Temporary fixing adhesive composition and method for temporarily fixing members using the same

Abstract

Provided are 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 removal, has excellent solvent removability, and has good solderability for component electrodes after removal of the temporary fixing adhesive; and provides a method for temporarily fixing and treating components using the same. [Solution] A temporary fixing adhesive composition containing a resin (A) and an organometallic compound (B), wherein the resin (A) contains an alcoholic hydroxyl group or a phenolic hydroxyl group, and when heated at a rate of 10°C / min in an air atmosphere using thermogravimetric differential thermal analysis, the resin has a temperature of 280°C to 550°C at which the mass loss rate relative to the mass before heating is 5%, and the film thickness loss rate (R) after immersion in toluene, cyclohexanone or N-methylpyrrolidone is 95% or more.

Description

[Technical Field]

[0001] The present invention relates to a temporary fixing adhesive composition and a method for temporarily fixing members using the same. [Background technology]

[0002] As mobile devices continue to become thinner, smaller, lighter, and more powerful, semiconductor-related components, such as the semiconductor chips incorporated into these devices and the package substrates and interposers used for their rewiring, are being required to be even thinner, not only due to size constraints but also due to the trend toward three-dimensional chip integration. These thinned components are manufactured through thinning processes such as grinding and polishing, wiring formation processes, and packaging processes. However, as the thickness of the components decreases, they are no longer able to maintain their shape, and they become prone to bending and loss of flatness, making them difficult to manufacture independently. Therefore, a method is becoming increasingly common in which the components are attached to a rigid, plate-like support with a temporary adhesive, and the components are handled together with this support and adhesive at each process.

[0003] On the other hand, in the various manufacturing processes, the member needs to be firmly fixed to the support with the temporary fixing adhesive, but since the member is 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 is completed, the member is peeled off from the support and the temporary fixing adhesive layer remaining on the member needs to be removed.

[0004] Known methods for peeling such a temporary fixing adhesive layer from a support include a method of peeling using a solvent and a method of peeling by applying physical stress, but a laser peeling method using laser light such as ultraviolet light, visible light, or infrared light has attracted attention because it allows peeling to be performed quickly and without applying stress load to the component.

[0005] As patent documents relating to the laser peeling method, for example, Patent Document 1 discloses a UV-curable temporary fixing adhesive made of an acrylate monomer, a photoinitiator that reduces mass loss when heated, and carbon black. Also, Patent Document 2 discloses a temporary fixing method using a temporary fixing adhesive made of a cycloolefin resin and an ultraviolet absorber, and Patent Document 3 discloses a temporary fixing adhesive made of a polysulfone resin. However, the method of Patent Document 1 has problems, for example, when forming a textured structure such as electrode pads or solder bumps on a component and then temporarily fixing the surface on which the electrode pads or solder bumps are formed with a temporary fixing adhesive in order to further process the backside, or when the surface roughness of the outermost insulating layer is high, such problems include impossibility of peeling using commonly used stripping solutions, or even if peeling is possible, leaving behind peeling residue. Furthermore, the methods of Patent Documents 2 and 3 allow for the temporary fixing adhesive layer remaining on the component to be dissolved and removed using an organic solvent, but the adhesive layer does not conform to the textured structure when formed on the component or when attached to the component. If the adhesive layer is heated at very high temperatures to conform to the textured structure, the thermal history can cause the thinned component to warp significantly after peeling from the support, hindering subsequent manufacturing processes. While the effects of warping can be avoided by curing or laminating at relatively low temperatures as in Patent Document 1, irreversible chemical crosslinking is required to ensure the heat resistance, which creates the dilemma of making it impossible to dissolve and remove from the textured surface. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-224316 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-33814 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-003270 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above background, and aims to provide a temporary fixing adhesive that has the ability to conform to uneven structures (step-conforming ability), high heat resistance (reflow resistance), and laser peelability, is capable of suppressing substrate warping after the support is peeled off, has excellent solvent removability, and has good solderability of component electrodes after the temporary fixing adhesive is removed, and to provide a method for temporarily fixing components using the same. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the problems of the present invention can be solved in the following aspects. The present invention has been completed based on the findings. The temporary fixing adhesive of the present invention is a temporary fixing adhesive composition containing a resin (A) and an organometallic compound (B), the resin (A) contains an alcoholic hydroxyl group or a phenolic hydroxyl group, Furthermore, when heated at a rate of 10°C / min in an air atmosphere using thermogravimetric differential thermal analysis, the resin has a temperature of 280°C or higher and 550°C or lower at which the mass loss rate relative to the mass before heating is 5%; The film thickness reduction rate (R) after immersion in an organic solvent calculated by the following (Equation 1) is 95% or more, The temporary fixing adhesive composition, wherein 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: Thickness (μm) of the film after a test piece obtained by heating a 30 μm thick film made of the temporary fixing adhesive composition at 180° C. for 1 hour was immersed in the organic solvent at 80° C. for 1 hour

[0009] In one embodiment of the temporary fixing adhesive of the present invention, the content of compound (C) (excluding the organometallic compound (B)) having two or more groups capable of reacting with alcoholic hydroxyl groups or phenolic hydroxyl groups is 2 parts by mass or less per 100 parts by mass of the resin (A).

[0010] In one embodiment of the temporary fixing adhesive of the present invention, the organometallic compound (B) is an organotitanium compound or an organozirconium compound.

[0011] In one embodiment of the temporary fixing adhesive of the present invention, 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.

[0012] In one embodiment of the temporary fixing adhesive of the present invention, the resin (A) is at least any one selected from the group consisting of polyimide resins, polyamide resins, polyphenylene ether resins, phenol resins, and phenoxy resins.

[0013] The laminate of the present invention is obtained by adhering and temporarily fixing a member and a support with the above-mentioned adhesive composition for temporary fixing.

[0014] The method for temporarily fixing members of the present invention comprises the following steps (1) to (3). (1) A step of temporarily fixing a member and a support by bonding them together using the adhesive composition for temporary fixing according to claim 1. (2) A process for processing the parts temporarily fixed in (1) (3) After the processing of (2), a step of irradiating the layer made of the temporary fixing adhesive composition with a laser to remove the support.

[0015] In one embodiment of the method for temporarily fixing members of the present invention, the laser is a near-infrared laser or an ultraviolet laser.

[0016] In one embodiment of the method for temporarily fixing members of the present invention, the support body is made of glass or silicon.

[0017] The treatment method of the present invention comprises immersing a member from which the support has been removed in the method for temporarily fixing a member, and from which a layer made of the temporary fixing adhesive composition remains, in an organic solvent, and removing the layer made of the temporary fixing adhesive composition from the member. [Effects of the Invention]

[0018] According to the present invention, a temporary fixing adhesive is provided which has the ability to conform to uneven structures (step-conforming ability), high heat resistance (reflow resistance), and laser peelability, can suppress substrate warping after the support is peeled off, has excellent solvent removability, and has good solderability of component electrodes after the temporary fixing adhesive is removed, and a method for temporarily fixing and treating components using the same can be provided. The temporary fixing adhesive layer of the present invention can be suitably used for producing semiconductor-related members such as semiconductor chips and package substrates and interposers used for rewiring thereof. [Brief explanation of the drawings]

[0019] [Figure 1] 1 is a schematic cross-sectional view partially illustrating a laminate of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view partially illustrating a scene in which a laminate of the present invention is irradiated with laser light. DETAILED DESCRIPTION OF THE INVENTION

[0020] The present invention will be described in detail below. Needless to say, other embodiments are also included within the scope of the present invention as long as they are consistent with the spirit of the present invention. Furthermore, in this specification, a numerical range specified using "to" includes the numerical values before and after "to" as the range of the lower and upper limits. Furthermore, in this specification, "film" and "sheet" are synonymous and are not distinguished by thickness. Furthermore, unless otherwise noted, the various components appearing in this specification may be used independently, either singly or in combination of two or more types. The numerical values described in this specification refer to values obtained by the methods described in the Examples below.

