Surface protection composition, surface protection film, and method for producing electronic device

Abstract

This surface protection composition can form a protective film able to be washed with water after at least one type of treatment selected from between irradiation with light and heating. The surface protection composition contains: a polymer (A) having a crosslinkable group; an acid generator (B) including at least one type of selected from among a photo-acid generator and a thermal acid generator; and an acid-dissociable crosslinking agent (C) which reacts with the crosslinkable group in the polymer (A) and can form an acid-dissociable crosslinked structure.

Description

Surface protection composition, surface protection film, and method for manufacturing electronic devices

[0001] The present invention relates to a surface protection composition, a surface protection film, and a method for manufacturing an electronic device.

[0002] Examples of surface protective film technologies used in the manufacture of electronic devices include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 describes a semiconductor processing tape comprising a water-soluble film containing a polymer compound with a weight-average molecular weight of 200,000 or more and a low-molecular-weight compound with a molecular weight of 800 or less, laminated with a surface protection tape that protects the circuit surface of a semiconductor wafer. Furthermore, Patent Document 1 describes that it is possible to provide a semiconductor processing tape that achieves both grooving resistance and wafer adhesion while enabling removal by washing with unheated water.

[0004] Patent Document 2 describes a surface protection composition for protecting at least one side of a substrate, comprising a polymer having hydrophilic groups in its molecule and a compound that generates an acid or a base upon heating or irradiation with active energy rays. Furthermore, Patent Document 2 describes that it is possible to provide a surface protection composition for forming a protective layer that covers and protects at least one side of a substrate in a manufactured electronic component device, and which can then be removed relatively easily upon contact with a liquid containing water.

[0005] Japanese Patent Publication No. 2023-043723, International Publication No. 2023 / 195445

[0006] The present invention provides a surface protection composition that is solvent-resistant and can form a water-washable protective film after at least one treatment selected from light irradiation and heating.

[0007] The inventors diligently conducted research to achieve the above objectives. As a result, they discovered that a surface protection composition comprising a polymer having a crosslinkable group, an acid generator, and an acid-degradable crosslinking agent can form a protective film that is solvent-resistant and washable with water after at least one treatment selected from light irradiation and heating.

[0008] [1] A surface protection composition that can form a water-washable protective film after at least one treatment selected from light irradiation and heating, comprising: a polymer (A) having crosslinkable groups; an acid generator (B) comprising at least one selected from a photoacid generator and a thermoacid generator; and an acid-degradable crosslinking agent (C) that reacts with the crosslinkable groups of the polymer (A) and is capable of forming an acid-degradable crosslinked structure. [2] The surface protection composition according to [1], wherein the polymer (A) comprises one or more selected from the group consisting of a poly(meth)acrylic polymer having crosslinkable groups, a polyvinyl alcohol polymer having crosslinkable groups, a polyvinylpyrrolidone polymer having crosslinkable groups, and a polyethylene oxide polymer having crosslinkable groups. [3] The surface protection composition according to [1] or [2], wherein the crosslinkable groups comprise one or more selected from the group consisting of a carboxyl group, a ketone group, a hydroxyl group, an amino group, and a vinyl ether group. [4] The surface protection composition according to any one of [1] to [3], wherein the polymer (A) further has an acid-degradable group. [5] The surface protection composition according to [4], wherein the functional group protected by the acid-degradable group comprises at least one selected from the group consisting of carboxyl groups and hydroxyl groups. [6] The surface protection composition according to [4] or [5], wherein the acid-degradable group comprises at least one selected from the group consisting of a group containing an ether bond, a group containing an ester bond, and an alkyl group. [7] The surface protection composition according to [6], wherein the group containing an ether bond comprises an alkyl group having 1 to 8 carbon atoms. [8] The surface protection composition according to any one of [1] to [7], wherein the acid-degradable crosslinking agent (C) comprises two or more crosslinking groups in the molecule, one or more selected from the group consisting of vinyl ether groups, amino groups, carboxyl groups, ketone groups, and hydroxyl groups. [9] The surface protection composition according to any one of [1] to [8], wherein the acid-degradable crosslinking agent (C) comprises one or more selected from the group consisting of polyvinyl ether compounds and polyamine compounds.

[10] The surface protection composition according to any one of [1] to [9], wherein the acid-degradable crosslinking agent (C) has a structure derived from (poly)alkylene glycol.

[11] The surface protection composition according to any one of [1] to

[10] , wherein the acid-degradable crosslinked structure formed by the polymer (A) and the acid-degradable crosslinking agent (C) comprises at least one selected from the group consisting of a group comprising an ether bond, a group comprising an ester bond, and a group comprising an imine bond.

[12] The surface protection composition according to any one of [1] to

[11] , wherein the weight-average molecular weight (Mw) of the polymer (A), measured by gel permeation chromatography, is 5,000 or more and 10,000,000 or less on a polystyrene basis.

[13] The surface protection composition according to any one of [1] to

[12] , wherein the acid generator (B) comprises a photoacid generator.

