Curable resin composition, temporary fixing material, and method for manufacturing electronic components

Abstract

The present invention provides a curable resin composition that can suppress the occurrence of voids and lifting between an adherend and a support, even when the adherend and support are subjected to a high-temperature processing treatment at 300°C or higher while they are fixed together, and that can be easily peeled off after the high-temperature processing treatment. The present invention also provides a temporary fixing material having an adhesive layer made of the curable resin composition, and a method for producing an electronic component using the temporary fixing material. The curable resin composition includes a reactive compound (1) having a maleimide group and a resin (2) having an imide skeleton in the repeating unit of the main chain.

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition that can suppress the occurrence of voids and lifting between an adherend and a support, even when the adherend and support are subjected to a high-temperature processing treatment at 300°C or higher while they are fixed together, and that can be easily peeled off after the high-temperature processing treatment. The present invention also relates to a temporary fixing material having an adhesive layer made of the curable resin composition, and a method for producing electronic components using the temporary fixing material. [Background technology]

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

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

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

[0005] In recent years, with the increasing performance of electronic components, various processing steps have been carried out on electronic components. For example, in the process of forming a metal thin film on the surface of an electronic component by sputtering, a metal thin film with superior conductivity can be formed by performing the processing at a high temperature of about 300 to 350°C. However, when electronic components protected using conventional pressure-sensitive adhesive compositions or pressure-sensitive adhesive tapes are subjected to high-temperature processing at 300°C or higher, voids or lifting may occur between the electronic components and the support on which they are fixed during the high-temperature processing, and increased adhesion may occur, resulting in insufficient reduction in adhesive strength upon peeling or the generation of adhesive residue. In particular, in recent years, polyimide resins have come to be used in many electronic components as materials with high heat resistance, and processes have been carried out in which adherends made of polyimide resins are fixed to supports made of inorganic materials such as glass and then subjected to various processes. When an adherend made of polyimide resin is subjected to high-temperature processing at 300°C or higher, adhesion tends to be enhanced more than when the adherend is made of an inorganic material. In such cases, pressure-sensitive adhesive compositions and pressure-sensitive adhesive tapes used to protect polyimide adherends are required to suppress adhesion enhancement with polyimide resin adherends, while also suppressing the occurrence of voids and lifting between the adherend and the support.

[0006] An object of the present invention is to provide a curable resin composition that can suppress the occurrence of voids and lifting between an adherend and a support, even when the adherend and support are subjected to a high-temperature processing treatment at 300°C or higher while they are fixed together, and that can be easily peeled off after the high-temperature processing treatment. Another object of the present invention is to provide a temporary fixing material having an adhesive layer made of the curable resin composition, and a method for producing electronic components using the temporary fixing material. [Means for solving the problem]

[0007] The present invention is a curable resin composition comprising a reactive compound (1) having a maleimide group and a resin (2) having an imide skeleton in the repeating unit of the main chain. The present invention will be described in detail below.

[0008] The present inventors have investigated a curable resin composition containing a reactive compound (1) having a maleimide group and a resin (2) having an imide skeleton in the repeating unit of the main chain. The present inventors have found that such a curable resin composition can suppress the occurrence of voids and lifting between an adherend, particularly an adherend made of a polyimide resin, and a support, even when the adherend and a support are subjected to a high-temperature processing treatment at 300°C or higher while the adherend and the support are fixed together, and that the adherend and the support can be easily peeled off after the high-temperature processing treatment, thereby completing the present invention.

[0009] The curable resin composition of the present invention contains a reactive compound (1) having a maleimide group and a resin (2) having an imide skeleton in the repeating unit of the main chain. By including the above-mentioned reactive compound (1) having a maleimide group, the curable resin composition of the present invention is polymerized and crosslinked uniformly and quickly throughout when heated or irradiated with light, and the adhesive strength is significantly reduced due to an increase in elastic modulus, thereby preventing increased adhesion to the adherend and preventing adhesive residue from being left behind when peeled from the adherend. Furthermore, resin (2) 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 300° C. or higher. Therefore, by including resin (2) having the imide skeleton in the repeating unit of the main chain, the curable resin composition of the present invention can suppress the occurrence of voids and lifting between the curable 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.

[0010] In the reactive compound (1) having a maleimide group, the maleimide group may be substituted or unsubstituted. The reactive compound (1) having a maleimide group is not particularly limited, but is preferably a bismaleimide compound (1-I) or a compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain. These reactive compounds (1) having a maleimide group may be used alone or in combination of two or more.

[0011] The bismaleimide compound (1-I) is a compound having two maleimide groups. The molecular weight of the bismaleimide compound (1-I) is not particularly limited, but is preferably 5,000 or less, and more preferably 2,000 or less. The bismaleimide compound (1-I) is preferably a compound having two maleimide groups and an aliphatic 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. By using an aliphatic diamine compound as the diamine compound, an adhesive layer formed using the curable resin composition can exhibit high flexibility, exhibit high conformability to an adherend having irregularities, and can be more easily peeled off.

[0012] Among the above aliphatic diamine compounds, dimer diamine is preferred from the viewpoint of increasing flexibility and increasing the compatibility of the bismaleimide compound (1-I) with solvents and other components, thereby facilitating the formation of an adhesive layer. The dimer diamine is a diamine compound obtained by reducing and amminating cyclic and acyclic dimer acids obtained as dimers of unsaturated fatty acids, and examples thereof include linear, monocyclic, and polycyclic dimer diamines. The dimer diamine may contain a carbon-carbon unsaturated double bond or may be a hydrogenated product to which hydrogen has been added.

[0013] More specifically, the aliphatic group derived from the dimer diamine is preferably at least one selected from the group consisting of a group represented by the following general formula (4-1), a group represented by the following general formula (4-2), a group represented by the following general formula (4-3), and a group represented by the following general formula (4-4). Among these, the group represented by the following general formula (4-2) is more preferred.

[0014] [ka]

[0015] In general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 each independently represents a linear or branched hydrocarbon group. In addition, * represents a bond. The bond * may be bonded directly to the maleimide group or may be bonded via another group.

[0016] In the above general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 The hydrocarbon group represented by R is not particularly limited, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 13 and R 14 , R 15 and R 16 , R 17 and R 18 , and R 19 and R 20The total number of carbon atoms is preferably 7 or more and 50 or less. When the total number of carbon atoms is within the above range, the adhesive layer formed using the curable resin composition can exhibit higher flexibility, and the compatibility of the bismaleimide compound (1-I) with solvents and other components is further increased. The total number of carbon atoms is more preferably 9 or more, even more preferably 12 or more, and even more preferably 14 or more. The total number of carbon atoms is more preferably 35 or less, even more preferably 25 or less, and even more preferably 18 or less.

[0017] The optical isomerism of the group represented by the general formula (4-1), the group represented by the general formula (4-2), the group represented by the general formula (4-3), and the group represented by the general formula (4-4) is not particularly limited, and includes any optical isomerism.

[0018] By including the compound (1-II) having the maleimide group and an imide skeleton in the repeating unit of the main chain, the curable resin composition can exhibit higher heat resistance, i.e., the occurrence of voids and lifting between the composition and the support during high-temperature processing can be further suppressed, and increased adhesion to the adherend and the occurrence of adhesive residue upon peeling from the adherend can be further prevented. The compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain preferably has a maleimide group functional group equivalent (weight average molecular weight / number of maleimide groups) of 4000 or less. When the functional group equivalent is 4000 or less, the curable resin composition can exhibit higher heat resistance. This is thought to be because the presence of maleimide groups at a certain density or higher in the molecule of the compound shortens the inter-crosslink distance, thereby further suppressing adhesion enhancement. The functional group equivalent is more preferably 3000 or less, and even more preferably 2000 or less. There is no particular restriction on the lower limit of the functional group equivalent, but the lower limit is substantially about 600.

[0019] The compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of its main chain preferably has a smaller weight-average molecular weight (Mw) than the resin (2) having an imide skeleton in the repeating unit of its main chain. More specifically, the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of its main chain preferably has a weight-average molecular weight (Mw) of 1,000 or more and less than 20,000. A weight-average molecular weight of 1,000 or more facilitates film formation of the curable resin composition, and the resulting adhesive layer exhibits a certain degree of flexibility, thereby exhibiting high conformability to an adherend having irregularities and facilitating peeling. A weight-average molecular weight of less than 20,000 enhances the solubility of the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of its main chain in a solvent. The weight-average molecular weight is more preferably 2,000 or more and less than 10,000. The weight-average molecular weight is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). More specifically, it can be measured using an APC system (Waters or equivalent) under the following conditions: THF mobile phase, flow rate 1.0 mL / min, column temperature 40°C, sample concentration 0.2 wt%, and RI-PDA detector. A column such as HR-MB-M 6.0 x 150 mm (Waters or equivalent) can be used.

