Temporary fixing material, and method for manufacturing electronic component

Abstract

Provided is a temporary fixing material that can be easily peeled after high-temperature processing even when the temporary fixing material is used in a state in which an adherend is fixed and the adherend is subjected to high-temperature processing of 300°C or higher. Also provided is a method for manufacturing an electronic component using the temporary fixing material. The temporary fixing material includes a photocurable adhesive containing a reactive resin that includes a resin (1) having an imide skeleton in a repeating unit of a main chain, and has a light transmittance of 10% or more at 405 nm and a 5% weight loss temperature of 350°C or higher.

Description

Temporary fixing materials and manufacturing methods for electronic components Technical Field

[0001] This invention relates to a temporary fixing material that can be easily peeled off after high-temperature processing, even when the adhered object is fixed at a temperature of 300°C or higher. Furthermore, this invention relates to a method for manufacturing electronic components using this temporary fixing material. Background Technology

[0002] In the processing of electronic components such as semiconductors, in order to facilitate the handling of electronic components and prevent damage, the electronic components are fixed to a support plate by an adhesive composition or protected by adhesive tape. For example, in the case of grinding a thick film wafer cut from high-purity single-crystal silicon to a specified thickness to form a thin film wafer, the thick film wafer is bonded to a support plate by an adhesive composition.

[0003] For adhesive compositions and adhesive tapes used for electronic components, high adhesion is required to firmly fix the electronic components during the processing steps, and peeling is required after the process without damaging the electronic components (hereinafter also referred to as "high adhesion and easy peel").

[0004] As a means of achieving high adhesion and easy peeling, Patent Document 1 discloses an adhesive sheet that uses an adhesive with multifunctional monomers or oligomers having radiopolymerizable functional groups bonded to the side chains or main chains of a polymer. Because of these radiopolymerizable functional groups, the polymer is cured by ultraviolet irradiation. Utilizing this, by irradiating the polymer with ultraviolet light during peeling, the adhesive strength is reduced, allowing for peeling without residue.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 5-32946 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] With the increasing performance of electronic components in recent years, various processing steps have been implemented to enhance their properties. For example, in the process of forming a metal thin film on the surface of electronic components by sputtering, processing at a high temperature of around 300–350°C can result in a metal thin film with superior conductivity. However, if electronic components protected using existing adhesive compositions or adhesive tapes are processed at temperatures above 300°C, it can lead to over-adhesion, insufficient reduction of adhesive force during peeling, or the formation of adhesive residue.

[0010] The object of this invention is to provide a temporary fixing material that can be easily peeled off after high-temperature processing, even when the adhered object is fixed at a temperature of 300°C or higher. Furthermore, the object of this invention is to provide a method for manufacturing electronic components using this temporary fixing material.

[0011] means for solving problems

[0012] The present invention relates to a temporary fixation material comprising a photocurable adhesive, wherein the photocurable adhesive contains a reactive resin, wherein the reactive resin comprises a resin (1) having an imide backbone in a repeating unit of the main chain, wherein the transmittance of the temporary fixation material at 405 nm is 10% or more, and the 5% weight reduction temperature is 350°C or more.

[0013] The present invention will now be described in detail.

[0014] The present inventors have investigated a method in which a reactive resin (1) containing an imide backbone in a repeating unit of a main chain is used in a temporary fixing material comprising a photocurable adhesive. Such a photocurable adhesive undergoes uniform and rapid polymerization and crosslinking upon irradiation with light, resulting in an increase in elastic modulus and a significant reduction in adhesive strength, thus promising easy peeling upon removal. However, if high-temperature processing at 300°C or higher is performed while the adhered material is fixed, it is difficult to adequately prevent over-adhesion or the formation of adhesive residue upon peeling.

[0015] Further research by the authors revealed that even when the temporary fixing material has high light transmittance and the photocuring reaction is fully carried out, residual adhesive will still be produced if the heat resistance is insufficient; even if the heat resistance is improved, excessive adhesion will still occur if the photocuring reaction is not fully carried out.

[0016] To address this, the inventors investigated how increasing the light transmittance of the temporary fixing material allows for a more complete photocuring reaction in the photocurable adhesive, suppressing excessive adhesion and improving the heat resistance of the temporary fixing material while also inhibiting decomposition at high temperatures. Further research revealed that by adjusting the light transmittance of the temporary fixing material to a specific range of 405 nm and a 5% weight reduction temperature, excessive adhesion and residue formation during peeling can be prevented even under high-temperature processing above 300°C, allowing for easy peeling, thus completing this invention.

[0017] The temporary fixing material of the present invention comprises a light-curing adhesive.

[0018] The temporary fixing material of the present invention is not particularly limited as long as it contains the above-mentioned photocurable adhesive. It can be a liquid temporary fixing adhesive or a sheet-like temporary fixing adhesive sheet having a photocurable adhesive layer containing the above-mentioned photocurable adhesive.

[0019] The above-mentioned photocurable adhesive contains a reactive resin, which is a resin having an imide backbone in the repeating unit of the main chain (1).

[0020] The resin (1) having an imide backbone in the repeating units of the main chain exhibits excellent heat resistance due to its imide backbone, and the main chain is not easily decomposed even under high-temperature processing at temperatures above 300°C. Therefore, by using a reactive resin containing the resin (1) having an imide backbone in the repeating units of the main chain, the aforementioned photocurable adhesive can prevent over-adhesion or residue formation during peeling, even under high-temperature processing at temperatures above 300°C.

[0021] The aforementioned reactive resin only needs to include the resin (1) having an imide skeleton in the repeating unit of the main chain, and the reactive resin as a whole needs to be reactive. The resin (1) having an imide skeleton in the repeating unit of the main chain can be reactive on its own, or it can be non-reactive. It should be noted that if the resin (1) having an imide skeleton in the repeating unit of the main chain is not reactive on its own, the reactive resin must also contain other components with reactive functional groups to make the reactive resin as a whole reactive.

[0022] The resin (1) having an imide skeleton in the repeating unit of the main chain is not particularly limited, but is preferably a resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain, or a resin (1-II) not having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain. These resins (1) having an imide skeleton in the repeating unit of the main chain can be used alone or in combination of two or more.

[0023] By using a resin (1-I) containing functional groups with double bonds and an imide backbone in the repeating units of the main chain, the aforementioned photocurable adhesive undergoes uniform and rapid polymerization and crosslinking upon light irradiation, resulting in an increase in elastic modulus and a significant reduction in adhesive strength. Therefore, it is possible to prevent over-adhesion or the formation of adhesive residue upon peeling.

[0024] Examples of functional groups possessing double bonds include substituted maleimide groups, citrile imide groups, vinyl ether groups, allyl groups, and (meth)acryloyl groups. Among these, substituted maleimide groups are preferred from the perspective of obtaining higher heat resistance.

[0025] In the resin (1-I) having double-bonded functional groups and an imide backbone in the repeating unit of the main chain, the functional group equivalent (weight-average molecular weight / number of double-bonded functional groups) is preferably 4000 or less. By setting the functional group equivalent to 4000 or less, the photocurable adhesive exhibits higher heat resistance. This is believed to be because: by having double-bonded functional groups at a certain or higher density in the resin molecule, the inter-crosslinking distance becomes shorter, thereby further suppressing adhesion hyperactivity. The functional group equivalent is more preferably 3000 or less, and more preferably 2000 or less. The lower limit of the functional group equivalent is not particularly limited, but is substantially around 600.

[0026] The weight-average molecular weight (Mw) of the resin (1-I) having double-bonded functional groups and an imide backbone in the repeating unit of the main chain is preferably 1,000 or more and 100,000 or less. By having a weight-average molecular weight of 1,000 or more, the film formation of the photocurable adhesive becomes easier, and the resulting photocurable adhesive layer exhibits a certain degree of flexibility. Therefore, it can exhibit high conformability to substrates with uneven surfaces and can be peeled off more easily. By having a weight-average molecular weight of 100,000 or less, the solubility of the resin (1-I) having double-bonded functional groups and an imide backbone in the repeating unit of the main chain in the solvent can be prevented from becoming excessively low. More preferably, the weight-average molecular weight is 1,500 or more and 50,000 or less, and even more preferably 2,000 or more and less than 20,000.

[0027] It should be noted that the above weight-average molecular weight was determined by gel permeation chromatography (GPC) and expressed as a polystyrene-converted molecular weight. More specifically, an APC system (Waters Corporation or equivalent) can be used, with a THF mobile phase, a flow rate of 1.0 mL / min, a column temperature of 40 °C, a sample concentration of 0.2 wt%, and an RI-PDA detector. As the column, an HR-MB-M 6.0 × 150 mm column (trade name, Waters Corporation or equivalent) can be used.

[0028] In the resin (1-I) described above, which has a double-bonded functional group and an imide backbone in the repeating unit of the main chain, the double-bonded functional group can be located at any position in the side chain or at the ends, preferably at both ends, and more preferably in the side chain in addition to the ends. The double-bonded functional groups at the ends of the resin (1-I) having a double-bonded functional group and an imide backbone in the repeating unit of the main chain are highly reactive, allowing for more complete curing of the photocurable adhesive by light irradiation. As a result, it is possible to further prevent over-adhesion or the formation of adhesive residue upon peeling.

[0029] Furthermore, by having double-bonded functional groups on the side chains of the resin (1-I) having a double-bonded functional group and an imide backbone in the repeating unit of the main chain, the aforementioned photocurable adhesive exhibits higher heat resistance. This is believed to be because the inter-crosslinking distance is shortened, thereby further suppressing adhesion hyperplasia. Additionally, by having double-bonded functional groups on the side chains of the resin (1-I) having a double-bonded functional group and an imide backbone in the repeating unit of the main chain, even if the weight-average molecular weight is set to 1000 or higher, the functional group equivalent can be easily adjusted to 4000 or lower. Therefore, the aforementioned photocurable adhesive, while possessing sufficient initial adhesive strength, can further prevent adhesion hyperplasia or residue formation during peeling.

[0030] As for the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain, examples of such resins include: resins having structural units shown in general formula (1a), general formula (1b), and general formula (1c) (where s > 0, t ≥ 0, u ≥ 0), and having X at both ends respectively. 1 and X 2 The resin represented is (1-i).

[0031] [Chemical Formula 1]

[0032]

[0033] In general formulas (1a) to (1c), P 1 P 2 and P 3 Each of the aromatic groups is represented independently, Q 1 Q represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group. 2 The group represents a substituted or unsubstituted aromatic structure, where R represents a substituted or unsubstituted branched aliphatic or aromatic group. (Selected from X) 1 X2 and X 3 At least one of them represents a functional group with a double bond.

[0034] In the above general formulas (1a) to (1c), P 1 P 2 and P 3 Preferably, it is an aromatic group having 5 to 50 carbon atoms. By making P... 1 P 2 and P 3 With aromatic groups having 5 to 50 carbon atoms, the aforementioned photocurable adhesives exhibit superior heat resistance. That is, even under high-temperature processing at temperatures above 300°C, they can further prevent over-adhesion or residue buildup during peeling.

[0035] In the above general formula (1a), Q 1 Preferably, it is a linear, branched, or cyclic aliphatic group with 2 to 100 carbon atoms, either substituted or unsubstituted. By making Q... 1 The aforementioned photocurable adhesives, by using substituted or unsubstituted linear, branched, or cyclic aliphatic groups with 2 to 100 carbon atoms, can exhibit high light transmittance. Furthermore, photocurable adhesive layers containing the aforementioned photocurable adhesives exhibit high flexibility, high conformability to uneven substrates, and easier peeling upon release.

[0036] In addition, Q 1 Preferably, it is an aliphatic group derived from a diamine compound, as described below. From the viewpoints of improving light transmittance, improving flexibility, and from the viewpoint that the resin (1-I) having a double-bonded functional group and an imide backbone in the repeating unit of the main chain increases compatibility with solvents and other components, thus facilitating the formation of a photocurable adhesive layer, Q 1 Preferably, it is an aliphatic group derived from a dimer diamine.

