Adhesive composition for temporary fixing, and method for temporarily fixing a component using the same.

Abstract

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 provides good solderability of component electrodes after removal of the temporary fixing adhesive, and to provide a method for temporarily fixing components and processing methods using the same. [Solution] A temporary fixing adhesive composition comprising a resin (A) and an organometallic compound (B), wherein the resin (A) contains an alcoholic hydroxyl group or a phenolic hydroxyl group, and is a resin whose mass loss rate relative to the mass before heating is 5% at a rate of 10°C / min in an atmospheric atmosphere using thermogravimetric differential thermal analysis, and the film thickness reduction rate (R) after immersion in toluene, cyclohexanone, or N-methylpyrrolidone is 95% or more.

Description

[Technical Field]

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

[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 is completed, it is necessary to peel the components off the support and remove any remaining temporary fixing adhesive layer from the components.

[0004] Methods for removing such temporary fixing adhesive layers from the support include methods using solvents and methods using physical stress to peel them off. However, laser peeling methods using laser light such as ultraviolet, visible, or infrared light are attracting attention because they allow for rapid peeling without stressing the component.

[0005] Regarding patent documents relating to laser peeling methods, for example, Patent Document 1 discloses a UV-curable 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 described in Patent Document 1 had problems, such as when forming an uneven structure like electrode pads or solder bumps on a component, and then temporarily fixing the surface with the electrode pads or solder bumps using a temporary fixing adhesive in order to process the back surface, or when the surface roughness of the outermost insulating layer was rough, it was impossible to remove the adhesive using commonly used stripping solutions, or even if removal was possible, residue would remain. Furthermore, in the methods described in Patent Documents 2 and 3, it was possible to dissolve and remove the temporary fixing adhesive layer remaining on the component using an organic solvent, but the adhesive layer did not conform well to the unevenness when forming the temporary fixing adhesive layer on an uneven structure or when bonding it to the component. If it was heated at a very high temperature to conform to the unevenness, the effects of the thermal history could cause the thinned component to warp significantly after peeling from the support, which would interfere with subsequent manufacturing processes. Although curing and bonding at relatively low temperatures, as 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 the uneven surface impossible. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2015-224316 [Patent Document 2] Japanese Patent Publication No. 2013-33814 [Patent Document 3] Japanese Patent Publication No. 2016-003270 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention has been 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 provides good solderability of component electrodes after removal of the temporary fixing adhesive, and a method for temporarily fixing components using the same. [Means for solving the problem]

[0008] After diligent research by the inventors, we discovered that the problems of the present invention can be solved in the following embodiment, and thus completed the present invention. 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, the resin is such that, when heated at a rate of 10°C / min in an atmospheric environment using thermogravimetric differential thermal analysis, the mass loss rate relative to the mass before heating is 5% at temperatures between 280°C and 550°C. The film thickness reduction rate (R) after immersion in an organic solvent, calculated from the following (Equation 1), is 95% or more. A temporary fixing adhesive composition wherein 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 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 the aforementioned 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 that can react with alcoholic hydroxyl groups or phenolic hydroxyl groups is 2 parts by mass or less per 100 parts by mass of resin (A).

[0010] One embodiment of the temporary fixing adhesive in the present invention is that the organometallic compound (B) is an organic titanium compound or an organic zirconium compound.

[0011] One embodiment of the temporary fixing adhesive in the present invention is that 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] One embodiment of the temporary fixing adhesive in the present invention is that the resin (A) is at least any one selected from the group consisting of a polyimide resin, a polyamide resin, a polyphenylene ether resin, a phenol resin, and a phenoxy resin.

[0013] [[ID=J12]]The laminate of the present invention is formed by adhering and temporarily fixing a member and a support with the temporary fixing adhesive composition.

[0014] The method for temporarily fixing a member of the present invention is composed of the following steps (1) to (3). (1) A step of adhering and temporarily fixing a member and a support using the temporary fixing adhesive composition according to claim 1 (2) A step of processing the member temporarily fixed in (1) (3) After the processing in (2), a step of irradiating a laser to a layer made of the temporary fixing adhesive composition to remove the support

[0015] One embodiment of the method for temporarily fixing a member of the present invention is that the laser is a near-infrared laser or an ultraviolet laser.

[0016] One embodiment of the method for temporarily fixing a member of the present invention is that the support is made of glass or silicon.

[0017] The treatment method of the present invention is to immerse a member having a layer made of the temporary fixing adhesive composition remaining after removing the support in the method for temporarily fixing a member in an organic solvent, and remove the layer made of the temporary fixing adhesive composition from the member.