[0021] In this specification, the compound (C) having two or more groups capable of reacting with an alcoholic hydroxyl group or a phenolic hydroxyl group may be simply referred to as the compound (C).

[0022] <Temporary fixing adhesive composition> The temporary fixing adhesive composition of the present invention 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 by the following (Equation 1), is 95% or more. If (R) is 95% or more, the film has good removability with an organic solvent, resulting in excellent solderability of the component electrode after removal of the temporary fixing adhesive. 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: Thickness (μm) of the film after a test piece obtained by heating a 30 μm thick film made of the temporary fixing adhesive composition at 180°C for 1 hour was immersed in an organic solvent at 80°C for 1 hour That is, it is important that the film thickness reduction rate (R1) after immersion in toluene calculated from the following (Equation 2), the film thickness reduction rate (R2) after immersion in cyclohexanone calculated from the following (Equation 3), or the film thickness reduction rate (R3) after immersion in N-methylpyrrolidone calculated from the following (Equation 4) is 95% or more. (Formula 2) R1(%)=(1-(T1 / 30))×100 (Formula 3) R2(%)=(1-(T2 / 30))×100 (Formula 4) R3(%)=(1-(T3 / 30))×100 T1: The thickness (μm) 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 and then immersing the test piece in toluene at 80°C for 1 hour T2: A test piece obtained by heating a 30 μm thick film made of the temporary fixing adhesive composition at 180°C for 1 hour is immersed in cyclohexanone at 80°C for 1 hour, and the thickness of the film (μm) is T3: The thickness (μm) 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 and then immersing the test piece in N-methylpyrrolidone at 80°C for 1 hour

[0023] The organic solvents used to dissolve and remove the temporary fixing adhesive composition are not limited to toluene, cyclohexanone, and N-methylpyrrolidone. The three organic solvents, toluene, cyclohexanone, and N-methylpyrrolidone, each have different solubility, and are therefore merely used as indicators of dissolution and removal. Therefore, although these three organic solvents are particularly suitable for dissolution and removal, they are not particularly preferred over other organic solvents. However, if the film thickness reduction rate after immersion in one of these three organic solvents at 80°C for 1 hour is 95% or more, it is possible to select an optimal organic solvent for dissolution and removal that takes into account factors such as economy, toxicity, and safety.

[0024] Conventional temporary fixing adhesive compositions are designed to impart heat resistance through the rigidity of their resin structure, so they require extremely high-temperature processes for substrate conformation and ring-closing reactions of the resin structure, and are unable to exhibit their inherent properties in low-temperature processes. High-temperature processes also pose the problem of increased susceptibility to defects such as warping due to differences in the thermal expansion coefficients of the constituent layers within each layer or member. After extensive research, the inventors have found that the temporary fixing adhesive composition of the present invention is capable of exhibiting substrate conformation and heat resistance at relatively low temperatures because crosslinking to exhibit heat resistance occurs after lamination and member conformation, and because this crosslinking has a certain degree of reversibility in dissociation and recombination.

[0025] <Resin (A)> The resin (A) of the present invention is a resin that contains an alcoholic hydroxyl group or a phenolic hydroxyl group, and when heated at a rate of 10°C / min in an air atmosphere using thermogravimetric differential thermal analysis, has a temperature of 280°C or higher and 550°C or lower at which the mass loss rate relative to the mass before heating is 5%. The type of resin is not particularly limited as long as it satisfies the above requirements. The alcoholic hydroxyl group of the present invention means a hydroxyl group directly bonded to an aliphatic carbon, and the phenolic hydroxyl group of the present invention means a hydroxyl group directly bonded to an aromatic carbon.

[0026] The presence of alcoholic hydroxyl groups or phenolic hydroxyl groups in resin (A) allows for the formation of coordinate-bonding crosslinks with the organometallic compound described below, imparting resistance to harsh heating processes such as solder reflow and various chemical solutions while enabling dissolution and removal in organic solvents. Resin (A) preferably contains phenolic hydroxyl groups in order to balance heat resistance and solubility in organic solvents. The total functional value of the phenolic hydroxyl group and the hydroxyl group is preferably 0.01 to 250 mgKOH / g. This range provides a particularly good balance between heat resistance and solubility in organic solvents.

[0027] When resin (A) is heated at a rate of 10°C / min in an air atmosphere using thermogravimetric differential thermal analysis, the temperature at which the mass loss relative to the mass before heating is 5% is 280°C or higher, making it possible to stably exhibit the required heat resistance in combination with the organometallic compound, and when the temperature is 550°C or lower, rapid peeling by laser irradiation is possible. The temperature is preferably 300°C or higher and 500°C or lower.

[0028] There are no particular limitations on the weight-average molecular weight of the resin (A), but in order to achieve both film-forming properties and coatability of the temporary fixing adhesive composition and to obtain good handleability, the weight-average molecular weight is preferably 2,000 to 150,000, and particularly preferably 2,500 to 100,000.

[0029] The glass transition temperature of the resin (A) is not particularly limited, but in order to achieve both the film-forming properties of the temporary fixing adhesive composition and high conformability to unevenness in a relatively low-temperature process, the glass transition temperature is preferably 0°C to 160°C, and particularly preferably 10°C to 140°C.

[0030] Specific examples of resins for resin (A) include polyimide resins, polyamide resins, polyphenylene ether resins, phenolic resins, phenoxy resins, (meth)acrylic resins, polyester resins, and polyurethane resins. Among these, at least one resin selected from the group consisting of polyimide resins, polyamide resins, polyphenylene ether resins, phenolic resins, and phenoxy resins is particularly preferred because it has an excellent balance between heat resistance and laser peelability. The position of the alcoholic hydroxyl group or phenolic hydroxyl group in the molecular structure of these resins is not particularly limited.

[0031] (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 acid dianhydrides and diamines through a dehydration condensation reaction. Furthermore, the molecular chain terminals of the polyimide resin may be capped by reaction with dicarboxylic acid anhydrides or monoamines. Polyimide resins having alcoholic hydroxyl groups or phenolic hydroxyl groups can be obtained by using tetracarboxylic acid dianhydrides or diamines, dicarboxylic acid anhydrides or monoamines having alcoholic hydroxyl groups or phenolic hydroxyl groups as at least a portion of the raw materials for the polyimide resin.

[0032] Examples of the tetracarboxylic dianhydride 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'-isopropylidenediphenoxy)diphthalic anhydride, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene. aromatic tetracarboxylic acids 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; and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic acid and cyclopentane-1,2,3,4-tetracarboxylic acid. -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]dec-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]oct-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]oct-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[8.2.11,11.Examples include cyclo-, bicyclo-, and tricyclotetracarboxylic acids such as 1,4,7,02,10,03,8]tetradecane-5,6,12,13-tetracarboxylic acid; spiro-ring-containing tetracarboxylic acids such as 2,8-dioxaspiro[4.5]decane-1,3,7,9-tetratone; and alicyclic tetracarboxylic dianhydrides such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic 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 anhydride.

[0033] 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'-diaminodiphenyl sulfone, 3,3 aromatic diamines such as 3,3'-diaminobenzophenone and 3,3'-diaminodiphenyl sulfone; 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, dimer diamines, and bisaminophenols.