[0037] The aliphatic group derived from the dimer diamine is preferably selected from at least one of the groups shown in general formula (4-1), general formula (4-2), general formula (4-3), and general formula (4-4). More preferably, it is the group shown in general formula (4-2).

[0038] [Chemical Formula 2]

[0039]

[0040] In general formulas (4-1) to (4-4), R 1 ~R 8 and R13 ~R 20 Each can be represented independently as a straight-chain or branched hydrocarbon group. It should be noted that * indicates a bonded bond. The bonded bond * is bonded to the N in the above general formulas (1a) to (1c).

[0041] In the above general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 The hydrocarbon group shown is not particularly limited and can be either saturated or unsaturated. Wherein, R... 1 With R 2 R 3 With R 4 R 5 With R 6 R 7 With R 8 R 13 With R 14 R 15 With R 16 R 17 With R 18 and R 19 With R 20 The total number of carbon atoms is preferably 7 or more and 50 or less. By keeping the total number of carbon atoms within the above range, the above-mentioned photocurable adhesive can have higher light transmittance. In addition, the photocurable adhesive layer containing the above-mentioned photocurable adhesive can exhibit higher flexibility. Furthermore, the compatibility of the above-mentioned resin (1-I) having functional groups with double bonds and having an imide skeleton in the repeating unit of the main chain with solvents and other components is further increased. The total number of carbon atoms is more preferably 9 or more, more preferably 12 or more, and more preferably 14 or more. The total number of carbon atoms is more preferably 35 or less, more preferably 25 or less, and more preferably 18 or less.

[0042] Optical isomerism is not particularly limited in the groups shown in general formula (4-1), general formula (4-2), general formula (4-3), and general formula (4-4), and includes any optical isomerism.

[0043] In the above general formula (1b), Q 2 Preferably, it has an aromatic structure with substituted or unsubstituted carbon groups having 5 to 50 carbon atoms. By making Q... 2 The above-mentioned photocurable adhesives, having aromatic groups with substituted or unsubstituted carbon atoms of 5 to 50, exhibit superior heat resistance. That is, even under high-temperature processing at 300°C or above, they can further prevent over-adhesion or residue buildup during peeling.

[0044] In the above general formula (1c), R is preferably a substituted or unsubstituted branched aliphatic or aromatic group with 2 to 100 carbon atoms. By making R a substituted or unsubstituted branched aliphatic or aromatic group with 2 to 100 carbon atoms, the photocurable adhesive layer containing the above-mentioned photocurable adhesive can exhibit high flexibility, high conformability to substrates with uneven surfaces, and easier peeling upon removal.

[0045] In the above general formula (1c), R is an aromatic group having an aromatic ester group or an aromatic ether group, and the aromatic ester group or the aromatic ether group in R is preferably related to X. 3 Bonding.

[0046] Here, "aromatic ester group" refers to a group with an ester group directly bonded to an aromatic ring, and "aromatic ether group" refers to a group with an ether group directly bonded to an aromatic ring. In this way, by making the portions bonded to the ester and ether groups aromatic groups, the aforementioned photocurable adhesive can exhibit higher heat resistance. That is, even under high-temperature processing above 300°C, it is possible to further prevent over-adhesion or residue formation during peeling. On the other hand, by making X... 3 X is bonded to R via an aromatic ester or aromatic ether group. 3 The double bonds in the R are not conjugated with R, therefore, they do not hinder the polymerization and crosslinking during heating or irradiation.

[0047] In the resin (1-I) described above, which has a double-bonded functional group and an imide backbone in the repeating unit of the main chain, the double-bonded functional group (crosslinked unsaturated bond) is selected from X. 1 X 2 and X 3 At least one of them is acceptable, preferably at least X. 3 It is a functional group possessing a double bond. By making at least X 3 Because it possesses double-bonded functional groups, the aforementioned photocurable adhesive exhibits superior heat resistance. That is, even under high-temperature processing at temperatures above 300°C, it can further prevent over-adhesion or the formation of adhesive residue upon peeling.

[0048] In the above X 1 X 2 and X 3If any of the functional groups in the formula is a functional group other than one possessing a double bond (a functional group without a double bond), examples of such functional groups without double bonds can be independently listed, such as: aliphatic groups, alicyclic groups, aromatic groups, acid anhydrides, amine compounds, etc. Specifically, examples include: unreacted single-terminal products of acid anhydrides and diamine compounds that serve as raw materials for the resin (1-I) that has a functional group possessing a double bond and has an imide skeleton in the repeating unit of the main chain.

[0049] In the resin (1-I) described above, which has a functional group possessing a double bond and an imide skeleton in the repeating unit of the main chain, examples of functional groups possessing a double bond include substituted maleimide groups, citrile imide groups, vinyl ether groups, allyl groups, (meth)acryloyl groups, etc. Among these, substituted maleimide groups or allyl groups are preferred from the viewpoint of obtaining higher heat resistance, and tri(iso)cyanurate groups having one or more allyl groups are further preferred from the viewpoint of obtaining particularly high adhesion.

[0050] In the above general formulas (1a) to (1c), s, t and u correspond to the content (mol%) of the structural unit shown in general formula (1a), the structural unit shown in general formula (1b) and the structural unit shown in general formula (1c) in the above resin (1-I) having a functional group with double bonds and having an imide skeleton in the repeating unit of the main chain.

[0051] The content (s) of the structural unit shown in the above general formula (1a) is greater than 0 mol%, preferably 30 mol% or more, more preferably 50 mol% or more, more preferably 90 mol% or less, and more preferably 80 mol% or less. The content (t) of the structural unit shown in the above general formula (1b) is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, preferably 50 mol% or less, and more preferably 30 mol% or less. The content (u) of the structural unit shown in the above general formula (1c) is 0 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 50 mol% or less, and more preferably 30 mol% or less. When the content of each structural unit in the above general formulas (1a) to (1c) is within the above range, the above-mentioned photocurable adhesive can further prevent the occurrence of adhesive over-adhesion or the generation of residual adhesive during peeling.

[0052] It should be noted that the structural unit shown in general formula (1a), the structural unit shown in general formula (1b), and the structural unit shown in general formula (1c) can have a block structure containing block components arranged continuously, or they can have a random structure in which the structural units are arranged randomly.

[0053] The method for manufacturing the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain is not particularly limited. For example, an imide compound can be prepared by reacting a diamine compound with an aromatic anhydride, and further reacted with the functional group of the imide compound, a compound having a functional group that reacts with the functional group and a functional group having double bonds (hereinafter referred to as an unsaturated compound containing functional groups). Alternatively, for example, an imide compound can be prepared by reacting a diamine compound with an aromatic anhydride, and further reacted with the end of the imide compound, such as maleic anhydride.

[0054] As the aforementioned diamine compound, any diamine compound from aliphatic or aromatic diamine compounds can be used.

[0055] By using an aliphatic diamine compound as the diamine compound, the aforementioned photocurable adhesive exhibits high light transmittance. Furthermore, the photocurable adhesive layer containing the aforementioned photocurable adhesive exhibits high flexibility, high conformability to uneven substrates, and easier peeling upon removal. By using an aromatic diamine compound as the diamine compound, the heat resistance of the aforementioned photocurable adhesive is further improved. Additionally, by using a diamine compound with a functional group as the diamine compound, and reacting the aforementioned unsaturated compound containing the functional group with the functional group, a resin (1-I) with a double bond functional group in its side chain can be manufactured.

[0056] These aliphatic diamine compounds, aromatic diamine compounds, and diamine compounds with functional groups can be used alone or in combination of two or more.

[0057] Examples of the aforementioned aliphatic diamine compounds include: 1,10-diaminodecane, 1,12-diaminododecane, dimerized 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-diaminomenthtane, 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.

[0058] Examples of the aforementioned aromatic diamine compounds include: 9,10-diaminophenanthrene, 4,4'-diaminooctafluorobiphenyl, 3,7-diamino-2-methoxyfluorene, 4,4'-diaminobenzophenone, 3,4-diaminobenzophenone, 3,4-diaminotoluene, 2,6-diaminoanthraquinone, 2,6-diaminotoluene, 2,3-diaminotoluene, 1,8-diaminonaphthalene, 2,4-diaminotoluene, 2,5-diaminotoluene, 1,4-diaminoanthraquinone, 1,5 -Diaminoanthraquinone, 1,5-diaminonaphthalene, 1,2-diaminoanthraquinone, 2,4-isopropylphenylenediamine, 1,3-diaminotoluene, 1,3-diaminomethylcyclohexane, 2-chloro-1,4-diaminobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-2,5-dimethylbenzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, bis(amino-3-chlorophenyl)ethane, bis(4-amino-3,5-dimethylphenyl)methane, bis( 4-Amino-3,5-Diethylphenyl)methane, bis(4-amino-3-ethyldiaminofluorene), 2,3-diaminonaphthalene, 2,3-diaminophenol, 5-methylphenyl)methane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, 4,4'-diaminophenyl sulfone, 3,3'-diaminophenyl sulfone, 2,2-bis(4,(4-aminophenoxy)phenyl)sulfone, 2,2-bis(4-(3-aminophenoxy)phenyl)sulfone 4,4'-Oxydiphenylamine, 4,4'-Diaminodiphenyl sulfide, 3,4'-Oxydiphenylamine, 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-toluidine sulfone, methylene bis(o-aminobenzoic acid), 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 3,3',5,5'-tetramethylbenzidine, 4,4'-diaminobenzoylaniline, 2,2-bis(4-aminophenyl)hexafluoropropane, polyoxyethylene diamines (e.g., Huntsman's Jeffamine D-230, D400, D-2000 and D-4000), 1,3-cyclohexanebis(methylamine), m-phenylenediamine, p-phenylenediamine, etc.

[0059] Among the aforementioned aliphatic diamine compounds, from the viewpoints of improving light transmittance, improving flexibility, and increasing the compatibility of the resin (1-I) having a double-bonded functional group and an imide skeleton in the repeating unit of the main chain with solvents and other components, thereby facilitating the formation of a photocurable adhesive layer, dimer diamine is preferred.

[0060] The aforementioned dimer diamines refer to diamine compounds obtained by reducing and amination of cyclic and acyclic dimer acids, which are dimers of unsaturated fatty acids. Examples of dimer diamines include linear, monocyclic, and polycyclic types. These dimer diamines may contain carbon-carbon unsaturated double bonds or may be hydrides with added hydrogen. More specifically, examples of dimer diamines include those capable of forming the groups shown in general formula (4-1), general formula (4-2), general formula (4-3), and general formula (4-4).

[0061] Examples of diamine compounds having functional groups include diamine compounds having hydroxyl groups, diamine compounds having carboxyl groups, and diamine compounds having halogen groups.

[0062] Examples of diamine compounds containing 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 diamine compounds containing a carboxyl group include 3,5-diaminobenzoic acid. Examples of diamine compounds containing a halogen group include 2,4-diaminochlorobenzene.

[0063] Examples of the aforementioned aromatic anhydrides include: pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyl ethertetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridine... Pyridine tetracarboxylic acid, 3,4,9,10-peryltetracarboxylic acid, 4,4'-sulfonyl diphthalic acid, 1-trifluoromethyl-2,3,5,6-benzyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic 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'-benzophenone tetracarboxylic acid, 2,3,3',4'-benzophenone tetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid Pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4,3',4'-biphenyltetracarboxylic acid, 2,3,2',3'-biphenyltetracarboxylic acid, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic acid), etc.

[0064] As the aforementioned unsaturated compounds containing functional groups, the choice of which to use depends on the functional groups at the end or side chain of the aforementioned imide compound.