Advantages of the Invention

[0018] According to the present invention, there are provided a temporary fixing adhesive having followability (step followability) with respect to a concavo-convex structure, high heat resistance (reflow resistance), laser peelability, capable of suppressing substrate warpage after support peeling, excellent solvent removability, and good solderability of a member electrode after removal of a temporary fixing adhesive, and a method for temporarily fixing a member and a processing method using the same. The temporary fixing adhesive layer of the present invention can be suitably used for manufacturing semiconductor-related members such as semiconductor chips, package substrates used for their rewiring, and interposers.

Brief Description of the Drawings

[0019] [Figure 1] The schematic cross-sectional view which shows the laminated body of this invention partially. [Figure 2] The schematic cross-sectional view which shows partially the scene which irradiates laser light on the laminated body of this invention.

Embodiments for Carrying Out the Invention

[0020] Hereinafter, the present invention will be described in detail. Needless to say, other embodiments are also included in the scope of the present invention as long as they are in line with the gist of the present invention. In addition, the numerical range specified using "~" in this specification includes the numerical values described before and after "~" as the range of the lower limit value and the upper limit value. In this specification, "film" and "sheet" are synonymous and are not distinguished by thickness. In addition, various components appearing in this specification may be used alone or in combination of two or more as long as they are not particularly noted. The numerical values described in this specification refer to the values obtained by the methods described in the examples described later.

[0021] In this specification, a 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 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 from the following formula (1), is 95% or more. If (R) is 95% or more, it has good removeability with an organic solvent, and therefore the solderability of the component electrodes after removal of the temporary fixing adhesive is excellent. 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 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 an organic solvent at 80°C for 1 hour. In other words, the rate of film thickness reduction after toluene immersion (R1) calculated from (Equation 2) below, or the rate of film thickness reduction after cyclohexanone immersion (R2) calculated from (Equation 3) below, or the rate of film thickness reduction after N-methylpyrrolidone immersion calculated from (Equation 4) below. It is important that the film thickness reduction rate (R3) in this case 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: Thickness (μm) of the film after immersion in toluene at 80°C for 1 hour, using a test specimen obtained by heating a 30 μm thick film made of a temporary fixing adhesive composition at 180°C for 1 hour. T2: Thickness of the film (μm) 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. T3: Thickness of the film (μm) 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 N-methylpyrrolidone at 80°C for 1 hour.

[0023] 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 1 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.

[0024] Conventional temporary fixing adhesive compositions are designed to provide heat resistance through the rigidity of the resin structure, requiring very high-temperature processes for substrate conformity and ring-closing reactions of the resin structure. Therefore, 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 material. As a result of diligent research by the inventors, the present invention has found that the temporary fixing adhesive composition exhibits heat resistance through crosslinking after bonding and material conformity, and that this crosslinking has a certain degree of reversibility through dissociation and recombination, enabling substrate conformity and heat resistance at relatively low temperatures.

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

[0026] The presence of alcoholic or phenolic hydroxyl groups in resin (A) allows for the formation of coordinate crosslinks with organometallic compounds described later, thereby providing resistance to harsh heating processes such as solder reflow and various chemicals, while also enabling dissolution and removal with organic solvents. The presence of phenolic hydroxyl groups in resin (A) is particularly preferable for achieving a balance between heat resistance and solubility in organic solvents. The total functional value of the phenolic hydroxyl groups and hydroxyl groups is preferably between 0.01 and 250 mg KOH / g. This range provides a particularly good balance between heat resistance and solubility in organic solvents.

[0027] By using thermogravimetric differential thermal analysis, when resin (A) is heated at a rate of 10°C / min in an atmospheric environment, 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 by keeping the temperature below 550°C, rapid delamination by laser irradiation becomes possible. The temperature is preferably between 300°C and 500°C.

[0028] There are no particular limitations on the weight-average molecular weight of resin (A), but it is preferable that the weight-average molecular weight be 2,000 to 150,000, and particularly preferable that it be 2,500 to 100,000, in order to achieve both film-thinning properties and coating properties for the temporary fixing adhesive composition and to obtain good handling properties.

[0029] 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 properties in relatively low-temperature processes, the glass transition temperature is preferably 0°C to 160°C, and particularly preferably 10°C to 140°C.

[0030] 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 alcoholic hydroxyl groups or phenolic hydroxyl groups in the molecular structure of these resins is not particularly limited.

[0031] (Polyimide resin) 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 reaction with dicarboxylic anhydride or monoamine. By using tetracarboxylic dianhydride or diamine, or dicarboxylic anhydride or monoamine having alcoholic or phenolic hydroxyl groups, as at least some of the raw materials for the polyimide resin, it is possible to obtain polyimide resins having alcoholic or phenolic hydroxyl groups.