[14] The surface protection composition according to

[13] , wherein the photoacid generator comprises one or more selected from a sulfonium salt type photoacid generator, an iodonium salt type photoacid generator, and a nonionic type photoacid generator.

[15] The surface protection composition according to any one of [1] to

[14] , wherein the content of the acid generator (B) in the surface protection composition is 0.5 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the polymer (A).

[16] The surface protection composition according to any one of [1] to

[15] , wherein when the following <Method 1> is performed, the film made of the surface protection composition satisfies at least one of the following conditions: (1) it does not dissolve in propylene glycol monomethyl ether acetate, (2) only the adhesion marks of propylene glycol monomethyl ether acetate remain, (3) it swells, and (4) it becomes a thin film but the film remains on the substrate surface. <Method 1> A film with a thickness of 5 ± 5 μm made of the surface protection composition containing an acid-degradable crosslinked structure is formed on a substrate. Then, one drop of propylene glycol monomethyl ether acetate (PGMEA) is applied to the film and left for 2 minutes, after which the PGMEA is wiped off and the state of the film is observed.

[17] A surface protective composition according to any one of [1] to

[16] , wherein when the following Method 2 is performed, the film made of the surface protective composition does not dissolve in water and adheres closely to the substrate. <Method 2> A film with a thickness of 5 ± 5 μm made of the surface protective composition containing an acid-degradable crosslinked structure is formed on a substrate.Next, the laminate consisting of the substrate and the film is immersed in purified water for 10 minutes, then the laminate is removed from the purified water and the state of the film is observed.

[18] The surface protection composition according to any one of [1] to

[17] , wherein the dissolution time or peeling time of the surface protection composition when the following <Method 3> is performed is 30 minutes or less. <Method 3> A film with a thickness of 5 ± 5 μm made of the surface protection composition containing an acid-degradable crosslinked structure is formed on a substrate. Next, the laminate consisting of the substrate and the film is irradiated with ultraviolet light from the film side under conditions that decompose the acid-degradable crosslinked structure. Next, the laminate consisting of the substrate and the film is immersed in purified water and the time until all of the film dissolves or peels off in the purified water (dissolution time or peeling time (minutes)) is measured.

[19] The surface protection composition according to any one of [1] to

[18] , wherein the pH of the water used for the water washing, measured in accordance with JIS Z 8802:2011, is 5.0 or more and 9.0 or less.

[20] A surface protection composition according to any one of [1] to

[19] , used to form a surface protection film for protecting the surface of an electronic component.

[21] The surface protection composition according to

[20] , wherein the surface protection film is a surface protection film that protects the surface of an electronic component and is ultimately removed.

[22] A surface protection film comprising a film formed by the surface protection composition according to any one of [1] to

[21] .

[23] A method for manufacturing an electronic device, comprising a cleaning step 1 of cleaning the surface protection film P of an electronic component having a surface protection film P formed by the surface protection composition according to any one of [1] to

[21] , after performing at least one treatment selected from light irradiation and heating on the surface protection film P.

[24] The method for manufacturing an electronic device according to

[23] , further comprising a step of bonding the side of the electronic component opposite to the side with the surface protection film P to a substrate U before the cleaning step 1.

[25] A method for manufacturing an electronic device according to

[23] or

[24] , further comprising a DC step of dicing a structure R comprising, in this order, a dicing tape, the surface protective film P, and the electronic component, before the cleaning step 1.

[26] The method for manufacturing an electronic device according to

[25] , further comprising a temporary fixing material and a substrate Q in this order on the side of the structure R opposite to the surface protective film P of the electronic component.

[27] The method for manufacturing an electronic device according to

[26] , further comprising a peeling step of peeling the temporary fixing material and the substrate Q from the structure R before the DC step.

[28] The method for manufacturing an electronic device according to

[26] or

[27] , further comprising a step of washing the temporary fixing material from the structure R with an organic solvent before the DC step.

[29] The method for manufacturing an electronic device according to any one of

[26] to

[28] , further comprising a step of preparing a structure S comprising the electronic component, the temporary fixing material and the substrate Q in this order, and a BG step of back grinding the side of the structure S opposite to the side of the electronic component that is facing the temporary fixing material.

[30] The method for manufacturing an electronic device according to any one of

[23] to

[29] , further comprising a step of laminating other electronic components on the side of the electronic component whose surface protective film P has been washed after the washing step 1.

[31] A method for manufacturing an electronic device according to any one of

[23] to

[30] , wherein the cleaning solution in the cleaning step 1 comprises one or more selected from the group consisting of organic solvents and water.

[32] A method for manufacturing an electronic device according to any one of

[23] to

[31] , wherein the electronic component has through electrodes.

[0009] According to the present invention, a surface protection composition is available that has solvent resistance and can form a protective film that can be washed with water after at least one treatment selected from light irradiation and heating.

[0010] This is a schematic cross-sectional view showing the manufacturing method of the electronic device according to the first embodiment. This is a schematic cross-sectional view showing the manufacturing method of the electronic device according to the second embodiment.