[0034] The dimer diamines can be obtained, for example, by converting the carboxyl group of a dimer acid to an amino group. Here, 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, and rapeseed oil fatty acid, and unsaturated fatty acids purified from these, such as linolenic acid, linoleic acid, oleic acid, and erucic acid. The unsaturated bonds may be hydrogenated as needed to reduce the degree of unsaturation. Dimer diamines with a reduced degree of unsaturation are advantageous in terms of oxidation resistance (especially against coloration at high temperatures) and suppression of gelation during synthesis.

[0035] 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 acids, tall oil fatty acids, and rapeseed oil fatty acids, or unsaturated fatty acids such as linoleic acid, linoleic acid, oleic acid, erucic acid, myristoleic acid, palmitoleic acid, sapienic acid, elaidic acid, stearic acid, vaccenic acid, gadoleic acid, eicosenoic acid, brassidic acid, nervonic acid, eicosadienoic acid, docosadienoic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, cetoleic acid, adrenic acid, bosseopentaenoic acid, osbondo acid, sardine acid, tetracosapentaenoic acid, eicosapentaenoic acid, docosahexaenoic acid, and herring acid. The unsaturated bond may be hydrogenated as needed to reduce the degree of unsaturation. Dimer acids with a reduced degree of unsaturation are suitable in terms of oxidation resistance (particularly coloration at high temperatures) and suppression of gelation during synthesis. Dimer acids are preferably compounds having 20 to 60 carbon atoms, more preferably compounds having 24 to 56 carbon atoms, even more preferably compounds having 28 to 48 carbon atoms, and even more preferably compounds having 36 to 44 carbon atoms. Dicarboxylic acid compounds having a branched structure obtained by subjecting a fatty acid to a Diels-Alder reaction are also preferred. The branched structure is preferably an aliphatic chain or a cyclic structure, more preferably a cyclic structure, in terms of achieving higher heat resistance. The cyclic structure is preferably one or more aromatic rings or an alicyclic structure, more preferably an alicyclic structure. When there are two cyclic structures, the two rings may be independent or continuous. One or more dimer acid compounds can be used. The alicyclic structure may have one or more double bonds within the ring, or may have no double bonds.

[0036] Examples of the bisaminophenols include aromatic diaminophenols 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 a bisaminophenol as a diamine in part or in whole, it is possible to impart phenolic hydroxyl groups to the side chains of the polyimide resin.

[0037] Examples of the dicarboxylic acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and 5-hydroxyphthalic anhydride.

[0038] 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, or the like, a phenolic hydroxyl group can be imparted to the terminal of the polyimide resin.

[0039] (Polyamide resin) Examples of polyamide resins used as resin (A) include resins having a repeating structure in which dicarboxylic acid residues and diamine residues are linked via amide groups. Such polyamide resins can be obtained, for example, by linking dicarboxylic acid dianhydrides and diamines through a dehydration condensation reaction. Furthermore, the molecular chain ends of the polyamide resin may be capped by reaction with monocarboxylic acids or monoamines. Polyamide resins having alcoholic hydroxyl groups or phenolic hydroxyl groups can be obtained by using diamines, dicarboxylic acids, monoamines, or monocarboxylic acids having alcoholic hydroxyl groups or phenolic hydroxyl groups as at least some of the raw materials for the polyamide resin.

[0040] Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone-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 dimer acids.

[0041] As the diamine and monoamine, the same diamines and monoamines as those exemplified for use in the polyimide resin can be suitably used.

[0042] Examples of the monocarboxylic acid include lower fatty acids such as acetic acid, propionic acid, and butyric acid; saturated fatty acids such as stearic acid (octadecanoic acid), tuberculostearic acid (nonadecanoic acid), arachidic acid (icosanoic acid), and henicosanoic acid; unsaturated fatty acids such as behenic acid (docosanoic acid), hydroxystearic acid (castor hardened fatty acid), oleic acid, linoleic acid, linolenic acid, gadoleic acid, eicosadienoic acid, mead acid, erucic acid, and docosadienoic acid; benzoic acid, methylbenzoic acid {toluic acid (p-, m-, o-)}, dimethylbenzoic acid (xylyl acid, hemerylic acid, mesitylene acid), and trimethylbenzoic acid {prenylic acid, durylic acid, isodurylic acid (α-, β-, γ-)}. Examples of aromatic monocarboxylic acids include 4-isopropylbenzoic acid (cumic acid), hydroxybenzoic acid (salicylic acid), dihydroxybenzoic acids {pyrocatechuic acid, resorcylic acid (α-, β-, γ-), gentisic acid, protocatechuic acid}, trihydroxybenzoic acid (gallic acid), hydroxymethylbenzoic acid {cresotinic acid (p-, m-, o-)}, dihydroxymethylbenzoic acid (orsellinic acid), methoxybenzoic acid {anisic acid (p-, m-, o-)}, dimethoxybenzoic acid (veratric acid), trimethoxybenzoic acid (asaronic acid), hydroxymethoxybenzoic acid (vanillic acid, isovanillic acid), and hydroxydimethoxybenzoic acid (syringic acid).

[0043] (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 and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.). Other examples include polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and poly(2,6-dimethyl-1,4-phenylene ether) or the like, which are obtained by heating poly(2,6-dimethyl-1,4-phenylene ether) or the like with phenolic compounds such as bisphenols or trisphenols in a solvent such as toluene in the presence of an organic peroxide, followed by a redistribution reaction, and having a linear or branched structure.

[0044] (phenolic resin) Examples of phenolic resins used as resin (A) include polymers obtained by condensation reaction of 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, and 4,4'-bis(chloromethyl)biphenyl in the presence of an acid catalyst. Phenol-modified xylene resins obtained by copolymerizing xylene with the above raw materials may also be used. Phenolic resins, due to their structure, necessarily contain phenolic hydroxyl groups.

[0045] (phenoxy resin) The phenoxy resin used as resin (A) is a polymer obtained by addition polymerization of a bisphenol compound and a diepoxy compound. The phenoxy resin necessarily has a hydroxyl group due to its structure.

[0046] Examples of the bisphenol compound 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'-diallyl bisphenol A, hydrogenated bisphenol, propylene oxide-added bisphenol A, resorcinol, biphenol, tetramethyl bisphenol F, tetramethyl bisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, tetramethyl biphenol, ethylidene bisphenol, methylethylidene bis(methylphenol), and cyclohexylidene bisphenol.

[0047] Examples of the diepoxy compound include bisphenol A type diepoxide, bisphenol F type diepoxide, bisphenol F type diepoxide, bisphenol S type diepoxide, bisphenol O type diepoxide, 2,2'-diallyl bisphenol A type diepoxide, hydrogenated bisphenol type diepoxide, propylene oxide-added bisphenol A type diepoxide, resorcinol type diepoxide, biphenyl type diepoxide, sulfide type diepoxide, diphenyl ether type diepoxide, dicyclopentadiene type diepoxide, and naphthalene type diepoxide.

[0048] <Organometallic compound (B)> The organometallic compound (B) of the present invention can be an organometallic complex having a structure in which a ligand consisting of an organic molecule coordinates to a metal ion. The organometallic compound (B) can form reversible crosslinks between the alcoholic or phenolic hydroxyl groups of the resin (A) via a coordinate bond to the metal ion through ligand exchange between the ligand and the alcoholic or phenolic hydroxyl groups of the resin (A). Most of these crosslinks can be formed during a relatively low-temperature heating process after lamination to a substrate. Furthermore, even crosslinks partially formed before lamination can be temporarily partially dissociated during lamination to a substrate due to their reversibility. This allows the resin to deform to conform to the surface shape of the substrate even at relatively low process temperatures, resulting in excellent conformability to the substrate surface. Furthermore, by using this metal coordination crosslinking as a crosslinking agent, it is possible to impart the heat resistance required for heating processes such as reflow processes, while also achieving removability with organic solvents due to the reversibility of the bond.