[0065] For example, when the terminal or side chain functional group of the aforementioned imide compound is a hydroxyl group, maleimide compounds having a carboxyl group can be cited. Examples of such carboxyl-containing maleimide compounds include: maleimide acetate, maleimide propionic acid, maleimide butyric acid, maleimide hexanoic acid, trans-4-(N-maleimidemethyl)cyclohexane-1-carboxylic acid, and 19-maleimide-17-oxo-4,7,10,13-tetraoxa-16-azanonadecanoic acid. Furthermore, examples include: vinyl compounds having an ether group such as butyl vinyl ether, allyl compounds having a glycidyl group such as diallyl monoglycidyl isocyanurate, allyl glycidyl ethers, and allyl ether compounds having a glycidyl group such as glyceryl diallyl monoglycidyl ether. In addition, examples include glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, glycidyl cyclohexanediethanol monovinyl ether, and other vinyl ether compounds containing a glycidyl group. Furthermore, examples include allyl compounds containing an isocyanate group, such as allyl isocyanate, and (meth)acryloyl compounds containing an isocyanate group, such as 2-(meth)acryloyloxyethyl isocyanate.

[0066] Furthermore, for example, when the terminal or side chain functional group of the aforementioned imide compound is a carboxyl group, examples include: allyl compounds with a hydroxyl group such as trimethylolpropane diallyl ether and pentaerythritol triallyl ether, and allyl compounds with a glycidyl group such as diallyl monoglycidyl isocyanurate. Additionally, examples include: allyl glycidyl ether and glyceryl diallyl monoglycidyl ether, which are allyl ether compounds with a glycidyl group. Furthermore, examples include: glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxyhexyl vinyl ether, glycidyl diethylene glycol vinyl ether, and glycidyl cyclohexanediethanol monovinyl ether, which are vinyl ether compounds with a glycidyl group.

[0067] When the reactive resin includes the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain, the content of the resin (1-I) is not particularly limited, but the preferred lower limit is 10 parts by weight and the preferred upper limit is 100 parts by weight in 100 parts by weight of the reactive resin. When the content of the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain is within this range, the photocurable adhesive can be peeled off more easily. From the viewpoint of further improving peelability, the more preferred lower limit of the content of the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain is 20 parts by weight, the more preferred lower limit is 30 parts by weight, the more preferred upper limit is 90 parts by weight, the more preferred upper limit is 80 parts by weight, and the more preferred upper limit is 70 parts by weight.

[0068] The weight-average molecular weight (Mw) of the resin (1-II) that does not have functional groups with double bonds and has an imide backbone in the repeating unit of the main chain is preferably 20,000 or more. By making the weight-average molecular weight 20,000 or more, the above-mentioned photocurable adhesive can exhibit higher heat resistance. That is, even when subjected to high-temperature processing at 300°C or above, it is possible to further prevent over-adhesion or residue formation during peeling. The weight-average molecular weight is more preferably 50,000 or more. There is no particular upper limit to the weight-average molecular weight, but from the viewpoint of solubility in solvents, a preferred upper limit is 600,000, and a more preferred upper limit is 300,000.

[0069] It should be noted that the above-mentioned weight-average molecular weight can be measured in the same way as the above-mentioned resin (1-I) which has a functional group with double bonds and an imide skeleton in the repeating unit of the main chain.

[0070] As a resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain, examples include: a resin having a structural unit shown in the following general formula (1d) and a structural unit shown in the following general formula (1e) (where s>0, t≥0), and having X at both ends respectively. 4 and X 5 The resin represented is (1-ii).

[0071] [Chemical Formula 3]

[0072]

[0073] In general formulas (1d) to (1e), P 4 and P 5 Each of the aromatic groups is represented independently, Q 3Q represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group. 4 This indicates a group having a substituted or unsubstituted aromatic structure. X 4 and X 5 This indicates a functional group that does not possess a double bond.

[0074] In the above general formulas (1d) to (1e), P 4 and P 5 Preferably, it is an aromatic group having 5 to 50 carbon atoms. By making P... 4 and P 5 With aromatic groups having 5 to 50 carbon atoms, the aforementioned photocurable adhesives exhibit superior heat resistance. That is, even under high-temperature processing at temperatures above 300°C, it is possible to further prevent over-adhesion or the formation of adhesive residue during peeling.

[0075] In the above general formula (1d), Q 3 Preferably, it is a linear, branched, or cyclic aliphatic group with 2 to 100 carbon atoms, either substituted or unsubstituted. By making Q... 3 The aforementioned photocurable adhesives, by using substituted or unsubstituted linear, branched, or cyclic aliphatic groups with 2 to 100 carbon atoms, can exhibit high light transmittance. Furthermore, photocurable adhesive layers containing the aforementioned photocurable adhesives exhibit high flexibility, high conformability to uneven substrates, and easier peeling upon release.

[0076] In addition, Q 3 Preferably, it is an aliphatic group derived from a diamine compound as described above. From the viewpoints of improving light transmittance, improving flexibility, and considering that the resin (1-II) without double-bonded functional groups and having an imide skeleton in the repeating unit of the main chain has increased compatibility with solvents and other components, thus facilitating the formation of a photocurable adhesive from the aforementioned photocurable adhesive, Q 3 Preferably, it is an aliphatic group derived from a dimer diamine.

[0077] That is, in the temporary fixation material of the present invention, preferably at least one of the above-mentioned resin (1-I) having a functional group with double bonds and having an imide skeleton in the repeating unit of the main chain, and the above-mentioned resin (1-II) not having a functional group with double bonds and having an imide skeleton in the repeating unit of the main chain, has an aliphatic group from a dimer diamine. In other words, the above-mentioned resin (1) having an imide skeleton in the repeating unit of the main chain preferably has an aliphatic group from a dimer diamine.

[0078] In the above general formula (1e), Q 4Preferably, it has an aromatic structure with substituted or unsubstituted carbon groups having 5 to 50 carbon atoms. By making Q... 4 The above-mentioned photocurable adhesives, having aromatic groups with substituted or unsubstituted carbon atoms of 5 to 50, exhibit superior heat resistance. That is, even under high-temperature processing at 300°C or above, they can further prevent over-adhesion or residue buildup during peeling.

[0079] As for the above X 4 and X 5 The functional groups that do not possess double bonds shown can be independently exemplified by, for example, aliphatic groups, alicyclic groups, aromatic groups, acid anhydrides, and amine compounds. Specifically, examples include unreacted single-terminal products of acid anhydrides and diamine compounds that serve as raw materials for the resin (1-II) that does not possess double bond functional groups and has an imide skeleton in the repeating unit of the main chain.

[0080] In the above general formulas (1d) to (1e), s, and t correspond to the content (mol%) of the structural unit shown in the above general formula (1d) and the structural unit shown in the above general formula (1e) in the above resin (1-II) which does not have a functional group with a double bond and has an imide skeleton in the repeating unit of the main chain.

[0081] The content (s) of the structural unit shown in the above general formula (1d) is greater than 0 mol%, preferably 30 mol% or more, more preferably 50 mol% or more, more preferably 90 mol% or less, and more preferably 80 mol% or less. The content (t) of the structural unit shown in the above general formula (1e) is 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, more preferably 50 mol% or less, and more preferably 30 mol% or less. When the content of each structural unit in the above general formulas (1d) to (1e) is within the above range, the above-mentioned photocurable adhesive can further prevent the occurrence of adhesive over-adhesion or the generation of residual adhesive during peeling.

[0082] It should be noted that the structural unit shown in the above general formula (1d) and the structural unit shown in the above general formula (1e) can have a block structure containing block components arranged continuously, or it can have a random structure in which the structural units are arranged randomly.

[0083] The method for manufacturing the resin (1-II) that does not have a functional group with a double bond and has 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 anhydride. The diamine compound and the aromatic anhydride described above can be the same as the diamine compound and aromatic anhydride in the resin (1-I) that has a functional group with a double bond and has an imide skeleton in the repeating unit of the main chain as described above.

[0084] When the reactive resin includes resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain, the content of resin (1-II) is not particularly limited, but the preferred lower limit is 10 parts by weight and the preferred upper limit is 90 parts by weight per 100 parts by weight of the reactive resin. When the content of resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain is within this range, the photocurable adhesive can be peeled off more easily. From the viewpoint of further improving peelability, the more preferred lower limit of the content of resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain is 20 parts by weight, and the more preferred upper limit is 80 parts by weight.

[0085] The reactive resin described above preferably further comprises a multifunctional monomer or multifunctional oligomer (2) having two or more functional groups with double bonds in the molecule and a molecular weight of 5,000 or less (hereinafter, sometimes simply referred to as "multifunctional monomer or multifunctional oligomer (2)").

[0086] By including the above-mentioned multifunctional monomers or multifunctional oligomers (2), the three-dimensional networking of the above-mentioned photocurable adhesive by means of light irradiation is carried out with better efficiency, and the situation of over-adhesion or residue during peeling can be further prevented.

[0087] It should be noted that, as described above, when the resin (1) having an imide skeleton in the repeating unit of the main chain is not reactive itself, it is necessary to make the reactive resin reactive as a whole by also containing other components having reactive functional groups. As such other components having reactive functional groups, the multifunctional monomer or multifunctional oligomer (2) described above is preferred. When the resin (1) having an imide skeleton in the repeating unit of the main chain is not reactive itself, examples can be given such as the case where the resin (1) having an imide skeleton in the repeating unit of the main chain contains only the resin (1-II) that does not have a double bond functional group and has an imide skeleton in the repeating unit of the main chain.

[0088] Examples of functional groups containing double bonds in the aforementioned multifunctional monomers or multifunctional oligomers (2) include substituted maleimide groups, citrile imide groups, vinyl ether groups, allyl groups, (meth)acryloyl groups, etc. Among these, substituted maleimide groups are preferred from the perspective of obtaining higher heat resistance.

[0089] The aforementioned multifunctional monomer or multifunctional oligomer (2) preferably has an aliphatic group derived from the diamine compound. As the diamine compound, any of an aliphatic or aromatic diamine compound can be used, with an aliphatic diamine compound being preferred. By using an aliphatic diamine compound as the diamine compound, the aforementioned photocurable adhesive can exhibit high light transmittance. Furthermore, the photocurable adhesive layer containing the aforementioned photocurable adhesive exhibits high flexibility, high conformability to uneven substrates, and easier peeling upon removal.

[0090] Among the above-mentioned aliphatic diamine compounds, from the viewpoints of improving light transmittance, improving flexibility, and increasing the compatibility of the above-mentioned multifunctional monomers or multifunctional oligomers (2) with solvents and other components, thereby making it easier to form a photocurable adhesive layer, the dimer diamine described above is preferred.

[0091] The content of the aforementioned multifunctional monomer or multifunctional oligomer (2) is not particularly limited, but the preferred lower limit for its proportion in 100 parts by weight of the aforementioned reactive resin is 5 parts by weight, and the preferred upper limit is 100 parts by weight. When the content of the aforementioned multifunctional monomer or multifunctional oligomer (2) is within this range, the aforementioned photocurable adhesive can be peeled off more easily upon peeling. From the viewpoint of further improving peelability, the more preferred lower limit for the content of the aforementioned multifunctional monomer or multifunctional oligomer (2) is 10 parts by weight, and the more preferred upper limit is 50 parts by weight.

[0092] When the reactive resin comprises the resin (1-I) having a functional group with double bonds and an imide backbone in the repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer (2), the content is not particularly limited. The preferred lower limit of the total content in 100 parts by weight of the reactive resin is 20 parts by weight, and the preferred upper limit is 80 parts by weight. When the total content of the resin (1-I) and the polyfunctional monomer or polyfunctional oligomer (2) is within this range, the photocurable adhesive can be peeled off more easily. From the viewpoint of further improving peelability, the more preferred lower limit of the total content of the resin (1-I) and the polyfunctional monomer or polyfunctional oligomer (2) is 30 parts by weight, the more preferred lower limit is 40 parts by weight, the more preferred lower limit is 50 parts by weight, and the more preferred upper limit is 70 parts by weight.