[0032] 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, and 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic acid dianhydride. Aqueous compounds, aromatic tetracarboxylic acids such as 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-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, 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, and 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 Cyclo, bicyclo, and tricyclotetracarboxylic acids such as rubonic 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, and 9,14-dioxopentacyclo[8.2.11,11.14,7.02,10.03,8]tetradecane-5,6,12,13-tetracarboxylic acid. Examples include tetracarboxylic acids containing a spiro ring, 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-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'-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.

[0034] The aforementioned dimer amines 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 or hydrogenated product of an unsaturated aliphatic carboxylic acid. 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, as well as purified unsaturated fatty acids such as linolenic acid, linoleic acid, oleic acid, and erucic acid. The degree of unsaturation may be reduced by hydrogenating the unsaturated bond as needed. Dimer amines with reduced unsaturation are preferable in terms of oxidation resistance (especially discoloration at high temperatures) and suppression of gelation during synthesis.

[0035] 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. The 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 coloration at high temperatures) and suppression of gelation during synthesis. Dimer acids are preferably compounds with 20 to 60 carbon atoms, and more preferably compounds with 24 to 56 carbon atoms. Compounds having 28 to 48 carbon atoms are more preferred, and compounds having 36 to 44 carbon atoms are even more preferred. Dicarboxylic acid compounds having a branched structure obtained by a 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. If there are two ring structures, the two rings may be independent or continuous. One or more types of dimer acids can be used. The alicyclic structure may have one or more double bonds within the ring, or it may not have double bonds.

[0036] Examples of the aforementioned 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 bisaminophenols as part or all of the diamine, phenolic hydroxyl groups can be imparted to the polyimide resin side chains.

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

[0038] Examples of the aforementioned monoamines 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 ends 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 a dicarboxylic acid dianhydride and a diamine through a dehydration condensation reaction. The molecular chain ends of the polyamide resin may also be capped by a reaction with a monocarboxylic acid or monoamine. By using diamines, dicarboxylic acids, monoamines, and monocarboxylic acids having alcoholic hydroxyl groups or phenolic hydroxyl groups as at least some of the raw materials for the polyamide resin, it is possible to obtain polyamide resins having alcoholic hydroxyl groups or phenolic hydroxyl groups.

[0040] The aforementioned dicarboxylic acids include isophthalic acid, terephthalic acid, diphenyl ether-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 Examples include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and the aforementioned dimer acids.

[0041] 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.

[0042] Examples of the monocarboxylic acids include lower fatty acids such as acetic acid, propionic acid, and butyric acid, and stearin. Saturated fatty acids such as acids (octadecanoic acid), tubercurostearic acid (nonadecanoic acid), arachidic acid (eicosanic acid), henicosanoic acid, etc., 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, docosadienoic acid, etc., benzoic acid, methylbenzoic acid {toluic acid (p-, m-, o-)}, dimethylbenzoic acid (xylylic acid, hemeritic acid, mesityleneic acid), trimethylbenzoic acid {prenicylic acid, duric acid, isoduric acid (α-, β-, γ-)}, 4-isopropylbenzoic acid (cumic acid), Examples of aromatic monocarboxylic acids include 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).

[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 with other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.). Also included are polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and poly(2,6-dimethyl-1,4-phenylene ether), etc., with phenol compounds such as bisphenols or trisphenols in a solvent such as toluene in the presence of organic peroxides, and obtained by redistributing them, resulting in linear or branched polyphenylene ethers.

[0044] (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, and 4,4'-bis(chloromethyl)biphenyl 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 their structure, phenolic resins inevitably have phenolic hydroxyl groups.

[0045] (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 contain hydroxyl groups.

[0046] The bisphenol compounds mentioned above 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, and tetramethylbisphenol. Examples include phenol F, tetramethylbisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, tetramethylbiphenol, ethylidenebisphenol, methylethylidenebis(methylphenol), and cyclohexylidenebisphenol.

[0047] 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.

[0048] <Organometallic compound (B)> The organometallic compound (B) of the present invention 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 the alcoholic hydroxyl groups or phenolic hydroxyl groups of resin (A) via coordination bonding to the metal ion through ligand exchange between its ligand and the alcoholic hydroxyl groups or 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. This allows deformation to conform to the surface shape of the member even at relatively low process temperatures, resulting in excellent conformability to the member surface. Furthermore, by using this metal-coordination crosslink as the main crosslink, 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.

[0049] Examples of metal ion species in 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, the organometallic compound (B) is preferably an organotitanium compound or an organozirconium compound, and is particularly preferably an organozirconium compound.