[0049] Examples of the metal ion species of the 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 and zirconium ions are preferred, and zirconium ions are particularly preferred, in that they can achieve high levels of both heat resistance and removability by organic solvents. That is, the organometallic compound (B) is preferably an organotitanium compound or an organozirconium compound, and particularly preferably an organozirconium compound.

[0050] Examples of the ligand consisting of an organic molecule of the organometallic compound (B) include monodentate ligands such as methanol, ethanol, isopropyl alcohol, normal butyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, octyl alcohol, stearyl alcohol, lactic acid, dodecylbenzenesulfonic acid, ammonium, triethanolamine, hydroxy anion, and chloride ion, as well as active methylene-type polydentate ligands such as acetylacetone, methyl acetoacetate, and ethyl acetoacetate. In terms of achieving both a long pot life during blending and a rapid crosslinking reaction, it is particularly preferred that the compound contains at least one polydentate ligand such as acetylacetone, methyl acetoacetate, or ethyl acetoacetate.

[0051] 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 metal ion content of 0.01% by mass or more allows the necessary heat resistance to be obtained, while a total metal ion content of 3.0% by mass or less allows rapid removability with an organic solvent to be obtained.

[0052] <Compound (C) Having Two or More Groups Reactive with Alcoholic Hydroxyl Groups or Phenolic Hydroxyl Groups> The temporary fixing adhesive composition of the present invention may contain a compound (C) having two or more groups reactive with alcoholic hydroxyl groups or phenolic hydroxyl groups, excluding the organometallic compound (B), in an amount of 2 parts by mass or less per 100 parts by mass of the resin (A). By setting the content of the compound (C) having two or more groups reactive with alcoholic hydroxyl groups or phenolic hydroxyl groups, excluding the organometallic compound (B), to 2 parts by mass or less per 100 parts by mass of the resin (A), good removability with an organic solvent is maintained. The lower the content of compound (C), the better, and it is particularly preferred that compound (C) is not contained.

[0053] Examples of the group capable of reacting with the alcoholic hydroxyl group or phenolic hydroxyl group of the compound (C) include an epoxy group, an oxetanyl group, an episulfide group, an isocyanate group, a thioisocyanate group, a blocked isocyanate group, an oxazoline group, a benzoxazine group, etc. The compound (C) corresponds to a compound having one kind of group selected from the above-listed group alone or two or more kinds of groups in total in the same molecule.

[0054] Specific examples of the compound (C) include the diepoxides and polyfunctional epoxy resins obtained by epoxidizing the phenolic resins 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-oxo-2-phenylene)-2-propanol. 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-oxetanylmethoxy) Examples of suitable oxetanyl compounds include polyfunctional oxetanyl compounds such as 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. Other suitable oxetanyl compounds include TDI (e.g., toluene diisocyanates such as 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), and 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-phenylene diisocyanate, diphenyl diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (1,5-NDI), diphenyl ether diisocyanate, aromatic polyisocyanates such as triphenylmethane triisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) and alicyclic polyisocyanates (H12MDI) such as cyclohexane diisocyanate, methylenebis(cyclohexylisocyanate), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (H6XDI), and dicyclohexylmethane diisocyanate; and polyfunctional isocyanate compounds such as carbodiimide-modified polyisocyanates, biuret-modified polyisocyanates, allophanate-modified polyisocyanates, polymethylene polyphenyl polyisocyanates (crude MDI or polymeric MDI), and isocyanurate-modified polyisocyanates of these aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Further examples include blocked isocyanate compounds in which these are blocked with a blocking agent such as phenol, cresol, ε-caprolactam, ethyl methyl ketone oxime, diethyl malonate, ethyl acetoacetate, diisopropylamine, 3,5-dimethylpyrazole, imidazole, and the like.In addition, polyfunctional oxazoline compounds such as 2,2'-bis(2-oxazolin-2-yl)ethane, 1,2-bis(2-oxazolin-2-yl)ethane, 1,4-bis(2-oxazolin-2-yl)butane, 1,8-bis(2-oxazolin-2-yl)butane, 1,4-bis(2-oxazolin-2-yl)cyclohexane, 1,2-bis(2-oxazolin-2-yl)benzene, and 1,3-bis(2-oxazolin-2-yl)benzene are also available. Specifically, o-cresolaniline-type benzoxazine, m-cresolaniline-type benzoxazine, p-cresolaniline-type benzoxazine, phenol-aniline-type benzoxazine, phenol-methylamine-type benzoxazine, phenol-cyclohexylamine-type benzoxazine, phenol-m-toluidine-type benzoxazine, phenol-3,5-dimethylamine-type benzoxazine, and phenol-3,5-dimethylamine-type benzoxazine are also available. Examples of polyfunctional benzoxazine compounds include, but are not limited to, aniline-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, as long as the above conditions are met.

[0055] <Other ingredients> In addition to the above components, the temporary fixing adhesive composition of the present invention may optionally contain laser absorbents, various fillers, dispersants, antifoaming agents, etc., within limits that do not impair the intended properties. Examples of laser absorbents include pigments such as carbon black, phthalocyanine blue, and silica, dyes such as nigrosine black, and various known and publicly used ultraviolet absorbents such as triazine-based and hydroxyphenylbenzotriazole-based ones, and these may be added depending on the laser wavelength to be used.

[0056] <Laminate> The laminate of the present invention is formed by bonding and temporarily fixing a member and a support with a temporary fixing adhesive composition. Specifically, the laminate is formed by bonding a support, a temporary fixing adhesive layer, and a member in this order as shown in Figure 1, which are temporarily formed in order to temporarily fix the member and perform various processes.

[0057] The support is not particularly limited as long as it is a plate-shaped material that has the rigidity and high flatness required to fix the member and transmits laser light of the wavelength to be used. The support material is preferably glass or silicon. Examples include glass such as soda-lime glass, borosilicate glass, and aluminoborosilicate glass, as well as silicon. Glass is preferred because of its excellent UV and infrared transmittance, and silicon is preferred because of its excellent infrared transmittance and dimensional stability during the heating process. The shape of the support is not particularly limited, and it may be a circular wafer or a square or rectangular panel.

[0058] Examples of the member include semiconductor chips and peripheral semiconductor members such as package substrates and interposers used for rewiring thereof. In particular, in the case of members having a surface with an uneven structure such as a solder bump or an electrode pad or a surface with high surface roughness on at least one side, and further requiring processing on the opposite side, the adhesive composition for temporary fixing of the present invention exhibits its effectiveness to the maximum due to its ability to conform to the surface shape and its high dissolving and removing performance in the process described below.

[0059] <<Method for temporarily fixing components>> The method for temporarily fixing members of the present invention comprises the following steps (1) to (3). (1) A step of temporarily fixing a member and a support by bonding them together using the adhesive composition for temporary fixing according to claim 1. (2) A process for processing the parts temporarily fixed in (1) (3) After the processing of (2), a step of irradiating the layer made of the temporary fixing adhesive composition with a near-infrared laser or an ultraviolet laser to remove the support.

[0060] Process (1) Step (1) is a step of producing the laminate. Specifically, for example, a solution of the temporary fixing adhesive dissolved in an organic solvent may be applied to a member, dried, and then pressed onto a support while heating as needed. Alternatively, the temporary fixing adhesive may be applied to a support and then pressed onto a member. Alternatively, the temporary fixing adhesive solution may be applied to a release-treated resin film in the form of a release film, dried, and then a temporary fixing adhesive film may be produced. This film may then be transferred to a support while heating as needed, and then pressed onto a member.