[0093] The above-mentioned photocurable adhesive may contain the above-mentioned reactive resin, and preferably also contains organosilicon compounds or fluorine compounds.

[0094] The aforementioned organosilicon compounds and fluorine compounds have excellent heat resistance. Therefore, even after high-temperature processing at temperatures above 300°C, the aforementioned photocurable adhesives are prevented from scorching and seeping into the interface of the adhered objects during peeling, making peeling easier.

[0095] The aforementioned organosilicon compounds are not particularly limited; examples include silicone oils, siloxane diacrylates, and organosilicon graft copolymers. The aforementioned fluorine compounds are not particularly limited; examples include hydrocarbon compounds containing fluorine atoms.

[0096] The aforementioned organosilicon compounds or fluorine compounds preferably have functional groups capable of crosslinking with the aforementioned reactive resins.

[0097] By incorporating functional groups into the aforementioned organosilicon or fluorine compound that enable crosslinking with the aforementioned reactive resin, the organosilicon or fluorine compound is introduced into the reactive resin through a chemical reaction via light irradiation or reaction with a crosslinking agent. Therefore, it is possible to suppress the adhesion of the organosilicon or fluorine compound to the adhered material, thus preventing contamination. The functional groups capable of crosslinking with the reactive resin are not particularly limited, but examples include: carboxyl groups, free radical polymerizable unsaturated bonds (e.g., vinyl, (meth)acryloyl, substituted maleimide groups), hydroxyl groups, amide groups, isocyanate groups, epoxy groups, etc.

[0098] From the perspective of environmental friendliness and ease of disposal, organosilicon compounds having functional groups capable of crosslinking with the aforementioned reactive resins are preferred.

[0099] As an organosilicon compound having functional groups capable of crosslinking with the aforementioned reactive resin, an organosilicon compound having a siloxane backbone in the main chain and functional groups having double bonds in the side chains or at the ends is preferred.

[0100] The organosilicon compounds having a siloxane backbone in the main chain and functional groups with double bonds in the side chains or at the ends are not particularly limited, but preferably contain at least one selected from the organosilicon compounds shown in general formula (I), general formula (II), and general formula (III). These organosilicon compounds have particularly high heat resistance and high polarity, and therefore readily exude from the aforementioned photocurable adhesives.

[0101] [Chemical Formula 4]

[0102]

[0103] In the above general formulas (I), (II), and (III), X and Y independently represent integers from 0 to 1200, and R represents a functional group with a double bond.

[0104] In the above general formulas (I), (II), and (III), examples of functional groups with double bonds represented by R include substituted maleimide groups, citrileimide groups, vinyl ether groups, allyl groups, and (meth)acryloyl groups. Among these, substituted maleimide groups are preferred from the perspective of obtaining higher heat resistance. It should be noted that in the above general formulas (I), (II), and (III), when multiple Rs are present, the multiple Rs may be the same or different.

[0105] Commercially available examples of organosilicon compounds represented by general formulas (I), (II), and (III) include EBECRYL 350 and EBECRYL 1360 (both manufactured by Daicel Cytec). Other examples include BYK-UV3500 (manufactured by BYKChemie) and TEGO RAD2250 (manufactured by Evonik) (where R stands for acryloyl).

[0106] The content of the aforementioned silicone or fluorine compound is not particularly limited, but the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 20 parts by weight relative to 100 parts by weight of the aforementioned reactive resin. When the content of the aforementioned silicone or fluorine compound is within this range, the aforementioned photocurable adhesive can exhibit excellent peelability without contaminating the adhered material. From the viewpoint of further improving peelability while suppressing contamination, the more preferred lower limit of the content of the aforementioned silicone or fluorine compound is 0.3 parts by weight, and the more preferred upper limit is 10 parts by weight.

[0107] It should be noted that the aforementioned photocurable adhesives exhibit excellent heat resistance; therefore, even with relatively low concentrations of the aforementioned organosilicon or fluorine compounds, they can still achieve sufficient effectiveness. This further reduces pollution caused by the aforementioned organosilicon or fluorine compounds.

[0108] The aforementioned photocurable adhesives may also contain inorganic fillers.

[0109] By including the aforementioned inorganic filler, the reduction in the elastic modulus of the aforementioned photocurable adhesive at high temperatures is suppressed. Therefore, even when subjected to high-temperature processing at temperatures above 300°C, peeling during high-temperature processing can be further suppressed.

[0110] The aforementioned inorganic filler is not particularly limited, and examples include inorganic fillers containing at least one selected from oxides of silicon, titanium, aluminum, calcium, boron, magnesium, and zirconium oxide, and their complexes. Among these, silica and talc are preferred from the perspective of being commercially available, inexpensive, and readily available.

[0111] The aforementioned inorganic filler can be surface-modified. The functional groups used for surface modification of the inorganic filler are not particularly limited, and examples include alkylsilyl, methacryl, and dimethylsiloxane. Among these, dimethylsiloxane is preferred from the perspective of providing moderate hydrophobicity.

[0112] The average particle size of the aforementioned 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 aforementioned inorganic filler is within this range, the aforementioned photocurable adhesive can further suppress peeling during high-temperature processing and can be peeled off during peeling. A more preferred lower limit for the average particle size of the aforementioned inorganic filler is 10 nm, a more preferred upper limit is 20 μm, a further preferred lower limit is 15 nm, and a further preferred upper limit is 15 μm.

[0113] It should be noted that the above-mentioned average particle size is preferably the number-average particle size. The above-mentioned average particle size can be calculated, for example, by observing any 50 inorganic fillers using an electron microscope or an optical microscope and calculating the average particle size of each inorganic filler; and by performing laser diffraction particle size distribution measurement.

[0114] The content of the aforementioned inorganic filler is not particularly limited, but the preferred lower limit is 1 part by weight relative to 100 parts by weight of the aforementioned reactive resin, and the preferred upper limit is 20 parts by weight. When the content of the aforementioned inorganic filler is within this range, the aforementioned photocurable adhesive can further suppress peeling during high-temperature processing and can be peeled off by a peeling treatment during peeling. The more preferred lower limit of the aforementioned inorganic filler content is 3 parts by weight, the more preferred upper limit is 15 parts by weight, the even more preferred lower limit is 5 parts by weight, and the even more preferred upper limit is 10 parts by weight.

[0115] The aforementioned photocurable adhesive preferably further comprises a photopolymerization initiator.

[0116] Examples of photopolymerization initiators include those activated by irradiation with light of wavelengths from 250 to 800 nm. From the perspective of minimizing overlap with the absorption wavelength of the reactive resin and ensuring sufficient activation when the temporary fixation material is irradiated with light, the photopolymerization initiator preferably contains a molar absorptivity of 1 or more at 405 nm. More preferably, it contains a photopolymerization initiator containing a molar absorptivity of 200 or more at 405 nm, and even more preferably, it contains a photopolymerization initiator containing a molar absorptivity of 350 or more at 405 nm. The upper limit of the molar absorptivity at 405 nm for the photopolymerization initiator containing a molar absorptivity of 1 or more at 405 nm is not particularly limited, but may be, for example, 2000 or 1500.

[0117] Examples of photopolymerization initiators include: acetophenone derivatives such as methoxyacetophenone, acetophenone propyl ether, acetophenone isobutyl ether, benzoin ether compounds, benzoin dimethyl ketal, acetophenone diethyl ketal, and phosphine oxide derivative compounds. Additionally, examples include: bis(n-5-cyclopentadienyl)dicenoctane derivatives, benzophenone, miconazole, chlorothioxanone, dodecylthioxanone, dimethylthioxanone, diethylthioxanone, α-hydroxycyclohexylphenyl ketone, and 2-hydroxymethylphenylpropane, among other photoradical polymerization initiators. These photopolymerization initiators can be used alone or in combination of two or more.

[0118] The content of the aforementioned photopolymerization initiator is not particularly limited, but the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 10 parts by weight relative to 100 parts by weight of the aforementioned reactive resin. When the content of the aforementioned photopolymerization initiator is within this range, the aforementioned photocurable adhesive undergoes uniform and rapid polymerization and cross-linking upon light irradiation, resulting in an increase in elastic modulus. Consequently, the adhesive strength is significantly reduced, preventing over-adhesion or residue formation during peeling. The more preferred lower limit of the aforementioned photopolymerization initiator content is 0.3 parts by weight, and the more preferred upper limit is 3 parts by weight.

[0119] The aforementioned photocurable adhesive may further include a gas-generating agent that produces gas upon exposure to light. By containing this gas-generating agent, even after processing at temperatures above 300°C, the gas generated by light exposure is released to the interface with the adhered materials, thus enabling easier and residue-free peeling of the adhered materials. Furthermore, even when peeling thin adhered materials after processing at temperatures above 300°C, damage to the adhered materials can be prevented.

[0120] In TG-DTA (thermogravimetric-differential calorimetry) measurements, the weight loss rate at 300°C when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere is preferably 5% or less. When the weight loss rate is 5% or less, the gas-generating agent is less likely to decompose even under high-temperature processing at temperatures above 300°C, and the photocurable adhesive exhibits higher heat resistance. That is, peeling can be further suppressed during high-temperature processing, and situations of over-adhesion or residue formation during peeling can be further prevented.

[0121] It should be noted that TG-DTA (thermogravimetric-differential calorimetry) determinations can be performed, for example, using a TG-DTA apparatus (STA7200RV, manufactured by Hitachi High-Tech Science, or equivalent).

[0122] Examples of gas generating agents include gas generating agents that generate gas by heating and gas generating agents that generate gas by irradiation with light. These gas generating agents can be used alone or in combination of two or more. Among them, gas generating agents that generate gas by irradiation with light are preferred, and gas generating agents that generate gas by irradiation with ultraviolet light are more preferred.

[0123] Examples of gas generating agents that produce gas by irradiation include tetrazolium compounds or their salts, triazole compounds or their salts, azo compounds, azido compounds, xanthonesone acetate, and carbonates. These gas generating agents can be used alone or in combination of two or more. Among them, tetrazolium compounds or their salts are preferred from the perspective of particularly excellent heat resistance.

[0124] The content of the aforementioned gas-generating agent is not particularly limited, but the preferred lower limit is 5 parts by weight and the preferred upper limit is 50 parts by weight relative to 100 parts by weight of the aforementioned reactive resin. When the content of the aforementioned gas-generating agent is within this range, the aforementioned photocurable adhesive can exhibit particularly excellent peelability. The more preferred lower limit of the content of the aforementioned gas-generating agent is 8 parts by weight, and the more preferred upper limit is 30 parts by weight.

[0125] The aforementioned photocurable adhesives may include, for example, known additives such as photosensitizers, heat stabilizers, antioxidants, antistatic agents, plasticizers, resins, surfactants, and waxes.

[0126] There are no particular limitations on the method for manufacturing the above-mentioned photocurable adhesive. For example, a method can be used to mix a reactive resin containing the above-mentioned resin (1) having an imide skeleton in the repeating unit of the main chain with additives as needed, such as a bead mill, ultrasonic disperser, homogenizer, high-output disperser, or roller mill.

[0127] As described above, the temporary fixing material of the present invention is not particularly limited as long as it contains the aforementioned photocurable adhesive. It can be a liquid temporary fixing adhesive or a sheet-like temporary fixing adhesive sheet having a photocurable adhesive layer containing the aforementioned photocurable adhesive.

[0128] The preferred lower limit for the gel content of the cured photocurable adhesive layer containing the aforementioned photocurable adhesive is 20% by weight, and the preferred upper limit is 99% by weight. By keeping the cured gel content within the above range, the photocurable adhesive layer can be peeled off more easily upon removal. A more preferred lower limit for the cured gel content is 40% by weight, a further preferred lower limit is 60% by weight, a further more preferred lower limit is 80% by weight, and a more preferred upper limit is 95% by weight.

