Adhesive composition for temporal fixing, layered body, method for temporarily fixing member, and removal method

Abstract

Provided is an adhesive for temporal fixing, the adhesive having followability (step followability) to an uneven structure, high heat resistance (reflow resistance), and laser peelability, wherein substrate warpage after peeling a support can be suppressed, solvent removability is excellent, and good solderability is provided when soldering an electrode formed on a member after the adhesive for temporal fixing is removed. Also provided are a method for temporarily fixing a member using the adhesive, and a removal method. An adhesive composition for temporal fixing according to the present disclosure contains a resin (A) and an organometallic compound (B), wherein: the resin (A) contains at least one of an alcoholic hydroxy group and a phenolic hydroxy group; when the resin (A) is subjected to thermogravimetry / differential thermal analysis in an air atmosphere, with a temperature increasing rate of 10°C per minute, the rate of mass loss with respect to the mass before heating reaches 5% at a temperature of 280°C -550°C; and the film thickness reduction rate (R) after immersion in toluene, cyclohexanone, or N-methylpyrrolidone is 95% or more.

Description

Temporary fixing adhesive composition, laminate, method for temporarily fixing a component, and method for removing the component.

[0001] This disclosure relates to a temporary fixing adhesive composition, a laminate, and a method for temporarily fixing a member using the temporary fixing adhesive composition. It also relates to a method for removing a layer made of the temporary fixing adhesive composition from a member.

[0002] As development progresses in making portable devices thinner, smaller, lighter, and more high-performance, semiconductor-related components such as semiconductor chips incorporated into the devices, as well as package substrates and interposers used for their rewiring, are required to be even thinner, not only due to size constraints but also because of the trend towards mounting forms that integrate chips three-dimensionally. These thinned components are manufactured through thinning processes such as grinding / polishing, wiring formation processes, and mounting processes. However, as the thinning progresses, the components cannot maintain their shape on their own, and are prone to bending and loss of flatness, making independent manufacturing difficult. Therefore, a method is becoming widespread in which the components are temporarily attached to a rigid plate-shaped support using adhesive, and the components are handled together with this support and adhesive in each process.

[0003] On the other hand, in the various manufacturing processes described above, the components need to be firmly fixed to the support with a temporary fixing adhesive. However, since they are exposed to high temperatures in the insulating film formation process and the solder bump formation process, the temporary fixing adhesive also needs to have high heat resistance. Furthermore, after the final process, it is necessary to remove the temporary fixing adhesive layer remaining on the component after peeling it off the support.

[0004] Methods for removing such temporary adhesive layers from a support include using solvents for removal and using physical stress to peel them off. On the other hand, laser removal methods using laser light such as ultraviolet, visible, and infrared light are attracting attention because they can remove the layer quickly without stressing the component.

[0005] Regarding patent documents relating to laser delamination methods, for example, Patent Document 1 discloses a UV-curing temporary fixing adhesive consisting of an acrylate monomer, a photoinitiator with minimal mass loss during heating, and carbon black. Furthermore, Patent Document 2 discloses a temporary fixing method using a temporary fixing adhesive consisting of a cycloolefin resin and an ultraviolet absorber, and Patent Document 3 discloses a temporary fixing adhesive consisting of a polysulfone resin. However, the method in Patent Document 1 has problems such as the inability to remove the material using commonly used delamination solutions, or the presence of residue even if removal is possible, when temporarily fixing the surface with the electrode pads or solder bumps formed on it with a temporary fixing adhesive in order to further process the back surface, or when the surface roughness of the outermost insulating layer is rough. Furthermore, while the methods described in Patent Documents 2 and 3 allowed for the dissolution and removal of the temporary fixing adhesive layer remaining on the member side using an organic solvent, they had poor conformability to the unevenness of the structure when forming the temporary fixing adhesive layer on an uneven surface or when bonding it to the member. If the conformability was achieved by heating at very high temperatures, the effects of the thermal history could cause the thinned member to warp significantly after peeling from the support, which would interfere with subsequent manufacturing processes. Although curing and bonding at relatively low temperatures, as described in Patent Document 1, could avoid such warping, ensuring the aforementioned heat resistance required irreversible chemical crosslinking, which presented a dilemma as it made dissolution and removal from uneven surfaces impossible.

[0006] Japanese Patent Publication No. 2015-224316, Japanese Patent Publication No. 2013-33814, Japanese Patent Publication No. 2016-003270

[0007] This disclosure is made in view of the above background, and aims to provide a temporary fixing adhesive that has conformability to uneven structures (step conformability), high heat resistance (reflow resistance), and laser peelability, can suppress substrate warping after support peeling, has excellent solvent removal properties, and has good solderability to electrodes formed on the member after removal of the temporary fixing adhesive. It also aims to provide a method for temporarily fixing laminates and members using the temporary fixing adhesive, as well as a method for removal.

[0008] After diligent research by the present inventors, they have found that the problems of this disclosure can be solved in the following embodiments, and have completed this disclosure. [1]: A temporary fixing adhesive composition comprising a resin (A) and an organometallic compound (B), wherein the resin (A) comprises at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group, and the temperature at which the mass reduction rate relative to the mass before heating becomes 5% when heated at a rate of 10°C / min in an atmospheric atmosphere using thermogravimetric differential thermal analysis is 280°C or higher and 550°C or lower, the film thickness reduction rate (R) after immersion in an organic solvent, calculated from the following formula (1), is 95% or higher, and the organic solvent is selected from the group consisting of toluene, cyclohexanone, and N-methylpyrrolidone. [1] (Formula 1) R (%) = (1 - (T / 30)) × 100 T: Thickness of the film (μm) after immersing a test piece obtained by heating a 30 μm thick film made of the temporary fixing adhesive composition at 180°C for 1 hour in the organic solvent at 80°C for 1 hour. [2]: The temporary fixing adhesive composition according to [1], further comprising 10 parts by mass or less of a compound (C) (excluding the organometallic compound (B)) having two or more groups that can react with at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group, per 100 parts by mass of the resin (A). [3]: The temporary fixing adhesive composition according to [1] or [2], wherein the organometallic compound (B) is at least one selected from the group consisting of organotitanium compounds, organozirconium compounds, and organoaluminum compounds. [4]: ​​The temporary fixing adhesive composition according to [4], wherein the total content of titanium ions and zirconium ions in the temporary fixing adhesive composition is 0.01% by mass or more and 3.0% by mass or less. [5]: The temporary fixing adhesive composition according to any one of [1] to [4], wherein the resin (A) is at least one selected from the group consisting of polyimide resin, polyamide resin, polyphenylene ether resin, phenol resin, and phenoxy resin. [6]: A laminate in which a member and a support are bonded and temporarily fixed with the temporary fixing adhesive composition according to any one of [1] to [5]. [7]: A method for temporarily fixing a member comprising the following steps (1) to (3): (1) A step of bonding and temporarily fixing the member and support using the temporary fixing adhesive composition according to [1].(2) A step of processing the member that has been temporarily fixed in (1). (3) A step of removing the support by irradiating a laser onto the layer made of the temporary fixing adhesive composition after processing in (2). [8]: The method for temporarily fixing a member according to [7], wherein the laser is a near-infrared laser or an ultraviolet laser. [9]: The method for temporarily fixing a member according to [8], wherein the support is made of glass or silicon.

[10] : A removal method for removing the layer made of the temporary fixing adhesive composition from a member that has had its support removed by the method of any one of [7] to [9], by immersing the member, which has a layer made of the temporary fixing adhesive composition remaining, in an organic solvent.

[0009] This disclosure provides a temporary fixing adhesive that has conformability to uneven structures (step conformability), high heat resistance (reflow resistance), and laser peelability, can suppress substrate warping after support peeling, has excellent solvent removal properties, and has good solderability to electrodes formed on the member after removal of the temporary fixing adhesive. It also provides a laminate, a method for temporarily fixing a member, and a method for removal using the temporary fixing adhesive. The temporary fixing adhesive layer of this disclosure can be suitably used in the manufacture of semiconductor-related members such as semiconductor chips, package substrates used for their redistribution, and interposers.

[0010] This is a schematic cross-sectional view partially showing an example of the laminate of the present disclosure. This is a schematic cross-sectional view partially showing an example of the laminate of the present disclosure being irradiated with laser light.

[0011] The present disclosure will be described in detail below. It goes without saying that other embodiments are also included within the scope of this disclosure, insofar as they are consistent with the spirit of this disclosure. Furthermore, numerical ranges specified using "~" in this specification include the numbers before and after "~" as the lower and upper limits. Also, in this specification, "film" and "sheet" are synonymous and are not distinguished by thickness. Furthermore, unless otherwise noted, the various components mentioned in this specification may be used individually or in combination of two or more. The numerical values ​​described in this specification refer to values ​​obtained by the methods described in the examples below.

[0012] In this specification, a compound (C) having two or more groups capable of reacting with at least one of alcoholic hydroxyl groups and phenolic hydroxyl groups may be simply referred to as the compound (C).