[0011] Embodiments of the present invention will be described below. In this specification, unless otherwise specified, "A to B" indicating a numerical range means A or greater and B or less.

[0012] <Surface Protection Composition> The surface protection composition of this embodiment is a surface protection composition that can form a water-washable protective film after at least one treatment selected from light irradiation and heating, and comprises a polymer (A) having crosslinkable groups, an acid generator (B) containing at least one selected from a photoacid generator and a thermoacid generator, and an acid-degradable crosslinking agent (C) that reacts with the crosslinkable groups of polymer (A) and can form an acid-degradable crosslinked structure.

[0013] The surface protection composition of this embodiment contains a polymer (A) and an acid-degradable crosslinking agent (C), so that an acid-degradable crosslinked structure can be formed in the resulting protective film, and as a result, the solvent resistance of the resulting protective film can be improved. Furthermore, since the surface protection composition of this embodiment contains an acid generator (B), when the resulting protective film is subjected to at least one treatment selected from light irradiation and heating, the acid generator (B) generates acid, and the acid-degradable crosslinked structure formed in the protective film can be decomposed by the acid. This improves the hydrophilicity of the protective film and makes it possible to wash the protective film with water. Hereinafter, the property that the resulting protective film can be washed with water after being subjected to at least one treatment selected from light irradiation and heating will be referred to as switching water washability.

[0014] The water used for washing the resulting protective film is preferably one or more selected from the group consisting of ion-exchanged water, pure water, purified water, and distilled water, from the viewpoint of suppressing damage to electronic components. Furthermore, the pH of the water used for washing the resulting protective film, as measured in accordance with JIS Z 8802:2011, is preferably 5.0 to 9.0, more preferably 5.5 to 8.0, even more preferably 6.0 to 7.5, and even more preferably 6.0 to 7.0, from the viewpoint of suppressing damage to electronic components.

[0015] (Polymer (A)) Polymer (A) has crosslinkable groups from the viewpoint of improving the solvent resistance of the resulting protective film. The crosslinkable groups in polymer (A) react with the acid-degradable crosslinking agent (C) to form an acid-degradable crosslinked structure. Polymer (A) preferably comprises one or more selected from the group consisting of a poly(meth)acrylic polymer having crosslinkable groups, a polyvinyl alcohol polymer having crosslinkable groups, a polyvinylpyrrolidone polymer having crosslinkable groups, and a polyethylene oxide polymer having crosslinkable groups, and more preferably comprises a poly(meth)acrylic polymer having crosslinkable groups.

[0016] From the viewpoint of further improving the solvent resistance of the resulting protective film, the crosslinkable groups in polymer (A) preferably include one or more selected from the group consisting of carboxyl groups, ketone groups, hydroxyl groups, amino groups, and vinyl ether groups, and more preferably include one or more selected from the group consisting of carboxyl groups, ketone groups, and hydroxyl groups.

[0017] The crosslinkable poly(meth)acrylic polymer preferably contains a crosslinkable structural unit (b). The crosslinkable structural unit (b) in the crosslinkable poly(meth)acrylic polymer preferably contains a structural unit derived from one or more monomers (b) selected from the group consisting of (meth)acrylates containing carboxyl groups and (meth)acrylates containing ketone groups, and more preferably contains a structural unit derived from one or more monomers (b) selected from the group consisting of (meth)acrylates containing carboxyl groups. The (meth)acrylate containing ketone groups preferably contains one or more selected from the group consisting of 2-(acetoacetyloxy)ethyl (meth)acrylate and diacetone acrylamide, and more preferably contains 2-(acetoacetyloxy)ethyl (meth)acrylate. The (meth)acrylate having a carboxyl group preferably comprises one or more selected from the group consisting of (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid, and more preferably comprises (meth)acrylic acid.

[0018] When a crosslinkable poly(meth)acrylic polymer contains a structural unit (b) derived from monomer (b), the content of structural unit (b) is preferably 1 mol% to 50 mol%, more preferably 2 mol% to 45 mol%, even more preferably 3 mol% to 40 mol%, even more preferably 4 mol% to 35 mol%, and even more preferably 5 mol% to 30 mol%, when the total content of structural units in the crosslinkable poly(meth)acrylic polymer is taken as 100 mol%, from the viewpoint of further improving the solvent resistance of the resulting protective film.

[0019] From the viewpoint of further improving the balance between the water resistance and switching water washability of the resulting protective film, polymer (A) preferably further has acid-degradable groups. From the viewpoint of further improving the balance between the water resistance and switching water washability of the resulting protective film, the acid-degradable groups are preferably those that are decomposed by the acid generated by the acid generator (B) when the protective film made of the surface protective composition is subjected to at least one treatment selected from light irradiation and heating, resulting in the generation of hydrophilic functional groups. As a result, when the protective film made of the surface protective composition is subjected to at least one treatment selected from light irradiation and heating, the acid generator (B) generates acid, and the acid-degradable groups of polymer (A) are removed, i.e., acid-decomposed, generating hydrophilic groups and improving the switching water washability.