[0129] It should be noted that the gel fraction after curing mentioned above is based on 1000 mJ / cm². 2 The irradiation intensity of 405nm on the photocurable adhesive layer is 70mW / cm. 2 After exposure to ultraviolet light, measurements were performed using the following method.

[0130] The UV-curable adhesive layer was cut into 50mm × 100mm rectangular pieces to prepare test specimens. The test specimens were 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 specimens was measured, and the gel fraction was calculated using the following formula (1). It should be noted that no release film for protecting the UV-curable adhesive layer was laminated onto the test specimens.

[0131] Gel fraction (wt%) = 100 × (W2 - W0) / (W1 - W0) (1)

[0132] (W0: Weight of the substrate, W1: Weight of the test piece before impregnation, W2: Weight of the test piece after impregnation and drying)

[0133] The elastic modulus of the photocurable adhesive layer containing the above-mentioned photocurable adhesive at 25°C after curing is preferably 1×10⁻⁶. 7 Pa or above.

[0134] By ensuring that the elastic modulus at 25°C after curing is within the aforementioned range, the temporary fixing material is less prone to breakage when peeled from the adhered object. As a result, residual adhesive can be further suppressed. More preferably, the elastic modulus at 25°C after curing is 5 × 10⁻⁶. 7 Pa or higher, more preferably 1×10 8 Pa or higher. The upper limit of the elastic modulus at 25°C after curing is not particularly limited, but from the viewpoint of adhesive strength, 1×10⁻⁶ is preferred.10 Below Pa.

[0135] The elastic modulus of the photocurable adhesive layer containing the above-mentioned photocurable adhesive at 300°C after curing is preferably 1×10⁻⁶. 5 Pa or above.

[0136] By ensuring that the elastic modulus at 300°C after curing is within the aforementioned range, the increase in adhesive force during heating of the temporary fixing material can be suppressed. More preferably, the elastic modulus at 300°C after curing is 5 × 10⁻⁶. 5 Pa or higher, more preferably 1×10 6 Pa or higher. The upper limit of the elastic modulus at 300°C after curing is not particularly limited, but from the viewpoint of adhesive strength, 1×10⁻⁶ is preferred. 8 Pa or less, more preferably 1×10 Pa 7 Below Pa.

[0137] The above-mentioned elastic modulus at 25°C after curing and the above-mentioned elastic modulus at 300°C after curing can be determined by the following methods.

[0138] Test specimens measuring 5 mm × 35 mm × 0.03 mm thickness were prepared for the UV-curable adhesive layer. The specimens were then cured. The cured samples were immersed in liquid nitrogen and cooled to -50°C. Then, using a viscoelastic spectrometer (e.g., DVA-200, manufactured by IT Measurement & Control Co., Ltd.), the temperature was raised to 300°C under constant-rate heating tensile mode, a heating rate of 10°C / min, and a frequency of 10 Hz. The storage modulus was measured. Based on the obtained storage modulus results, the elastic modulus at 25°C and the elastic modulus at 300°C after curing were determined.

[0139] It should be noted that curing is achieved at 1000 mJ / cm². 2 The irradiation intensity of 405nm on the photocurable adhesive layer is 70mW / cm. 2 It is carried out by ultraviolet rays.

[0140] The thickness of the photocurable adhesive layer containing the aforementioned photocurable adhesive is not particularly limited, but a preferred lower limit is 5 μm, and a preferred upper limit is 550 μm. When the thickness is 5 μm or more, the photocurable adhesive layer can have sufficient initial adhesive force. When the thickness is 550 μm or less, the photocurable adhesive layer can have high light transmittance, high flexibility, high conformability to uneven substrates, and easier peeling. A more preferred lower limit is 10 μm, a more preferred upper limit is 400 μm, a further preferred lower limit is 20 μm, a further preferred upper limit is 300 μm, a further more preferred lower limit is 30 μm, a further more preferred upper limit is 200 μm, and an even more preferred upper limit is 150 μm.

[0141] The temporary fixing material of the present invention is more preferably a sheet-shaped adhesive sheet for temporary fixing having a photocurable adhesive layer comprising the aforementioned photocurable adhesive. In this case, the temporary fixing material of the present invention may have the aforementioned photocurable adhesive layer on one or both sides of a substrate, or it may not have a substrate. Without the aforementioned substrate, it is not necessary to select a substrate that simultaneously possesses light transmittance and heat resistance, and the temporary fixing material can have a lower cost and simpler configuration.

[0142] When the above-mentioned substrate is used, examples of such substrates include: acrylic, olefins, polycarbonate, vinyl chloride, ABS, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), nylon, urethane, polyimide, polyetheretherketone (PEEK), polyamide (PA), and other resin sheets. Resin sheets with high light transmittance are preferred. Additionally, sheets with a mesh structure, perforated sheets, and glass can also be used.

[0143] The thickness of the aforementioned substrate is not particularly limited. From the viewpoints of improving light transmittance and improving flexibility, the preferred lower limit is 5 μm, the preferred upper limit is 150 μm, the more preferred lower limit is 10 μm, and the more preferred upper limit is 100 μm.

[0144] When the aforementioned photocurable adhesive contains the aforementioned gas generating agent, the temporary fixing material of the present invention preferably has a first photocurable adhesive layer and a second adhesive layer comprising the aforementioned photocurable adhesive.

[0145] The first photocurable adhesive layer contains the gas generator and is a curable adhesive layer capable of generating gas.

[0146] The temporary fixing material of the present invention, having the first photocurable adhesive layer and the second adhesive layer described above, may further have the substrate described above, and the first photocurable adhesive layer and the second adhesive layer are respectively laminated on both sides of the substrate.

[0147] The preferred lower limit of the gel fraction of the first photocurable adhesive layer after curing is 50% by weight. By keeping the gel fraction within the above range after curing, the first photocurable adhesive layer can be peeled off more easily upon peeling. A more preferred lower limit of the gel fraction after curing is 80% by weight.

[0148] It should be noted that, regarding the gel fraction after curing mentioned above, when measured at 1000 mJ / cm... 2 The irradiation intensity at 405 nm is 70 mW / cm². 2 After curing by ultraviolet light, the following methods are used for measurement.

[0149] The first UV-curable adhesive layer was cut into a 50mm × 100mm rectangular shape to prepare a test piece. The test piece 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 dried test piece was measured, and the gel fraction was calculated using the following formula (1). It should be noted that no release film for protecting the first UV-curable adhesive layer was laminated on the test piece.

[0150] Gel fraction (wt%) = 100 × (W2 - W0) / (W1 - W0) (1)

[0151] (W0: Weight of the substrate, W1: Weight of the test piece before impregnation, W2: Weight of the test piece after impregnation and drying)

[0152] After curing and heating at 300°C for 10 minutes (followed by heating and cooling), the adhesion force of the first photocurable adhesive layer relative to glass at 25°C is preferably 1.5 N / inch or less. By ensuring that the adhesion force relative to glass is within the aforementioned range, the first photocurable adhesive layer can be peeled off more easily upon removal. More preferably, the adhesion force relative to glass is 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.

[0153] It should be noted that the adhesive force relative to glass mentioned above was measured using the following method.

[0154] The first UV-curable adhesive layer was heated and laminated onto quartz glass (Matsunami Glass Industry Co., Ltd., Large Slide White Edge Grinding Machine No. 2S9112) using a laminator (LAMI Corporation "leon3DX" or equivalent) at 100°C. As a heat lamination, the lamination was performed once at a temperature setting of 100°C and a speed setting of 5. After heat lamination, the glass was heated using an ultra-high pressure mercury lamp at 1000 mJ / cm². 2 The irradiation intensity at 405 nm is 70 mW / cm². 2 After curing with ultraviolet light, the adhesive is heated from the glass side with a hot plate at 300°C for 10 minutes. The adhesive strength is measured by performing a 180° peel test at a tensile speed of 300 mm / min in an environment of 25°C and 50% relative humidity.

[0155] The thickness of the first photocurable adhesive layer is not particularly limited, but a preferred lower limit is 5 μm, and a preferred upper limit is 550 μm. When the thickness is 5 μm or more, the first photocurable adhesive layer can have sufficient initial adhesive force. When the thickness is 550 μm or less, the first photocurable adhesive layer can exhibit high flexibility, high conformability to uneven substrates, and easier peeling. A more preferred lower limit of the thickness is 10 μm, a further preferred lower limit is 20 μm, and a further more preferred lower limit is 30 μm. A more preferred upper limit of the thickness is 400 μm, a further preferred upper limit is 300 μm, a further more preferred upper limit is 200 μm, and an even more preferred upper limit is 150 μm.

[0156] The second adhesive layer is not particularly limited, and a curable adhesive layer having the same composition, physical properties, thickness, etc., as the first photocurable adhesive layer can be used. The second adhesive layer may or may not contain the gas generating agent described above.

[0157] The temporary fixing material of the present invention has a light transmittance of 10% or more at 405 nm. By ensuring that the light transmittance at 405 nm is 10% or more, the photocuring reaction of the aforementioned photocurable adhesive proceeds sufficiently, preventing over-adhesion or residue buildup during peeling. The light transmittance at 405 nm is preferably 15% or more, more preferably 30% or more, even more preferably 40% or more, and even more preferably 55% or more. There is no particular upper limit to the light transmittance at 405 nm; the upper limit is substantially around 90%.

[0158] It should be noted that the transmittance at 405 nm was measured using an ultraviolet cumulative illuminance meter (UVPF-A2, manufactured by Eyegripics). More specifically, this can be determined based on an irradiation intensity of 70 mW / cm² at 405 nm. 2 The cumulative light intensity (I0) of ultraviolet light over 10 seconds, and the irradiation intensity of 70 mW / cm² when the temporary fixing material is attached to the photodetector of the illuminometer and irradiated at 405 nm. 2 The cumulative light intensity (I1) of ultraviolet radiation over 10 seconds is calculated using the following formula.

[0159] Transmittance at 405nm (%) = 100 × I1 / I0

[0160] The temporary fixing material of the present invention has a 5% weight reduction temperature of 350°C or higher. By setting the 5% weight reduction temperature to 350°C or higher, the aforementioned photocurable adhesive can exhibit high heat resistance. That is, even under high-temperature processing at 300°C or higher, it is possible to prevent over-adhesion or residue formation during peeling. More preferably, the 5% weight reduction temperature is 380°C or higher, and even more preferably 400°C or higher. The upper limit of the 5% weight reduction temperature is not particularly limited, but is substantially around 600°C.

[0161] It should be noted that the aforementioned 5% weight loss temperature was measured using a differential thermal gravimetric analyzer (STA7200RV, manufactured by Hitachi High-Tech Science, or an equivalent). More specifically, it was measured at 1000 mJ / cm². 2 The irradiation intensity of 405nm on the photocurable adhesive is 70mW / cm. 2 After exposure to ultraviolet light, the UV-curable adhesive was weighed into an aluminum pan. The aluminum pan was placed in the apparatus, and the temperature was increased from 30°C to 500°C at a rate of 10°C / min in a nitrogen atmosphere. The temperature at which the sample weight decreased by 5% compared to its initial weight was defined as the 5% weight reduction temperature.

[0162] There are no particular limitations on the method for adjusting the transmittance of 405 nm to the aforementioned range. For example, a method to improve transmittance by adjusting the composition of the aforementioned photocurable adhesive can be cited. More specifically, for example, as at least one of the resin (1) having an imide backbone in the repeating unit of the main chain and the aforementioned multifunctional monomer or multifunctional oligomer (2), it is preferable to use a substance having aliphatic groups from a diamine compound, and more preferably a substance having aliphatic groups from a dimer diamine. In addition, as a method for adjusting the transmittance of 405 nm to the aforementioned range, for example, a method to adjust the thickness of the photocurable adhesive layer containing the aforementioned photocurable adhesive can be cited; in the case of having the aforementioned substrate, a method to adjust its material and thickness, etc.