[0013] ≪Adhesive composition for temporary fixing≫ The adhesive composition for temporary fixing of the present disclosure contains a resin (A) and an organometallic compound (B), and it is important that the film thickness reduction rate (R) after immersion in an organic solvent calculated from the following (Formula 1) is 95% or more. If (R) is 95% or more, it has good removability by an organic solvent, and thus has excellent solderability to an electrode formed on a member after removing the adhesive for temporary fixing. The organic solvent is any one selected from the group consisting of toluene, cyclohexanone, and N-methylpyrrolidone. (Formula 1) R(%) = (1 - (T / 30)) × 100 T: The film thickness (μm) of a test piece obtained by heating a 30-μm-thick film made of the adhesive composition for temporary fixing at 180°C for 1 hour and then immersing it in an organic solvent at 80°C for 1 hour. That is, the film thickness reduction rate (R １ ) after immersion in toluene calculated from the following (Formula 2) or the film thickness reduction rate (R ２ ) after immersion in cyclohexanone calculated from the following (Formula 3) or the film thickness reduction rate (R ３ ) after immersion in N-methylpyrrolidone calculated from the following (Formula 4) is important to be 95% or more. (Formula 2) R １ (%) = (1 - (T １ / 30)) × 100 (Formula 3) R ２ (%) = (1 - (T ２ / 30)) × 100 (Formula 4) R ３ (%) = (1 - (T ３ / 30)) × 100 T １ : The film thickness (μm) of a test piece obtained by heating a 30-μm-thick film made of the adhesive composition for temporary fixing at 180°C for 1 hour and then immersing it in toluene at 80°C for 1 hour. T ２ : The film thickness (μm) of a test piece obtained by heating a 3*0-μm-thick film made of the adhesive composition for temporary fixing at 180°C for 1 hour and then immersing it in cyclohexanone at 80°C for 1 hour. T ３: The thickness (μm) of the film after a test piece obtained by heating a 30 μm thick film made of a temporary fixing adhesive composition at 180°C for 1 hour and then immersing it in N-methylpyrrolidone at 80°C for 1 hour.

[0014] Furthermore, the organic solvents used for dissolving and removing the temporary fixing adhesive composition are not limited to toluene, cyclohexanone, and N-methylpyrrolidone. The three organic solvents, toluene, cyclohexanone, and N-methylpyrrolidone, are simply used as indicators of dissolution and removal capabilities because they are organic solvents with different solubility. Therefore, while these three organic solvents can be suitably used for dissolution and removal, they are not particularly preferable to other organic solvents. However, if the film thickness reduction rate after immersion in any of the three organic solvents at 80°C for one hour is 95% or more, it is possible to select the optimal organic solvent for dissolution and removal considering other factors such as economy, toxicity, and safety.

[0015] Conventional temporary fixing adhesive compositions are designed to provide heat resistance through the rigidity of their resin structure, resulting in poor conformability to the substrate and requiring high-temperature processes to promote the ring-closing reaction of the resin structure. As a result, they could not exhibit their intended properties in low-temperature processes. Furthermore, high-temperature processes were prone to problems such as warping due to differences in the thermal expansion coefficients of each layer and the constituent layers within the member. As a result of diligent research by the inventors, it has been found that the temporary fixing adhesive composition of this disclosure undergoes crosslinking for heat resistance after bonding and conformability to the member, and that this crosslinking has a certain degree of reversibility through dissociation and recombination, enabling substrate conformability and heat resistance to be exhibited at relatively low temperatures.

[0016] <Resin (A)> Resin (A) of the present disclosure is a resin that contains at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group, and whose temperature at which the mass loss rate relative to the mass before heating is 5% when heated at a rate of 10°C / min in an atmospheric atmosphere using thermogravimetric differential thermal analysis is 280°C or higher and 550°C or lower. The type of resin is not particularly limited as long as the above requirements are satisfied. In this disclosure, an alcoholic hydroxyl group means a hydroxyl group directly attached to an aliphatic carbon, and a phenolic hydroxyl group means a hydroxyl group directly attached to an aromatic carbon. In resin (A), "containing at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group" means that resin (A) only needs to contain at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group, and may have both an alcoholic hydroxyl group and a phenolic hydroxyl group.

[0017] The resin (A) having at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group allows it to form crosslinks with organometallic compounds (described later) that have coordination bonding properties, thereby providing resistance to harsh heating processes such as solder reflow and various chemicals, while also enabling dissolution and removal with organic solvents. It is particularly preferable for resin (A) to have a phenolic hydroxyl group in order to balance heat resistance and solubility in organic solvents. The combined functional value of the phenolic hydroxyl group value and the alcoholic hydroxyl group value is preferably 0.01 to 250 mg KOH / g, and particularly preferably 0.5 to 220 mg KOH / g. By keeping it within this range, a particularly good balance between heat resistance and solubility in organic solvents is achieved.

[0018] When resin (A) is heated at a rate of 10°C / min in an atmospheric atmosphere using thermogravimetric differential thermal analysis, the temperature at which the mass reduction rate relative to the mass before heating becomes 5% is 280°C or higher. This allows the combination with the organometallic compound to stably exhibit the necessary heat resistance, and if the temperature is 550°C or lower, rapid delamination by laser irradiation becomes possible. Preferably, this temperature is 300°C or higher and 500°C or lower, and particularly preferably 330°C or higher and 480°C or lower.

[0019] There are no particular limitations on the weight-average molecular weight of resin (A), but in order to achieve both film-thinning properties and coating properties of the temporary fixing adhesive composition and obtain good handling properties, the weight-average molecular weight is preferably 2,000 to 150,000, more preferably 2,500 to 100,000, and particularly preferably 5,000 to 90,000.

[0020] There are no particular limitations on the glass transition temperature of resin (A), but in order to achieve both film-forming properties and high step-following ability in relatively low-temperature processes for the temporary fixing adhesive composition, the glass transition temperature is preferably 0°C to 160°C, more preferably 10°C to 140°C, and particularly preferably 15°C to 120°C.

[0021] Specific resin types for resin (A) include, for example, polyimide resins, polyamide resins, polyphenylene ether resins, phenolic resins and phenoxy resins, (meth)acrylic resins, polyester resins, and polyurethane resins. Among these, it is particularly preferable that at least one of the group consisting of polyimide resins, polyamide resins, polyphenylene ether resins, phenolic resins, and phenoxy resins is selected because it provides an excellent balance between heat resistance and laser peelability. The position of at least one of the alcoholic hydroxyl group and the phenolic hydroxyl group in the molecular structure of these resins is not particularly limited.

[0022] (Polyimide Resin) Examples of polyimide resins used as resin (A) include resins having a repeating structure in which tetracarboxylic acid residues and diamine residues are linked via a cyclic imide structure. Such polyimide resins can be obtained, for example, by linking tetracarboxylic dianhydride and diamine through a dehydration condensation reaction. The molecular chain ends of the polyimide resin may also be capped by a reaction with dicarboxylic anhydride or monoamine. By using tetracarboxylic dianhydride or diamine, or dicarboxylic anhydride or monoamine having at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group, as at least a portion of the raw materials for the polyimide resin, it is possible to obtain a polyimide resin having at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group.

[0023] Examples of the tetracarboxylic dianhydrides include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene Aromatic tetracarboxylic acids such as n-1,2-dicarboxylic acid anhydride and 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 1,2,4,5-pentanetetracarboxylic acid, 1,2,3,4-hexanetetracarboxylic acid, and 1,2,5,6-hexanetetracarboxylic acid, as well as cyclobutane-1,2,3,4-tetracarboxylic acid and cyclopentane-1,2,3, 4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, rel-dicyclohexyl-3,3',4,4'-tetracarboxylic acid, tricyclo[4.2.2.02,5]deca-9-ene-3,4,7,8-tetracarboxylic acid, 5-carboxymethylbicyclo[2.2.1]heptane-2,3,6-tricarboxylic acid, bicyclo[2.2. 1] Heptane-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2] Octa-7-ene-2,3,6,7-tetracarboxylic acid, bicyclo[3.3.0] Octane-2,4,6,7-tetracarboxylic acid, 7,8-diphenylbicyclo[2.2.2] Octa-7-ene-2,3,5,6-tetracarboxylic acid, 4,8-diphenyl-1,5-diazabicyclooctane-2,3,6,7-tetracarboxylic acid, 9-oxatricyclo[4.2.1.02,5] Nonane-3,4,7,8-tetracarboxylic acid, 9,14-dioxopentacyclo[8.2.11,Examples include cyclo, bicyclo, and tricyclotetracarboxylic acids such as [11.14, 7.02, 10.03, 8]tetradecane-5,6,12,13-tetracarboxylic acid; spiro-ring-containing tetracarboxylic acids such as 2,8-dioxaspiro[4.5]decane-1,3,7,9-terotone; and alicyclic tetracarboxylic dianhydrides such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride.