[0020] From the viewpoint of further improving the balance between the water resistance and switching water washability of the resulting protective film, the acid-degradable groups in polymer (A) preferably include at least one selected from the group consisting of a group containing an ether bond, a group containing an ester bond, and an alkyl group, more preferably include at least one selected from the group consisting of a group containing an ether bond and an alkyl group, even more preferably include a group containing an ether bond that includes an alkyl group having 1 to 8 carbon atoms, and even more preferably include a group containing an ether bond that includes an alkyl group having 1 to 4 carbon atoms.

[0021] The acid-degradable groups in polymer (A) preferably include groups containing ether bonds. This ensures that the acid-degradable groups are more reliably deprotected after at least one treatment selected from light irradiation and heating, thereby improving the water washability of the resulting protective film. The ether-bonding group preferably includes one or more selected from the group consisting of ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, butoxyethyl group, isobutoxyethyl group, (cyclohexyloxy)ethyl group, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl group, and tetrahydropyranyl group, from the viewpoint of further improving the switching water washability of the resulting protective film. More preferably, it includes one or more selected from the group consisting of ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, butoxyethyl group, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl group, and tetrahydropyranyl group. Even more preferably, it includes one or more selected from the group consisting of ethoxyethyl group, propoxyethyl group, isopropoxyethyl group, butoxyethyl group, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl group.

[0022] Furthermore, the group containing the ether bond preferably includes an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, even more preferably an alkylene group having 1 to 2 carbon atoms, even more preferably an ethylene group, and even more preferably a 1,1-ethylene group.

[0023] The group containing the ether bond preferably includes an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. Furthermore, when the group containing the ether bond includes an alkyl group having 1 to 8 carbon atoms, the alkyl group is preferably linear in shape, from the viewpoint of further improving the switching water washability of the resulting protective film.

[0024] If the crosslinkable poly(meth)acrylic polymer further contains acid-degradable groups, the crosslinkable poly(meth)acrylic polymer preferably contains structural units (a) derived from (meth)acrylate (a) having acid-degradable groups. The (meth)acrylate (a) having acid-degradable groups in the structural units (a) of the crosslinkable poly(meth)acrylic polymer preferably contains methacrylate having acid-degradable groups, from the viewpoint of improving the balance of water resistance, switching water washability, and coating film properties of the resulting protective film.

[0025] When a crosslinkable poly(meth)acrylic polymer further contains structural units (a) derived from (meth)acrylate (a) having acid-degradable groups, the content of structural units (a) is preferably 50 mol% to 99 mol%, more preferably 55 mol% to 98 mol%, even more preferably 60 mol% to 97 mol%, even more preferably 65 mol% to 96 mol%, and even more preferably 70 mol% to 95 mol%, when the total content of structural units in the crosslinkable poly(meth)acrylic polymer is taken as 100 mol%, in order to further improve the balance of water resistance and switching water washability of the resulting protective film.

[0026] The functional group protected by the acid-decomposable group in the polymer (A) preferably contains at least one selected from the group consisting of a carboxyl group and a hydroxyl group from the viewpoint of further improving the performance balance between the water resistance and the switching water washability of the resulting protective film. Thereby, when at least one treatment selected from light irradiation and heating is performed on the protective film made of the surface protection composition, the acid generator (B) generates an acid, and the acid-decomposable group of the polymer (A) is eliminated by the acid, that is, acid-decomposed, and at least one hydrophilic group selected from the group consisting of a carboxyl group and a hydroxyl group is generated. Since the product derived from the polymer (A) after acid-decomposing the acid-decomposable group has a hydrophilic group, the hydrophilicity of the protective film made of the surface protection composition is improved, and the switching water washability can be improved. Note that "protected by an acid-decomposable group" means being modified with an acid-decomposable group that is eliminated by an acid, that is, acid-decomposed. Further, the product derived from the polymer (A) after acid-decomposing the acid-decomposable group represents the polymer (A) after the acid-decomposable group is eliminated by acid decomposition.

[0027] The weight average molecular weight (Mw) in terms of polystyrene, measured by gel permeation chromatography of the polymer (A), is preferably 5,000 or more and 10,000,000 or less, more preferably 10,000 or more and 1,000,000 or less, still more preferably 15,000 or more and 500,000 or less, still more preferably 20,000 or more and 180,000 or less, still more preferably 25,000 or more and 100,000 or less, still more preferably 30,000 or more and 80,000 or less. When the weight average molecular weight (Mw) in terms of polystyrene, measured by gel permeation chromatography of the polymer (A), is within the above range, the performance balance between the solvent resistance and the switching water washability of the resulting protective film can be further improved.

