups at both ends (KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd., siloxane unit repeat number = 60, weight-average molecular weight 4400) was added. Furthermore, 16 g (0.03 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 26 g (0.05 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added, in this order. A Dean-Stark tube and condenser were attached to the flask, and the mixture was refluxed for 2 hours to obtain a toluene solution of polyimide compound C having the following formula (8-1), formula (8-2), and the structural units shown in Table 1. The weight-average molecular weight of the obtained polyimide compound C was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M (manufactured by Waters Corporation) as a column, and was found to be 100,000.

[0136] [ka]

[0137] [Table 1]

[0138] (Preparation of Acrylic Copolymer D) A reactor equipped with a thermometer, stirrer, and cooling tube was prepared. 94 parts by weight of 2-ethylhexyl acrylate as a (meth)acrylic acid alkyl ester, 6 parts by weight of hydroxyethyl methacrylate as a functional group-containing monomer, 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate were added to the reactor, and the reactor was heated to initiate reflux. Subsequently, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator was added to the reactor, and polymerization was initiated under reflux. Next, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added one hour and two hours after the start of polymerization, and 0.05 parts by weight of t-hexylperoxypivalate was added four hours after the start of polymerization to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% by mass and a weight-average molecular weight of 600,000 was obtained. 3.5 parts by mass of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound was added to 100 parts by mass of the resin solid content of the obtained ethyl acetate solution containing the functional group-containing (meth)acrylic polymer, and the mixture was reacted to obtain acrylic copolymer D. The weight average molecular weight of the obtained acrylic copolymer D was measured by gel permeation chromatography (GPC, apparatus name: Acquity APC system (manufactured by Waters Corporation)) using THF as an eluent and an HR-MB-M (trade name, manufactured by Waters Corporation) as a column, and was found to be 600,000.

[0139] Example 1 (1) Preparation of adhesive resin composition A toluene solution of an adhesive resin composition was prepared by adding 60 parts by mass of polyimide compound A, 40 parts by mass of ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 2 parts by mass of Omnirad 819 (manufactured by IGM Resins) as a photopolymerization initiator, and 1 part by mass of BYK-3500 (manufactured by BYK-Chemie) as a silicone compound to 150 mL of toluene and mixing them.

[0140] (2) Measurement of Haze of Adhesive Resin Composition A toluene solution of the adhesive resin composition obtained in the above "(1) Preparation of Adhesive Resin Composition" was applied to the release-treated surface of a 50 μm-thick PET film, one side of which had been treated for release, using a doctor knife to form a 50 μm-thick dry coating. The coating solution was dried by heating at 110°C for 5 minutes, and a test piece with the PET film was cut into a size of 50 mm wide and 50 mm long. The PET film was removed, and the haze of the adhesive resin composition was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., "NDH-2000") in accordance with JIS K 7136. The results are shown in Table 5.

[0141] (3) Measurement of the weight loss temperature of the adhesive resin composition A toluene solution of the adhesive resin composition obtained in the above "(1) Preparation of Adhesive Resin Composition" was applied to the release-treated surface of a 50 μm-thick PET film, one side of which had been treated for release, using a doctor knife to form a 50 μm-thick dry coating. The coating solution was then dried by heating at 110°C for 5 minutes, and the resulting adhesive resin composition was weighed into an aluminum pan, which was then placed in a thermogravimetric analyzer (STA7200, Hitachi High-Tech Science Corporation). The temperature was increased from 25°C to 500°C at a rate of 10°C / min under a nitrogen atmosphere, and the temperatures at which the adhesive resin composition lost 1%, 5%, and 10% of its weight were measured. The results are shown in Table 5.

[0142] (4) Manufacturing of temporary fixing materials The toluene solution of the adhesive resin composition obtained by the above-mentioned "(1) Preparation of adhesive resin composition" was applied to the release-treated surface of a 50 μm-thick PET film (release PET film) that had been subjected to one-side release treatment so that the dry film thickness was 50 μm with a doctor knife, and the coating solution was dried by heating at 110 ° C. for 5 minutes to form an adhesive layer (a). In addition, 70 parts by mass of polyimide compound A and 30 parts by mass of bismaleimide compound were added to 150 mL of toluene, and the mixed solution was applied to the release-treated surface of a 50 μm-thick PET film that had been subjected to one-side release treatment so that the dry film thickness was 20 μm with a doctor knife, and the coating solution was dried by heating at 110 ° C. for 5 minutes to form an adhesive layer (b). An adhesive layer (a) was laminated on one side of a polyether ether ketone (PEEK)-containing substrate, and an adhesive layer (b) was laminated on the other side to form a laminated, integrated temporary fixing material having adhesive layers on both sides of the substrate. In the section "(1) Evaluation of releasability against irregularities" described below, it is the adhesive layer (a) that is bonded to the irregularities of the silicon wafer and the releasability is evaluated. The bismaleimide compound is a bismaleimide compound represented by the following formula (9) (manufactured by Designer Molecules, "BMI-689").