[0024] Examples of diamines include 1,4-diaminobenzene, 1,3-diaminobenzene, 1,2-diaminobenzene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diamino-1,2-diphenylethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3 Examples include aromatic diamines such as '-diaminobenzophenone and 3,3'-diaminodiphenylsulfone; aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,9-nonanediamine, 1,12-dodecamethylenediamine and metaxylenediamine; alicyclic diamines such as isophoronediamine, norbornanediamine, 1,2-cyclohexanediamine, 1,-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane and piperazine, as well as dimeramines and bisaminophenols.

[0025] The dimer diamines can be obtained, for example, by converting the carboxy groups of dimer acids into amino groups. Here, the dimer acid refers to a dimer of an unsaturated aliphatic carboxylic acid or its hydrogenated product. For example, dimer acids can be obtained by dimerizing natural fatty acids such as soybean oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, and unsaturated fatty acids such as purified linolenic acid, linoleic acid, oleic acid, and erucic acid. If necessary, the unsaturated bonds can be hydrogenated to reduce the degree of unsaturation. The dimer diamines with reduced degrees of unsaturation are suitable in terms of oxidation resistance (especially coloring in the high-temperature range) and suppression of gelation during synthesis.

[0026] Dimer acids refer to dimers or hydrogenated products of unsaturated aliphatic carboxylic acids. For example, dimer acids can be obtained by dimerizing natural fatty acids such as soybean oil fatty acids, tall oil fatty acids, and rapeseed oil fatty acids, or unsaturated fatty acids such as linolenic acid, linoleic acid, oleic acid, erucic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, stearolic acid, vaccenic acid, gadoleic acid, eicosenoic acid, brassic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, pinolenic acid, eleostearic acid, meadic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, cetoleic acid, adrenalineic acid, bosopentaenoic acid, osbondic acid, sardine acid, tetracosapentaenoic acid, eicosapentaenoic acid, docosahexaenoic acid, and herringic acid. Unsaturated bonds may be hydrogenated as needed to reduce the degree of unsaturation. Dimer acids with reduced unsaturation are preferable in terms of oxidation resistance (especially coloring at high temperatures) and suppression of gelation during synthesis. Dimer acids are preferably compounds with 20 to 60 carbon atoms, more preferably compounds with 24 to 56 carbon atoms, even more preferably compounds with 28 to 48 carbon atoms, and even more preferably compounds with 36 to 44 carbon atoms. Dicarboxylic acid compounds having a branched structure obtained by the Diels-Alder reaction of fatty acids are also preferred. The branched structure is preferably a fatty chain or a ring structure, with the ring structure being more preferred, in terms of obtaining higher heat resistance. The ring structure is preferably one or more aromatic rings or alicyclic structures, with the alicyclic structure being more preferred. When there are two ring structures, the two rings may be independent or continuous. One or more types of compounds can be used as dimer acids. The alicyclic structure may have one or more double bonds within the ring, or it may not have double bonds.

[0027] Examples of the bisaminophenols include aromatic diamino phenols such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, and 2,2'-dihydroxybenzidine. By using bisaminophenols as part or all of the diamine, phenolic hydroxyl groups can be imparted to the side chains of the polyimide resin.

[0028] Examples of the dicarboxylic acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-hydroxyphthalic anhydride, and the like.

[0029] Examples of the monoamine include aniline, o-toluidine, m-toluidine, p-toluidine, o-aminophenol, m-aminophenol, p-aminophenol, and oleylamine. By using o-aminophenol, m-aminophenol, p-aminophenol, etc., phenolic hydroxyl groups can be imparted to the terminals of the polyimide resin.

[0030] (Polyamide resin) Examples of the polyamide resin used as the resin (A) include resins having a repeating structure in which dicarboxylic acid residues and diamine residues are linked via amide groups. Such a polyamide resin can be obtained, for example, by linking a dicarboxylic dianhydride and a diamine through a dehydration condensation reaction. Also, the molecular chain terminals of the polyamide resin may be capped by reaction with a monocarboxylic acid or a monoamine. By using a diamine, a dicarboxylic acid, a monoamine, or a monocarboxylic acid having at least one of alcoholic hydroxyl groups and phenolic hydroxyl groups as at least part of the raw materials of the polyamide resin, it is possible to obtain a polyamide resin having at least one of alcoholic hydroxyl groups and phenolic hydroxyl groups.

[0031] Examples of the dicarboxylic acids include isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 5-hydroxyisophthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-bis(4-carboxyphenyl)hexafluoropropane, 1,3-bis(carboxyphenyl)-1,1,3,3-tetramethyldisiloxane, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and the aforementioned dimer acids.

[0032] As the diamine and monoamine mentioned above, those similar to those exemplified as diamines and monoamines used in the polyimide resin can be suitably used.

[0033] The aforementioned monocarboxylic acids include lower fatty acids such as acetic acid, propionic acid, and butyric acid; saturated fatty acids such as stearic acid (octadecanoic acid), tubercurostearic acid (nonadecanoic acid), arachidic acid (eicosanoic acid), and henicosanoic acid; unsaturated fatty acids such as behenic acid (docosanoic acid), hydroxystearic acid (castor hydrogenated fatty acid), oleic acid, linoleic acid, linolenic acid, gadoleic acid, eicosadienoic acid, meadic acid, erucic acid, and docosadienoic acid; benzoic acid; methylbenzoic acid {toluic acid (p-, m-, o-)}; dimethylbenzoic acid (xylylic acid, hemeritic acid, mesityleneic acid); and trimethylbenzoic acid {prenicylic acid, durylic acid, isodurylic acid (α-, β-, γ-)}. Aromatic monocarboxylic acids such as 4-isopropylbenzoic acid (cumic acid), hydroxybenzoic acid (salicylic acid), dihydroxybenzoic acid {pyrocatechuic acid, resorcylic acid (α-, β-, γ-), gentisic acid, protocatechuic acid}, trihydroxybenzoic acid (gallic acid), hydroxymethylbenzoic acid {cresotic acid (p-, m-, o-)}, dihydroxymethylbenzoic acid (orceric acid), methoxybenzoic acid {anisic acid (p-, m-, o-)}, dimethoxybenzoic acid (veratorumic acid), trimethoxybenzoic acid (asalonic acid), hydroxymethoxybenzoic acid (vanillic acid, isovanillic acid), and hydroxydimethoxybenzoic acid (syringic acid) can be cited.

[0034] (Polyphenylene ether resin) Examples of polyphenylene ether resins used as resin (A) include poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), and copolymers of 2,6-dimethylphenol with other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.). Also, examples of polyphenylene ethers having a linear or branched structure are obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols to obtain polyphenylene ether copolymers and poly(2,6-dimethyl-1,4-phenylene ether), etc., and by heating them in a solvent such as toluene in the presence of organic peroxides and undergoing a redistribution reaction with phenol compounds such as bisphenols and trisphenols.

[0035] (Phenolic Resin) Examples of phenolic resins used as resin (A) include polymers obtained by condensing phenolic compounds such as phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-phenylphenol, cardanol, bisphenol A, and hydroquinone with formaldehyde, acetaldehyde, acetone, salicylaldehyde, 1,3-bis(1-methyl-1-hydroxyethyl)benzene, α,α'-dichloro-p-xylene, 4,4'-bis(chloromethyl)biphenyl, etc., in the presence of an acid catalyst. In addition, a phenol-modified xylene resin obtained by copolymerizing xylene in addition to the above raw materials may also be used. Due to its structure, phenolic resin inevitably has phenolic hydroxyl groups.

[0036] (Phenoxy resin) Examples of phenoxy resins used as resin (A) include polymers obtained by addition polymerization of bisphenol compounds and diexo compounds. Due to their structure, phenoxy resins inevitably have alcoholic hydroxyl groups.

[0037] Examples of the bisphenol compounds include bisphenol A, bisphenol F, bisphenol B, bisphenol C, bisphenol G, bisphenol S, bisphenol Z, bisphenol E, bisphenol M, bisphenol P, bisphenol AP, bisphenol AP, bisphenol AF, bisphenol BP, bisphenol PH, bisphenol TMC, 2,2'-diallylbisphenol A, hydrogenated bisphenol, propylene oxide-added bisphenol A, resorcinol, biphenol, tetramethylbisphenol F, tetramethylbisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, tetramethylbiphenol, ethylidenebisphenol, methylethylidenebis(methylphenol), cyclohexylidenebisphenol, and the like.

[0038] Examples of the aforementioned diepoxy compounds include bisphenol A type diepoxy, bisphenol F type diepoxy, bisphenol S type diepoxy, bisphenol O type diepoxy, 2,2'-diallylbisphenol A type diepoxy, hydrogenated bisphenol type diepoxy, propylene oxide-added bisphenol A type diepoxy, resorcinol type diepoxy, biphenyl type diepoxy, sulfide type diepoxy, diphenyl ether type diepoxy, dicyclopentadiene type diepoxy, naphthalene type diepoxy, and the like.