[0028] The Mw / Mn ratio, calculated from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polymer (A) measured by gel permeation chromatography in polystyrene terms, is preferably 1.0 to 10.0, more preferably 1.5 to 8.0, even more preferably 2.0 to 6.0, and even more preferably 2.5 to 4.5. By having the Mw / Mn ratio, calculated from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polymer (A) measured by gel permeation chromatography in polystyrene terms, within the above range, the balance between the solvent resistance and switching water washability of the resulting protective film can be further improved.

[0029] The weight-average molecular weight (Mw) and Mw / Mn of polymer (A), measured by gel permeation chromatography in terms of polystyrene, can be adjusted in the synthesis of polymer (A) described later by appropriately adjusting conditions such as the type of polymerization initiator, polymerization temperature, polymerization pressure, and polymerization time.

[0030] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polymer (A) can be measured, for example, by gel permeation chromatography (GPC) under the following conditions: (Conditions) Detector: Differential refractive index detector Eluent: Tetrahydrofuran Column temperature: 40°C Flow rate: 1.0 mL / min

[0031] (Synthesis Method of Polymer (A)) The synthesis of the polymer (A) of the present embodiment can be carried out by a method known per se as appropriate. For example, when the polymer (A) is a poly(meth)acrylic polymer having a crosslinkable group and an acid-degradable group, a (meth)acrylate (a) having an acid-degradable group and a monomer (b) having a crosslinkable group can be polymerized in the presence of a polymerization catalyst or a polymerization initiator known per se as appropriate. As the polymerization initiator, for example, one or more selected from the group consisting of azo compounds, organic peroxides, and photoinitiators can be used. As the azo compound, for example, 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile) can be used. When an azo compound is used as the polymerization initiator, for example, a solution containing (meth)acrylate (a), monomer (b), and the azo compound is heated at 50 to 80 °C or 50 to 110 °C for 1 hour or more and 20 hours or less to polymerize the monomers. As the photoinitiator, for example, 1-hydroxycyclohexyl phenyl ketone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide can be used. When a photoinitiator is used as the polymerization initiator, for example, a solution containing (meth)acrylate (a), monomer (b), and the photoinitiator is irradiated with UV at a UV intensity of 20 to 50 mW / cm ２ for about 10 to 60 minutes to polymerize the monomers. As a commercially available product of the organic peroxide, Perbutyl (registered trademark) O (manufactured by NOF Corporation) can be used.

[0032] (Acid Generator (B)) The acid generator (B) of the present embodiment contains at least one selected from a photoacid generator and a thermal acid generator, and preferably contains a photoacid generator from the viewpoint of reducing thermal damage to the adherend when generating an acid from the acid generator.

[0033] The photoacid generator of this embodiment preferably comprises one or more selected from sulfonium salt type photoacid generators, iodonium salt type photoacid generators, and nonionic type photoacid generators, from the viewpoint of further improving the balance of water resistance and switching water washability of the resulting protective film; more preferably comprises one or more selected from sulfonium salt type photoacid generators and nonionic type photoacid generators; even more preferably comprises one or more selected from sulfonium salt type photoacid generators and nonionic type photoacid generators having a diazomethane structure; and even more preferably comprises a sulfonium salt type photoacid generator.

[0034] Examples of sulfonium salt type photoacid generators include triarylsulfonium salts and diarylsulfonium salts, preferably containing a triarylsulfonium salt, more preferably containing a triarylsulfonium salt with an anion selected from the group consisting of hexafluorophosphate, hexafluoroantimonic acid, and tetrakis(pentafluorophenyl)borate, and even more preferably containing a triarylsulfonium salt with tetrakis(pentafluorophenyl)borate as an anion. A commercially available product is CPI-110B (manufactured by Sunapro Co., Ltd.).

[0035] Examples of nonionic photoacid generators include imidosulfonates, diazodisulfones, and oximesulfonates, with diazodisulfones being preferred. Examples of imidosulfonates include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, and N-(trifluoromethylsulfonyloxy)diphenylmaleimide. Examples of diazodisulfones include bis(tert-butylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(4-methylphenylsulfonyl)diazomethane. Examples of oximesulfonates include α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile-phenylacetonitrile, and α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile.

[0036] Examples of thermal acid generators include aromatic sulfonium salts, aromatic iodonium salts, ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

[0037] Here, the non-acid products after acid generation by the acid generator (B) preferably have a molecular weight of 20 to 1,200, more preferably 30 to 1,000, even more preferably 50 to 800, even more preferably 100 to 500, even more preferably 150 to 350, and 200 to 300.

[0038] The content of the acid generator (B) in the surface protection composition of this embodiment is preferably 0.5 parts by mass or more and 50.0 parts by mass or less, more preferably 1.0 part by mass or more and 45.0 parts by mass or less, even more preferably 1.3 parts by mass or more and 40.0 parts by mass or less, and even more preferably 1.5 parts by mass or more and 38.0 parts by mass or less, per 100 parts by mass of polymer (A).