[0143] [ka]

[0144] (5) Measurement of haze of adhesive layer (a) An adhesive layer (a) was formed in the same manner as in "(3) Production of temporary fixing material" above, and the haze of the adhesive layer (a) was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., "NDH-2000") in accordance with JIS K 7136. The results are shown in Table 5.

[0145] (6) Measurement of substrate haze The haze (%) of the substrate was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., "NDH-2000") in accordance with JIS K 7136. The results are shown in Table 5.

[0146] (7) Measurement of the temperature at which temporary fixing material loses weight The obtained temporary fixing material was weighed into an aluminum pan, and the aluminum pan was placed in a thermogravimetric measuring device (STA7200, Hitachi High-Tech Science Corporation). In a nitrogen atmosphere, the material was heated from 25°C to 500°C at a temperature increase rate of 10°C / min, and the temperatures at which the weight of the temporary fixing material decreased by 1%, 5%, and 10% were measured. The results are shown in Table 5. Note that the weight loss temperature was measured after peeling off the release PET film protecting the adhesive layer.

[0147] (Examples 2 to 13, Comparative Examples 1 and 2) Adhesive resin compositions and temporary fixing materials were produced and measured in the same manner as in Example 1, except that the compositions of the adhesive resin compositions prepared in the above-mentioned "(1) Preparation of adhesive resin compositions" were those shown in Tables 2 to 4, and the substrates used in the above-mentioned "(3) Production of temporary fixing materials" were those shown in Tables 2 to 4. The results are shown in Tables 5 to 7.

[0148] (Examples 14 to 18) An adhesive layer (a) having the composition shown in Table 3 was formed by the same method as in "(3) Production of temporary fixing material" described above, and a 50 μm thick PET film with one side subjected to release treatment was placed on top of it so that the release-treated surface faced the adhesive layer (a), thereby obtaining a temporary fixing material without a substrate. Except for this, measurements were carried out by the same method as in Example 1. The results are shown in Table 6. In Tables 2 to 4, the resin having a maleimide group and an imide skeleton in the repeating unit of the main chain is a bismaleimide compound represented by the following formula (10) (manufactured by Designer Molecules, "BMI-3000Gel").

[0149] [ka]

[0150] In formula (10), n is the number of repetitions.

[0151] <Evaluation> The temporary fixing materials obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Tables 5 to 7.

[0152] (1) Evaluation of peelability against unevenness The obtained temporary fixing material was cut into a circle with a diameter of 200 mm. Next, the release PET film on the adhesive layer (b) side was peeled off from the cut temporary fixing material, and it was attached to a glass substrate (manufactured by Mitrica, thickness 600 μm) using a vacuum laminator (manufactured by Takatori, "ATM-812M") at a temperature of 40 ° C. Next, the release PET film on the adhesive layer (a) side was peeled off, and using a vacuum bonding device (manufactured by Takatori, "GWSM-300M"), it was attached to the uneven surface (the surface having bumps) of a TEG wafer (manufactured by Waltz, "WALTS-TEG FBW40A-0001JY", wafer thickness 775 ± 25 μm, Cu pillar and Ag-containing Sn bump height 30 μm) cut into 5 cm square under conditions of a vacuum of 100 Pa, a temperature of 90 ° C, and a pressure of 0.5 MPa × 300 sec. A glass wafer laminate was produced. The glass side of the obtained glass wafer laminate was irradiated with a wavelength of 405 nm and an intensity of 480 mW / cm 2 After irradiating the sample with light for 60 seconds, the sample was placed in an oven heated to 250°C and left to stand in an environment of 250°C for 30 minutes, thereby carrying out a heat treatment to prepare a measurement sample. The obtained measurement sample was fixed to a peel tester ("VPA-2" manufactured by Kyowa Interface Science Co., Ltd.) equipped with a flat cross stage in accordance with JIS Z0237, and the flat cross stage was set so that the peel angle between the temporary fixing material and the wafer was 180°. While maintaining the peel angle at 180°, a peel test was performed at 40°C and a peel speed of 300 mm / min, and the peel force (N / inch) was measured. Furthermore, the surface of the TEG wafer from which the temporary fixing material had been peeled was observed, and the releasability of the temporary fixing material relative to the unevenness was evaluated according to the following criteria. · ◯: The peeling force against the uneven wafer was less than 10 N / inch, and the base material did not separate from the adhesive layer when the temporary fixing material was peeled off, and no residue of the temporary fixing material remained on the wafer surface. · △: The peel force against the uneven wafer was 10 N / inch or more and less than 15 N / inch, and the base material did not separate from the adhesive layer when the temporary fixing material was peeled off, and no temporary fixing material residue was found on the wafer surface. ×: At least one of the following was satisfied: the peel force against the uneven wafer was 15 N / inch or more, the substrate separated from the adhesive layer when the temporary fixing material was peeled off, and there was residue of the temporary fixing material on the wafer surface. In addition, if the substrate separated from the adhesive layer when the temporary fixing material was peeled off, or if residue of the temporary fixing material was generated on the wafer surface, the 180° peel force for the uneven wafer at 40°C in Tables 2 to 4 was recorded as "-".