[0050] Examples of ligands consisting of organic molecules of 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.

[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 provides the necessary heat resistance, while a content of 3.0% by mass or less provides rapid removal with organic solvents.

[0052] <Compounds having two or more groups that can react with alcoholic hydroxyl groups or phenolic hydroxyl groups (C)> The temporary fixing adhesive composition of the present invention may contain a compound (C) having two or more groups that can react 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 limiting the content of compound (C) having two or more groups that can react 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 removal with organic solvents is maintained. The lower the content of compound (C), the better, and it is particularly preferable that it is not included.

[0053] Groups that can react with the alcoholic hydroxyl group or phenolic hydroxyl group of compound (C) include epoxy groups, oxetanyl groups, episulfide groups, isocyanate groups, thioisocyanate groups, blocked isocyanate groups, oxazoline groups, benzoxazine groups, and the like. Compound (C) may be one of the groups listed above, or a compound having a total of two or more of these groups in the same molecule.

[0054] Specific examples of compound (C) include the 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-oxyphenyl) Tanyl)-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 1,3-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 polyfunctional oxetanyl compounds include methyl)benzene, 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-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), or mixtures thereof), MDI (e.g., 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), Aromatic polyisocyanates such as diphenylmethane diisocyanate (or mixtures thereof), 1,4-phenylenediisocyanate, diphenyl diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine diisocyanate (TODI), 1,5-naphthalenediisocyanate (1,5-NDI), diphenyl ether diisocyanate, triphenylmethane triisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, etc. Aliphatic polyisocyanates such as cyanate (HDI), pentamethylene diisocyanate, trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), cyclohexane diisocyanate, methylenebis(cyclohexyl isocyanate), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate Examples include alicyclic polyisocyanates (H12MDI) such as cyanate (IPDI), bis(isocyanate-methyl)cyclohexane (H6XDI), and dicyclohexylmethane diisocyanate, as well as polyfunctional isocyanate compounds such as aromatic polyisocyanates, aliphatic polyisocyanates, carbodiimide-modified polyisocyanates, biuret-modified polyisocyanates, allophanate-modified polyisocyanates, polymethylene polyphenyl polyisocyanates (crude MDI or polymeric MDI), and isocyanurate-modified polyisocyanates. Also included are blocked isocyanate compounds obtained by blocking these with blocking agents such as phenol, cresol, ε-caprolactam, ethyl methyl ketone oxime, diethyl malonate, ethyl acetoethyl acetate, diisopropylamine, 3,5-dimethylpyrazole, and imidazole. In addition, 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, Polyfunctional oxazoline compounds such as 1,2-bis(2-oxazolin-2-yl)benzene and 1,3-bis(2-oxazolin-2-yl)benzene, 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-dimethylaniline type benzoxazine, bisphenol A-aniline type benzoxazine, bisphenol A-amine type benzoxazine, bispheno Examples include polyfunctional benzoxazine compounds such as benzoxazine-F-aniline type, bisphenol-S-aniline type, dihydroxydiphenylsulfone-aniline type, dihydroxydiphenylether-aniline type, benzoxazine, benzophenone type, biphenyl type, bisphenol-AF-aniline type, bisphenol-A-methylaniline type, phenol-diaminodiphenylmethane type, triphenylmethane type, and phenolphthalein type, but are not limited to these as long as the above conditions are met.

[0055] <Other ingredients> In addition to the components mentioned above, the temporary fixing adhesive composition of the present invention may optionally contain laser absorbers, various fillers, dispersants, defoamers, etc., to the extent that they do 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 and used ultraviolet absorbers such as triazine-based and hydroxyphenylbenzotriazole-based absorbers, which may be added depending on the laser wavelength used.

[0056] ≪Laminated structure≫ The laminate of the present invention is formed by bonding and temporarily fixing a member and a support using a temporary fixing adhesive composition. Specifically, it is formed by joining a support, a temporary fixing adhesive layer, and a member in the order shown in Figure 1, which are temporarily formed to temporarily fix the member and perform various processing.

[0057] 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 of its excellent UV and infrared transmittance, while 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 may be a circular wafer, or a square or rectangular panel.

[0058] Examples of the aforementioned components include semiconductor chips, package substrates used for their rewiring, and semiconductor peripheral components such as interposers. In particular, the conformability of the temporary fixing adhesive composition to the surface shape and the high dissolution and removal performance of the process described later are most effective when the component has at least one side with an uneven structure such as solder bumps or electrode pads, or a surface with high surface roughness, and further requires processing of the opposite side.