[0020] In the compound (1-II) having the maleimide group and an imide skeleton in the repeating unit of the main chain, the maleimide group may be located either on a side chain or at a terminal, but preferably at both terminals, and more preferably at both terminals and also on a side chain. The maleimide groups at both terminals of the compound (1-II) having the maleimide group and an imide skeleton in the repeating unit of the main chain are highly reactive, allowing the curable resin composition to be cured more sufficiently by heating or light irradiation. As a result, it is possible to more effectively prevent increased adhesion to the adherend and the generation of adhesive residue when peeled from the adherend. Furthermore, by having a maleimide group on the side chain of the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain, the curable resin composition can exhibit higher heat resistance. This is thought to be because the shorter inter-crosslink distance further suppresses adhesion enhancement. Furthermore, by having a maleimide group on the side chain of the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain, it is 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 curable resin composition to have sufficient pressure-sensitive or heat-sensitive adhesive strength initially, while further suppressing the occurrence of voids and lifting during high-temperature processing. It also further prevents adhesion enhancement to the adherend and adhesive residue upon peeling from the adherend.

[0021] Specific examples of the compound (1-II) having the maleimide group and an imide skeleton in the repeating unit of the main chain include the following compounds: That is, a compound having a constitutional unit represented by the following general formula (1a), a constitutional unit represented by the following general formula (1b), and a constitutional unit represented by the following general formula (1c) (where s>0, t≧0, u≧0), and both ends of which are each X 1 and X 2 Compound (1-ii) represented by the following formula (1-ii) is exemplified.

[0022] [ka]

[0023] In general formulas (1a) to (1c), P 1 , P 2 and P 3 each independently represents an aromatic group; 1 represents a substituted or unsubstituted linear, branched or cyclic aliphatic group; Q 2 represents a group having a substituted or unsubstituted aromatic structure, and R represents a substituted or unsubstituted branched aliphatic group or aromatic group. 1 , X 2 and X 3At least one selected from the group consisting of represents a maleimide group-containing group.

[0024] In the above general formulas (1a) to (1c), P 1 , P 2 and P 3 is preferably an aromatic group having 5 to 50 carbon atoms. 1 , P 2 and P 3 is an aromatic group having 5 to 50 carbon atoms, the curable resin composition can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the support and the 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.

[0025] In the above general formula (1a), Q 1 is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. 1 is a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, the adhesive layer formed using the curable resin composition can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off. Also, Q 1 is preferably an aliphatic group derived from a diamine compound. The aliphatic group derived from the diamine compound may be the same as the aliphatic group derived from the diamine compound in the bismaleimide compound (1-I) described above. Among them, from the viewpoint of enhancing flexibility and increasing the compatibility of the compound (1-II) having the maleimide group and an imide skeleton in the main chain repeating unit with solvents and other components, thereby facilitating the formation of an adhesive layer, Q is preferably 1 is preferably an aliphatic group derived from dimer diamine. The aliphatic group derived from dimer diamine may be the same as the aliphatic group derived from dimer diamine in the bismaleimide compound (1-I) described above.

[0026] In the above general formula (1b), 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 of 5 to 50 carbon atoms, the curable resin composition can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the support and the composition during high-temperature processing can be further suppressed, and increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend can be further prevented.

[0027] In the above general formula (1c), R is preferably a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms. When R is a substituted or unsubstituted branched aliphatic or aromatic group having 2 to 100 carbon atoms, the adhesive layer formed using the curable resin composition can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off.

[0028] In the general formula (1c), R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or the aromatic ether group in R is X 3 It is preferred that the compound is bonded to Here, "aromatic ester group" means a group in which an ester group is directly bonded to an aromatic ring, and "aromatic ether group" means a group in which an ether group is directly bonded to an aromatic ring. By making the moiety bonded to the ester group or ether group an aromatic group in this way, the curable resin composition can exhibit higher heat resistance. That is, the occurrence of voids and lifting during high-temperature processing can be further suppressed, and increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend can be further prevented. On the other hand, X 3 is bonded to R via an aromatic ester group or an aromatic ether group, whereby X 3 Since the double bond in the hydroxyl group is not conjugated with R, polymerization and crosslinking are not hindered when heated or irradiated with light.

[0029] In the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain, the maleimide group-containing group is X 1 , X 2 and X 3 At least one selected from the group consisting of 3 is preferably a maleimide group-containing group. 3 is a maleimide group-containing group, the curable resin composition can exhibit higher heat resistance, that is, the occurrence of voids and lifting during high-temperature processing can be further suppressed, and enhanced adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend can be further prevented. Above X 1 , X 2 and X 3 When either of the above is a functional group other than a maleimide group-containing group, the functional group other than a maleimide group-containing group may each independently be, for example, an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride, an amine compound, etc. Specific examples include an acid anhydride or a diamine compound that is a raw material for compound (1-II) having the maleimide group and an imide skeleton in the main chain repeating unit, and is unreacted at one end. Furthermore, the functional group may be, for example, a group containing a functional group having a double bond, such as a citraconic group, a vinyl ether group, an allyl group, or a (meth)acrylic group.

[0030] In the general formulas (1a) to (1c), s, t, and u correspond to the respective contents (mol %) of the structural unit represented by the general formula (1a), the structural unit represented by the general formula (1b), and the structural unit represented by the general formula (1c) in the compound (1-II) having the maleimide group and an imide skeleton in the repeating unit of the main chain. The content (s) of the structural unit represented by the general formula (1a) is greater than 0 mol%, preferably 30 mol% or more, more preferably 50 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less. The content (t) of the structural unit represented by the general formula (1b) is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. The content (u) of the structural unit represented by the general formula (1c) is 0 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. When the content of each structural unit in the general formulas (1a) to (1c) is within the above range, the curable resin composition can further suppress the occurrence of voids and lifting between the curable resin composition and the support during high-temperature processing, and can be more easily peeled from the adherend. The structural unit represented by the general formula (1a), the structural unit represented by the general formula (1b), and the structural unit represented by the general formula (1c) may 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.

[0031] The method for producing the compound (1-II) having the maleimide group and an imide skeleton in the repeating unit of the main chain is not particularly limited. For example, it can be obtained by reacting a diamine compound with an aromatic acid anhydride to prepare an imide compound, and then reacting the functional group of the imide compound with a compound having a functional group reactive with the functional group and a maleimide group-containing group (hereinafter referred to as a functional group-containing maleimide compound). Alternatively, it can 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.

[0032] 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 layer formed using the curable resin composition can exhibit high flexibility, can exhibit high conformability to an adherend having unevenness, and can be more easily peeled off. By using an aromatic diamine compound as the diamine compound, the heat resistance of the curable resin composition can be further improved. Furthermore, by using a diamine compound having a functional group as the diamine compound and reacting the functional group with the functional group-containing maleimide compound, a compound (1-II) having a maleimide group in the side chain can be produced. These aliphatic diamine compounds, aromatic diamine compounds and diamine compounds having a functional group may be used alone or in combination of two or more kinds.

[0033] 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.

[0034] Examples of the aromatic diamine compound include 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, and 1,5 -Diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-cumenediamine, 1,3-bisaminomethylbenzene, 1,3-bisaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)ethane )methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-ethyldiaminofluorene, 2,3-diaminonaphthalene, 2,3-diaminophenol, -5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenyl sulfone, 3,3'-diaminophenyl sulfone, 2,2-bis(4,(4-aminophenoxy)phenyl)sulfone, 2,2-bis(4-(3-aminophenoxy)phenyl)sulfone (oxy)phenyl) sulfone, 4,4'-oxydianiline, 4,4'-diaminodiphenyl sulfide, 3,4'-oxydianiline, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, Bisaniline M, Bisaniline P, 9,9-bis(4-aminophenyl)fluorene, o-tolidine sulfone, methylenebis(anthranilic acid), 1,3-bis(4-aminophenoxy)-2,Examples of suitable alkyl ethers include 2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzanilide, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyalkylenediamines (e.g., Huntsman's Jeffamine D-230, D400, D-2000, and D-4000), 1,3-cyclohexanebis(methylamine), m-xylylenediamine, and p-xylylenediamine.

[0035] Among these, as described above, aliphatic diamine compounds are preferred, and dimer diamine is more preferred from the viewpoint of increasing flexibility and increasing the compatibility of the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of its main chain with solvents and other components, thereby facilitating the formation of an adhesive layer.

[0036] Examples of the diamine compound having a functional group include a diamine compound having a hydroxyl group, a diamine compound having a carboxyl group, and a diamine compound having a halogen group. Examples of the diamine compound having a hydroxyl group include 1,3-diamino-2-propanol, 2,4-diaminophenoxyethanol, 3,5-diaminophenoxyethanol, 2,4-diaminophenol, 3,5-diaminophenol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol dihydrochloride, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. Examples of the diamine compound having a carboxyl group include 3,5-diaminobenzoic acid. Examples of the diamine compound having a halogen group include 2,4-diaminochlorobenzene.