[0039] <Organometallic Compound (B)> The organometallic compound (B) of this disclosure can be an organometallic complex having a structure in which a ligand made of an organic molecule is coordinated to a metal ion. The organometallic compound (B) can form a reversible crosslink between at least one of the alcoholic hydroxyl groups and phenolic hydroxyl groups of resin (A) via a coordination bond to the metal ion by ligand exchange between its ligand and at least one of the alcoholic hydroxyl groups and phenolic hydroxyl groups of resin (A). Most of these crosslinks can be formed in a relatively low-temperature heating process after bonding to the member, and even crosslinks that have already been partially formed before bonding can be temporarily separated during bonding to the member due to their reversibility. As a result, deformation along the surface shape of the member is possible even at relatively low process temperatures, and excellent conformability to the member surface can be obtained. Furthermore, by substantially using this metal coordination crosslink as the main crosslinking structure, it is possible not only to impart the heat resistance required for heating processes such as reflow processes, but also to achieve removal with organic solvents due to the reversibility of the bond.

[0040] Examples of metal ion species for organometallic compound (B) include divalent or higher metal ions such as titanium ions, zirconium ions, aluminum ions, iron ions, calcium ions, zinc ions, and tin ions. Titanium ions or zirconium ions are preferred, and zirconium ions are particularly preferred, as they offer a high level of both heat resistance and removal by organic solvents. In other words, organometallic compound (B) is preferably at least one selected from organotitanium compounds, organozirconium compounds, and organoaluminum compounds, more preferably organotitanium compounds or organozirconium compounds, and particularly preferably organozirconium compounds.

[0041] Examples of ligands consisting of organic molecules for organometallic compound (B) include monodentate ligands such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, octyl alcohol, stearyl alcohol, lactic acid, dodecylbenzenesulfonic acid, ammonium, triethanolamine, hydroxyanion, and chloride ion, as well as active methylene-type polydentate ligands such as acetylacetone, methyl acetoacetate, and ethyl acetoacetate. It is particularly preferable to include at least one polydentate ligand such as acetylacetone, methyl acetoacetate, or ethyl acetoacetate, as this allows for both a good pot life during formulation and a rapid crosslinking reaction. In particular, it is preferable that the organoaluminum compound contains at least one ligand consisting of an organic molecule selected from the group consisting of acetylacetone, methyl acetoacetate, and ethyl acetoacetate.

[0042] The total content of titanium ions and zirconium ions in the temporary fixing adhesive composition is preferably 0.01% by mass or more and 3.0% by mass or less. A total content of 0.01% by mass or more of titanium ions and zirconium ions provides the necessary heat resistance, while a content of 3.0% by mass or less provides rapid removal with organic solvents.

[0043] <Compound (C) having two or more groups that can react with at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group> The temporary fixing adhesive composition of this disclosure may contain compound (C) (hereinafter also referred to as compound (C)) having two or more groups that can react with at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group. Compound (C) excludes the organometallic compound (B). From the viewpoint of maintaining good removeability with organic solvents, the content of compound (C) is preferably 10 parts by mass or less per 100 parts by mass of resin (A), and the upper limit may be, for example, 8 parts by mass, 7 parts by mass, 6 parts by mass, 4 parts by mass, 2 parts by mass, or 1 part by mass. The lower the content of compound (C), the better, and it is particularly preferable that it is not included.

[0044] Groups that can react with at least one of the alcoholic hydroxyl group and the phenolic hydroxyl group of compound (C) include epoxy groups, oxetanyl groups, episulfide groups, isocyanate groups, thioisocyanate groups, blocked isocyanate groups, oxazoline groups, and benzoxazine groups. Compound (C) is a compound having one or more of the above-listed groups in the same molecule.

[0045] Specific examples of compound (C) include the aforementioned diepoxide, polyfunctional epoxy resins obtained by epoxidizing the phenol resin with epichlorohydrin, polyfunctional epoxy compounds such as tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminomethyl)cyclohexane, O,N,N-triglycidyl-p-aminophenol, and 1,1,2,2-tetrakis(4-glycidyloxyphenyl)ethane, and 3,7-bis(3-oxetane (L)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, bis[1-ethyl(3-oxetanyl)]methyl ether, bis(3-ethyl-3-oxetanylmethyl) ether, ethylene glycol bis(3-ethyl-3-oxetanylmethyl ) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,3-bis(3-ethyl-3-oxetanylmethoxy)propane, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,4-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene, 1,3-bis(3-ethyl-3-oxetanylmethoxymethyl) Examples of polyfunctional oxetanyl compounds include 1,2-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene, 4,4'-bis(3-ethyl-3-oxetanylmethoxymethyl)biphenyl, 2,2'-bis(3-ethyl-3-oxetanylmethoxymethyl)biphenyl, 1,6-bis((3-methyloxetan-3-yl)methoxy)hexane, and 1,6-bis((3-ethyloxetan-3-yl)methoxy)hexane.Also, TDI (e.g., toluene diisocyanates such as 2,4-tole diisocyanate (2,4-TDI), 2,6-tole diisocyanate (2,6-TDI), or mixtures thereof), MDI (e.g., 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), Or mixtures thereof, such as diphenylmethane diisocyanate, 1,4-phenylenediisocyanate, diphenyl diisocyanate, polymethylene polyphenylene polyisocyanate, toridine diisocyanate (TODI), 1,5-naphthalenediisocyanate (1,5-NDI), diphenyl ether diisocyanate, triphenylmethane triisocyanate, and other aromatic polyisocyanates, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), xylylene diisocyanate (XDI), and tetramethylxylylene diisocyanate (TMXDI). Examples include aliphatic polyisocyanates such as cyclohexane diisocyanate, methylene bis(cyclohexyl isocyanate), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanate methyl)cyclohexane (H6XDI), dicyclohexylmethane diisocyanate, and alicyclic polyisocyanates (H12MDI), as well as polyfunctional isocyanate compounds such as aromatic polyisocyanates, carbodiimide-modified polyisocyanates, biuret-modified polyisocyanates, allophanate-modified polyisocyanates, polymethylene polyphenyl polyisocyanate (crude MDI or polymeric MDI), and isocyanurate-modified polyisocyanates. Other examples include blocked isocyanate compounds that have been blocked with blocking agents such as phenol, cresol, ε-caprolactam, ethyl methyl ketone oxime, diethyl malonate, ethyl acetoacetate, diisopropylamine, 3,5-dimethylpyrazole, and imidazole.In addition, polyfunctional oxazoline compounds such as 2,2'-bis(2-oxazoline), 1,2-bis(2-oxazoline-2-yl)ethane, 1,4-bis(2-oxazoline-2-yl)butane, 1,8-bis(2-oxazoline-2-yl)butane, 1,4-bis(2-oxazoline-2-yl)cyclohexane, 1,2-bis(2-oxazoline-2-yl)benzene, and 1,3-bis(2-oxazoline-2-yl)benzene, specifically o-cresol-aniline type benzoxazine, m-cresol-aniline type benzoxazine, p-cresol-aniline type benzoxazine, phenol-aniline type benzoxazine, phenol-methylamine type benzoxazine, phenol-cyclohexylamine type benzoxazine, phenol-m-toluidine type benzoxazine, and phenol-3,5-dimethylamine Examples include polyfunctional benzoxazine compounds such as diline-type benzoxazine, bisphenol A-aniline-type benzoxazine, bisphenol A-amine-type benzoxazine, bisphenol F-aniline-type benzoxazine, bisphenol S-aniline-type benzoxazine, dihydroxydiphenylsulfone-aniline-type benzoxazine, dihydroxydiphenylether-aniline-type benzoxazine, benzophenone-type benzoxazine, biphenyl-type benzoxazine, bisphenol AF-aniline-type benzoxazine, bisphenol A-methylaniline-type benzoxazine, phenol-diaminodiphenylmethane-type benzoxazine, triphenylmethane-type benzoxazine, and phenolphthalein-type benzoxazine, but are not limited to these as long as the above conditions are met.

[0046] <Other Components> In addition to the above components, the temporary fixing adhesive composition of this disclosure may optionally contain laser absorbers, various fillers, dispersants, defoamers, etc., to the extent that it does not impair the desired properties. Examples of laser absorbers include pigments such as carbon black, phthalocyanine blue, and silica, dyes such as nigrosine black, and various known ultraviolet absorbers such as triazine-based and hydroxyphenylbenzotriazole-based absorbers. These can be appropriately selected and added depending on the laser wavelength used.

[0047] <Laminate> The laminate of this disclosure is formed by bonding and temporarily fixing a member and a support with a temporary fixing adhesive composition. Specifically, as shown in Figure 1, in order to temporarily fix the member and perform various processing, the support, temporary fixing adhesive layer, and member are laminated in this order.

[0048] The support material is not particularly limited as long as it is a plate-shaped material that has rigidity and high flatness for fixing the member and transmits laser light of the wavelength used. Glass or silicon are preferred as the material of the support. Examples include soda-lime glass, borosilicate glass, aluminoborosilicate glass, and silicon. Glass is preferred because it has excellent UV and infrared transmittance, while silicon is preferred because it has excellent infrared transmittance and dimensional stability in the heating process. The shape of the support is not particularly limited and may be a circular wafer, or a square or rectangular panel.