[0153] (2) Recognition evaluation The obtained temporary fixing material was cut into a test piece 50 mm wide and 50 mm long, and the haze (%) of the temporary fixing material was measured using a haze meter ("NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136. Note that the haze of the temporary fixing material was measured after peeling off the release PET film that protects the adhesive layer. Based on the haze of the obtained temporary fixing material, the recognizability was evaluated according to the following criteria. ·Good: The haze of the temporary fixing material was 50% or less. · △: The haze of the temporary fixing material was greater than 50% and less than 90%. · ×: The haze of the temporary fixing material was greater than 90%.

[0154] The types of substrates shown in Tables 2 to 4 are as follows. PEEK-containing substrate: EXPEEK (Kurabo) Polyamide-containing base material: Uniamide EX-25 (manufactured by Unitika Ltd.)

[0155] [Table 2]

[0156] [Table 3]

[0157] [Table 4]

[0158] [Table 5]

[0159] [Table 6]

[0160] [Table 7] [Industrial Applicability]

[0161] According to the present invention, it is possible to provide an adhesive resin composition that allows the details of the adhered adherend to be clearly recognized and that can be easily peeled from an adherend having unevenness. Furthermore, according to the present invention, it is possible to provide a temporary fixing material containing the adhesive resin composition.

Claims

1. The composition contains a resin having an imide skeleton in the repeating unit of the main chain and a compound having a (meth)acryloyl group, the resin having an imide skeleton in a repeating unit of the main chain does not have a (meth)acryloyl group, The compound having a (meth)acryloyl group has a molecular weight of 200,000 or less. An adhesive resin composition characterized by:

2. 2. The adhesive resin composition according to claim 1, wherein the adhesive resin composition has a haze of 90% or less.

3. 3. The adhesive resin composition according to claim 1, wherein the resin having an imide skeleton in a repeating unit of the main chain includes a resin having no maleimide group and having an imide skeleton in a repeating unit of the main chain.

4. 4. The adhesive resin composition according to claim 3, wherein the resin having no maleimide group and having an imide skeleton in the repeating unit of the main chain has an aliphatic group derived from dimer diamine.

5. 3. The adhesive resin composition according to claim 1, further comprising a compound having a maleimide group.

6. 6. The adhesive resin composition according to claim 5, comprising at least one selected from the group consisting of bismaleimide compounds and resins having a maleimide group and an imide skeleton in a repeating unit of the main chain.

7. 3. The adhesive resin composition according to claim 1, wherein the compound having a (meth)acryloyl group includes a monomer having a (meth)acryloyl group.

8. 3. The adhesive resin composition according to claim 1, wherein the compound having a (meth)acryloyl group does not have an imide bond.

9. 3. The adhesive resin composition according to claim 1, wherein the compound having a (meth)acryloyl group has two or more (meth)acryloyl groups in one molecule.

10. 3. The adhesive resin composition according to claim 1, wherein the compound having a (meth)acryloyl group has a molecular weight of 50,000 or less.

11. 3. An adhesive resin composition according to claim 1, wherein the content of the compound having a (meth)acryloyl group is 2 parts by mass or more and 70 parts by mass or less relative to 100 parts by mass of the resin having the imide skeleton in the main chain repeating unit.

12. 3. The adhesive resin composition according to claim 1, wherein the adhesive resin composition is photocurable or thermosetting.

13. 3. The adhesive resin composition according to claim 1, wherein the adhesive resin composition has a 5% weight loss temperature of 350[deg.] C. or higher.

14. A temporary fixing material comprising the adhesive resin composition according to claim 1 or 2.

15. The temporary fixing material according to claim 14, which has an adhesive layer containing the adhesive resin composition.

16. The temporary fixing material according to claim 15, further comprising a substrate.

17. The temporary fixing material according to claim 16, wherein the haze of the substrate is 90% or less.

18. The temporary fixing material according to claim 15, wherein the temporary fixing material is in the form of a tape.

19. The temporary fixing material according to claim 18, wherein the temporary fixing material has a haze of 90% or less.

20. The temporary fixing material according to claim 14, which is used for producing electronic parts.

Images