[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, 1,1-bis(3,4-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2',3'-benzophenonetetracarboxylic acid, 2,3,3',4'-benzophenonetetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid Examples of suitable carboxylic acids include carboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4,3',4'-biphenyltetracarboxylic acid, 2,3,2',3'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, and 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid).

[0038] The functional group-containing maleimide compound is selected and used 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, a maleimide compound having a carboxyl group can be used. Examples of the maleimide compound having a carboxyl group include maleimide acetate, maleimidopropionic acid, maleimidobutyric acid, maleimidohexanoic acid, trans-4-(N-maleimidomethyl)cyclohexane-1-carboxylic acid, and 19-maleimido-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid.

[0039] The content of the reactive compound (1) having a maleimide group is not particularly limited, but a preferred lower limit is 20 parts by weight and a preferred upper limit is 80 parts by weight, based on 100 parts by weight of the total of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in the main chain repeating unit. When the content of the reactive compound (1) having a maleimide group is within this range, the curable resin composition can be more easily peeled from an adherend. From the viewpoint of further improving peelability, a more preferred lower limit of the content of the reactive compound (1) having a maleimide group is 30 parts by weight and a more preferred upper limit is 70 parts by weight.

[0040] The resin (2) having an imide skeleton in its main chain repeating unit is not particularly limited as long as it has an imide skeleton in its main chain repeating unit. However, it preferably has a maleimide group and a weight-average molecular weight (Mw) greater than that of the compound (1-II) having an imide skeleton in its main chain repeating unit. More specifically, the resin (2) having an imide skeleton in its main chain repeating unit preferably has a weight-average molecular weight (Mw) of 20,000 or more. By having the resin (2) having an imide skeleton in its main chain repeating unit have a weight-average molecular weight of 20,000 or more, the curable resin composition can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the resin 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 weight-average molecular weight of the resin (2) having an imide skeleton in its main chain repeating unit is more preferably 50,000 or more. The upper limit of the weight average molecular weight of the resin (2) having the imide skeleton in the main chain repeating unit is not particularly limited, but from the viewpoint of solubility in solvents, the upper limit is preferably 150,000, and more preferably 100,000.

[0041] The resin (2) having an imide skeleton in the repeating unit of the main chain is preferably a resin (2-I) having no maleimide group and having an imide skeleton in the repeating unit of the main chain. Specific examples of the resin (2-I) that does not have a maleimide group and has an imide skeleton in the repeating unit of the main chain include a resin having a constitutional unit represented by the following general formula (1d) and a constitutional unit represented by the following general formula (1e) (where s>0, t≧0), and both ends of which are each X 4 and X 5 Examples of the resin include resin (2-i) represented by the following formula:

[0042] [ka]

[0043] In general formulas (1d) to (1e), P 4 and P 5each independently represents an aromatic group; 3 represents a substituted or unsubstituted linear, branched or cyclic aliphatic group; Q 4 represents a group having a substituted or unsubstituted aromatic structure. 4 and X 5 represents a group that does not contain a maleimide group.

[0044] In the above general formulas (1d) to (1e), P 4 and P 5 is preferably an aromatic group having 5 to 50 carbon atoms. 4 and P 5 is an aromatic group having 5 to 50 carbon atoms, the curable resin composition can exhibit higher heat resistance, that is, the occurrence of voids and lifting during high-temperature processing can be further suppressed, and increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend can be further prevented.

[0045] In the above general formula (1d), Q 3 is preferably a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms. 3 is a substituted or unsubstituted linear, branched or cyclic aliphatic group having 2 to 100 carbon atoms, the adhesive layer formed using the curable resin composition can exhibit high flexibility, can exhibit high conformability to an adherend having irregularities, and can be more easily peeled off. Also, Q 3 is preferably an aliphatic group derived from a diamine compound. The aliphatic group derived from the diamine compound may be the same as the aliphatic group derived from the diamine compound in the bismaleimide compound (1-I) and the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain as described above. Among these, from the viewpoint of enhancing flexibility and increasing the compatibility of the resin (2-I) having no maleimide group and an imide skeleton in the repeating unit of the main chain with solvents and other components, thereby facilitating the formation of an adhesive layer, Q 3is preferably an aliphatic group derived from dimer diamine. The aliphatic group derived from dimer diamine may be the same as the aliphatic group derived from dimer diamine in the above-described bismaleimide compound (1-I) and compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain. That is, in the curable resin composition of the present invention, it is preferable that at least one selected from the group consisting of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in the repeating unit of the main chain has an aliphatic group derived from dimer diamine.

[0046] In the above general formula (1e), Q 4 is preferably a substituted or unsubstituted group having an aromatic structure having 5 to 50 carbon atoms. 4 is a substituted or unsubstituted group having an aromatic structure of 5 to 50 carbon atoms, the curable resin composition can exhibit higher heat resistance. That is, the occurrence of voids and lifting during high-temperature processing can be further suppressed, and increased adhesion to the adherend and the occurrence of adhesive residue when peeled from the adherend can be further prevented.

[0047] Above X 4 and X 5 Examples of the group not containing a maleimide group represented by the formula (2) include, independently, an aliphatic group, an alicyclic group, an aromatic group, an acid anhydride, an amine compound, etc. Specific examples include an unreacted end of an acid anhydride or diamine compound that is a raw material for the resin (2-I) that does not contain a maleimide group and has an imide skeleton in the repeating unit of its main chain. Furthermore, the group may be a group containing a functional group with a double bond, such as a citraconic group, a vinyl ether group, an allyl group, or a (meth)acrylic group.

[0048] In the general formulas (1d) to (1e) above, s and t correspond to the respective contents (mol %) of the structural unit represented by the general formula (1d) and the structural unit represented by the general formula (1e) above in the resin (2-I) that does not have a maleimide group and has an imide skeleton in the repeating unit of the main chain. The content (s) of the structural unit represented by the general formula (1d) is greater than 0 mol%, preferably 30 mol% or more, more preferably 50 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less. The content (t) of the structural unit represented by the general formula (1e) is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. When the content of each structural unit in the general formulas (1d) to (1e) is within the above range, the curable resin composition can further suppress the occurrence of voids and lifting between the support and the curable resin composition during high-temperature processing, and can be more easily peeled from the adherend. The structural unit represented by the general formula (1d) and the structural unit represented by the general formula (1e) 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.

[0049] The method for producing the resin (2) having an imide skeleton in the repeating unit of the main chain is not particularly limited, and it can be obtained, for example, by reacting a diamine compound with an aromatic acid anhydride. The diamine compound and the aromatic acid anhydride may be the same as the diamine compound and the aromatic acid anhydride in the compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain.

[0050] The content of the resin (2) having an imide skeleton in the repeating unit of the main chain is not particularly limited, but a preferred lower limit is 20 parts by weight and a preferred upper limit is 80 parts by weight, based on 100 parts by weight of the total of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in the repeating unit of the main chain. When the content of the resin (2) having an imide skeleton in the repeating unit of the main chain is within this range, the curable resin composition can further suppress the occurrence of voids and lifting during high-temperature processing and can be more easily peeled from an adherend. From the viewpoints of further suppressing the occurrence of voids and lifting and further improving peelability, a more preferred lower limit of the content of the resin (2) having an imide skeleton in the repeating unit of the main chain is 30 parts by weight and a more preferred upper limit is 70 parts by weight.

[0051] The curable resin composition of the present invention preferably further contains a silicone compound or a fluorine compound. The silicone compound and fluorine compound have excellent heat resistance, and therefore prevent the curable resin composition from burning even after high-temperature processing at 300°C or higher, and bleed out to the interface with the adherend during peeling, making peeling easier. The silicone compound is not particularly limited, and examples thereof include silicone oil, silicone diacrylate, silicone graft copolymer, etc. The fluorine compound is not particularly limited, and examples thereof include hydrocarbon compounds having fluorine atoms.

[0052] The silicone compound or fluorine compound preferably has a functional group that can crosslink with the reactive compound (1) having a maleimide group or the resin (2) having an imide skeleton in the repeating unit of the main chain, and more preferably has a functional group that can crosslink with a maleimide group. The silicone compound or fluorine compound has a functional group capable of crosslinking with a maleimide group, and upon heating or light irradiation, the silicone compound or fluorine compound chemically reacts with the reactive compound (1) having the maleimide group and is incorporated into the reactive compound (1) having the maleimide group. This prevents the silicone compound or fluorine compound from adhering to and contaminating the adherend. The functional group capable of crosslinking with the maleimide group is not particularly limited, and examples thereof include radically polymerizable unsaturated bonds (e.g., vinyl groups, (meth)acryloyl groups, and optionally substituted maleimide groups). Among these, silicone compounds having a functional group capable of crosslinking with a maleimide group are preferred from the viewpoint of being environmentally friendly and easy to dispose of.