[0061] Process (2) Step (1) is a step of processing the member temporarily fixed as the laminate of the present invention. Specific steps include cutting and thinning steps such as physical polishing and CMP, chemical steps for forming wiring layers and insulating layers and soldering, and heating steps such as solder reflow. Through these steps, the member is thinned, and wiring layers, insulating layers, vias, components, solder bumps, etc. are formed on the surface opposite the surface of the member that contacts the temporary fixing adhesive layer.

[0062] Process (3) Step (3) is a step of irradiating a layer made of the temporary fixing adhesive composition with a near-infrared laser or an ultraviolet laser to remove the support. Specifically, as shown in Figure 2, this step is a step of irradiating a temporary fixing adhesive layer 2 with laser light through a support 1 that transmits laser light, thereby decomposing or altering the adhesive layer 2 and separating the member 3 from the support 1.

[0063] The wavelength of the laser light used in the laser peeling step may be appropriately selected depending on the wavelength of light absorbed by the adhesive layer 2 and the transmittance of the support 1. For example, light in the ultraviolet, visible, or infrared wavelength range of 200 to 1100 nm can be used. However, ultraviolet lasers with wavelengths of 200 to 380 nm are preferred because they cause minimal thermal damage to the substrate, and near-infrared lasers with wavelengths of 780 to 1100 nm are preferred because they can be used with general-purpose substrates that do not transmit visible light, such as silicone wafers. The types of laser light used include solid-state lasers such as YAG lasers, YVO4 lasers, and fiber lasers; liquid lasers such as dye lasers; gas lasers such as CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers; semiconductor lasers; and free electron lasers, as well as laser light composed of their harmonics. This decomposes or alters the adhesive layer 2, making it possible to easily separate the support 1 and the member 3.

[0064] When irradiating with laser light, the following conditions can be given as examples 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 amount of the laser light is 50 mJ / cm 2 More than 5000mJ / cm 2 Less than 100 mJ / cm is preferred 2 More than 1000mJ / cm 2 The following are preferred: However, the preferred conditions are not limited to the above, as other conditions may be preferred depending on the specifications and configuration of the laser light irradiation device.

[0065] <Dissolving and removing the temporary fixing adhesive composition with an organic solvent> As a method for dissolving and removing the temporary fixing adhesive layer, the laminate after the support is peeled off after the laser peelability test may be immersed in a tank containing an organic solvent, or the temporary fixing adhesive layer may be dissolved and washed away with a shower of organic solvent. In this case, the temperature of the organic solvent is not particularly limited as long as the temporary fixing adhesive layer can be dissolved and removed within a practical processing time. It may be room temperature, but it may be heated to shorten the processing time. Heating the organic solvent promotes bond exchange of the crosslinks formed between the resin (A) and the organometallic compound (B), thereby enabling more rapid dissolution and removal. The heating temperature of the organic solvent is not particularly limited as long as it allows for rapid dissolution and removal, but 40 to 100°C is preferred.

[0066] 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 that can dissolve the 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. [Example]

[0067] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples. Unless otherwise specified, "%" and "parts" are based on mass. Furthermore, the "parts" of blended raw materials in a composition are expressed as the value of the nonvolatile content even when blended as a solution in an organic solvent.

[0068] (i) Measurement of weight average molecular weight (Mw) Mw was measured using a Showa Denko GPC (gel permeation chromatography) "GPC-101." The mobile phase was THF (tetrahydrofuran), and the stationary phase column was two "KF-805L" (Showa Denko: GPC column: 8 mm ID x 300 mm size) connected in series. The sample concentration was 1% by mass, the flow rate was 1.0 mL / min, the pressure was 3.8 MPa, and the column temperature was 40°C. Mw was determined in polystyrene equivalent terms. Data analysis was performed using the manufacturer's built-in software to calculate the calibration curve, molecular weight, and peak area, and Mw was calculated for the retention time range of 17.9 to 30.0 minutes.

[0069] (ii) Measurement of hydroxyl value The hydroxyl value is the amount of hydroxyl groups contained in 1 g of sample, expressed as the amount (mg) of potassium hydroxide required to neutralize the acetic acid bonded when the hydroxyl groups are acetylated. The hydroxyl value was measured in accordance with JIS K0070. In the present invention, when calculating the hydroxyl value of a sample having an acid value other than hydroxyl groups, the calculation is performed taking into account the acid value as shown in the following formula. Approximately 1 g of sample was precisely weighed into a stoppered Erlenmeyer flask and dissolved in 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1). Exactly 5 ml of an acetylating agent (25 g of acetic anhydride dissolved in pyridine to a volume of 100 ml) was then added and stirred for approximately 1 hour. Phenolphthalein TS was added as an indicator and the mixture was allowed to stand for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color. The hydroxyl value was calculated using the following formula (unit: mgKOH / g). Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.05} / S] + D however, S: Amount of sample collected (g) a: Amount of 0.1N alcoholic potassium hydroxide solution consumed (mL) b: Amount of 0.1N alcoholic potassium hydroxide solution consumed in the blank experiment (mL) F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

[0070] (iii) Acid value measurement Approximately 1 g of sample was accurately weighed into a stoppered Erlenmeyer flask and dissolved in 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2 / 1). Phenolphthalein test solution was added as an indicator and the mixture was allowed to stand for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color. The acid value was calculated using the following formula (unit: mgKOH / g). Acid value (mgKOH / g)=(5.611×a×F) / S however, S: Amount of sample collected (g) a: Amount of 0.1N alcoholic potassium hydroxide solution consumed (mL) F: Potency of 0.1N alcoholic potassium hydroxide solution

[0071] (iv) Thermogravimetric differential thermal analysis Approximately 10 mg of measurement specimens were cut to an appropriate size from a small piece of film of each composition described below, and placed in a small aluminum pan. Using a thermogravimetric differential thermal analyzer "TG / DTA-6300" (Seiko Instruments Inc.), the specimen was heated to 30°C in an air atmosphere (gas flow rate 200 mL / min.), allowed to stabilize for 5 minutes, and then heated to 550°C at a heating rate of 10°C / min, and the change in weight was measured. The temperature at which the weight loss first reached 5% or more of the initial weight was determined from the ratio of the initial weight to the weight loss at each temperature.

[0072] (v) Measurement of glass transition temperature Each resin was dissolved in cyclohexanone to a nonvolatile content of 40%. The coating solution was applied to a heat-resistant release film using a doctor blade with a 6-mil gap and dried at 130°C for 10 minutes to obtain a 30-μm-thick resin sheet. (However, for resins (a)-1 and (a)-5 described below, the resin sheet was transferred to a Teflon-coated metal pan for imidization and sintered at 300°C for 1 hour under a nitrogen atmosphere.) The resulting resin sheet was peeled from the release film, and its storage modulus and Tg were measured using a dynamic viscoelasticity analyzer "DVA200" (manufactured by IT Measurement & Control Co., Ltd.). The glass transition temperature was determined by cooling the resin sheet to 0°C and then heating it to 300°C at a heating rate of 10°C / min. The viscoelasticity was measured at a vibration frequency of 10 Hz and a grip length of 10 mm, and the temperature at which the loss tangent (tanδ) peak reached its maximum was determined. Heating rate: 10℃ / min Measurement frequency: 10Hz Grip length: 10 mm Width: 5mm

[0073] [Synthesis Example 1] <Synthesis of Resin (A)-1> A 1L separable flask equipped with an oil bath and a stirrer was charged with 295g of cyclohexanone while introducing nitrogen gas, and then 148.5g of Y1 (Priamine 1075) as a diamine and 5.4g of Z1 (m-aminophenol) as a monoamine compound were added with stirring. Next, 156.0g of X1 (4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride) as a tetracarboxylic acid was added and stirred at room temperature for 30 minutes. The mixture was heated to 100°C and stirred for 3 hours, after which the oil bath was removed and the mixture was returned to room temperature to obtain a varnish-like polyimide precursor. Thereafter, while distilled water was removed from the system using a Dean-Stark trap, the mixture was heated at 170°C for 10 hours to effect imidization, thereby obtaining a phenolic hydroxyl group-containing polyimide resin (A)-1 having a weight average molecular weight of 24,000, a phenolic hydroxyl group value of 4.6 mgKOH / g, a glass transition temperature of 48°C, and a mass loss temperature of 5% of 410°C.