[0163] The method for adjusting the temperature to the above range by reducing the weight by 5% is not particularly limited. For example, the method of improving the heat resistance by adjusting the composition of the above-mentioned light-curing adhesive can be cited. More specifically, for example, a resin having aromatic groups is preferably used as the above-mentioned resin (1) having an imide backbone in the repeating unit of the main chain.

[0164] In order to adjust the transmittance of 405 nm and the 5% weight reduction temperature to the above range, it is necessary to appropriately adjust the ratio of aliphatic groups to aromatic groups in the resin (1) with an imide skeleton in the repeating unit of the main chain and the polyfunctional monomer or polyfunctional oligomer (2).

[0165] The temporary fixing material of the present invention, after curing and heating at 300°C for 10 minutes (after heating and natural cooling), preferably exhibits an adhesion force relative to glass of 1.5 N / inch or less at 25°C. By ensuring that the adhesion force relative to glass is within the aforementioned range, the aforementioned photocurable adhesive can be more easily peeled off upon removal. More preferably, the adhesion force relative to glass is 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.

[0166] It should be noted that the adhesive force relative to glass mentioned above was measured using the following method.

[0167] Temporary fixing material was heated and laminated onto glass (Matsunami Glass Industry Co., Ltd., Large Slide White Edge Grinding No. 2) using a laminator (LAMI Corporation, Leon 13DX) at 100°C. As a heated lamination, lamination was performed once at a temperature setting of 100°C and a speed setting of 5. After heated lamination, an ultra-high pressure mercury lamp was used to apply 1000 mJ / cm² of heat from the glass side. 2 The irradiation intensity at 405 nm is 70 mW / cm². 2The material was exposed to ultraviolet light. After curing, it was heated from the glass side with a hot plate at 300°C for 10 minutes. After heating, it was allowed to cool naturally to room temperature. For the temporary fixing material after curing and heating at 300°C for 10 minutes, a 180° peel test was performed at 25°C and a tensile speed of 300 mm / min to determine the adhesion.

[0168] The temporary fixing material of the present invention has initial adhesive force, and on the other hand, it can prevent over-adhesion or residual adhesive during peeling, and can be easily peeled off.

[0169] Therefore, the temporary fixing material of the present invention is suitable for the protection and temporary fixing of objects subjected to high-temperature processing at 300°C or above. Especially in the processing of electronic components such as semiconductors, it is suitable for fixing electronic components to a support plate or attaching the temporary fixing material to the electronic components for protection, in order to facilitate handling of the electronic components without damage. That is, the temporary fixing material of the present invention is preferably used in the manufacturing process of electronic components.

[0170] In addition, a method for manufacturing electronic components is also one of the present invention, which includes: a temporary fixing step, in which electronic components are temporarily fixed to the temporary fixing material of the present invention; a curing step, in which the photocurable adhesive of the temporary fixing material of the present invention is cured; a heat treatment step, in which the electronic components are heat treated; and a peeling step, in which the electronic components are peeled off from the temporary fixing material of the present invention.

[0171] The curing process of curing the photocurable adhesive of the temporary fixing material of the present invention can be performed just before the peeling process of detaching the electronic component from the temporary fixing material of the present invention, but it is preferable to perform it after the temporary fixing process of temporarily fixing the electronic component to the temporary fixing material of the present invention and before the heat treatment process of heat treatment of the electronic component. By performing the curing process of curing the photocurable adhesive of the temporary fixing material of the present invention before the heat treatment process of heat treatment of the electronic component, the temporary fixing material can exhibit better heat resistance.

[0172] In addition, a method for manufacturing electronic components is also part of this invention. This method utilizes the temporary fixing material of this invention. The temporary fixing material comprises a first photocurable adhesive layer and a second adhesive layer containing the aforementioned photocurable adhesive with the aforementioned gas generating agent. The method for manufacturing the electronic components includes: a support attachment step, in which the first photocurable adhesive layer of the temporary fixing material is attached to a support; an adherend attachment step, in which the second adhesive layer of the temporary fixing material is attached to the electronic component; a curing step, in which the first photocurable adhesive layer and the second adhesive layer are cured; a heat treatment step, in which the electronic component is heat-treated; a gas generation step, in which gas is generated from the first photocurable adhesive layer; and a peeling step, in which the support is peeled from the temporary fixing material.

[0173] The curing process described above can be performed immediately before the gas generation process described above, preferably after the support attachment process and the adhered object attachment process, and before the heat treatment process described above. By performing the curing process before the heat treatment process described above, the temporary fixing material can exhibit superior heat resistance.

[0174] Examples of supports include glass and quartz substrates. Examples of adhered materials include silicon wafers.

[0175] Invention Effects

[0176] According to the present invention, a temporary fixing material can be provided that can be easily peeled off after high-temperature processing, even when the adhered object is subjected to high-temperature processing at 300°C or higher (e.g., heating to 300–450°C) while still fixed. Furthermore, according to the present invention, a method for manufacturing electronic components using this temporary fixing material can be provided. Detailed Implementation

[0177] The present invention will be described in more detail below with examples, but the present invention is not limited to these examples.

[0178] (Preparation of a resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain)

[0179] (Synthesis example 1)

[0180] 250 mL of toluene was added to a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 56 g (0.1 mol) of dimerized diamine (Croda, Priamine 1075) and 19.1 g (0.09 mol) of pyromellitic anhydride were added sequentially. A Dean-Stark separator and condenser were attached to the flask, and the mixture was refluxed for 2 hours to form amine-terminated diimides. After cooling the reactants to 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 further refluxed for 12 hours, cooled to room temperature, and 300 mL of toluene was added to the flask. Impurities were precipitated and removed by standing. After filtering the obtained solution through a glass frit funnel filled with silica gel, the solvent is removed under vacuum to obtain an amber-colored waxy resin (1-I) of the following formula (A), which has maleimide groups at both ends and an imide skeleton in the repeating unit of the main chain.

[0181] The obtained resin was determined by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (trade name, manufactured by Waters) as the column, and the weight-average molecular weight was 5000.

[0182] [Chemical Formula 5]

[0183]

[0184] (Preparation of a resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain)

[0185] (Synthesis example 2)

[0186] 250 mL of toluene was added to a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 36 g (0.1 mol) of 4,4'-bis(4-aminophenoxy)biphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) and 19.1 g (0.09 mol) of pyromellitic anhydride were added sequentially. A Dean-Stark separator and condenser were attached to the flask, and the mixture was refluxed for 2 hours to form an amine-terminated diimide. After cooling the reactants to 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 further refluxed for 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 by passing it through a glass frit funnel filled with silica gel, and the solvent was removed under vacuum to obtain an amber-colored waxy resin (1-I) of the following formula (B), which has maleimide groups at both ends and an imide skeleton in the repeating unit of the main chain.

[0187] The obtained resin was determined by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (trade name, manufactured by Waters) as the column, and the weight-average molecular weight was 10,000.

[0188] [Chemical Formula 6]

[0189]

[0190] (Preparation of a resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain)

[0191] (Synthesis example 3)

[0192] 250 mL of toluene was added to a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 200 g (0.1 mol) of polyethylene oxide diamine (JEFFAMINE D-2000, Huntsman) and 20 g (0.09 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (Mitsubishi Gas Chemical Co., Ltd., HPMDA) were added sequentially. A Dean-Stark separator and condenser were attached to the flask, and the mixture was refluxed for 2 hours to form an amine-terminated diimide. After cooling the reactants to below room temperature, 12.8 g (0.13 mol) of maleic anhydride was added, followed by 5 g (0.05 mol) of methanesulfonic anhydride. After refluxing the mixture for another 12 hours and cooling it to room temperature, 300 mL of toluene was added to the flask, and the impurities were allowed to precipitate and be removed by standing. The resulting solution was filtered through a glass frit funnel filled with silica gel, and the solvent was removed under vacuum to obtain an amber-colored, waxy resin (1-I) with maleimide groups at both ends and an imide backbone in the repeating units of the main chain.

[0193] The obtained resin was determined by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (trade name, manufactured by Waters) as the column, and the weight-average molecular weight was 40,000.

[0194] (Preparation of resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain)

[0195] 250 mL of toluene was added to a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar. Next, 35 g (0.35 mol) of triethylamine and 35 g (0.36 mol) of methanesulfonic anhydride were added and stirred to form a salt. After stirring for 10 minutes, 31.9 g (0.06 mol) of dimerized 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)phthalic anhydride were added sequentially. A Dean-Stark tube and condenser were attached to the flask, and the mixture was refluxed for 2 hours. After cooling to room temperature, 300 mL of toluene was added to the flask, and the mixture was allowed to stand to precipitate and remove impurities. The resulting solution was filtered through a glass frit funnel filled with silica gel, and the solvent was removed under vacuum to obtain a brown solid resin (1-II) of the following formula (D), which does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain.

[0196] The obtained resin was determined by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (trade name, manufactured by Waters) as the column, and the weight-average molecular weight was 72,000.

[0197] [Chemical Formula 7]

[0198]

[0199] (Preparation of multifunctional monomers or multifunctional oligomers (2))

[0200] 250 mL of toluene was added to a 500 mL round-bottom flask containing a Teflon (registered trademark) stir bar. 56 g (0.1 mol) of dimerized diamine (Croda, Priamine 1075) 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 silica gel-filled glass frit funnel, and the solvent was removed under vacuum to obtain a brown liquid bismaleimide monomer (2) as shown in formula (E).

[0201] [Chemical Formula 8]

[0202]

[0203] (Preparation of acrylic-based curable resins)

[0204] A reactor equipped with a thermometer, stirrer, and condenser was prepared. 94 parts by weight of 2-ethylhexyl acrylate (an alkyl methacrylate), 6 parts by weight of hydroxyethyl methacrylate (a functionalized monomer), 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate were added to the reactor, and the reactor was heated to initiate reflux. Next, 0.01 parts by weight of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane was added as a polymerization initiator, and polymerization was initiated under reflux. Then, 0.01 parts by weight of 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane were added 1 hour and 2 hours after the start of polymerization, respectively. Further, 0.05 parts by weight of tert-hexyl peroxypentanoate 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 (meth)acrylic acid polymer containing functional groups was obtained, with a solid content of 55% by weight and a weight average molecular weight of 500,000.

[0205] To a ratio of 100 parts by weight of the resin solids component containing an ethyl acetate solution of a (meth)acrylic polymer with functional groups, 3.5 parts by weight of ethyl 2-isocyanate methacrylate, an unsaturated compound containing functional groups, were added to react the resin to obtain an acrylic reactive resin.

[0206] The obtained acrylic reactive resin was determined by gel permeation chromatography (GPC) using THF as the eluent and HR-MB-M (trade name, manufactured by Waters) as the column, and the weight-average molecular weight was 550,000.

[0207] (Example 1)

[0208] (1) Manufacturing of temporary fixing materials

[0209] 70 parts by weight of the resin (1-II) and 30 parts by weight of the bismaleimide monomer (2) obtained above were added to 150 mL of toluene. Further, 2 parts by weight of Irgacure 819 (manufactured by BASF, molar absorptivity of 450 at 405 nm), used as a photopolymerization initiator, were added to prepare a toluene solution of the photocurable adhesive.

[0210] Using a scraper, a toluene solution of the obtained photocurable adhesive was applied to the release surface of a 50 μm PET film that had undergone single-sided release treatment, in a manner that resulted in the thickness of the dried film as shown in Table 1. The solution was then heated at 130°C for 10 minutes to allow it to dry. This yielded a temporary fixing material (unsupported type) with a photocurable adhesive layer.

[0211] (Examples 2-14, Comparative Examples 1-4)

[0212] The composition and thickness of the photocurable adhesive were modified as shown in Tables 1-2. Otherwise, the toluene solution of the photocurable adhesive and the temporary fixing material were obtained in the same manner as in Example 1. The materials used are shown below.