[0053] The silicone compound having a functional group capable of crosslinking with a maleimide group is preferably a silicone compound having a siloxane skeleton in the main chain and a functional group having a double bond in the side chain or at the end. The silicone compound having a siloxane skeleton in its main chain and a functional group with a double bond in its side chain or at its terminal is not particularly limited, but preferably contains at least one selected from the group consisting of a silicone compound represented by the following general formula (I), a silicone compound represented by the following general formula (II), and a silicone compound represented by the following general formula (III): These silicone compounds have particularly high heat resistance and are highly polar, so they easily bleed out from the curable resin composition.

[0054] [ka]

[0055] In the above general formulae (I), (II) and (III), X and Y each independently represent an integer of 0 to 1200, and R represents a functional group having a double bond.

[0056] In the above general formulas (I), (II), and (III), examples of the functional group having a double bond represented by R include an optionally substituted maleimide group, a citraconic group, a vinyl ether group, an allyl group, and a (meth)acrylic group. Among these, an optionally substituted maleimide group is preferred because it provides higher heat resistance. In addition, when there are multiple Rs in the above general formulas (I), (II), and (III), the multiple Rs may be the same or different.

[0057] Among the silicone compounds represented by the general formula (I), general formula (II), and general formula (III), commercially available examples include EBECRYL350 and EBECRYL1360 (both manufactured by Daicel-Cytec Co., Ltd.), etc. Further examples include BYK-UV3500 (manufactured by BYK-Chemie Co., Ltd.) and TEGO RAD2250 (manufactured by Evonik Co., Ltd.) (in both cases, R is an acrylic group).

[0058] The content of the silicone compound or fluorine compound is not particularly limited, but a preferred lower limit is 0.1 parts by weight and a preferred upper limit is 20 parts by weight relative to 100 parts by weight of the total of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in the main chain repeating unit. When the content of the silicone compound or fluorine compound is within this range, the curable resin composition can exhibit excellent releasability without contaminating the adherend. From the viewpoint of further improving releasability while suppressing contamination, a more preferred lower limit of the content of the silicone compound or fluorine compound is 0.3 parts by weight and a more preferred upper limit is 10 parts by weight. Furthermore, since the curable resin composition of the present invention has excellent heat resistance, it can exhibit sufficient effects even when 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.

[0059] The curable resin composition of the present invention preferably further contains a polymerization initiator. The polymerization initiator is not particularly limited and may be a thermal polymerization initiator or a photopolymerization initiator, but a photopolymerization initiator is preferred.

[0060] 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 preferably contains a photopolymerization initiator having a molar absorption coefficient of 1 or greater at 405 nm, since this photopolymerization initiator is unlikely to overlap with the absorption wavelengths of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in the main chain repeating unit, and is sufficiently activated when the curable resin composition is irradiated with light. The photopolymerization initiator more preferably contains a photopolymerization initiator having a molar absorption coefficient of 200 or greater at 405 nm, and even more preferably contains a photopolymerization initiator having a molar absorption coefficient of 350 or greater at 405 nm. The upper limit of the molar absorption coefficient at 405 nm of the photopolymerization initiator having a molar absorption coefficient of 1 or greater at 405 nm is not particularly limited, but may be, for example, 2000 or 1500. Examples of the photopolymerization initiator include acetophenone derivative compounds such as methoxyacetophenone, benzoin ether compounds such as benzoin propyl ether and benzoin isobutyl ether, ketal derivative compounds such as benzyl dimethyl ketal and acetophenone diethyl ketal, and phosphine oxide derivative compounds. Further examples include photoradical polymerization initiators such as bis(η5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, α-hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane. These photopolymerization initiators may be used alone or in combination of two or more.

[0061] The content of the polymerization initiator is not particularly limited, but a preferred lower limit is 0.1 parts by weight and a preferred upper limit is 10 parts by weight based on 100 parts by weight of the total of the maleimide group-containing reactive compound (1) and the resin (2) having an imide skeleton in the main chain repeating unit. When the content of the polymerization initiator is within this range, the entire curable resin composition undergoes uniform and rapid polymerization and crosslinking upon heating or light irradiation, and the elastic modulus increases, significantly reducing the adhesive strength, preventing increased adhesion to the adherend and the generation of adhesive residue upon peeling from the adherend. A more preferred lower limit of the content of the polymerization initiator is 0.3 parts by weight and a more preferred upper limit is 3 parts by weight.

[0062] The curable resin composition of the present invention may further contain a gas generating agent that generates gas upon irradiation with light. By including the gas generating agent, even after high-temperature processing at 300°C or higher, the gas generated upon irradiation with light is released at the interface with the adherend, making it possible to peel the adherend more easily and without leaving any adhesive residue. Furthermore, even when peeling a thin adherend after high-temperature processing at 300°C or higher, damage to the adherend can be prevented.

[0063] 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 curable resin composition can exhibit higher heat resistance. In other words, peeling can be more effectively suppressed during high-temperature processing, and increased adhesion and adhesive residue upon peeling can be more effectively prevented. The TG-DTA (thermogravimetry-differential thermal analysis) measurement can be carried out using, for example, a TG-DTA device (STA7200RV, manufactured by Hitachi High-Tech Science Corporation, or an equivalent product).

[0064] Examples of the gas generating agent include a gas generating agent that generates gas by heating, a gas generating agent that generates gas by irradiating with light, etc. These gas generating agents may be used alone or in combination of two or more. Among them, 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. 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. These gas generating agents may be used alone or in combination of two or more. Among them, tetrazole compounds or salts thereof are particularly preferred because of their excellent heat resistance.

[0065] The content of the gas generating agent is not particularly limited, but a preferred lower limit is 5 parts by weight and a preferred upper limit is 50 parts by weight relative to 100 parts by weight of the total of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in the main chain repeating unit. When the content of the gas generating agent is within this range, the curable resin composition can exhibit particularly excellent releasability. A more preferred lower limit of the content of the gas generating agent is 8 parts by weight and a more preferred upper limit is 30 parts by weight.

[0066] The curable resin composition of the present invention may further contain an inorganic filler. By including the inorganic filler, the curable resin composition can suppress a decrease in elastic modulus at high temperatures, and therefore peeling during high-temperature processing can be further suppressed even when high-temperature processing is performed at 300°C or higher.

[0067] The inorganic filler is not particularly limited, and examples thereof include inorganic fillers consisting of at least one selected from the group consisting of oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconia, and composites thereof. Among these, silica and talc are preferred because they are commercially available at low cost and easily available.

[0068] The inorganic filler may be surface-modified. The functional group used to modify the surface of the inorganic filler is not particularly limited, and examples thereof include an alkylsilane group, a methacryloyl group, and a dimethylsiloxane group. Among these, a dimethylsiloxane group is preferred because it has appropriate hydrophobicity.

[0069] The average particle size of the inorganic filler is not particularly limited, but a preferred lower limit is 5 nm and a preferred upper limit is 30 μm. When the average particle size of the inorganic filler is within this range, peeling of the curable resin composition during high-temperature processing can be further suppressed, and the curable resin composition can be peeled by peeling treatment. A more preferred lower limit of the average particle size of the inorganic filler is 10 nm, a more preferred upper limit is 20 μm, an even more preferred lower limit is 15 nm, and an even more preferred upper limit is 15 μm. The average particle size is preferably a number-average particle size, which 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.

[0070] The content of the inorganic filler is not particularly limited, but a preferred lower limit is 1 part by weight and a preferred upper limit is 20 parts by weight per 100 parts by weight of the total of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in the main chain repeating unit. When the content of the inorganic filler is within this range, the curable resin composition can be more effectively prevented from peeling during high-temperature processing and can be peeled off by peel treatment. A more preferred lower limit of the content of the inorganic filler is 3 parts by weight, a more preferred upper limit is 15 parts by weight, an even more preferred lower limit is 5 parts by weight, and an even more preferred upper limit is 10 parts by weight.

[0071] The curable resin composition of the present invention may contain known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, resins, surfactants, and waxes.

[0072] The curable resin composition of the present invention preferably has a 5% weight loss temperature of 350°C or higher. By having the 5% weight loss temperature of 350°C or higher, the curable resin composition can exhibit higher heat resistance. That is, the occurrence of voids and lifting between the support and the composition 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 5% weight loss temperature is more preferably 380°C or higher, and even more preferably 400°C or higher. The upper limit of the 5% weight loss temperature is not particularly limited, but is substantially approximately 600°C. The 5% weight loss temperature can be measured as follows. After curing, the curable 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 at a heating rate of 10°C / min using a thermogravimetric analyzer (STA7200 (Hitachi High-Tech Science Corporation) or its equivalent), and the temperature at which the weight is reduced by 5% is measured. When the curable resin composition is a photocurable type, the curing conditions are, for example, 405 nm ultraviolet light at 20 mW / cm 2 When the curable resin composition is a thermosetting type, it can be cured by heating in an oven at 150° C. for 10 minutes, for example.