[0049] Examples of the aforementioned components include semiconductor chips, package substrates used for their redistribution, and semiconductor peripheral components such as interposers. In particular, the conformability to surface shape and the high dissolution and removal performance described later of the temporary fixing adhesive composition of this disclosure are especially effective when the component has a surface with an uneven structure such as solder bumps or electrode pads on at least one side, or a surface with high surface roughness, and further processing of the opposite side is required.

[0050] ≪Method for Temporarily Fixing Components≫ The method for temporarily fixing components according to this disclosure consists of the following steps (1) to (3): (1) A step of temporarily fixing the component and the support using the temporary fixing adhesive composition according to this disclosure. (2) A step of processing the component that has been temporarily fixed in (1). (3) A step of removing the support by irradiating the layer made of the temporary fixing adhesive composition with a near-infrared laser or ultraviolet laser after processing in (2).

[0051] Step (1) Step (1) is a step in which the laminate is manufactured. Specifically, for example, first a solution is prepared by dissolving the temporary fixing adhesive composition in any organic solvent on a member. Then, this may be applied and dried, and then pressed onto the support while heating as needed, or conversely, it may be applied to the support and then pressed onto the member. Alternatively, the solution of the temporary fixing adhesive composition may be applied to any resin film that has been subjected to a release treatment to form a release film, dried to produce a temporary fixing adhesive film, then transferred to the support while heating as needed, and then pressed onto the member.

[0052] Step (2) Step (2) is a process for processing the temporarily fixed member in the laminate of the present disclosure. Specific steps include cutting and thinning steps such as physical polishing and CMP, chemical solution steps for forming wiring layers and insulating layers and soldering, and heating steps such as solder reflow steps. Through each of the above steps, the member is thinned, and a wiring layer is formed on the side opposite to the side in contact with the adhesive layer for temporary fixing of the member, an insulating layer is formed, vias are formed, components are mounted and solder bumps are formed, etc.

[0053] Step (3) Step (3) is a step of removing the support by irradiating a layer made of a temporary fixing adhesive composition (hereinafter also referred to as the temporary fixing adhesive layer) with a near-infrared laser or ultraviolet laser. Specifically, as shown in Figure 2, this step separates the member 3 and the support 1 by irradiating the temporary fixing adhesive layer 2 with laser light through the support 1 which transmits laser light, thereby decomposing or altering the temporary fixing adhesive layer 2.

[0054] The wavelength of the laser light used in the laser peeling process can be appropriately selected according to the wavelength of light absorbed by the temporary fixing adhesive layer 2 and the transmittance of the support 1. For example, light in the ultraviolet, visible, and infrared wavelength ranges of 200 to 1100 nm can be used, but ultraviolet lasers with a wavelength of 200 to 380 nm are preferred because they cause less thermal damage to the substrate, and near-infrared lasers with a wavelength of 780 to 1100 nm are preferred because they allow the use of general-purpose substrates that do not transmit visible light, such as silicone wafers. As for the type of laser light to be irradiated, for example, YAG lasers, YVO ４Solid-state lasers such as lasers and fiber lasers, liquid lasers such as dye lasers, CO2 ２ Lasers such as lasers, excimer lasers, Ar lasers, He-Ne lasers and other gas lasers, semiconductor lasers, and free-electron lasers, as well as laser light consisting of their harmonics, can be used. This allows the temporary fixing adhesive layer 2 to be decomposed or altered, making it possible to easily separate the support 1 and the component 3.

[0055] When irradiating with laser light, the following conditions can be cited as an example of laser light irradiation conditions: The average output value of the laser light is preferably 1.0 W or more and 5.0 W or less, and more preferably 2.0 W or more and 4.0 W or less. The repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser light is preferably 100 mm / s or more and 10,000 mm / s or less. The total energy of the laser light is 50 mJ / cm². ２ More than 5000mJ / cm ２ The following is preferable: 100 mJ / cm ２ More than 1000mJ / cm ２ The following conditions are preferable. However, other conditions may be preferable depending on the specifications and configuration of the laser light irradiation device, and are therefore not limited to the above conditions.

[0056] ≪Dissolution and Removal of Temporary Fixing Adhesive Composition with Organic Solvents≫ As a method for dissolving and removing the temporary fixing adhesive layer, the laminate after the support has been peeled off following the laser peelability test may be immersed in a tank filled with an organic solvent, or the temporary fixing adhesive layer may be washed away while dissolving it with a shower of organic solvent. In this case, there are no particular restrictions on the temperature of the organic solvent as long as the temporary fixing adhesive layer can be dissolved and removed in a realistic processing time, and it may be at room temperature, but it may be heated to shorten the processing time. By heating the organic solvent, the exchange of crosslinks formed between the resin (A) and the organometallic compound (B) is promoted, thereby enabling faster dissolution and removal. There are no particular restrictions on the heating temperature of the organic solvent as long as rapid dissolution and removal is possible, but 40 to 100°C is preferred.

[0057] The organic solvent used to dissolve and remove the temporary fixing adhesive composition is not particularly limited as long as it is an organic solvent capable of dissolving resin (A). Examples include ketone solvents such as acetone, ethyl methyl ketone, and cyclohexanone; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; alcohol solvents such as methanol, ethanol, and isopropyl alcohol; hydrocarbon solvents such as benzene, toluene, and hexane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; nitrile solvents such as acetonitrile; and ether solvents such as tetrahydrofuran and 1,2-dimethoxyethane.

[0058] The present disclosure will be further described below with reference to examples. The present disclosure is not limited to the following examples. Unless otherwise specified, "%" and "parts" are based on mass. Furthermore, the "parts" of the blending ingredients in the composition shall be expressed as the non-volatile content even when blended as a solution in an organic solvent.

[0059] (i) Measurement of weight-average molecular weight (Mw) Mw was measured using a GPC (gel permeation chromatograph) "GPC-101" manufactured by Showa Denko. The fluid phase was THF (tetrahydrofuran), and two "KF-805L" (Showa Denko: GPC column: 8 mm ID x 300 mm size) columns connected in series were used as the stationary phase column. The analysis was performed under the conditions of sample concentration 1% by mass, flow rate 1.0 mL / min, pressure 3.8 MPa, and column temperature 40°C, and Mw was determined in polystyrene equivalent. For data analysis, calibration curves, molecular weights, and peak areas were calculated using the manufacturer's built-in software, and Mw was determined for the range of retention times from 17.9 to 30.0 minutes.

[0060] (ii) Measurement of Hydroxyl Value The hydroxyl value is expressed as the amount of potassium hydroxide (mg) required to neutralize the acetic acid bonded when the hydroxyl groups are acetylated, based on the amount of hydroxyl groups contained in 1 g of the sample. The hydroxyl value was measured in accordance with JIS K0070. In this disclosure, when calculating the hydroxyl value of a sample that has an acid value other than hydroxyl groups, the calculation is performed considering the acid value as shown in the following formula. Approximately 1 g of the sample was accurately weighed into a stoppered Erlenmeyer flask and dissolved in 100 mL of toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1) mixture. Then, an acetylating agent (a solution of 25 g of acetic anhydride dissolved in pyridine and made to a volume of 100 mL) was accurately added and stirred for about 1 hour. Phenolphthalein reagent was added as an indicator and kept for 30 seconds. After that, the solution was titrated with 0.1 N alcoholic potassium hydroxide solution until it turned pale pink. The hydroxyl value was determined by the following formula (unit: mgKOH / g). Hydroxyl value (mgKOH / g) = [{(b-a) × F × 28.05} / S] + D where, S: Amount of sample taken (g) a: Amount of 0.1N alcoholic potassium hydroxide solution consumed (mL) b: Amount of 0.1N alcoholic potassium hydroxide solution consumed for the blank experiment (mL) F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

[0061] (iii) Measurement of Acid Value Approximately 1 g of the sample is accurately weighed into a stoppered Erlenmeyer flask, and 100 mL of toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1) is added to dissolve it. Phenolphthalein reagent is added as an indicator and held for 30 seconds. Then, the solution is titrated with 0.1 N alcoholic potassium hydroxide solution until it turns pale pink. The acid value was determined by the following formula (unit: mgKOH / g): Acid value (mgKOH / g) = (5.611 × a × F) / S where, S: Amount of sample taken (g) a: Amount of 0.1 N alcoholic potassium hydroxide solution consumed (mL) F: Titer of 0.1 N alcoholic potassium hydroxide solution

[0062] (iv) Thermogravimetric Differential Thermal Analysis Approximately 10 mg of a test specimen, cut to an appropriate size from a small film piece of each composition described later, was placed in a small aluminum pan. Using a thermogravimetric differential thermal analyzer "TG / DTA-6300" (manufactured by Seiko Instruments Inc.), the temperature was raised to 30°C in an atmospheric atmosphere (gas flow rate 200 mL / min.), stabilized for 5 minutes, and then raised to 550°C at a heating rate of 10°C / min. The change in mass was measured. From the ratio of the initial mass to the mass decrease at each temperature, the temperature at which the mass decrease first exceeded 5% of the initial mass was determined.