[0213] • Acrylic non-curing resin (SK-Dyne1604N, manufactured by Zongyan Chemical Co., Ltd.)

[0214] • Multifunctional acrylic monomers (SR-387, manufactured by ARKEMA, tris(2-acryloxyethyl) isocyanurate)

[0215] ·Organic silicon compound (bifunctional siloxane acrylate (Japanese: シリコーンアクリレート), manufactured by DAICEL-ALLNEX Co., Ltd., EBECRYL350)

[0216] • Organosilicon compounds (polyether-modified polydimethylsiloxane with acryloyl groups, manufactured by BYK Chemie, BYK-UV3500)

[0217] • Crosslinking agent (isocyanate-based crosslinking agent, Coronate L, manufactured by Nippon Polyurethane Kogyo Co., Ltd.)

[0218] (Example 15)

[0219] (1) Formation of the first photocurable adhesive layer (a curable adhesive layer containing a gas generator)

[0220] A toluene solution containing 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 generator, 5 parts by weight of EBECRYL350 as an organosilicon compound, and 2 parts by weight of Irgacure 819 (manufactured by BASF) as a photopolymerization initiator were prepared.

[0221] Using a scraper, the toluene solution of the obtained photocurable adhesive is applied to a 50 μm thick polyethylene terephthalate film prepared as a spacer, after surface demolding. The coating solution is dried in an oven preheated to 110°C for 10 minutes to obtain the first photocurable adhesive layer (a cured adhesive layer containing a gas-generating agent).

[0222] (2) Formation of the second adhesive layer

[0223] A toluene solution of a photocurable adhesive was prepared by adding 100 parts by weight of the reactive resin shown in Table 3, 5 parts by weight of EBECRYL350 (as an organosilicon compound), and 2 parts by weight of Irgacure 819 (manufactured by BASF) (as a photopolymerization initiator) to 300 mL of toluene.

[0224] Using a scraper, the toluene solution of the obtained photocurable adhesive is applied to a 50 μm thick polyethylene terephthalate film prepared as a spacer, after the surface has been demolded. The coating solution is dried in an oven preheated to 110°C for 10 minutes to obtain the second adhesive layer.

[0225] (3) Manufacturing of temporary fixing materials

[0226] The surfaces of the first photocurable adhesive layer (a curable adhesive layer containing a gas generator) and the second adhesive layer are laminated together to obtain a temporary fixing material whose two surfaces are covered by spacers.

[0227] (Example 16)

[0228] The composition and thickness of the photocurable adhesive layer were modified as shown in Table 3. Otherwise, the photocurable adhesive and temporary fixing material were obtained in the same manner as in Example 15.

[0229] (Examples 17-22)

[0230] The composition, thickness, and inorganic filler content of the photocurable adhesive were modified as shown in Table 4. Otherwise, a toluene solution of the photocurable adhesive and a temporary fixing material were obtained in the same manner as in Example 1. The materials used are shown below.

[0231] Fluorine compounds (photoreactive fluorine compounds, manufactured by DIC, Megaface RS-56)

[0232] • Inorganic filler (silica particles, manufactured by Tokuyama Corporation, MT-10, average particle size 15nm)

[0233] • Inorganic filler (silica particles, manufactured by Ryusei Corporation, 5x, average particle size 1μm)

[0234] <Physical Property Determination>

[0235] (Measurement of light transmittance)

[0236] The obtained temporary fixing material was attached to the receiver of an ultraviolet accumulator (UVPF-A2, manufactured by EYE GRAPHICS), and irradiated at a 405nm irradiation intensity of 70mW / cm². 2 The ultraviolet light was exposed for 10 seconds, and the cumulative light intensity (I1) was measured. The irradiation intensity at 405 nm was measured to be 70 mW / cm². 2 The cumulative light intensity (I0) of ultraviolet light over 10 seconds is used to calculate the transmittance of the temporary fixation material at 405 nm using the following formula.

[0237] Transmittance at 405nm (%) = 100 × I1 / I0

[0238] (Determination of temperature at 5% weight reduction)

[0239] At 1000mJ / cm 2 The irradiation intensity at 405 nm for the obtained temporary fixation material was 70 mW / cm. 2Under ultraviolet light, 10 mg was weighed into an aluminum pan. The aluminum pan was placed in the apparatus, and the temperature was increased from 30°C to 500°C at a rate of 10°C / min in a nitrogen atmosphere. The temperature at which the sample weight decreased by 5% compared to before the heating was defined as the 5% weight reduction temperature.

[0240] (Determination of the adhesive strength relative to glass at 25°C after curing and heating at 300°C for 10 minutes)

[0241] The obtained temporary fixing material was cut into 1-inch widths and then laminated to a 1mm thick glass (Matsunami Glass Industry Co., Ltd., Large Slide White Edge Grinding No. 2) using a 100°C laminator (LAMICorporation Co., Ltd., Leon 13DX, Fast Memory Grinding) at 100°C. After lamination, it was heated and laminated to a 1mm thick glass (Matsunami Glass Industry Co., Ltd., Large Slide White Edge Grinding No. 2) using an ultra-high pressure mercury lamp at 1000mJ / cm². 2 The irradiation intensity at 405 nm from the glass side is 70 mW / cm². 2 UV light. After curing, peel off the release PET film of the temporary fixing material and heat it from the glass side with a 300°C hot plate for 10 minutes.

[0242] A 180° peel test was conducted on the temporary fixing material after curing and heating at 300°C for 10 minutes (after heating and natural cooling) at 25°C and a tensile speed of 300 mm / min.

[0243] It should be noted that in Examples 15 and 16, measurements were taken on each surface of the first and second UV-curable adhesive layers. For the adhesion of the first UV-curable adhesive layer to the glass, after heating at 300°C for 10 minutes and allowing it to cool naturally, a high-pressure mercury lamp at 20 mW / cm² was used. 2 The glass side was irradiated with 254nm ultraviolet light for 180 seconds to generate gas. Then, a 180° peel test was conducted at 25°C and a tensile speed of 300mm / min.

[0244] (Determination of elastic modulus)

[0245] For the obtained temporary fixation material, a test piece measuring 5mm × 35mm × 0.03mm in thickness was prepared. The material was then subjected to a test at 1000mJ / cm². 2 The irradiation intensity of the obtained test piece at 405 nm was 70 mW / cm. 2The sample was cured by ultraviolet light. The cured sample was then immersed in liquid nitrogen and cooled to -50°C. Then, using a viscoelastic spectrometer (DVA-200, manufactured by IT Measurement & Control Co.), the temperature was raised to 300°C under constant-rate heating and tensile conditions (10°C / min, 10Hz) to determine the storage modulus. Based on the obtained storage modulus results, the elastic modulus at 25°C and the elastic modulus at 300°C were calculated.

[0246] <Evaluation>

[0247] The temporary fixation materials obtained in the examples and comparative examples were evaluated using the following methods. The results are shown in Tables 1 to 4.

[0248] (1) Determination of gel fraction after curing

[0249] At 1000mJ / cm 2 The photocurable adhesive layer of the obtained temporary fixing material was irradiated at a 405 nm irradiation intensity of 70 mW / cm. 2 After exposure to ultraviolet light, the gel fraction was determined using the following method.

[0250] The temporary fixing material was cut into 50mm × 100mm rectangular shapes to prepare test pieces. The test pieces were 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 pieces was measured, and the gel fraction was calculated using the following formula (1). It should be noted that no release film for protecting the UV-curable adhesive layer was laminated on the test pieces.

[0251] In addition, in Examples 15 and 16, 1000 mJ / cm 2 The irradiation intensity of 405 nm on the second adhesive layer is 70 mW / cm. 2 After the second adhesive layer is cured by ultraviolet light, a portion of the second adhesive layer is weighed and used as a test piece. The gel fraction of the weighed test piece is also measured. It should be noted that this test piece does not have a substrate; therefore, W0 is set to 0.

[0252] Gel fraction (wt%) = 100 × (W2 - W0) / (W1 - W0) (1)

[0253] (W0: Weight of the substrate, W1: Weight of the test piece before impregnation, W2: Weight of the test piece after impregnation and drying)

[0254] The following benchmarks will be used for evaluation.

[0255] ◎: Gel fraction of 80% or higher

[0256] 〇: Gel fraction ≥ 60% and < 80%

[0257] △: Gel fraction ≥ 20% and < 60%

[0258] ×: Gel fraction less than 20%

[0259] (2) Evaluation of the residue after curing and heating at 300°C for 10 minutes

[0260] The obtained temporary fixing material was cut into 1-inch widths and then heated and laminated to a 1mm thick glass (Matsunami Glass Industry Co., Ltd., Large Slide White Edge Grinding No. 2) using a 100°C laminator (LAMICorporation, Leon 13DX). As a heat lamination, it was laminated once at a temperature setting of 100°C and a speed setting of 5. After heat lamination, an ultra-high pressure mercury lamp was used at 1000mJ / cm². 2 The irradiation intensity at 405 nm from the glass side is 70 mW / cm². 2 UV light. After curing, peel off the release PET film of the temporary fixing material and heat it from the glass side with a hot plate at 300°C for 10 minutes.

[0261] For the test samples after the temporary fixing material, which had been cured and heated to 300°C, had cooled naturally, a 180° peel test was performed at 25°C and a tensile speed of 300 mm / min. It should be noted that in Examples 15 and 16, the second adhesive layer was attached to glass, and test samples were prepared and evaluated in the same manner.

[0262] The surface of the glass after the temporary fixing material has been removed is visually inspected and evaluated according to the following criteria.

[0263] ◎: No residual glue observed

[0264] 〇: Residual adhesive was observed in less than 5% of the glass area.

[0265] △: Residual adhesive was observed in more than 5% but less than 10% of the glass area.

[0266] ×: Residual adhesive was observed in more than 10% of the glass area.

[0267] (3) Evaluation of peelability and exfoliation after curing and heating at 300℃ for 20 minutes

[0268] The temporary fixation materials obtained in Examples 1, 10, and 17–22 were further evaluated as follows.

[0269] The obtained temporary fixing material was cut into 1-inch widths and then laminated once with glass to a thickness of 1 mm using a hot laminator (Leon 13DX) at 100°C and rapid memory 3 conditions. After lamination, an ultra-high pressure mercury lamp at 1000 mJ / cm² was used. 2 The irradiation intensity at 405 nm from the glass side is 70 mW / cm². 2 The material was exposed to ultraviolet light. After curing, the release film was peeled off, and the material was heated from the glass side with a hot plate at 300°C for 20 minutes. It should be noted that this test was performed five times. The appearance of the cured temporary fixative material after heating at 300°C for 20 minutes was visually observed and evaluated according to the following criteria.

[0270] 〇: No peeling was observed between the glass and the surface in all 5 tests.

[0271] ×: In more than one of the five tests, a portion bulged out between the glass and the surface.

[0272] For the temporary fixing material after curing and heating at 300°C for 20 minutes, a 180° peel test was performed at 25°C and a tensile speed of 300 mm / min. It should be noted that this test was performed 5 times. The peelability of the temporary fixing material was evaluated using the following criteria. It should be noted that cases where bulges occurred during the peel test were not evaluated.

[0273] ◎: It was able to peel off in all 5 tests.

[0274] ○: It was able to peel off in 1 to 4 out of 5 tests.

[0275] ×: Unable to peel off in all 5 tests.

[0276]

[0277]

[0278]

[0279]

[0280] Industrial availability

[0281] According to the present invention, a temporary fixing material can be provided that can be easily peeled off after high-temperature processing, even when the object to be glued is subjected to high-temperature processing at 300°C or above while the object is fixed in the state of the high-temperature processing. Furthermore, according to the present invention, a method for manufacturing electronic components using this temporary fixing material can be provided.