[0073] The adhesive layer made of the curable resin composition of the present invention has a gel fraction after curing of preferably 70% by weight (lower limit) and 95% by weight (upper limit). When the gel fraction after curing is within the above range, the curable resin composition can be more easily peeled from the adherend. The more preferred lower limit of the gel fraction after curing is 75% by weight (lower limit), and the more preferred upper limit is 90% by weight. In the case of a photocurable type, the gel fraction after curing was measured by irradiating an adhesive layer formed using a curable resin composition with 405 nm ultraviolet light at 20 mW / cm using an ultra-high pressure mercury lamp. 2 After curing by irradiating with light at an intensity of 1000 nm for 150 seconds, or in the case of a heat-curing type, by heating at 150°C for 10 minutes, the viscosity is measured by the following method. The adhesive layer is cut into a flat rectangular shape of 50 mm x 100 mm to prepare a test specimen. The test specimen is immersed in toluene at 23°C for 24 hours, then removed from the toluene and dried at 110°C for 1 hour. The weight of the dried test specimen is measured, and the gel fraction is calculated using the following formula (1). Note that no release film to protect the adhesive layer is laminated on the test specimen. Gel fraction (wt%) = 100 × (W2 - W0) / (W1 - W0) (1) (W0: weight of substrate, W1: weight of test piece before immersion, W2: weight of test piece after immersion and drying)

[0074] The method for producing the curable resin composition of the present invention is not particularly limited, and examples thereof include a method in which the reactive compound (1) having a maleimide group, the resin (2) having an imide skeleton in the repeating unit of the main chain, and additives to be blended as necessary are mixed using a bead mill, ultrasonic dispersion, homogenizer, high-power disperser, roll mill, or the like.

[0075] A temporary fixing material having an adhesive layer made of the curable resin composition of the present invention also constitutes the present invention. Such a temporary fixing material is called the first temporary fixing material of the present invention.

[0076] When the curable resin composition of the present invention contains the gas-generating agent, a temporary fixing material having a first adhesive layer made of the curable resin composition of the present invention containing the gas-generating agent and a second adhesive layer also constitutes one aspect of the present invention. Such a temporary fixing material is called the second temporary fixing material of the present invention. In the temporary fixing material of the second aspect of the present invention, the first adhesive layer contains the gas generating agent and is a curable adhesive layer capable of generating gas.

[0077] The first adhesive layer has a gel fraction after curing of preferably 50% by weight. When the gel fraction after curing is within the above range, the first adhesive layer can be more easily peeled. The more preferable lower limit of the gel fraction after curing is 80% by weight. In the case of a photocurable adhesive, the gel fraction after curing is determined by irradiating the first adhesive layer with 405 nm ultraviolet light at 20 mW / cm. 2 After curing by irradiating with light at an intensity of 1000 nm for 150 seconds, or in the case of a heat-curing type, by heating at 150°C for 10 minutes, the viscosity is measured by the following method. The first adhesive layer is cut into a 50 mm x 100 mm flat rectangular shape to prepare a test specimen. The test specimen is immersed in toluene at 23°C for 24 hours, then removed from the toluene and dried at 110°C for 1 hour. The weight of the dried test specimen is measured, and the gel fraction is calculated using the following formula (1). Note that no release film to protect the first adhesive layer is laminated on the test specimen. Gel fraction (wt%) = 100 × (W2 - W0) / (W1 - W0) (1) (W0: weight of substrate, W1: weight of test piece before immersion, W2: weight of test piece after immersion and drying)

[0078] The first adhesive layer preferably has an adhesive strength to glass of 1.5 N / inch or less at 25°C after curing and heating at 300°C for 10 minutes (after heating and cooling). With the adhesive strength to glass within the above range, the first adhesive layer can be more easily peeled off. The adhesive strength to glass is more preferably 1.2 N / inch or less, even more preferably 1.1 N / inch or less, and even more preferably 1.0 N / inch or less. The adhesive strength to glass is measured by the following method. The first adhesive layer is heat-laminated onto quartz glass (large slide glass with white polished edges, No. 2 S9112, manufactured by Matsunami Glass Industrial Co., Ltd.) using a laminator ("Leon13DX" manufactured by Lamy Corporation, or an equivalent product) at 100°C. The heat lamination is performed once under the conditions of a temperature setting of 100°C and a speed setting of 5. After heat lamination, an ultra-high pressure mercury lamp is used to irradiate the glass with 405 nm ultraviolet light at 20 mW / cm. 2The adhesive is cured by irradiating the adhesive with light at an intensity of 100°C for 150 seconds, or by heating in an oven at 150°C for 10 minutes, and then heating from the glass side on a hot plate at 300°C for 10 minutes. After curing and heating at 300°C for 10 minutes, the first adhesive layer is subjected to a 180° peel test at a pulling rate of 300 mm / min in an environment of 25°C and relative humidity of 50%, and the adhesive strength is measured.

[0079] The thickness of the first adhesive layer is not particularly limited, but a preferred lower limit is 5 μm and a preferred upper limit is 550 μm. If the thickness is 5 μm or more, the first adhesive layer can initially have sufficient pressure-sensitive or heat-sensitive adhesive strength. If the thickness is 550 μm or less, the first adhesive layer can exhibit high flexibility, exhibit high conformability to an adherend having irregularities, and be more easily peeled off. A more preferred lower limit of the thickness is 10 μm, an even more preferred lower limit is 20 μm, and an even more preferred lower limit is 30 μm. A more preferred upper limit of the thickness is 400 μm, an even more preferred upper limit is 300 μm, an even more preferred upper limit is 200 μm, and an even more preferred upper limit is 150 μm.

[0080] The second adhesive layer is not particularly limited, and a curable adhesive layer having the same composition, physical properties, thickness, etc. as the first adhesive layer can be used. Among these, a thermosetting adhesive layer is preferable. By using a thermosetting adhesive layer as the second adhesive layer, the second adhesive layer can be sufficiently cured by heating, even when a substrate with low light transmittance is used and the first adhesive layer is a photocurable adhesive layer and light is irradiated from the first adhesive layer side. The second adhesive layer may or may not contain the gas generating agent.

[0081] The first temporary fixing material of the present invention and the second temporary fixing material of the present invention may have an adhesive layer made of the curable resin composition of the present invention on one or both surfaces of a substrate, or may not have a substrate. When the temporary fixing material does not have the above-mentioned substrate, there is no need to select a substrate that has both light transparency and heat resistance, and the temporary fixing material has a cheaper and simpler configuration. Furthermore, when the temporary fixing material does not have the above-mentioned substrate, even when the first adhesive layer and the second adhesive layer are both photocurable adhesive layers in the second temporary fixing material of the present invention, light can be sufficiently allowed to reach the curable adhesive layer on the side opposite to the side where light is irradiated. When the temporary fixing material of the second aspect of the present invention has the above-mentioned base material, it is preferable that the above-mentioned first adhesive layer and the above-mentioned second adhesive layer are laminated on both sides of the above-mentioned base material, respectively, in the order of the above-mentioned first adhesive layer, the above-mentioned base material, and the above-mentioned second adhesive layer.

[0082] Examples of the substrate include sheets made of transparent resins such as acrylic, olefin, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, etc. Also usable are sheets with a mesh structure, sheets with holes, glass, etc.

[0083] The thickness of the substrate is not particularly limited, but from the viewpoint of improving light transmittance and flexibility, the lower limit is preferably 5 μm, the upper limit is preferably 150 μm, the lower limit is more preferably 10 μm, and the upper limit is more preferably 100 μm.

[0084] The temporary fixing material of the present invention preferably has an adhesive strength to glass of 1.5 N / inch or less at 25°C after curing and after heating at 300°C for 10 minutes (after heating and cooling). When the adhesive strength to glass is within the above range, the temporary fixing material can be more easily peeled off. The adhesive strength to glass is more preferably 1.2 N / inch or less, even more preferably 1.1 N / inch or less, and even more preferably 1.0 N / inch or less. The adhesive strength to glass is measured by the following method. The temporary fixing material is heat-laminated onto glass (large glass slides with white edges, No. 2, manufactured by Matsunami Glass Industrial Co., Ltd.) using a laminator (Leon 13DX, manufactured by Lamy Corporation) at 100°C. The heat lamination is performed once under the conditions of a temperature setting of 100°C and a speed setting of 5. After heat lamination, an ultra-high pressure mercury lamp is used to irradiate the glass with 405 nm ultraviolet light at 20 mW / cm. 2 The material is cured by irradiating it with light at an intensity of 100°C for 150 seconds, or by heating it in an oven at 150°C for 10 minutes. After curing, the material is heated from the glass side on a hot plate at 300°C for 10 minutes. After heating, the material is allowed to cool to room temperature, and the temporary fixing material after curing and heating at 300°C for 10 minutes is subjected to a 180° peel test at 25°C and a pulling speed of 300 mm / min to measure its adhesive strength.