[0039] (Acid-degradable crosslinking agent (C)) The acid-degradable crosslinking agent (C) of this embodiment is a crosslinking agent that reacts with the crosslinkable groups in the polymer (A) and can form an acid-degradable crosslinked structure. The acid-degradable crosslinked structure is formed, for example, by heating, which causes a crosslinking reaction between the crosslinkable groups in the polymer (A) and the acid-degradable crosslinking agent (C). The crosslinking reaction between the crosslinkable groups in the polymer (A) and the acid-degradable crosslinking agent (C) may be carried out when forming a protective film using the surface protective composition of this embodiment, by heating the surface protective composition before forming the protective film, or by heating the protective film after forming the protective film. However, if the acid generator (B) in the surface protective composition of this embodiment includes a thermal acid generator, it is preferable to cause the crosslinking reaction between the crosslinkable groups in the polymer (A) and the acid-degradable crosslinking agent (C) at a temperature lower than the heating temperature required for the thermal acid generator to generate acid. The acid-degradable crosslinking agent (C) of this embodiment contains two or more crosslinkable groups selected from the group consisting of vinyl ether groups, amino groups, carboxyl groups, ketone groups, and hydroxyl groups, and more preferably contains two or more crosslinkable groups selected from the group consisting of vinyl ether groups and amino groups.

[0040] The acid-degradable crosslinking agent (C) of this embodiment comprises one or more selected from the group consisting of polyvinyl ether compounds and polyamine compounds. Here, a polyvinyl ether compound means a compound in which two or more vinyl groups are bonded in the molecule via ether bonds, and a polyamine compound means a compound having two or more amino groups in the molecule.

[0041] The polyvinyl ether compound preferably includes a divinyl ether compound, from the viewpoint of further improving the balance of water resistance, solvent resistance, and switching water washability of the resulting protective film. The divinyl ether compound preferably includes one or more selected from the group consisting of diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,4-cyclohexanedimethanol divinyl ether, and preferably includes one or two selected from the group consisting of diethylene glycol divinyl ether and triethylene glycol divinyl ether, from the viewpoint of further improving the balance of water resistance and switching water washability of the resulting protective film.

[0042] The polyamine compound preferably includes a diamine compound, from the viewpoint of further improving the balance between the water resistance and switching water washability of the resulting protective film. The diamine compound preferably includes one or more selected from the group consisting of dihydrazides and alkylenediamines, and more preferably includes one or more selected from the group consisting of dihydrazides with 2 to 8 carbon atoms and alkylenediamines with 2 to 8 carbon atoms, and more preferably includes one or two selected from the group consisting of adiposihydrazides and ethylenediamines.

[0043] When the acid-degradable crosslinking agent (C) of this embodiment contains a divinyl ether compound, the acid-degradable crosslinking agent (C) preferably has a structure derived from (poly)alkylene glycol, more preferably from (poly)ethylene glycol, even more preferably from (poly)ethylene glycol with a repeating unit number of 1 to 4, and even more preferably from (poly)ethylene glycol with a repeating unit number of 1 to 3.

[0044] The acid-degradable crosslinked structure formed by the polymer (A) and the acid-degradable crosslinking agent (C) preferably includes at least one selected from the group consisting of a group containing an ether bond, a group containing an ester bond, and a group containing an imine bond, from the viewpoint of improving the balance of solvent resistance, water resistance, and switching water washability of the resulting protective film.

[0045] The content of the acid-degradable crosslinking agent (C) in the surface protection composition of this embodiment is preferably 0.05 parts by mass or more and 50 parts by mass or less, more preferably 0.1 parts by mass or more and 45 parts by mass or less, even more preferably 0.2 parts by mass or more and 40 parts by mass or less, and even more preferably 0.3 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of polymer (A). When the acid-degradable crosslinking agent (C) contains a divinyl ether compound, the content of the acid-degradable crosslinking agent (C) in the surface protection composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 2 parts by mass or more and 45 parts by mass or less, even more preferably 3 parts by mass or more and 40 parts by mass or less, and even more preferably 4 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of polymer (A). When the acid-degradable crosslinking agent (C) contains a diamine compound, the content of the acid-degradable crosslinking agent (C) in the surface protective composition is preferably 0.05 parts by mass or less, more preferably 0.10 parts by mass or more and 8 parts by mass or less, even more preferably 0.15 parts by mass or more and 5 parts by mass or less, and even more preferably 0.20 parts by mass or more and 4 parts by mass or less, per 100 parts by mass of polymer (A).

[0046] <Method for Producing the Surface Protection Composition> The surface protection composition of this embodiment can be produced by any known method. For example, it can be produced by mixing the polymer (A), acid generator (B), acid-degradable crosslinking agent (C), and solvent described above using a mixing rotor or the like until homogeneous. As the solvent, one or more selected from the group consisting of water, acetone, ethyl acetate, toluene, ethanol, propylene carbonate, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and butyl acetate can be used. Only one solvent may be used, or two or more may be used in combination.