[0074] [Synthesis Examples 2 to 8] <Synthesis of (A)-2 to (A)-8> Phenolic hydroxyl group-containing polyimide resins (A)-2 to (A)-8 were obtained in the same manner as in Synthesis Example 1, except that the monomers and blending amounts were changed as shown in Table 1. In the table, regarding the types of functional groups, a phenolic hydroxyl group is represented as "PhOH" and an alcoholic hydroxyl group is represented as "OH."

[0075] The abbreviations in Table 1 are as follows: X1: 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride X2: 3,3',4,4'-biphenyltetracarboxylic dianhydride X3: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride X4: 5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride X5: 1,2,4,5-cyclohexanetetracarboxylic dianhydride Y1: Priamine 1075 (dimer diamine, manufactured by Cargill Japan) Y2: 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol) Y3: 1,12-dodecanediamine Z1: m-aminophenol Z2: 1-aminodecane

[0076] [Table 1]

[0077] [Synthesis Example 9] <Synthesis of (A)-9> A four-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, inlet tube, and thermometer was charged with 171.8 g of Pripol 1009 (a polybasic acid compound), 0.6 g of 5-hydroxyisophthalic acid, 79.0 g of Priamine 1074 (a polyamine compound), and 100 g of ion-exchanged water. The mixture was stirred until the exothermic temperature stabilized. Once the temperature stabilized, the mixture was heated to 110°C. After confirming the outflow of water, the temperature was raised to 120°C after 30 minutes. The dehydration reaction was then continued by increasing the temperature by 10°C every 30 minutes. After the temperature reached 230°C, the reaction was continued at this temperature for 3 hours, then held under a vacuum of approximately 2 kPa for 1 hour, followed by cooling. 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 mgKOH / g, and a mass loss temperature of 5% at 384°C.

[0078] (A)-10: PKHA, manufactured by Gabriel Phonoxies, phenoxy resin, weight average molecular weight 25,000, hydroxyl value 211 mg KOH / g, glass transition temperature 104°C, temperature at which mass loss rate reaches 5%: 330°C (A)-11: PKFE, manufactured by Gabriel Phonoxies, phenoxy resin, weight average molecular weight 60,000, hydroxyl value 208 mg KOH / g, glass transition temperature 121°C, temperature at which mass loss rate reaches 5%: 345°C (A)-12: MEHC-7851H, manufactured by Meiwa Kasei Co., Ltd., biphenylene type phenolic resin, weight average molecular weight: 2800, phenolic hydroxyl value: 217 mg KOH / g, glass transition temperature: 87°C, temperature at which mass loss rate reaches 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 reaches 5%: 315°C (A)-14: Vylon 800, manufactured by Toyobo Co., Ltd., polyester resin, weight average molecular weight 84,000, hydroxyl value 7 mg KOH / g, glass transition temperature 68°C, temperature at which mass loss rate reaches 5%: 290°C

[0079] [Comparative Synthesis Example 1] <Synthesis of (a)-1> A reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot and cold water, and a stirrer was charged with 1,120.0 g of α,ω-bis(3-aminopropyl)polydimethylsiloxane (average molecular weight: 1,600), 60.1 g of 4,4'-diaminodiphenyl ether, and 190.3 g of dipropylene glycol dimethyl ether (DMM). After dissolution, 310.2 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was added and the reaction was continued at room temperature for 1 hour, then at 60°C for 1 hour, and then at 150°C for 4 hours. After adjusting the concentration with DMM solvent, a polyimide resin precursor (polyamic acid) solution (a)-1 was obtained. The solution had a weight-average molecular weight of 35,000, was 50% by mass, had no hydroxyl groups or phenolic hydroxyl groups, a glass transition temperature of 42°C, and a mass loss temperature of 395°C.

[0080] The following resins (a)-2 to (a)-6 were used. (a)-2: Udel P3707, manufactured by Solvay Advanced Polymers, polysulfone resin, weight average molecular weight 44,000, no hydroxyl group or phenolic hydroxyl group, glass transition temperature 181°C, temperature at which mass loss rate reaches 5%: 405°C (a)-3: Joncryl 61J, manufactured by BASF, an aqueous solution of water-soluble acrylic resin with a non-volatile content of 30.5%, a weight average molecular weight of 12,000, no hydroxyl groups or phenolic hydroxyl groups, a glass transition temperature of 107°C, and a temperature at which the mass loss rate reaches 5% of 255°C (a)-4: Kuraray Poval PVA-205, manufactured by Kuraray Co., Ltd., polyvinyl alcohol (saponification degree 88%), weight average molecular weight 50,000, hydroxyl value 1,120 mg KOH / g, glass transition temperature 80°C, temperature at which mass loss rate reaches 5%: 240°C (a)-5: U Imide Varnish BH, manufactured by Unitika Ltd., N,N'-dimethylacetamide solution of polyamic acid (polyimide precursor) with a non-volatile resin content of 26%, weight average molecular weight of 40,000, no hydroxyl group or phenolic hydroxyl group, glass transition temperature of 300°C or higher (not measurable), temperature at which mass loss rate reaches 5%: 560°C (a)-6: Zeonex 480R, manufactured by Zeon Corporation, cycloolefin polymer, weight average molecular weight 40,000, no hydroxyl group or phenolic hydroxyl group, glass transition temperature 167°C, temperature at which mass loss rate reaches 5%: 430°C

[0081] The following organometallic compounds (B)-1 to (B)-6 were used. (B)-1: TC-401, manufactured by Matsumoto Fine Chemical Co., Ltd., titanium tetraacetylacetonate, metal ion content: 7.0% by mass (metal ion content in non-volatile matter: 10.8% by mass), 65% non-volatile matter solution (B)-2: TC-100, manufactured by Matsumoto Fine Chemical Co., Ltd., titanium diisopropoxybisacetylacetonate, metal ion content: 9.8% by mass (metal ion content in nonvolatile matter: 13.1% by mass), 75% nonvolatile matter solution (B)-3: ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd., zirconium tetraacetylacetonate, metal ion content: 19.0% by mass, non-volatile content: 100% (B)-4: ZC-45, manufactured by Matsumoto Fine Chemical Co., Ltd., zirconium normal propylate, metal ion content: 21.0 mass% (metal ion content in nonvolatile matter: 28.0 mass%), nonvolatile matter 75% solution (B)-5: ALCH, manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum diisopropoxyacetylacetonate, metal ion content: 9.8% by mass, non-volatile content: 100% (B)-6: TC-310, manufactured by Matsumoto Fine Chemical Co., Ltd., titanium lactate, metal ion content: 8.2% by mass (metal ion content in non-volatile matter: 12.3% by mass), 75% non-volatile matter solution