[0059] ≪Temporary fixing method for components≫ The method for temporarily fixing the component of the present invention consists of the following steps (1) to (3). (1) A step of bonding and temporarily fixing a member and a support using the temporary fixing adhesive composition described in claim 1. (2) Process of processing the components that were temporarily fixed in (1) (3) After processing in (2), the support is removed by irradiating the layer made of the temporary fixing adhesive composition with a near-infrared laser or ultraviolet laser.

[0060] Process (1) Step (1) is a step in which the laminate is manufactured. Specifically, the step may involve first applying a solution of the temporary fixing adhesive dissolved in any organic solvent onto the component, drying it, and then pressing it onto the support while heating it as needed, or conversely, applying it to the support and then pressing it onto the component. Alternatively, the solution of the temporary fixing adhesive may be applied to any resin film in the form of a release film after a release treatment has been applied, drying it to create a temporary fixing adhesive film, transferring it to the support while heating it as needed, and then pressing it onto the component.

[0061] Process (2) Step (1) is a process for processing the member that has been temporarily fixed as the laminate of the present invention. Specific steps include cutting and thinning processes such as physical polishing and CMP, chemical processes for forming wiring layers and insulating layers and for soldering, and heating processes such as solder reflow processes. After 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.

[0062] Process (3) Step (3) is a step of removing the support by irradiating a layer made of the temporary fixing adhesive composition 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 adhesive layer 2.

[0063] 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 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, 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, free electron lasers, and lasers consisting of their harmonics can be used. This decomposes or alters the adhesive layer 2, making it possible to easily separate the support 1 and the component 3.

[0064] When irradiating with laser light, the following conditions are given as an example of laser light irradiation conditions. The average output power of the laser light is preferably 1.0W or more and 5.0W or less, and more preferably 2.0W or more and 4.0W or less. The repetition frequency of the laser light is preferably 20kHz or more and 60kHz or less, and more preferably 30kHz or more and 50kHz or less. The scanning speed of the laser light is preferably 100mm / s or more and 10000mm / s or less. The total energy of the laser light is 50mJ / cm². 2 More than 5000mJ / cm 2 The following is preferable: 100 mJ / cm² 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.

[0065] <<Dissolution and removal of temporary fixing adhesive compositions using 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 bath 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 reasonable processing time, and it may be at room temperature, but it may be heated to shorten the processing time. Heating the organic solvent promotes the exchange of crosslinks formed between the resin (A) and the organometallic compound (B), 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.

[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 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. [Examples]

[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, even when the "parts" of the blending ingredients in the composition are blended as a solution of an organic solvent, the value is given as the non-volatile content.

[0068] (i) Measurement of weight-average molecular weight (Mw) Mw was measured using a Showa Denko GPC (gel permeation chromatography) system, model "GPC-101". The fluid phase was THF (tetrahydrofuran), and two "KF-805L" (Showa Denko GPC column: 8mm ID × 300mm size) columns connected in series were used as the stationary phase column. The analysis was performed under conditions of sample concentration 1% by mass, flow rate 1.0 mL / min, pressure 3.8 MPa, and column temperature 40°C. Mw was determined in polystyrene equivalent. Data analysis involved calculating calibration curves, molecular weight, and peak area using the manufacturer's built-in software. Mw was determined for the analyte range of retention times from 17.9 to 30.0 minutes.

[0069] (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 invention, 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 is accurately weighed into a stoppered Erlenmeyer flask, and toluene / ethanol (volume ratio: toluene) is used. Add 100 ml of the ruen / ethanol (1 / 2) mixture and dissolve. Then, add exactly 5 ml of the acetylating agent (a solution of 25 g of acetic anhydride dissolved in pyridine, to a volume of 100 ml) and stir for about 1 hour. Add phenolphthalein reagent as an indicator and maintain the mixture for 30 seconds. After that, titrate with 0.1 N alcoholic potassium hydroxide solution until the solution turns pale pink. The hydroxyl value was calculated using the following formula (unit: mgKOH / g). Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.05} / S] + D however, S: Sample volume (g) a: Consumption volume (mL) of 0.1N alcoholic potassium hydroxide solution b: Amount of 0.1N alcoholic potassium hydroxide solution consumed in the blank experiment (mL) F: Titer of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

[0070] (iii) Measurement of acid value Precisely weigh approximately 1 g of the sample into a stoppered Erlenmeyer flask and dissolve it in 100 ml of a toluene / ethanol mixture (volume ratio: toluene / ethanol = 2 / 1). Add phenolphthalein reagent as an indicator and hold for 30 seconds. Then, titrate with 0.1 N alcoholic potassium hydroxide solution until the solution turns pale pink. The acid value was determined by the following formula (unit: mgKOH / g). Acid value (mgKOH / g)=(5.611×a×F) / S however, S: Sample volume (g) a: Consumption volume (mL) of 0.1N alcoholic potassium hydroxide solution F: Titer of 0.1N alcoholic potassium hydroxide solution