[0063] (v) Measurement of glass transition temperature Each resin was dissolved in cyclohexanone to a non-volatile content of 40%, and the resulting coating solution was applied onto a heat-resistant release film using a doctor blade with a 6 ml gap. The solution was then dried at 130°C for 10 min to obtain a resin sheet with a thickness of 30 μm. (However, for resins (a)-1 and (a)-5 described later, the resin sheet was transferred to a Teflon® coated metal pan for the imidation reaction and sintered at 300°C for 1 hour under a nitrogen atmosphere.) The obtained resin sheet was peeled off the release film, and the storage modulus and Tg of the resin sheet were measured using a dynamic viscoelasticity measuring device "DVA200" (manufactured by IT Measurement Control Co., Ltd.). The glass transition temperature was determined by cooling the resin sheet to 0°C, then heating it to 300°C at a heating rate of 10°C / min, measuring the viscoelasticity at an oscillation frequency of 10 Hz and a gripping length of 10 mm, and confirming the temperature at which the loss tangent (tanδ) peak was maximum. Heating rate: 10°C / min; Measurement frequency: 10Hz; Grip length: 10mm; Width: 5mm

[0064] [Synthesis Example 1] <Synthesis of Resin (A)-1> In a 1 L separable flask equipped with a stirring rod and an oil bath, 295 g of cyclohexanone was added while introducing nitrogen gas. 148.5 g of Y1 (priamine 1075) as a diamine and 5.4 g of Z1 (m-aminophenol) as a monoamine compound were added while stirring. Subsequently, 156.0 g of X1 (4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride) as a tetracarboxylic acid was added and the mixture was stirred at room temperature for 30 minutes. The mixture was then heated to 100°C and stirred for 3 hours. After that, the oil bath was removed and the mixture returned to room temperature to obtain a varnish-like polyimide precursor. Subsequently, while removing the distilled water from the system using a Dean-Stark trap, the mixture was heated at 170°C for 10 hours to perform imidization, yielding (A)-1, a phenolic hydroxyl group-containing polyimide resin with a weight-average molecular weight of 24,000, a phenolic hydroxyl group value of 4.6 mg KOH / g, a glass transition temperature of 48°C, and a mass loss rate of 5% at 410°C.

[0065] [Synthesis Examples 2-8] <Synthesis of (A)-2 to (A)-8> (A)-2 to (A)-8, which are phenolic hydroxyl group-containing polyimide resins, were obtained by the same method as in Synthesis Example 1, except that the monomers and their proportions were changed as shown in Table 1. In the table, "Type of Functional Group" is denoted as "PhOH" for phenolic hydroxyl groups and as "OH" for alcoholic hydroxyl groups.

[0066] The abbreviations for Table 1 are shown below. X1: 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride X2: 3,3',4,4'-biphenyltetracarboxylic dianhydride X3: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride X4: 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride X5: 1,2,4,5-cyclohexanetetracarboxylic dianhydride Y1: Priamine 1075 (dimer amine, manufactured by Cargill Japan) Y2: 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) Y3: 1,12-dodecanediamine Z1: m-aminophenol Z2: 1-aminodecane

[0067]

[0068] [Synthesis Example 9] <Synthesis of (A)-9> In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 171.8 g of Pripol 1009 as a polybasic acid compound, 0.6 g of 5-hydroxyisophthalic acid, 79.0 g of Priamine 1074 as a polyamine compound, and 100 g of deionized water were charged, and the mixture was stirred until the exothermic temperature became constant. Once the temperature stabilized, the temperature was raised to 110°C, and after confirming the outflow of water, the temperature was raised to 120°C after 30 minutes, and the dehydration reaction was continued while raising the temperature by 10°C every 30 minutes thereafter. When the temperature reached 230°C, the reaction was continued at that temperature for 3 hours, and then the mixture was held under a vacuum of approximately 2 kPa for 1 hour to lower the temperature. Finally, an antioxidant was added to obtain (A)-9, a phenolic hydroxyl group-containing polyamide resin with a weight-average molecular weight of 96,000, a phenolic hydroxyl value of 0.6 mg KOH / g, and a mass loss rate of 5% at a temperature of 384°C.

[0069] The following resins were used as resins (A)-10 to (A)-14. (A)-10: PKHA, manufactured by GabrielPhonoxys, phenoxy resin, weight-average molecular weight 25000, alcoholic hydroxyl value 211 mg KOH / g, glass transition temperature 104°C, temperature at which mass loss rate is 5%: 330°C (A)-11: PKFE, manufactured by GabrielPhonoxys, phenoxy resin, weight-average molecular weight 60000, alcoholic hydroxyl value 208 mg KOH / g, glass transition temperature 121°C, temperature at which mass loss rate is 5%: 345°C (A)-12: MEHC-7851H, manufactured by Meiwa Kasei Co., Ltd., biphenylene-type phenol resin, weight-average molecular weight 2800, phenolic hydroxyl value: 217 mg KOH / g, glass transition temperature 87°C, temperature at which mass loss rate is 5%: 310°C (A)-13: Noryl SA90, manufactured by SABIC, polyphenylene ether resin, polyphenylene ether containing phenolic hydroxyl groups at both ends, weight-average molecular weight 3800, phenolic hydroxyl value: 67 mg KOH / g, glass transition temperature 145°C, temperature at which mass loss rate is 5%: 315°C (A)-14: Vylon 800, manufactured by Toyobo, polyester resin, weight-average molecular weight 84000, alcoholic hydroxyl value 7 mg KOH / g, glass transition temperature 68°C, temperature at which mass loss rate is 5%: 290°C

[0070] [Comparative Synthesis Example 1] <Synthesis of (a)-1> In a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating and cooling device using hot and cold water, and a stirring device, 1120.0 g of α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecular weight: 1600) and 60.1 g of 4,4'-diaminodiphenyl ether were charged together with 190.3 g of dipropylene glycol dimethyl ether (DMM) and dissolved. Then, 310.2 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was added, and the reaction proceeded at room temperature for 1 hour, followed by 1 hour at 60°C, followed by 4 hours at 150°C. The concentration was then adjusted using the solvent DMM to obtain a 50% by mass polyimide resin precursor (polyamic acid) solution (a)-1 with a weight-average molecular weight of 35000, no alcoholic or phenolic hydroxyl groups, a glass transition temperature of 42°C, and a mass loss rate of 5% at a temperature of 395°C.

[0071] The following resins were used as (a)-2 to (a)-6. (a)-2: Udel P3707, manufactured by Solvay Advanced Polymers, polysulfone resin, weight-average molecular weight 44000, no alcoholic hydroxyl groups or phenolic hydroxyl groups, glass transition temperature 181°C, temperature at which mass loss rate is 5%: 405°C (a)-3: Joncryl 61J, manufactured by BASF, aqueous solution of water-soluble acrylic resin with a resin non-volatile content of 30.5%, weight-average molecular weight 12000, no alcoholic hydroxyl groups or phenolic hydroxyl groups, glass transition temperature 107°C, temperature at which mass loss rate is 5%: 255°C (a)-4: Kuraray Poval PVA-205, manufactured by Kuraray, polyvinyl alcohol (saponification degree 88%), weight-average molecular weight 50000, hydroxyl value 1120 mg KOH / g, glass transition temperature 80°C, temperature at which mass loss rate is 5%: 240°C (a)-5: U-imide varnish BH, manufactured by Unitika Corporation, N,N'-dimethylacetamide solution of polyamic acid (polyimide precursor) with 26% resin non-volatile content, weight-average molecular weight 40,000, no alcoholic hydroxyl groups or phenolic hydroxyl groups, glass transition temperature 300°C or higher (not measurable), temperature at which the mass loss rate is 5%: 560°C (a)-6: Zeonex 480R, manufactured by Nippon Zeon Corporation, cycloolefin polymer, weight-average molecular weight 40,000, no alcoholic hydroxyl groups or phenolic hydroxyl groups, glass transition temperature 167°C, temperature at which the mass loss rate is 5%: 430°C

[0072] The following organometallic compounds were used as (B)-1 to (B)-6: (B)-1: TC-401, manufactured by Matsumoto Fine Chemicals, titanium tetraacetylacetonate, metal ion content: 7.0% by mass (metal ion content in non-volatile matter: 10.8% by mass), 65% non-volatile solution (B)-2: TC-100, manufactured by Matsumoto Fine Chemicals, titanium diisopropoxy bisacetylacetonate, metal ion content: 9.8% by mass (metal ion content in non-volatile matter: 13.1% by mass), 75% non-volatile solution (B)-3: ZC-150, manufactured by Matsumoto Fine Chemicals, zirconium tetraacetylacetonate, metal ion content: 19.0% by mass, 100% non-volatile (B)-4: ZC-45, manufactured by Matsumoto Fine Chemicals, zirconium n-propylate, metal ion content: 21.0% by mass (metal ion content in non-volatile matter: 28.0% by mass), 75% non-volatile solution (B)-5: ALCH, manufactured by Kawaken Fine Chemicals, aluminum diisopropoxyacetylacetonate, metal ion content: 9.8% by mass, 100% non-volatile content (B)-6: TC-310, manufactured by Matsumoto Fine Chemicals, titanium lactate, metal ion content: 8.2% by mass (metal ion content in non-volatile matter: 12.3% by mass), 75% non-volatile solution