[0082] The following compounds (C)-1 to (C)-4 having two or more groups capable of reacting with an alcoholic hydroxyl group or a phenolic hydroxyl group were used. (C)-1: Epicron N-660, manufactured by DIC Corporation, cresol novolac epoxy resin, with two or more epoxy groups per molecule, 50% non-volatile solution (C)-2: jER-1003F, manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin, with two epoxy groups per molecule, 100% non-volatile content (C)-3: Duranate TKA-100: manufactured by Asahi Kasei Corporation, HDI-based isocyanurate-type modified polyisocyanate, with three isocyanate groups per molecule, 100% non-volatile content (C)-4: Ba: Shikoku Chemicals Co., Ltd., benzoxazine compound, containing two benzoxazine groups per molecule, 100% non-volatile content

[0083] The following were used as other compounds (D)-1 to (D)-4. (D)-1: Tinuvin 326: BASF, UV absorber (D)-2: Nubian Black NH807: Nigrosine black dye manufactured by Orient Chemical Industries, Ltd. (D)-3: MA-100: Mitsubishi Chemical Corporation, carbon black pigment (D)-4: MEK-ST-40: manufactured by Nissan Chemical Industries, Ltd., MEK solvent-dispersed silica, silica concentration 40% by mass, average particle size 12 nm

[0084] [Example 1] <Production of coating solution> A container was charged with 100 parts of the resin (A)-1 of Synthesis Example 1 and 2.0 parts of the organometallic compound (B)-1 in terms of solid content, and a mixed solvent (toluene:MEK=8:2 (mass ratio)) was added so that the nonvolatile content concentration became 35%, followed by stirring for 10 minutes with a disper to obtain a coating solution.

[0085] <Production of temporary fixing adhesive composition sheet> The obtained coating liquid was uniformly coated using a doctor blade onto a 50 μm-thick heavy release film (a polyethylene terephthalate (PET) film coated with a heavy release agent) so that the dried thickness would be 30 μm, and then dried at 100°C for 2 minutes. This was then cooled to room temperature to obtain a single-sided release film-attached temporary fixing adhesive composition sheet. The temporary fixing adhesive composition sheet surface of the obtained single-sided release film-attached temporary fixing adhesive composition sheet was then superimposed on a 50 μm-thick light release film (a polyethylene terephthalate (PET) film coated with a light release agent), to obtain a double-sided release film-attached temporary fixing adhesive composition sheet consisting of a heavy release film / temporary fixing adhesive composition sheet / light release film. The evaluations described below were then carried out. The results are shown in Tables 2 to 5.

[0086] [Examples 2 to 36, Comparative Examples 1 to 7] In the same manner as in Example 1, coating solutions and double-sided release film-attached temporary fixing adhesive composition sheets were obtained with the solid content-based compositions shown in Tables 2 to 5, and the evaluations described below were carried out.

[0087] <Film thickness reduction rate after immersion in organic solvent> The release films on both sides of the double-sided release film-attached temporary fixing adhesive composition sheets of Examples 1 to 36 and Comparative Examples 1 to 7 were peeled off, placed on a Teflon (registered trademark)-coated tray, heated at 180°C for 1 hour under a nitrogen atmosphere, and then cut into several small pieces. In Comparative Examples 1 and 6 only, the heating temperature was increased to 300°C and sintered under a nitrogen atmosphere for 1 hour to complete the imidization. The obtained film pieces were also used for the thermogravimetric differential thermal analysis measurement. Each small piece was used as a sample and immersed in an organic solvent (toluene, cyclohexanone, or N-methylpyrrolidone) adjusted to 80°C for 1 hour, then removed, lightly wiped to remove any remaining solvent, and dried. The film thickness of the temporary fixing adhesive composition sheet with a release film after solvent immersion, measured with a contact film thickness meter, minus the thickness of the remaining release film (T1, T2, T3) was used to calculate the film thickness reduction rate after immersion in toluene (R1), cyclohexanone (R2), and N-methylpyrrolidone (R3) using the following formula. The results are shown in Tables 2 to 5. (Formula 2) R1(%)=(1-(T1 / 30))×100 (Formula 3) R2(%)=(1-(T2 / 30))×100 (Formula 4) R3(%)=(1-(T3 / 30))×100 T1: The thickness (μm) 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 and then immersing the test piece in toluene at 80°C for 1 hour T2: A test piece obtained by heating a 30 μm thick film made of the temporary fixing adhesive composition at 180°C for 1 hour is immersed in cyclohexanone at 80°C for 1 hour, and the thickness of the film (μm) is T3: The thickness (μm) 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 and then immersing the test piece in N-methylpyrrolidone at 80°C for 1 hour

[0088] <1. Step-following ability> The release film on only one side of the double-sided release film-attached temporary fixing adhesive composition sheet of Examples 1 to 36 and Comparative Examples 1 to 7 was peeled off, and the sheet was pressure-bonded to an alkali-free glass plate (Corning Eagle XG, 0.8 mm thick) as a support using a vacuum laminator (Nichigo-Morton V-130) at 100°C and 0.5 MPa. Note that, in Comparative Examples 1 and 6 only, in order to complete the imidization, after pressure bonding to the alkali-free glass plate, sintering was carried out at 300°C for 1 hour in a nitrogen atmosphere. The remaining release film on the other side was then peeled off, and the sheet was pressure-bonded to a comb-shaped electrode FPC board with an L / S=50 / 50 μm and a copper foil thickness of 10 μm, which had an electrode pad design for soldering on the edge, using the vacuum laminator at 180°C and 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 conformability of the temporary fixing adhesive composition sheet to the comb-shaped electrode circuit was confirmed using a digital optical microscope (Keyence Corporation, VHX-700) and evaluated according to the following criteria. ○: The recesses between the circuits are filled without any gaps (good) ×: The recesses between the circuits are not completely filled, resulting in gaps and voids (unusable)

[0089] <2. Reflow resistance test> The release film on only one side of the double-sided release film-attached adhesive sheets of Examples 1 to 36 and Comparative Examples 1 to 7 was peeled off, and the sheets were pressure-bonded to an alkali-free glass plate (Corning Eagle XG, 0.8 mm thick) as a support using a vacuum laminator (Nichigo-Morton V-130) at 100°C and 0.5 MPa. In Comparative Examples 1 and 6 only, to complete the imidization, sintering was performed at 300°C for 1 hour in a nitrogen atmosphere after pressure bonding to the alkali-free glass plate. The remaining release film on the other side was then peeled off, and the sheets were pressure-bonded to a 10 μm thick copper foil FPC board with a 50 / 50 μm L / S comb-shaped electrode design on the edge for soldering using the vacuum laminator at 180°C and 0.5 MPa to obtain a laminate for reflow resistance testing. In addition, for the adhesive sheets with double-sided release film of Comparative Examples 2, 3, 5, and 6, adhesion and filling of the recesses between the circuits during compression were not possible under the above temperature conditions, so the compression temperature for the support and components was set to 280°C to obtain laminates for the reflow resistance test. Next, the laminate for the reflow resistance test was subjected to a heating process equivalent to a solder reflow process, with a total of three passes, at a maximum measured temperature of 260°C in an air atmosphere, using a conveyor-type reflow device (UNI-5016F manufactured by Antom), and the reflow resistance was evaluated according to the following criteria. ◎: No voids even after 3 passes (very good) ○: Voids occurred on the third pass (good) △: Void occurs on the second pass (usable) ×: Void occurs on the first pass (cannot be used)