[0071] (iv) Thermogravimetric differential thermal analysis Approximately 10 mg of a test specimen, cut to an appropriate size from the film fragments 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 under 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 weight change was measured. The temperature at which the weight loss first exceeded 5% 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 obtain a coating solution with a non-volatile content of 40%. This 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 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 from 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℃ / min Measurement frequency: 10Hz Grip distance: 10mm Width: 5mm

[0073] [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. Then, 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 imide it, 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.

[0074] [Synthesis Examples 2-8] <(A)-2 to (A)-8 synthesis> (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, phenolic hydroxyl groups are denoted as "PhOH" and alcoholic hydroxyl groups as "OH".

[0075] The abbreviations in Table 1 are shown below. X1: 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride X2: 3,3',4,4'-biphenyltetracarboxylic acid 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 acid 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

[0076] [Table 1]

[0077] [Synthesis Example 9] <(A)-9 synthesis> 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 stabilized. 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 by 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 temperature was lowered by holding it under a vacuum of approximately 2 kPa for 1 hour. Finally, an antioxidant was added to obtain (A)-9, a phenolic hydroxyl group-containing polyamide resin with a weight-average molecular weight of 96000, a phenolic hydroxyl value of 0.6 mg KOH / g, and a mass loss rate of 5% at a temperature of 384°C.

[0078] (A)-10: PKHA, manufactured by Gabriel Phonoxies, phenoxy resin, weight-average molecular weight 25000, 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 Gabriel Phonoxies, phenoxy resin, weight-average molecular weight 60000, 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 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 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: Vylon800, manufactured by Toyobo Co., Ltd., polyester resin, weight-average molecular weight 84000, hydroxyl value 7 mgKOH / g, glass transition temperature 68°C, temperature at which mass loss rate is 5%: 290°C

[0079] [Comparative Synthesis Example 1] <(a)-1 synthesis> 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 mixture was reacted 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 hydroxyl groups or phenolic hydroxyl groups, a glass transition temperature of 42°C, and a mass loss rate of 5% at a temperature of 395°C.

[0080] 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 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 non-volatile content of 30.5%, weight-average molecular weight 12000, no hydroxyl groups or phenolic hydroxyl groups, glass transition temperature 107°C, temperature at which the mass loss rate is 5%: 255°C (a)-4: Kuraray Poval PVA-205, manufactured by Kuraray Co., Ltd., 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, a solution of polyamic acid (polyimide precursor) with 26% non-volatile resin content in N,N'-dimethylacetamide, weight-average molecular weight 40,000, no 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: Zeonex480R, manufactured by Zeon Corporation, cycloolefin polymer, weight-average molecular weight 40,000, no hydroxyl groups or phenolic hydroxyl groups, glass transition temperature 167°C, temperature at which mass loss rate is 5%: 430°C

[0081] The following organometallic compounds were used as (B)-1 to (B)-6. (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 solution (B)-2:TC-100, manufactured by Matsumoto Fine Chemical Co., Ltd., 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 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-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 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 solution

[0082] 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 an alcoholic hydroxyl group or a phenolic hydroxyl group. (C)-1: Epiclon N-660, manufactured by DIC Corporation, cresol novolac type epoxy resin, containing two or more epoxy groups per molecule, 50% non-volatile content solution. (C)-2: jER-1003F, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, containing 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, containing 3 isocyanate groups per molecule, 100% non-volatile content. (C)-4: Ba: Manufactured by Shikoku Chemicals Corporation, benzoxazine compound, containing 2 benzoxazine groups per molecule, 100% non-volatile content.

[0083] The following were used as other formulations (D)-1 to (D)-4. (D)-1: Tinuvin326: Manufactured by BASF, UV absorber (D)-2: NubianBlackNH807: Manufactured by Orient Chemical Industries, Ltd., negrosine black dye (D)-3: MA-100: Manufactured by 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] <Manufacturing of coating solution> Based on the following solid content, 100 parts of resin (A)-1 and 2.0 parts of organometallic compound (B)-1 from Synthesis Example 1 were placed in a container, and a mixed solvent (toluene:MEK = 8:2 (mass ratio)) was added to achieve a non-volatile content of 35%. The mixture was then stirred with a disperser for 10 minutes to obtain the coating solution.