[0073] The following compounds (C)-1 to (C)-4 were used as compounds (C)-1 to (C)-4 having two or more groups that can react with at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group: (C)-1: Epiclon N-660, manufactured by DIC Corporation, cresol novolac type epoxy resin, having two or more epoxy groups in one molecule, 50% non-volatile content solution (C)-2: jER-1003F, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, having two epoxy groups in one molecule, 100% non-volatile content (C)-3: Duranate TKA-100, manufactured by Asahi Kasei Corporation, HDI-based isocyanurate type modified polyisocyanate, having three isocyanate groups in one molecule, 100% non-volatile content (C)-4: B-a, manufactured by Shikoku Chemicals, benzoxazine compound, having two benzoxazine groups in one molecule, 100% non-volatile content

[0074] The following were used as other formulations (D)-1 to (D)-4: (D)-1: Tinuvin 326: BASF, UV absorber (D)-2: Nubian Black NH807: Orient Chemical Industries, nigrosine black dye (D)-3: MA-100: Mitsubishi Chemical Corporation, carbon black pigment (D)-4: MEK-ST-40: Nissan Chemical Industries, MEK solvent-dispersed silica, silica concentration 40% by mass, average particle size 12 nm

[0075] [Example 1] <Preparation of coating solution> Based on solid content, 100 parts of resin (A)-1 from Synthesis Example 1 and 2.0 parts of organometallic compound (B)-1 were placed in a container, and a mixed solvent (toluene:MEK = 8:2 (mass ratio)) was added so that the non-volatile content concentration was 35%, and the mixture was stirred with a disperser for 10 minutes to obtain a coating solution.

[0076] <Manufacturing of Temporary Fixing Adhesive Composition Sheet> The obtained coating solution was uniformly applied to a 50 μm thick heavy release film (polyethylene terephthalate (PET) film coated with a heavy release agent) using a doctor blade so that the thickness after drying was 30 μm, and dried at 100°C for 2 minutes. After that, it was cooled to room temperature to obtain a temporary fixing adhesive composition sheet with a single-sided release film. Next, the temporary fixing adhesive composition sheet surface of the obtained temporary fixing adhesive composition sheet with a single-sided release film was superimposed on a 50 μm thick light release film (polyethylene terephthalate (PET) film coated with a light release agent) to obtain a temporary fixing adhesive composition sheet with a double-sided release film consisting of heavy release film / temporary fixing adhesive composition sheet / light release film. The evaluation described later was then performed. The results are shown in Tables 2 to 5.

[0077] [Examples 2-36, Comparative Examples 1-7] Using the same method as in Example 1, coating solutions and temporary fixing adhesive composition sheets with double-sided release films were obtained with the solid content equivalent compositions shown in Tables 2-5, and the evaluations described later were performed.

[0078] <Thickness Reduction Rate of Film After Immersion in Organic Solvents> The release films on both sides of the temporary fixing adhesive composition sheets with double-sided release films for Examples 1-36 and Comparative Examples 1-7 were peeled off, placed on a Teflon-coated tray, heated at 180°C for 1 hour under a nitrogen atmosphere, and then cut into several small pieces. For Comparative Examples 1 and 6 only, the heating temperature was increased to 300°C and sintering was performed under a nitrogen atmosphere for 1 hour to complete the imidization. The film pieces obtained here were also used in the thermogravimetric differential thermal analysis measurements. Each piece was immersed as a sample in toluene, cyclohexanone, and N-methylpyrrolidone organic solvents adjusted to 80°C for 1 hour, then removed, the attached solvent was lightly wiped off, and it was dried. The value obtained by subtracting the thickness of the remaining release film from the film thickness of the temporary fixing adhesive composition sheet with release film after solvent immersion, as measured by a contact film thickness gauge (T １ , T ２ , T ３ The rate of film thickness reduction after toluene immersion (R) can be calculated using the following formula. １ ), the rate of film thickness reduction after cyclohexanone immersion (R ２ ), the rate of film thickness reduction after N-methylpyrrolidone immersion (R ３ The formula was calculated. The results are shown in Tables 2 to 5. (Equation 2) R １ (%) = (1 - (T １ / 30))×100 (Formula 3) R ２ (%) = (1 - (T ２ / 30))×100 (Formula 4) R ３ (%) = (1 - (T ３ / 30))×100T １ : The thickness (μm) of the film after immersing a test specimen, obtained by heating a 30 μm thick film made of a temporary fixing adhesive composition at 180°C for 1 hour, in toluene at 80°C for 1 hour. T ２ : The thickness (μm) of the film after immersing a test specimen, obtained by heating a 30 μm thick film made of a temporary fixing adhesive composition at 180°C for 1 hour, in cyclohexanone at 80°C for 1 hour. T ３: The thickness (μm) of the film after a test piece obtained by heating a 30 μm thick film made of a temporary fixing adhesive composition at 180°C for 1 hour and then immersing it in N-methylpyrrolidone at 80°C for 1 hour.

[0079] <1. Step-following ability> For the temporary fixing adhesive composition sheets with double-sided release films of Examples 1 to 36 and Comparative Examples 1 to 7, the release film was peeled off from only one side, and the sheets were pressed onto an alkali-free glass plate (EagleXG, Corning, 0.8 mm thick) as a support using a vacuum laminator (V-130, Nichigo-Morton, 100°C, 0.5 MPa) at 100°C. In Comparative Examples 1 and 6 only, in order to complete the imidization, sintering was performed at 300°C for 1 hour under a nitrogen atmosphere after pressing onto the alkali-free glass plate. Furthermore, the remaining release film on the other side was peeled off, and the sheets were pressed onto a comb-type electrode FPC substrate with L / S = 50 / 50 μm and copper foil thickness of 10 μm, which has an electrode pad design for soldering at the end, using the vacuum laminator at 180°C, 0.5 MPa to obtain a laminate. The above laminate was cut perpendicular to the circuit length direction of the comb-shaped electrode circuit using a razor to expose the cross-section, and the step-following ability of the temporary fixing adhesive composition sheet to the comb-shaped electrode circuit was checked using a digital optical microscope (Keyence Corporation, VHX-700) and evaluated according to the following criteria: ++: The recesses between circuits are filled without gaps. (Good) NG: The recesses between circuits are not completely filled, resulting in gaps or voids. (Target not met)

[0080] <2. Reflow Resistance Test> For Examples 1-36 and Comparative Examples 1-7, the release film on one side of the double-sided release film adhesive sheets was peeled off, and the sheets were pressed onto an alkali-free glass plate (EagleXG, Corning, 0.8 mm thick) as a support using a vacuum laminator (V-130, Nichigo Morton, 100°C, 0.5 MPa) at 100°C. In Comparative Examples 1 and 6 only, in order to complete the imidization, sintering was performed at 300°C for 1 hour under a nitrogen atmosphere after pressing onto the alkali-free glass plate. Furthermore, the remaining release film on the other side was peeled off, and the sheets were pressed onto a comb-type electrode FPC substrate with L / S = 50 / 50 μm and copper foil thickness of 10 μm, which has an electrode pad design for soldering at the edge, using the vacuum laminator at 180°C, 0.5 MPa to obtain a laminate for reflow resistance testing. For Comparative Examples 2, 3, 5, and 6, adhesive sheets with double-sided release films could not be bonded or the recesses between circuits filled during pressing under the above temperature conditions. Therefore, the pressing temperature of the support and components was set to 280°C to obtain laminates for reflow resistance testing. Next, the laminates for reflow resistance testing were subjected to a heating process equivalent to a total of three solder reflow processes using a conveyor-type reflow apparatus (Antom UNI-5016F) at a maximum measured temperature of 260°C in an atmospheric environment. The reflow resistance was evaluated according to the following criteria: +++: No voids even after the third pass. (Very good) ++: Voids occurred after the third pass. (Good) +: Voids occurred after the second pass. (Usable) NG: Voids occurred after the first pass. (Target not met)