Claims

1. A temporary fixing material, characterized in that, It comprises a photocurable adhesive containing a reactive resin, the reactive resin comprising a resin (1) having an imide backbone in a repeating unit of the main chain, the reactive resin comprising a resin (1-II) having no functional groups having double bonds and having an imide backbone in a repeating unit of the main chain, the reactive resin further comprising a resin (1-I) having functional groups having double bonds and having an imide backbone in a repeating unit of the main chain, and / or a multifunctional monomer or multifunctional oligomer (2) having two or more functional groups having double bonds within the molecule and having a molecular weight of less than 5000, the temporary fixation material having a transmittance of 405 nm of more than 10%, and a 5% weight reduction temperature of more than 350°C.

2. The temporary fixing material according to claim 1, characterized in that, The transmittance of the temporary fixing material at 405 nm is below 90%.

3. The temporary fixing material according to claim 1, characterized in that, The temporary fixing material is reduced by 5% by weight at a temperature below 600°C.

4. The temporary fixing material according to claim 1, characterized in that, The photocurable adhesive layer containing the aforementioned photocurable adhesive has an elastic modulus of 1×10⁻⁶ at 25°C after curing. 7 Pa or above.

5. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The photocurable adhesive layer containing the aforementioned photocurable adhesive has an elastic modulus of 1×10⁻⁶ at 300°C after curing. 8 Below Pa.

6. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The resin (1) having an imide backbone in the repeating unit of the main chain has aliphatic groups derived from the dimer diamine.

7. The temporary fixing material according to claim 6, characterized in that, The aliphatic group derived from the dimer diamine is selected from at least one of the groups shown in general formula (4-1), general formula (4-2), general formula (4-3), and general formula (4-4). In general formulas (4-1) to (4-4), R 1 ~R 8 and R 13 ~R 20 Each can be used to independently represent a straight-chain or branched hydrocarbon group.

8. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The weight-average molecular weight (Mw) of the resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain is 20,000 or more.

9. The temporary fixing material according to claim 8, characterized in that, The weight-average molecular weight (Mw) of the resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain is less than 600,000.

10. The temporary fixing material according to claim 8, characterized in that, The resin (1-II) that does not have a functional group with double bonds and has an imide skeleton in the repeating unit of the main chain is a structural unit having the structural unit shown in the following general formula (1d) and the structural unit shown in the following general formula (1e), and having X at both ends respectively. 4 and X 5 The resin represented is (2-i), where s>0, t≥0. In general formulas (1d) to (1e), P 4 and P 5 Each of the aromatic groups is represented independently, Q 3 Q represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group. 4 X represents a group having a substituted or unsubstituted aromatic structure. 4 and X 5 This indicates a group that does not contain a functional group with a double bond.

11. The temporary fixing material according to claim 10, characterized in that, In the general formulas (1d) to (1e), P 4 and P 5 Each of the aromatic groups having 5 to 50 carbon atoms can be represented independently.

12. The temporary fixing material according to claim 10, characterized in that, In the general formula (1d), Q 3 It is a linear, branched, or cyclic aliphatic group with 2 to 100 carbon atoms, whether substituted or unsubstituted.

13. The temporary fixing material according to claim 10, characterized in that, In the general formula (1e), Q 4 It is a group having an aromatic structure with 5 to 50 carbon atoms, either substituted or unsubstituted.

14. The temporary fixing material according to claim 10, characterized in that, The content of the structural unit shown in the general formula (1d) is greater than 0 mol% and less than 90 mol%.

15. The temporary fixing material according to claim 10, characterized in that, The content of the structural unit shown in the general formula (1e) is more than 0 mol% and less than 50 mol%.

16. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The resin (1) having an imide skeleton in the repeating unit of the main chain comprises a resin (1-I) having a functional group with double bonds and having an imide skeleton in the repeating unit of the main chain.

17. The temporary fixing material according to claim 16, characterized in that, The weight-average molecular weight (Mw) of the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain is 1,000 or more and less than 100,000.

18. The temporary fixing material according to claim 16, characterized in that, In the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain, the functional group with double bonds is present at both ends.

19. The temporary fixing material according to claim 16, characterized in that, In the resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain, the functional group with double bonds is present at both ends and the side chain.

20. The temporary fixing material according to claim 16, characterized in that, The resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain is a structural unit having the following general formula (1a), the following general formula (1b), and the following general formula (1c), and having X at both ends respectively. 1 and X 2 The compound represented is (1-i), where s>0, t≥0, u≥0. In general formulas (1a) to (1c), P 1 P 2 and P 3 Each of the aromatic groups is represented independently, Q 1 Q represents a substituted or unsubstituted linear, branched, or cyclic aliphatic group. 2 R represents a group having a substituted or unsubstituted aromatic structure, where R represents a substituted or unsubstituted branched aliphatic or aromatic group selected from X. 1 X 2 and X 3 At least one of them represents a functional group with a double bond.

21. The temporary fixing material according to claim 20, characterized in that, In the general formulas (1a) to (1c), P 1 P 2 and P 3 Each of the aromatic groups having 5 to 50 carbon atoms can be represented independently.

22. The temporary fixing material according to claim 20, characterized in that, In the general formula (1a), Q 1 It is a linear, branched, or cyclic aliphatic group with 2 to 100 carbon atoms, whether substituted or unsubstituted.

23. The temporary fixing material according to claim 20, characterized in that, In the general formula (1b), Q 2 It is a group having an aromatic structure with 5 to 50 carbon atoms, either substituted or unsubstituted.

24. The temporary fixing material according to claim 20, characterized in that, In the general formula (1c), R is a substituted or unsubstituted branched aliphatic or aromatic group with 2 to 100 carbon atoms.

25. The temporary fixing material according to claim 20, characterized in that, In the general formula (1c), R is an aromatic group having an aromatic ester group or an aromatic ether group, wherein the aromatic ester group or the aromatic ether group is related to X. 3 Bonding.

26. The temporary fixing material according to claim 20, characterized in that, In the resin (1-I) having functional groups with double bonds and an imide skeleton in the repeating unit of the main chain, at least X 3 It is a functional group with double bonds.

27. The temporary fixing material according to claim 20, characterized in that, The content of the structural unit shown in the general formula (1a) is greater than 0 mol% and less than 90 mol%.

28. The temporary fixing material according to claim 20, characterized in that, The content of the structural unit shown in the general formula (1b) is more than 0 mol% and less than 50 mol%.

29. The temporary fixing material according to claim 20, characterized in that, The content of the structural unit shown in the general formula (1c) is more than 0 mol% and less than 50 mol%.

30. The temporary fixing material according to claim 16, characterized in that, The functional group containing the double bond is an optional substituted maleimide group.

31. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The reactive resin further comprises a multifunctional monomer or multifunctional oligomer having two or more functional groups with double bonds and a molecular weight of less than 5,000 (2).

32. The temporary fixing material according to claim 31, characterized in that, The multifunctional monomer or multifunctional oligomer (2) has an aliphatic group derived from a diamine compound.

33. The temporary fixing material according to claim 31, characterized in that, The multifunctional monomer or multifunctional oligomer (2) having two or more functional groups with double bonds and a molecular weight of less than 5000 accounts for more than 5 parts by weight and less than 100 parts by weight in 100 parts by weight of the reactive resin.

34. The temporary fixing material according to claim 16, characterized in that, The resin (1-I) having a functional group with double bonds and an imide skeleton in the repeating unit of the main chain accounts for 10 parts by weight or more and less than 100 parts by weight in 100 parts by weight of the reactive resin.

35. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The resin (1-II) that does not have a functional group with a double bond and has an imide skeleton in the repeating unit of the main chain accounts for 10 parts by weight or more and 90 parts by weight or less in 100 parts by weight of the reactive resin.

36. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The photocurable adhesive also contains a polymerization initiator, which is a photopolymerization initiator, and the photopolymerization initiator contains a photopolymerization initiator with a molar absorptivity of 1 or more at 405 nm.

37. The temporary fixing material according to claim 36, characterized in that, The content of the photopolymerization initiator is 0.1 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the reactive resin.

38. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The photocurable adhesive also contains organosilicon compounds or fluorine compounds.

39. The temporary fixing material according to claim 38, characterized in that, The content of the organosilicon compound or fluorine compound is 0.1 parts by weight or more and 20 parts by weight or less per 100 parts by weight of the reactive resin.

40. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The photocurable adhesive also contains inorganic fillers.

41. The temporary fixing material according to claim 40, characterized in that, The inorganic filler has an average particle size of 5 nm or more and 20 μm or less.

42. The temporary fixing material according to claim 40, characterized in that, The inorganic filler is present in a content of more than 1 part by weight and less than 20 parts by weight relative to 100 parts by weight of the reactive resin.

43. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The photocurable adhesive also contains a gas generator.

44. The temporary fixing material according to claim 43, characterized in that, In the TG-DTA (thermal gravimetric differential thermal analysis) determination, the weight loss rate of the gas generator at 300°C when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere is less than 5%.

45. The temporary fixing material according to claim 43, characterized in that, The content of the gas generating agent is 5 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the reactive resin.

46. ​​The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The temporary fixing material is a sheet-shaped temporary fixing adhesive sheet having a light-curable adhesive layer containing the light-curable adhesive.

47. The temporary fixing material according to claim 46, characterized in that, The cured gel fraction of the photocurable adhesive layer is more than 20% by weight and less than 99% by weight.

48. The temporary fixing material according to claim 46, characterized in that, The photocurable adhesive layer has an elastic modulus of 1×10⁻⁶ at 25°C after curing. 7 Pa or higher and 1×10 10 Below Pa.

49. The temporary fixing material according to claim 46, characterized in that, The photocurable adhesive layer has an elastic modulus of 1×10⁻⁶ at 300°C after curing. 5 Pa or higher and 1×10 7 Below Pa.

50. The temporary fixing material according to claim 46, characterized in that, The thickness of the photocurable adhesive layer is more than 5 μm and less than 550 μm.

51. The temporary fixing material according to claim 43, characterized in that, It has a first photocurable adhesive layer and a second adhesive layer, wherein the first photocurable adhesive layer contains the photocurable adhesive.

52. The temporary fixing material according to claim 51, characterized in that, The first photocurable adhesive layer has a gel content of 50% by weight or more after curing.

53. The temporary fixing material according to claim 51, characterized in that, The thickness of the first photocurable adhesive layer is more than 5 μm and less than 550 μm.

54. The temporary fixing material according to claim 51, characterized in that, It also has a substrate, on which a first photocurable adhesive layer and a second adhesive layer are respectively laminated on both sides.

55. The temporary fixing material according to claim 51, characterized in that, After the first photocurable adhesive layer has been cured and heated at 300°C for 10 minutes, its adhesion to glass at 25°C is less than 1.5 N / inch.

56. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, After curing and heating at 300°C for 10 minutes, the temporary fixing material exhibits an adhesion force of less than 1.5 N / inch relative to glass at 25°C.

57. The temporary fixing material according to claim 1, 2, 3 or 4, characterized in that, The temporary fixing material is used in the manufacturing process of electronic components.

58. A method for manufacturing an electronic component, characterized in that, It includes: The process includes a temporary fixing step, in which the electronic component is temporarily fixed to the temporary fixing material as described in claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, or 57; a curing step, in which the light-curing adhesive of the temporary fixing material is cured; a heat treatment step, in which the electronic component is heat-treated; and a peeling step, in which the electronic component is peeled off from the temporary fixing material.

59. A method for manufacturing an electronic component, characterized in that, It uses the temporary fixing material as described in claims 51, 52, 53, 54, or 55, and the manufacturing method of the electronic component includes: a support attachment step, in which a first photocurable adhesive layer of the temporary fixing material is attached to a support; an adherend attachment step, in which a second adhesive layer of the temporary fixing material is attached to the electronic component; a curing step, in which the first photocurable adhesive layer and the second adhesive layer are cured; a heat treatment step, in which the electronic component is heat-treated; a gas generation step, in which gas is generated from the first photocurable adhesive layer; and a peeling step, in which the support is peeled off from the temporary fixing material.

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