[0047] <Formation of surface protection composition into a film> The surface protection composition of this embodiment can be formed into a film by any known method. For example, the surface protection composition can be applied to a substrate such as glass or a silicon wafer to a thickness of about 1 to 120 μm, and then dried to form a film. The drying conditions are preferably a temperature of 30°C to 200°C, more preferably 40°C to 190°C, and preferably for 1 minute to 72 hours, more preferably 3 minutes to 72 hours. As described above, the crosslinking reaction between the crosslinkable group in the polymer (A) and the acid-degradable crosslinking agent (C) may occur when the surface protection composition is applied to the substrate and dried to form a film.

[0048] <Method for Cleaning a Film Composed of a Composition for Surface Protection> The cleaning of the film composed of the composition for surface protection (i.e., the surface protection film) of the present embodiment is carried out as follows. It is assumed that the crosslinking reaction between the crosslinkable group in the polymer (A) and the acid-decomposable crosslinking agent (C) has already been carried out either before the composition for surface protection is formed into a film by drying or after the composition for surface protection is formed into a film by drying. When the acid generator (B) contains a photoacid generator, it is preferable to perform light irradiation on the film composed of the composition for surface protection of the present embodiment formed on a substrate or the like. By performing light irradiation, the film composed of the composition for surface protection can be peeled off or dissolved from the substrate or the like, and the water washability can be further improved. The light irradiation is specifically UV irradiation. Regarding the illuminance, it is preferably 5 mW / cm ２ or more and 9000 mW / cm ２ or less, more preferably an illuminance of 5 mW / cm ２ or more and 8500 mW / cm ２ or less, even more preferably an illuminance of 5 mW / cm ２ or more and 8000 mW / cm ２ or less. Regarding the irradiation time, it is preferably 5 seconds or more and 250 seconds or less, more preferably 10 seconds or more and 200 seconds or less. Regarding the integrated light quantity, it is preferably 200 mJ / cm ２ or more and 300 J / cm ２ or less, more preferably 200 mJ / cm ２ or more and 250 J / cm ２ or less, even more preferably 500 mJ / cm ２ or more and 250 J / cm ２The following steps are carried out under ultraviolet conditions with a wavelength of preferably 200 nm to 420 nm, more preferably 250 nm to 380 nm. If the acid generator (B) includes a thermal acid generator, it is preferable to heat the film made of the surface protection composition of this embodiment that is formed on a substrate or the like. The heating temperature is preferably 100°C to 200°C, more preferably 120°C to 180°C, and even more preferably 140°C to 160°C. The heating time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 15 minutes. After heating, light irradiation, or heating and light irradiation, it is preferable to immerse the film made of the surface protection composition and the substrate or the like in water. Alternatively, the film made of the surface protection composition can be washed with water by performing one or more of the following methods selected from the group consisting of jet washing, two-fluid washing, spray washing, shower washing, and ultrasonic washing.

[0049] After cleaning under the above conditions, it is preferable that the entire film made of the surface protection composition peels off from the substrate, and more preferably that the entire film made of the surface protection composition dissolves. By completely dissolving the film made of the surface protection composition, the residue of the film made of the surface protection composition on the substrate after cleaning can be further suppressed. In addition, the treatment of wastewater generated when cleaning the film made of the surface protection composition becomes easier.

[0050] Furthermore, the solvent resistance of the surface protective film composition of this embodiment is evaluated as follows. A film with a thickness of 5 ± 5 μm made of the surface protective film composition of this embodiment, which includes an acid-degradable crosslinked structure, is formed on a substrate such as a glass plate or a silicon wafer. Then, one drop of propylene glycol monomethyl ether acetate (PGMEA) is applied to the film and left to stand for 2 minutes. After wiping off the PGMEA, the state of the film is observed. At that time, it is preferable that the film made of the surface protective film composition of this embodiment, which includes an acid-degradable crosslinked structure, satisfies at least one of the following conditions: (1) it does not dissolve in propylene glycol monomethyl ether acetate, (2) only the adhesion trace of propylene glycol monomethyl ether acetate remains, (3) it swells, and (4) it becomes a thin film but the film remains on the substrate surface. This further improves the solvent resistance of the film made of the surface protective film composition.

[0051] The solvent resistance of the surface protection composition of this embodiment can be evaluated, for example, as described in <Method 1> below.

[0052] <Method 1> A film with a thickness of 5 ± 5 μm is formed on a substrate using the surface protection composition of this embodiment, which includes an acid-degradable crosslinked structure. Then, one drop of propylene glycol monomethyl ether acetate (PGMEA) is applied to the film and left to stand for 2 minutes, after which the PGMEA is wiped off and the state of the film is observed.

[0053] The water resistance of the surface protection composition of this embodiment can be evaluated, for example, as described in <Method 2> below. A film with a thickness of 5 ± 5 μm made of the surface protection composition of this embodiment, which includes an acid-degradable crosslinked structure, is formed on a substrate such as a glass plate or a silicon wafer. Then, the laminate consisting of the substrate and the film is immersed in purified water for 10 minutes, and when the laminate is removed from the purified water, it is preferable that the film made of the surface protection composition of this embodiment does not dissolve in water and adheres closely to the substrate. This further improves the water resistance of the film made of the surface protection composition.