[0085] The curable resin composition of the present invention, the first temporary fixing material of the present invention, and the second temporary fixing material of the present invention have sufficient pressure- or heat-sensitive adhesive strength initially and can suppress the occurrence of voids and lifting between the substrate and the material during high-temperature processing. At the same time, they can prevent increased adhesion to the adherend and the generation of adhesive residue during peeling, allowing for easy peeling from the adherend. Therefore, the curable resin composition of the present invention, the first temporary fixing material of the present invention, and the second temporary fixing material of the present invention are suitable for protecting and temporarily fixing adherends that undergo high-temperature processing at 300°C or higher, particularly adherends made of polyimide resins. In particular, they are suitable for protecting electronic components such as semiconductors by fixing them to a support plate via the curable resin composition or temporary fixing material or by attaching the temporary fixing material to the electronic component to facilitate handling and prevent damage during processing of the electronic component.

[0086] The present invention also provides a method for producing an electronic component, which includes a temporary fixing step of temporarily fixing an electronic component to the temporary fixing material of the first present invention, a curing step of curing the adhesive layer of the temporary fixing material of the first present invention, a heat treatment step of heat treating the electronic component, and a peeling step of peeling the electronic component from the temporary fixing material of the first present invention. The curing step of curing the adhesive layer of the first temporary fixing material of the present invention may be carried out immediately before the peeling step of peeling the electronic component from the temporary fixing material of the present invention, but is preferably carried out after the temporary fixing step of temporarily fixing the electronic component to the first temporary fixing material of the present invention and before the heat treatment step of heat treating the electronic component. By carrying out the curing step of curing the adhesive layer of the first temporary fixing material of the present invention before the heat treatment step of heat treating the electronic component, the temporary fixing material can exhibit better heat resistance.

[0087] The present invention also provides a method for producing an electronic component using the temporary fixing material of the second invention, the method comprising: a support attachment step of attaching a first adhesive layer of the temporary fixing material to a support; an adherend attachment step of attaching a second adhesive layer of the temporary fixing material to an electronic component; a curing step of curing the first adhesive layer and the second adhesive layer; a heat treatment step of heat treating the electronic component; a gas generation step of generating a gas from the first adhesive layer; and a peeling step of peeling the temporary fixing material from the support. The curing step may be carried out immediately before the gas generating step, but is preferably carried out after the support attaching step and the adherend attaching step and before the heat treatment step. By carrying out the curing step before the heat treatment step, the temporary fixing material can exhibit better heat resistance. Examples of the support include glass and quartz substrates, etc. Examples of the adherend include silicon wafers, etc. [Effects of the Invention]

[0088] According to the present invention, it is possible to provide a curable resin composition that can suppress the occurrence of voids and lifting between an adherend and a support, even when the adherend and support are subjected to a high-temperature processing treatment at 300°C or higher (for example, heating at 300 to 450°C) while they are fixed together, and that can be easily peeled off after the high-temperature processing treatment. Furthermore, according to the present invention, it is possible to provide a temporary fixing material having an adhesive layer made of the curable resin composition, and a method for producing an electronic component using the temporary fixing material. DETAILED DESCRIPTION OF THE INVENTION

[0089] The following examples will further illustrate aspects of the present invention, but the present invention is not limited to these examples.

[0090] (Preparation of bismaleimide compound (1-I)) 250 mL of toluene was placed in a 500 mL round-bottom flask equipped with a Teflon (registered trademark) stirrer. 56 g (0.1 mol) of dimer diamine (Priamine 1075, manufactured by Croda) and 19.6 g (0.2 mol) of maleic anhydride were added, followed by 5 g of methanesulfonic anhydride. The solution was refluxed for 12 hours, cooled to room temperature, and 300 mL of toluene was added to the flask. The salt was precipitated and removed by standing. The resulting solution was filtered through a glass-fritted funnel filled with silica gel, and the solvent was removed under vacuum to obtain a brown liquid bismaleimide compound (1-I) represented by the following formula (A).

[0091] [ka]

[0092] (Preparation of Compound (1-II) Having a Maleimide Group and an Imide Skeleton in the Main Chain Repeating Unit) A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 56 g (0.1 mol) of dimer diamine (Croda, Priamine 1075) and 19.1 g (0.09 mol) of pyromellitic anhydride were added, in that order. A Dean-Stark trap and condenser were attached to the flask, and the mixture was refluxed for 2 hours to form the amine-terminated diimide. After cooling the reaction mixture below room temperature, 12.8 g (0.13 mol) of maleic anhydride was added, followed by 5 g (0.05 mol) of methanesulfonic anhydride. The mixture was refluxed for an additional 12 hours, cooled to room temperature, and 300 mL of toluene was added to the flask. Impurities were precipitated and removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel, and the solvent was then removed under vacuum to obtain an amber wax-like compound (1-II) represented by the following formula (B), which has maleimide groups at both ends and an imide skeleton in the repeating unit of the main chain. The weight average molecular weight of the resulting compound was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (trade name, manufactured by Waters Corporation) as a column, and was found to be 5,000.

[0093] [ka]

[0094] (Preparation of Resin (2-I) Having No Maleimide Group and an Imide Skeleton in the Main Chain Repeating Unit) A 500 mL round-bottom flask equipped with a Teflon stirrer was charged with 250 mL of toluene. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 31.9 g (0.06 mol) of dimer diamine (Croda, Priamine 1075), 5.5 g (0.015 mol) of Bis-AP-AF, and 39 g (0.075 mol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride were added, in this order. A Dean-Stark trap and condenser were attached to the flask, and the mixture was refluxed for 2 hours, cooled to room temperature, and 300 mL of toluene was added to the flask. Impurities were precipitated and removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel, and the solvent was then removed under vacuum to obtain a brown solid resin (2-I) represented by the following formula (C), which had no maleimide group and had an imide skeleton in the repeating unit of the main chain. The weight average molecular weight of the obtained resin was measured by gel permeation chromatography (GPC) using THF as an eluent and an HR-MB-M (product name, manufactured by Waters Corporation) as a column, and was found to be 72,000.

[0095] [ka]

[0096] (Preparation of acrylic reactive resin) A reactor equipped with a thermometer, stirrer, and condenser was prepared. 94 parts by weight of 2-ethylhexyl acrylate as a (meth)acrylic acid alkyl ester, 6 parts by weight of hydroxyethyl methacrylate as a functional group-containing monomer, 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate were added to the reactor. The reactor was then heated to initiate reflux. Subsequently, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane as a polymerization initiator was added to the reactor, and polymerization was initiated under reflux. Next, 0.01 parts by weight of 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane was added at 1 hour and 2 hours after the start of polymerization. Furthermore, 0.05 parts by weight of t-hexylperoxypivalate was added 4 hours after the start of polymerization to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% by weight and a weight-average molecular weight of 500,000 was obtained. To 100 parts by weight of the resin solids content of the obtained ethyl acetate solution containing the functional group-containing (meth)acrylic polymer, 3.5 parts by weight of 2-isocyanatoethyl methacrylate as a functional group-containing unsaturated compound was added and reacted to obtain an acrylic reactive resin. The weight average molecular weight of the obtained acrylic reactive resin was measured by gel permeation chromatography (GPC) using THF as an eluent and HR-MB-M (trade name, manufactured by Waters Corporation) as a column, and was found to be 550,000.

[0097] Example 1 (1) Manufacturing of temporary fixing materials To 150 mL of toluene, 70 parts by weight of compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain and 30 parts by weight of resin (2-I) having no maleimide group and an imide skeleton in the repeating unit of the main chain were added. Furthermore, 5 parts by weight of bifunctional silicone acrylate (manufactured by Daicel Ornex Co., Ltd., EBECRYL350) as a silicone compound and 2 parts by weight of Irgacure 819 (manufactured by BASF) as a photopolymerization initiator were added to prepare a toluene solution of a curable resin composition. The obtained toluene solution of the curable resin composition was applied with a doctor knife 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 would be 40 μm, and the coating solution was dried by heating at 110° C. for 5 minutes. Thereafter, the coating was left to stand and cured at 40° C. for 3 days to obtain a temporary fixing material having an adhesive layer.

[0098] (2) Measurement of 5% weight loss temperature The adhesive layer of the obtained temporary fixing material was cured, and then weighed into an aluminum pan, and the aluminum pan was set in the device. In a nitrogen atmosphere, the measurement sample was 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), and the temperature at which the weight decreased by 5% was measured. The curing conditions were 405 nm ultraviolet light at 20 mW / cm. 2 The coating was cured by irradiating the coating with light at an intensity of 1000 kJ / cm2 for 150 seconds, or by heating in an oven at 150° C. for 10 minutes instead of ultraviolet irradiation.