[0090] 3. Laser peelability The laminates of Examples 1 to 36 and Comparative Examples 1 to 7 after the reflow resistance test were irradiated with a laser from the glass surface using a UV laser marker (Keyence laser marker, MD-U1000C, laser wavelength 355 nm (laser)). For Example 36 only, an IR laser marker (Keyence laser marker, MD-X2500, laser wavelength 1064 nm) was used as the laser marker. The total energy amount of the laser was adjusted to determine the minimum total energy amount required to easily peel the support from the laminate, and the laser peelability was evaluated according to the following criteria. The results are shown in Tables 2 to 5. 300mJ / cm or less ◎: The total energy required for peeling is 300mJ / cm 2 Less than. (Very good) ○: The total energy required for peeling is 300 mJ / cm 2 More than 600mJ / cm 2 Less than. (Good) △: The total energy required for peeling is 600 mJ / cm 2 More than 1000mJ / cm 2 Less than. (Available) ×: The total energy required for peeling is 1000mJ / cm 2 or more (unusable)

[0091] <4. Warpage of the substrate after peeling off the support> 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 member on which the layer made of the temporary fixing adhesive composition remained when cut into a 10 x 10 cm piece was placed on a flat surface with the temporary fixing adhesive facing up, and the height of the warp at the edge was evaluated according to the following criteria. ◎: The height of the warp at the edge is less than 0.5 mm (very good) ○: The height of the warp at the edge is 0.5 mm to 1 mm (good) △: The height of the warp at the edge is 1mm to 2mm (usable) ×: The height of the warp at the edge is 2 mm or more (unusable)

[0092] <5. Solvent removability> After the laser peelability test, the laminates of Examples 1 to 36 and Comparative Examples 1 to 7 were immersed in organic solvents (toluene, cyclohexanone, and N-methylpyrrolidone) heated to 80°C after the support was peeled off, and evaluated according to the following criteria. The best solvent removability scores are shown in Tables 2 to 5. ◎: The layer made of the temporary fixing adhesive composition was dissolved in any organic solvent to a thickness of 0 μm in less than 20 minutes (very good) ○: The layer made of the temporary fixing adhesive composition was dissolved in any of the organic solvents within 20 minutes to 1 hour to a thickness of 0 μm (good) ×: The residual thickness of the layer made of the temporary fixing adhesive composition does not reach 0 μm within 1 hour with any of the organic solvents (unusable).

[0093] <6. Soldering characteristics after dissolution and removal> For the components of Examples 1 to 36 and Comparative Examples 1 to 7 that had achieved the best results in the solvent removability test, a metal mask was printed using solder paste (M705-RGS800 Type 6, manufactured by Senju Metal Industry Co., Ltd., lead-free solder paste), and then soldered by reflow using a conveyor-type reflow machine (UNI-5016F manufactured by Antom Co., Ltd.) at a maximum measured temperature of 260°C in an atmospheric environment, and the components were evaluated according to the following criteria. ○: Soldering is possible without gaps (good) △: Solder does not stick to some parts of the edge, but soldering is generally possible without any problems (usable) ×: There are many areas where the solder does not adhere, making practical soldering impossible (unusable)

[0094] [Table 2]

[0095] [Table 3]

[0096] [Table 4]

[0097] [Table 5]

[0098] Temporary fixing adhesive compositions that did not contain resin (A) or organometallic compound (B) had good heat resistance, as shown in Comparative Examples 1, 2, and 7. Although the temporary fixing adhesive layer remaining on the component after laser peeling could be dissolved and removed to some extent with an organic solvent at 80°C, the dissolution and removal process took a long time, and the solderability to the component after dissolution and removal was poor, likely due to the small amount of adhesive layer residue remaining. Furthermore, the lamination and sintering temperatures required for processing were extremely high, resulting in severe warping of the component after removal of the support, making it unsuitable for practical use. Comparative Example 6, which used a resin with a temperature higher than 550°C at which a mass loss of 5% relative to the mass before heating occurred when heated at a rate of 10°C / min in air using thermogravimetric differential thermal analysis, not only had the above-mentioned problems but also was extremely difficult to remove with a laser. Furthermore, temporary fixing adhesive compositions that contained an organometallic compound (B) but not resin (A) had poor heat resistance and were unable to be dissolved and removed with a solvent after laser peeling, as shown in Comparative Examples 3 and 4. Furthermore, a temporary fixing adhesive composition containing a resin (A) and an organometallic compound (B) but containing more than 2 parts by mass of a compound (C) having two or more groups reactive with alcoholic hydroxyl groups or phenolic hydroxyl groups, excluding the organometallic compound (B), per 100 parts by mass of the resin (A) also failed 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, since the member had unevenness due to circuits and the like, the anchor effect made it impossible to peel the temporary fixing adhesive layer with a commonly used release agent, and it was difficult to remove the temporary fixing adhesive layer from the member by any method other than dissolving and removing it. On the other hand, in Examples 1 to 36 according to the present invention, processing at a relatively low temperature was possible, which suppressed warping of the component after laser peeling, and the component could be dissolved and removed relatively quickly using a heated solvent. Furthermore, the electrode surface after dissolution and removal was clean enough to have no problems with solderability, so that the component could be processed quickly and with a high level of cleanliness, and the productivity was excellent. [Explanation of symbols]

[0099] 1 Support 2. Temporary fixing adhesive layer 3. Components 4 Laminate 5. Laser light

Claims

1. A temporary fixing adhesive composition containing a resin (A) and an organometallic compound (B), the resin (A) contains an alcoholic hydroxyl group or a phenolic hydroxyl group, and when heated at a rate of 10°C / min in an air atmosphere using thermogravimetric differential thermal analysis, the temperature at which the mass loss rate relative to the mass before heating is 5% is 280°C or higher and 550°C or lower; the resin (A) is at least one selected from the group consisting of a polyimide resin, a polyamide resin, a polyphenylene ether resin, a phenol resin, and a phenoxy resin, the organometallic compound (B) is at least one selected from the group consisting of an organotitanium compound, an organozirconium compound, and an organoaluminum compound; the organoaluminum compound contains, as a ligand composed of an organic molecule, at least one selected from the group consisting of acetylacetone, methyl acetoacetate, and ethyl acetoacetate; further comprising 2 parts by mass or less of a compound (C) (excluding the organometallic compound (B)) having two or more groups capable of reacting with an alcoholic hydroxyl group or a phenolic hydroxyl group per 100 parts by mass of the resin (A), The film thickness reduction rate (R) after immersion in an organic solvent calculated by the following (Equation 1) is 95% or more, The temporary fixing adhesive composition, wherein the organic solvent is any one selected from the group consisting of toluene, cyclohexanone, and N-methylpyrrolidone. (Formula 1) R (%) = (1-(T / 30)) x 100 T: A test piece obtained by heating a 30 μm thick film made of the temporary fixing adhesive composition at 180° C. for 1 hour is immersed in the organic solvent at 80° C. for 1 hour, and the thickness of the film (μm) is obtained.

2. The temporary fixing adhesive composition according to claim 1, 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.

3. A laminate in which a member and a support are bonded and temporarily fixed with the adhesive composition for temporary fixing according to claim 1 or 2.

4. A method for temporarily fixing a member comprising the following steps (1) to (3): (1) A step of temporarily fixing a member and a support by bonding them together using the adhesive composition for temporary fixing according to claim 1. (2) A process for processing the members temporarily fixed in (1) (3) After the processing of (2), a step of irradiating the layer made of the temporary fixing adhesive composition with a laser to remove the support.

5. The method for temporarily fixing members according to claim 4, wherein the laser is a near-infrared laser or an ultraviolet laser.

6. 6. The method for temporarily fixing members according to claim 5, wherein the support is made of glass or silicon.

7. A treatment method comprising immersing a member from which the support has been removed by the method according to any one of claims 4 to 6, and from which a layer made of the temporary fixing adhesive composition remains, in an organic solvent, to remove the layer made of the temporary fixing adhesive composition from the member.

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