[0085] <Manufacturing of temporary fixing adhesive composition sheets> 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.

[0086] [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 to 5, and the evaluations described later were performed.

[0087] <Percentage of film thickness reduction after immersion in organic solvent> 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 process. The resulting film pieces were also used in the thermogravimetric differential thermal analysis measurements. Each piece was then immersed as a sample in toluene, cyclohexanone, and N-methylpyrrolidone organic solvents adjusted to 80°C for 1 hour, removed, lightly wiped off the adhering solvent, and dried. The film thickness reduction rates after toluene immersion (R1), cyclohexanone immersion (R2), and N-methylpyrrolidone immersion (R3) were calculated using the following formulas, 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 (T1, T2, T3), as measured by a contact-type film thickness gauge. The results are shown in Tables 2-5. (Formula 2) R1(%)=(1-(T1 / 30))×100 (Formula 3) R2(%)=(1-(T2 / 30))×100 (Formula 4) R3(%)=(1-(T3 / 30))×100 T1: Thickness (μm) of the film after immersion in toluene at 80°C for 1 hour, using a test specimen obtained by heating a 30 μm thick film made of a temporary fixing adhesive composition at 180°C for 1 hour. T2: Thickness of the film (μm) 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. T3: Thickness of the film (μm) 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 N-methylpyrrolidone at 80°C for 1 hour.

[0088] <1. Ability to follow uneven surfaces> For Examples 1-36 and Comparative Examples 1-7, the release film on one side of the double-sided release film-attached temporary fixing adhesive composition sheets was peeled off, and the sheets were pressed onto an alkali-free glass plate (Corning EagleXG, 0.8 mm thick) using a vacuum laminator (Nichigo-Morton V-130) at 100°C and 0.5 MPa. For Comparative Examples 1 and 6 only, in order to complete the imidization process, the sheets were subjected to a 300°C treatment under a nitrogen atmosphere after pressing onto the alkali-free glass plate. Sintering was performed at 1°C for 1 hour. The remaining release film on the other side was then peeled off, and the laminate was obtained by pressing it onto a comb-type electrode FPC substrate with L / S=50 / 50μm and copper foil thickness of 10μm, which has an electrode pad design for soldering at the edges, using the vacuum laminator at 180°C and 0.5MPa. 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 confirmed using a digital optical microscope (Keyence Corporation, VHX-700) and evaluated according to the following criteria. ○: The recesses between circuits are filled without any gaps (good). ×: The recesses between circuits are not completely filled, resulting in gaps or voids (unusable).

[0089] <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) using a vacuum laminator (V-130, Nichigo-Morton) at 100°C and 0.5 MPa. For Comparative Examples 1 and 6 only, in order to complete the imidization process, 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 had electrode pads for soldering at the edges, using the same 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 films in Comparative Examples 2, 3, 5, and 6, adhesion and filling of recesses between circuits were not possible during compression under the above temperature conditions. Therefore, the compression temperature of the support and components was set to 280°C to obtain laminates for reflow resistance testing. Next, the laminate for reflow resistance testing was subjected to a heating process equivalent to a total of three solder reflow steps using a conveyor-type reflow apparatus (Antom UNI-5016F) at a maximum measured temperature of 260°C in an atmospheric environment, and the reflow resistance was evaluated according to the following criteria. ◎: No voids in the 3rd pass (very good) ○: Void occurred on the 3rd pass (good) △: Void appears on the second pass (usable) ×: Void occurs on the first pass (unusable)

[0090] <3. Laser peelability> For the laminates after the reflow resistance tests of Examples 1 to 36 and Comparative Examples 1 to 7, laser irradiation was performed from the glass surface using a UV laser marker (Keyence laser marker, MD-U1000C, laser wavelength 355 nm (laser)). Only for Example 36, laser irradiation was performed using an IR laser marker (Keyence laser marker, MD-X2500, laser wavelength 1064 nm) as the laser marker. 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 to 5. 300 mJ / cm or less ◎: The total energy amount required for peeling is 300 mJ / cm 2 Less. (Very good) ○: The total energy amount required for peeling is 300 mJ / cm 2 Or more and less than 600 mJ / cm 2 Less. (Good) △: The total energy amount required for peeling is 600 mJ / cm 2 Or more and less than 1000 mJ / cm 2 Less. (Usable) ×: The total energy amount required for peeling is 1000 mJ / cm 2 Or more (Unusable)