[0099] (3) Measurement of gel fraction after curing The adhesive layer of the obtained temporary fixing material was irradiated with 405 nm ultraviolet light at 20 mW / cm using an ultra-high pressure mercury lamp. 2 After irradiating with ultraviolet light at an intensity of 1000 kJ / s for 150 seconds, the measurement was carried out by the following method. The temporary fixing material was cut into a flat rectangular shape of 50 mm x 100 mm to prepare a test specimen. The test specimen was immersed in toluene at 23°C for 24 hours, then removed from the toluene and dried at 110°C for 1 hour. The weight of the test specimen after drying was measured, and the gel fraction was calculated using the following formula (1). Note that no release film to protect the adhesive layer was laminated on the test specimen. Gel fraction (wt%) = 100 × (W2 - W0) / (W1 - W0) (1) (W0: weight of substrate, W1: weight of test piece before immersion, W2: weight of test piece after immersion and drying)

[0100] In Example 18 described later, the first adhesive layer of the obtained temporary fixing material was irradiated with 405 nm ultraviolet light at 20 mW / cm 2The first and second adhesive layers were cured by irradiating them with ultraviolet light at an intensity of 100°C for 150 seconds, and then each adhesive layer was weighed and used as a test piece. In Example 19 described below, instead of ultraviolet irradiation, the first and second adhesive layers were cured by heating them in a 150°C oven for 10 minutes, and then each adhesive layer was weighed and used as a test piece. Since these test pieces did not have a substrate, W0 was 0.

[0101] (Examples 2 to 11, Comparative Examples 1 to 4) A curable resin composition and a temporary fixing material were obtained in the same manner as in Example 1, except that the formulation of the curable resin composition was changed as shown in Table 1. The materials used are shown below. Fluorine compounds (photoreactive fluorine compounds, DIC, Megafac RS-56) Gas generator (5,5'-Bi-1H-tetorazole disodium salt (BHT-2Na))

[0102] (Examples 12 to 17) A curable resin composition and a temporary fixing material were obtained in the same manner as in Example 1, except that the formulation of the curable resin composition was changed as shown in Table 2. The materials used are shown below. Inorganic filler (silica particles, Tokuyama Corporation, MT-10, average particle size 15 nm) Inorganic filler (silica particles, manufactured by Tatsumori Co., Ltd., 5x, average particle size 1 μm)

[0103] Example 18 (1) Formation of the first adhesive layer (gas-generating agent-containing curable adhesive layer) To 300 mL of toluene, 100 parts by weight of the reactive resin shown in Table 3, 30 parts by weight of 5,5'-Bi-1H-tetorazole disodium salt (BHT-2Na) as a gas generating agent, 5 parts by weight of EBECRYL350 as a silicone compound, and 3 parts by weight of Irgacure 369 (manufactured by BASF) as a photopolymerization initiator were added. This prepared a toluene solution of a curable resin composition in which 5,5'-Bi-1H-tetorazole disodium salt (BHT-2Na) was dispersed. The obtained toluene solution of the curable resin composition was applied to a 50 μm-thick polyethylene terephthalate film with a release-treated surface, which was prepared as a separator, using a doctor knife so that the dried film would be 50 μm thick. The coating solution was dried for 10 minutes in an oven preheated to 110°C, to obtain a first adhesive layer (a gas-generating agent-containing curable adhesive layer).

[0104] (2) Formation of a second adhesive layer To 300 mL of toluene, 100 parts by weight of the reactive resin shown in Table 3, 5 parts by weight of EBECRYL350 as a silicone compound, and 3 parts by weight of IRGACURE 369 (manufactured by BASF) as a photopolymerization initiator were added, thereby preparing a toluene solution of the curable resin composition. The obtained toluene solution of the curable resin composition was applied to a 50 μm thick polyethylene terephthalate film with a release-treated surface, which had been prepared as a separator, using a doctor knife so that the dried film would be 50 μm thick.The coating solution was then dried for 10 minutes in an oven that had been preheated to 110°C, to obtain a second adhesive layer.

[0105] (3) Manufacturing of temporary fixing materials The adhesive layer surfaces of the obtained first adhesive layer (gas-generating agent-containing curable adhesive layer) and second adhesive layer were laminated together to obtain a temporary fixing material in which both surfaces were covered with a separator.

[0106] Example 19 Curable resin compositions and temporary fixing materials were obtained in the same manner as in Example 1, except that the formulation of the curable resin composition was changed as shown in Table 3 and substrates were used as shown below. Specifically, when forming the second adhesive layer, the resulting toluene solution of the curable resin composition was applied to the corona-treated surface of a 25 μm-thick polyimide film (Kapton film, manufactured by Ube Industries, Ltd.) that had been corona-treated on one side, using a doctor knife to obtain a 50 μm-thick dried film. The coating solution was dried for 10 minutes in an oven preheated to 110°C. After drying, a 50 μm-thick polyethylene terephthalate film with a release-treated surface was laminated as a separator on the adhesive layer surface opposite the Kapton film to obtain a second adhesive layer. Perbutyl O, manufactured by NOF Corporation, was used as the polymerization initiator.

[0107] <Evaluation> The temporary fixing materials obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Tables 1 to 3.

[0108] (1) Evaluation of voids and floats The obtained temporary fixing material was cut to a width of 1 inch and then heat-laminated onto a glass plate (large slide glass with white polished edges, No. 2, manufactured by Matsunami Glass Industrial Co., Ltd.) using a heat laminator (Leon 13DX) at 100°C and speed setting 3. In Examples 18 and 19, the second adhesive layer side was heat-laminated onto the glass plate. After lamination, an ultra-high pressure mercury lamp was used to irradiate the glass with 405 nm ultraviolet light at 20 mW / cm. 2 The adhesive was irradiated for 150 seconds at an intensity of 100°C. In Example 19, instead of ultraviolet irradiation, the first and second adhesive layers were cured by heating in an oven at 150°C for 10 minutes. After curing, the release PET film of the temporary fixing material was peeled off, and the temporary fixing material was heated from the glass side on a hot plate at 300°C for 10 minutes. After hardening and heating at 300°C, the appearance of the temporary fixing material was visually observed and evaluated according to the following criteria. ○: No voids or lifting were observed between the glass plate and the surface ×: Fine voids were observed between the glass plate and the sheet, or there was a partial gap between the glass plate and the sheet.

[0109] (2) Evaluation of peelability after curing and heating at 300°C for 10 minutes The obtained temporary fixing material was cut to a width of 1 inch, and then heat-laminated onto a wafer having a photosensitive polyimide film using a laminator at 100° C. In Examples 18 and 19, the second adhesive layer side was heat-laminated onto the wafer. After lamination, an ultra-high pressure mercury lamp was used to irradiate the temporary fixing material with 405 nm ultraviolet light at 20 mW / cm. 2 The adhesive was irradiated for 150 seconds at an intensity of 1000 . In Example 19, instead of ultraviolet irradiation, the first and second adhesive layers were cured by heating in an oven at 150°C for 10 minutes. After curing, the release PET film of the temporary fixing material was peeled off, and the wafer side having the photosensitive polyimide film was heated on a hot plate at 300°C for 10 minutes. The temporary fixing materials after curing and heating to 300°C were subjected to a 180° peel test at 25°C and a tensile speed of 300 mm / min. After peeling off the temporary fixing material, the wafer surface having the photosensitive polyimide film was visually observed and evaluated according to the following criteria. 〇: No adhesive residue was observed ×: No adhesive residue was found, but cloudiness was observed on the peeled surface. ××: Adhesive residue was observed

[0110] (3) Measurement of adhesive strength to glass at 25°C after curing and heating at 300°C for 10 minutes The obtained temporary fixing material was cut into a width of 1 inch and then heat-laminated onto a 1 mm thick glass (large slide glass with white edge polished No. 2, manufactured by Matsunami Glass Industrial Co., Ltd.) using a laminator (Leon 13DX, speed memory 5, manufactured by Lamy Corporation) at 100°C. After lamination, 405 nm ultraviolet light was applied from the glass side at 20 mW / cm using an ultra-high pressure mercury lamp. 2 The adhesive layer was irradiated for 150 seconds at an intensity of 100°C. In Example 19, instead of ultraviolet irradiation, the first and second adhesive layers were cured by heating in an oven at 150°C for 10 minutes. After curing, the release PET film of the temporary fixing material was peeled off, and the temporary fixing material was heated from the glass side on a hot plate at 300°C for 10 minutes. After hardening, the temporary fixing material was heated at 300°C for 10 minutes and allowed to cool, and then a 180° peel test was carried out at 25°C and a tensile speed of 300 mm / min. Measurements were made on each of the first and second adhesive layers in Examples 18 and 19. The adhesive strength of the first adhesive layer to glass was measured by heating the layer at 300°C for 10 minutes, allowing it to cool, and then irradiating the layer with 254 nm ultraviolet light at 20 mW / cm from the glass side using a high-pressure mercury lamp. 2 After irradiating the sample for 180 seconds at an intensity of 1000 kJ / s for 180 seconds to generate gas, a 180° peel test was carried out at 25°C and a pulling speed of 300 mm / min. In Comparative Examples 1, 2, and 4, measurement was not possible because floating and voids occurred between the glass plate after heating at 300°C for 10 minutes, and in Comparative Example 3, measurement was not possible because the film solidified after heating at 300°C for 10 minutes.