[0081] <3. Laser Peelability> For the laminates of Examples 1-36 and Comparative Examples 1-7 after the reflow resistance test, a UV laser marker (Keyence MD-U1000C, laser wavelength 355 nm (laser)) was used to irradiate the glass surface. Only for Example 36, an IR laser marker (Keyence MD-X2500, laser wavelength 1064 nm) was used as the laser marker for laser irradiation. The total energy amount of the laser was adjusted to determine the minimum total energy amount required for the support to be easily peeled off from the laminate, and the laser peelability was evaluated according to the following criteria. The results are shown in Tables 2-5. +++: Total energy amount required for peeling is 300 mJ / cm ２ Less than . (Very good) ++: Total energy required for peeling is 300 mJ / cm ２ More than 600mJ / cm ２ Less than . (Good) +: Total energy required for peeling is 600 mJ / cm ２ More than 1000mJ / cm ２ Less than . (Usable) NG: Total energy required for peeling is 1000 mJ / cm ２ That's all. (Goal not met)

[0082] <4. Substrate Warpage After Support Peeling> For the laminates of Examples 1-36 and Comparative Examples 1-7 after the laser peelability test, after peeling off the support, the members with a layer of temporary fixing adhesive composition remaining when cut to 10 x 10 cm were placed on a flat surface with the temporary fixing adhesive composition layer facing upwards, and the warpage height at the edges was evaluated according to the following criteria: +++: Warpage height at the edges is less than 0.5 mm. (Very good) ++: Warpage height at the edges is 0.5 mm or more and 1 mm or less. (Good) +: Warpage height at the edges is 1 mm or more and 2 mm or less. (Usable) NG: Warpage height at the edges is 2 mm or more. (Target not met)

[0083] <5. Solvent Removability 1> After the laser peelability test of Examples 1 to 36 and Comparative Examples 1 to 7, the laminates were immersed in toluene, cyclohexanone, and N-methylpyrrolidone organic solvents heated to 80°C after the support was peeled off, and evaluated according to the following criteria. The best-rated solvent removal performance is shown in Tables 2 to 5. +++: The layer consisting of the temporary fixing adhesive composition dissolves to a thickness of 0 μm in less than 20 minutes with any of the organic solvents. (Very good) ++: The layer consisting of the temporary fixing adhesive composition dissolves to a thickness of 0 μm in 20 minutes to 1 hour with any of the organic solvents. (Good) NG: The remaining thickness of the layer consisting of the temporary fixing adhesive composition does not become 0 μm within 1 hour with any of the organic solvents. (Target not met)

[0084] <6. Solvent Removability 2> For the laminates of Examples 1 to 36 and Comparative Examples 1 to 7 after the laser peelability test, after peeling off the support, the organic solvents toluene, cyclohexanone, and N-methylpyrrolidone, heated to 80°C, were poured onto the surface exposed by peeling off the support of the laminate using a pump, and the removeability of the layer consisting of the temporary fixing adhesive composition was evaluated based on the following criteria. The best evaluation of solvent removeability is shown in Tables 2 to 5. +++: The layer consisting of the temporary fixing adhesive composition dissolves to a thickness of 0 μm in less than 4 minutes with any of the organic solvents. (Very good) ++: The layer consisting of the temporary fixing adhesive composition dissolves to a thickness of 0 μm in 4 minutes or more but less than 10 minutes with any of the organic solvents. (Good) +: The layer consisting of the temporary fixing adhesive composition dissolves to a thickness of 0 μm in 10 minutes or more but less than 20 minutes with any of the organic solvents. (Good) NG: The remaining thickness of the layer consisting of the temporary fixing adhesive composition does not become 0 μm within 20 minutes with any of the organic solvents. (Target not achieved)

[0085] <7. Soldering Characteristics After Dissolution and Removal> For the components of Examples 1 to 36 and Comparative Examples 1 to 7, which showed the best results in the solvent removal test described above, printing was performed using a metal mask with solder paste (M705-RGS800 Type 6, manufactured by Senju Metal Industry Co., Ltd., lead-free solder paste) after the solvent removal test. Subsequently, reflow soldering was performed using a conveyor-type reflow machine (UNI-5016F, manufactured by Antom Corporation) at a maximum measured temperature of 260°C under an atmospheric environment, and evaluated according to the following criteria: ++: Soldering is possible without gaps. (Good) +: Solder does not adhere to some parts of the edges, but soldering is generally possible without problems. (Usable) NG: There are many areas where solder does not adhere, making practical soldering impossible. (Target not met)

[0086]

[0087]

[0088]

[0089]

[0090] Temporary fixing adhesive compositions that do not contain resin (A) and organometallic compound (B) exhibited good heat resistance, as shown in Comparative Examples 1, 2, and 7. Although the layer of the temporary fixing adhesive composition remaining on the member after laser peeling could be partially dissolved and removed with an organic solvent at 80°C, this dissolution and removal took a long time, and the solderability to the member after dissolution and removal was poor, possibly due to the remaining small amount of adhesive layer residue, resulting in poor practicality. Furthermore, the lamination and sintering temperatures required for processing were extremely high, causing severe warping of the member after the support was removed, making it unsuitable for practical use. Comparative Example 6, which used a resin at a temperature higher than 550°C where the mass reduction rate relative to the mass before heating was 5% when heated at a rate of 10°C / min in an atmospheric atmosphere using thermogravimetric differential thermal analysis, exhibited the above problems in addition to being extremely difficult to peel off with a laser. Moreover, temporary fixing adhesive compositions containing organometallic compound (B) but not resin (A) exhibited poor heat resistance, as shown in Comparative Examples 3 and 4, and could not be dissolved and removed with a solvent after laser peeling. Furthermore, although the material contains resin (A) and organometallic compound (B), if the film thickness reduction rate (R) after immersion in an organic solvent, calculated from (Formula 1), does not meet the requirement of 95% or more, it was impossible to dissolve and remove the temporary fixing adhesive layer with a solvent after laser peeling, as shown in Comparative Example 5. In the above evaluation, because the component had irregularities due to circuits, etc., it was impossible to peel off the temporary fixing adhesive layer with commonly used release agents due to the anchoring effect, and it was difficult to remove the temporary fixing adhesive layer from the component by methods other than dissolution and removal. On the other hand, Examples 1 to 36 of this disclosure allowed processing at relatively low temperatures, which suppressed warping of the component after laser peeling, and allowed for relatively rapid dissolution and removal using a heated solvent. Moreover, the solderability of the electrode surface after dissolution and removal was cleaned to a level where there were no problems, making it possible to process the component quickly and achieve a high degree of cleanliness, resulting in excellent productivity.

[0091] This application claims priority based on Japanese Patent Application No. 2024-192698, filed on November 1, 2024, and incorporates all of its disclosures herein.

[0092] 1. Support 2. Temporary fixing adhesive layer 3. Component 4. Laminate 5. Laser light

Claims

1. A temporary fixing adhesive composition comprising a resin (A) and an organometallic compound (B), wherein the resin (A) contains at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group, and the temperature at which the mass loss rate relative to the mass before heating is 5% when heated at a rate of 10°C / min in an atmospheric atmosphere using thermogravimetric differential thermal analysis is 280°C or higher and 550°C or lower, the film thickness reduction rate (R) after immersion in an organic solvent, calculated from the following (Formula 1), is 95% or higher, and the organic solvent is selected from the group consisting of toluene, cyclohexanone, and N-methylpyrrolidone. (Formula 1) R (%) = (1 - (T / 30)) × 100 T: Thickness of the film (μm) after immersion of a test piece obtained by heating a 30 μm thick film made of the temporary fixing adhesive composition at 180°C for 1 hour in the organic solvent at 80°C for 1 hour.

2. The temporary fixing adhesive composition according to claim 1, further comprising 10 parts by mass or less of a compound (C) (excluding the organometallic compound (B)) having two or more groups that can react with at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group, per 100 parts by mass of the resin (A).

3. The temporary fixing adhesive composition according to claim 1, wherein the organometallic compound (B) is at least one selected from the group consisting of organotitanium compounds, organozirconium compounds, and organoaluminum compounds.

4. The temporary fixing adhesive composition according to claim 3, wherein the total content of titanium ions and zirconium ions in the temporary fixing adhesive composition is 0.01% by mass or more and 3.0% by mass or less.

5. The temporary fixing adhesive composition according to claim 4, wherein the resin (A) is at least one selected from the group consisting of polyimide resin, polyamide resin, polyphenylene ether resin, phenol resin, and phenoxy resin.

6. A laminate in which a member and a support are bonded and temporarily fixed together with the temporary fixing adhesive composition according to any one of claims 1 to 5.

7. A method for temporarily fixing a member, comprising the following steps (1) to (3): (1) A step of temporarily fixing the member and the support by bonding them using the temporary fixing adhesive composition described in claim 1. (2) A step of processing the member that has been temporarily fixed in (1). (3) A step of removing the support by irradiating the layer made of the temporary fixing adhesive composition with a laser after processing in (2).

8. The method for temporarily fixing a member according to claim 7, wherein the laser is a near-infrared laser or an ultraviolet laser.

9. The method for temporarily fixing a member according to claim 8, wherein the support is made of glass or silicon.

10. A removal method comprising immersing a member, from which a support has been removed by the method described in any one of claims 7 to 9, in an organic solvent to remove the layer made of the temporary fixing adhesive composition from the member.

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