[0091] <4. Warpage of the substrate after peeling of the support> For the laminates after the laser peelability tests of Examples 1 to 36 and Comparative Examples 1 to 7, after peeling the support, a member with a layer made of the temporary fixing adhesive composition remaining when cut into 10 × 10 cm was placed flat with the temporary fixing adhesive on top, and the warpage height at the end was evaluated according to the following criteria ◎: The warpage height at the end is less than 0.5 mm (Very good) ○: The warpage height at the end is 0.5 mm or more and 1 mm or less (Good) △: The warpage height at the end is 1 mm or more and 2 mm or less (Usable) ×: The warpage height at the end is 2 mm or more (Unusable)

[0092] <5. Solvent removability> For the laminates of Examples 1-36 and Comparative Examples 1-7 after laser peelability testing, the support was removed and then immersed in toluene, cyclohexanone, and N-methylpyrrolidone, respectively, heated to 80°C, and evaluated according to the following criteria. The best-performing solvent removal method is shown in Tables 2-5. ◎: The layer consisting of the temporary fixing adhesive composition dissolves to a thickness of 0 μm in less than 20 minutes with any organic solvent (very good). ○: The layer consisting of the temporary fixing adhesive composition dissolves to a thickness of 0 μm in any organic solvent within 20 minutes to 1 hour (good). ×: Regardless of the organic solvent used, the remaining thickness of the layer consisting of the temporary fixing adhesive composition does not become 0 μm within 1 hour. (Not usable)

[0093] <6. Soldering characteristics after dissolution and removal> For the components of Examples 1-36 and Comparative Examples 1-7, which showed the best evaluation results in the solvent removal test described above, printing was performed using a metal mask with solder paste (M705-RGS800Type6, manufactured by Senju Metal Industry Co., Ltd., lead-free solder paste). 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 the components were evaluated according to the following criteria. ○: Allows for soldering without gaps (good) △: Solder does not adhere to some parts of the edges, but soldering is generally possible without problems (usable). ×: Many areas do not accept solder, making practical soldering impossible (unusable).

[0094] [Table 2]

[0095] [Table 3]

[0096] [Table 4]

[0097] [Table 5]

[0098] Temporary fixing adhesive compositions that do not contain resin (A) and organometallic compound (B) exhibit 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 can be partially dissolved and removed with an 80°C organic solvent, this dissolution and removal takes a long time, and the solderability to the component after dissolution and removal is 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 are extremely high, causing severe warping of the component after the support is 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 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, a temporary fixing adhesive composition containing resin (A) and an organometallic compound (B), but containing more than 2 parts by mass of compound (C) having two or more groups that can react with alcoholic hydroxyl groups or phenolic hydroxyl groups other than the organometallic compound (B) per 100 parts by mass of 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, because the member has 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 other methods of removal were not possible. It was difficult to remove the temporary fixing adhesive layer from the component using this method. On the other hand, Examples 1 to 36 of the present invention allow processing at relatively low temperatures, which suppresses warping of the material after laser peeling. Furthermore, the material can be dissolved and removed relatively quickly using a heated solvent, and the solderability of the electrode surface after dissolution and removal is cleaned to a level where there are no problems. As a result, it is possible to process the material quickly and achieve a high degree of cleanliness in the finished product, resulting in excellent productivity. [Explanation of symbols]

[0099] 1 Support 2. Adhesive layer for temporary fixing 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 alcoholic hydroxyl groups or phenolic hydroxyl groups, and is a resin 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 film thickness reduction rate (R) after immersion in an organic solvent, calculated from the following (Equation 1), is 95% or more. A temporary fixing adhesive composition wherein the organic solvent is selected from the group consisting of toluene, cyclohexanone, and N-methylpyrrolidone. (Formula 1) R (%) = (1-(T / 30)) x 100 T: Thickness of the film (μm) after immersing a test piece obtained by heating a 30 μm thick film made of a temporary fixing adhesive composition at 180°C for 1 hour in the aforementioned organic solvent at 80°C for 1 hour.

2. Furthermore, the temporary fixing adhesive composition according to claim 1 contains 2 parts by mass or less of a compound (C) (excluding the organometallic compound (B)) having two or more groups that can react with alcoholic hydroxyl groups or phenolic hydroxyl groups, 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 an organotitanium compound or an organozirconium compound.

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 components, consisting of the following steps (1) to (3). (1) A step of bonding and temporarily fixing a member and a support using the temporary fixing adhesive composition described in claim 1. (2) Process of processing the components that were temporarily fixed in (1) (3) After processing in (2), a step of removing the support by irradiating a layer made of a temporary fixing adhesive composition with a laser.

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 method for removing the support by the method described in any one of claims 7 to 9, wherein a layer made of a temporary fixing adhesive composition remains on a member, and the member is immersed in an organic solvent to remove the layer made of the temporary fixing adhesive composition.

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