[0111] (4) Evaluation of peeling and peelability after curing and heating at 300°C for 20 minutes The temporary fixing materials obtained in Examples 2 to 4 and 12 to 17 were further evaluated as follows. The obtained temporary fixing material was cut into a width of 1 inch and then heat-laminated once onto a 1 mm thick glass sheet using a thermal laminator (Leon13DX) at 100°C with speed setting 3. After lamination, an ultra-high pressure mercury lamp was used to irradiate the glass sheet with 405 nm ultraviolet light at 20 mW / cm. 2 The test was performed five times. After hardening and heating at 300°C for 20 minutes, the appearance of the temporary fixing material was visually observed and evaluated according to the following criteria. Peeling: No peeling was observed between the film and the glass in all five tests. No peeling: In one or more of the five tests, there was some separation between the film and the glass.

[0112] After hardening and heating at 300°C for 20 minutes, the temporary fixing materials were subjected to a 180° peel test at 25°C and a tensile speed of 300 mm / min. This test was performed five times. The peelability of the temporary fixing materials was evaluated according to the following criteria. Note that materials that showed lifting (peeling) in the peel test were not evaluated. ◎: Peeling was possible in all five tests ○: Peeling was possible in 1 to 4 of the 5 tests ×: Peeling was not possible in all five tests

[0113] [Table 1]

[0114] [Table 2]

[0115] [Table 3] [Industrial Applicability]

[0116] According to the present invention, it is possible to provide a curable resin composition that can suppress the occurrence of voids and lifting between an adherend and a support, even when a high-temperature processing treatment of 300°C or higher is performed while the adherend and the support are fixed together, and that can be easily peeled off after the high-temperature processing treatment. Furthermore, according to the present invention, it is possible to provide a temporary fixing material having an adhesive layer made of the curable resin composition, and a method for producing an electronic component using the temporary fixing material.

Claims

1. A curable resin composition comprising (1) a reactive compound having a maleimide group and (2) a resin having an imide skeleton in the repeating unit of its main chain.

2. 2. The curable resin composition according to claim 1, wherein the 5% weight loss temperature is 350° C. or higher.

3. 3. The curable resin composition according to claim 1, wherein at least one selected from the group consisting of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in a repeating unit of its main chain has an aliphatic group derived from a dimer diamine.

4. The curable resin composition according to claim 1, 2 or 3, characterized in that the reactive compound (1) having a maleimide group is a bismaleimide compound (1-I) or a compound (1-II) having a maleimide group and an imide skeleton in a repeating unit of the main chain.

5. The curable resin composition according to claim 1, 2, 3 or 4, characterized in that the resin (2) having an imide skeleton in a repeating unit of its main chain is a resin (2-I) having no maleimide group and having an imide skeleton in a repeating unit of its main chain.

6. The curable resin composition according to claim 4, wherein the bismaleimide compound (1-I) is a compound having two maleimide groups and an aliphatic group derived from dimer diamine, and the aliphatic group derived from dimer diamine is at least one selected from the group consisting of a group represented by the following general formula (4-1), a group represented by the following general formula (4-2), a group represented by the following general formula (4-3), and a group represented by the following general formula (4-4): 【Chemistry 1】 In general formulas (4-1) to (4-4), R １ ~R ８ and R １３ ~R ２０ each independently represents a linear or branched hydrocarbon group.

7. The compound (1-II) having a maleimide group and an imide skeleton in the repeating unit of the main chain has a constitutional unit represented by the following general formula (1a), a constitutional unit represented by the following general formula (1b), and a constitutional unit represented by the following general formula (1c) (where s>0, t≧0, u≧0), and both ends are each X １ and X ２ The curable resin composition according to claim 4, wherein the compound (1-ii) is represented by the following formula: 【Chemistry 2】 In general formulas (1a) to (1c), P １ , P ２ and P ３ each independently represents an aromatic group; １ represents a substituted or unsubstituted linear, branched or cyclic aliphatic group; Q ２ represents a group having a substituted or unsubstituted aromatic structure, and R represents a substituted or unsubstituted branched aliphatic group or aromatic group. １ , X ２ and X ３ At least one selected from the group consisting of represents a maleimide group-containing group.

8. The resin (2-I) having no maleimide group and an imide skeleton in the repeating unit of the main chain has a constitutional unit represented by the following general formula (1d) and a constitutional unit represented by the following general formula (1e) (where s>0, t≧0), and both ends thereof are each X ４ and X ５ The curable resin composition according to claim 5, wherein the resin (2-i) is represented by the following formula: 【Transformation 3】 In general formulas (1d) to (1e), P ４ and P ５ each independently represents an aromatic group; ３ represents a substituted or unsubstituted linear, branched or cyclic aliphatic group; Q ４ represents a group having a substituted or unsubstituted aromatic structure. ４ and X ５ represents a group that does not contain a maleimide group.

9. 9. The curable resin composition according to claim 1, wherein the resin (2) having an imide skeleton in the repeating unit of the main chain has a weight average molecular weight (Mw) of 20,000 or more.

10. 10. The curable resin composition according to claim 1, wherein the content of the resin (2) having an imide skeleton in a repeating unit of its main chain relative to a total of 100 parts by weight of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in a repeating unit of its main chain is 20 parts by weight or more and 80 parts by weight or less.

11. 11. The curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein the content of the reactive compound (1) having a maleimide group relative to 100 parts by weight of the total of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in a repeating unit of its main chain is 20 parts by weight or more and 80 parts by weight or less.

12. 12. The curable resin composition according to claim 1, further comprising a polymerization initiator.

13. 13. The curable resin composition according to claim 12, wherein the polymerization initiator is a photopolymerization initiator, and the photopolymerization initiator contains a photopolymerization initiator having a molar absorption coefficient at 405 nm of 1 or more.

14. 14. The curable resin composition according to claim 1, further comprising a silicone compound or a fluorine compound.

15. 15. The curable resin composition according to claim 1, further comprising an inorganic filler.

16. 16. The curable resin composition according to claim 15, wherein the inorganic filler has an average particle size of 5 nm or more and 20 μm or less.

17. 17. The curable resin composition according to claim 15, wherein the content of the inorganic filler is 1 part by weight or more and 20 parts by weight or less, relative to 100 parts by weight of a total of the reactive compound (1) having a maleimide group and the resin (2) having an imide skeleton in a repeating unit of its main chain.

18. 18. The curable resin composition according to claim 1, further comprising a gas generating agent.

19. The curable resin composition according to claim 18, characterized in that the gas generating agent 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).

20. 20. A temporary fixing material comprising an adhesive layer made of the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19.

21. A temporary fixing material comprising a first adhesive layer made of the curable resin composition according to claim 18 or 19, and a second adhesive layer.

22. 22. The temporary fixing material according to claim 21, wherein the first adhesive layer has a gel fraction of 50% by weight or more after hardening.

23. 23. The temporary fixing material according to claim 21 or 22, further comprising a substrate, the first adhesive layer and the second adhesive layer being laminated on both sides of the substrate, respectively.

24. 24. The temporary fixing material according to claim 20, 21, 22 or 23, wherein the adhesive strength to glass at 25°C after curing and heating at 300°C for 10 minutes is 1.5 N / inch or less.

25. a temporary fixing step of temporarily fixing an electronic component to the temporary fixing material according to claim 20, 21, 22, 23 or 24; a curing step of curing the adhesive layer of the temporary fixing material; a heat treatment step of performing heat treatment on the electronic component; a peeling step of peeling the electronic component from the temporary fixing material. A method for manufacturing an electronic component, comprising:

26. A method for manufacturing an electronic component using the temporary fixing material according to claim 21, 22 or 23, a support attachment step of attaching a first adhesive layer of the temporary fixing material to a support; an adherend attachment step of attaching an electronic component to the second adhesive layer of the temporary fixing material; a curing step of curing the first adhesive layer and the second adhesive layer; a heat treatment step of performing heat treatment on the electronic component; a gas generating step of generating a gas from the first adhesive layer; a peeling step of peeling the support body from the temporary fixing material. A method for manufacturing an electronic component, comprising:

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