[0054] <Method 2> A film with a thickness of 5 ± 5 μm is formed on a substrate using the surface protection composition of this embodiment, which includes an acid-degradable crosslinked structure. Next, the laminate consisting of the substrate and the film is immersed in purified water for 10 minutes, and then the laminate is removed from the purified water and the state of the film is observed.

[0055] The switching cleanability of the surface protection composition of this embodiment can be evaluated, for example, as described in <Method 3> below.

[0056] <Method 3> A film with a thickness of 5 ± 5 μm made of the surface protection composition of this embodiment, which includes an acid-degradable crosslinked structure, is formed on a substrate. Next, the laminate consisting of the substrate and the film is irradiated with ultraviolet light from the film side under conditions that decompose the acid-degradable crosslinked structure. Next, the laminate consisting of the substrate and the film is immersed in purified water, and the time (dissolution time or peeling time (minutes)) until the entire film dissolves or peels off in the purified water is measured. As ultraviolet irradiation conditions that decompose the acid-degradable crosslinked structure, for example, the following light irradiation conditions A or B can be used. (Light irradiation condition A) The substrate with the film is placed on a SUS stand, and the illuminance is 7705 mW / cm². ２ Irradiation time 30 seconds, cumulative light intensity 231 J / cm² ２ Under these conditions, ultraviolet light with a wavelength of 365 nm is irradiated onto the film-side surface of the substrate. (Light irradiation conditions B) The substrate with the obtained film is placed on a SUS stand, and the irradiance is set to 20 mW / cm². ２ Irradiation time 150 seconds, integrated light intensity 3000 mJ / cm² ２ Under these conditions, ultraviolet light including a wavelength of 365 nm is irradiated onto the film-side surface of the substrate using a high-pressure mercury lamp.

[0057] When Method 3 described above is performed, the dissolution time or peeling time of the surface protection composition is preferably within 30 minutes, more preferably 25 minutes or less, even more preferably 20 minutes or less, even more preferably 15 minutes or less, even more preferably 12 minutes or less, and even more preferably 10 minutes or less, from the viewpoint of further improving the switching water washability. There is no lower limit to the dissolution time of the surface protection composition, but it may be, for example, 10 seconds or more, or 30 seconds or more.

[0058] <Surface protective film> The surface protective film of this embodiment includes a film formed by the surface protective composition of this embodiment. The surface protective film of this embodiment may be formed by coating the surface protective composition of this embodiment onto a substrate or the like to form a film, or it may be formed as a film.

[0059] The surface protective film of this embodiment can be used as a surface protective film that protects the surface of electronic components and is ultimately removed during the manufacturing process of electronic devices. Examples of electronic components include semiconductor chips such as ICs, LSIs, discrete components, light-emitting diodes, and photodetectors, as well as semiconductor panels, semiconductor packages, and wafers.

[0060] The thickness of the surface protective film in this embodiment is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more, from the viewpoint of further improving the balance of water resistance, solvent resistance, and surface protection performance, and is 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less, from the viewpoint of further improving water washability.

[0061] <Method for Manufacturing an Electronic Device> (First Embodiment) The first embodiment of the method for manufacturing an electronic device according to this embodiment will be described with reference to Figure 1. Figure 1 is a schematic cross-sectional view showing the method for manufacturing an electronic device according to the first embodiment.

[0062] (Cleaning Step 1) The manufacturing method of the electronic device of this embodiment includes a cleaning step 1 (Figure 1(h)) in which, after performing at least one treatment selected from light irradiation and heating on the surface protective film P(10) of an electronic component (20) having a surface protective film P(10) formed with the surface protective composition of this embodiment, the surface protective film P(10) is cleaned.

[0063] In this embodiment, the manufacturing method for an electronic device allows for the cleaning of a surface protective film P provided on one surface of an electronic component after performing at least one treatment selected from light irradiation and heating. Therefore, before performing at least one treatment selected from light irradiation and heating, the surface protective film P can protect the electronic component from external particles, external stresses, etc. On the other hand, after performing at least one treatment selected from light irradiation and heating, the surface protective film P can be cleaned, thereby reducing the residue of the surface protective film P on the surface where it was provided on the electronic component. Thus, residue originating from the surface protective film can be reduced on the surface of the electronic component before and after performing at least one treatment selected from light irradiation and heating.

[0064] The cleaning step 1 (Figure 1(h)) is carried out, for example, as follows: By performing at least one treatment selected from light irradiation and heating on the surface protective film P(10), the structure of the surface protective film P(10) is changed, making it possible to peel or dissolve and remove the surface protective film P(10) from the electronic component (20) with the cleaning solution. As a result, by cleaning the surface protective film P(10) with the cleaning solution, residue originating from the surface protective film on the surface of the electronic component can be further reduced.

[0065] If the acid generator (B) in the surface protective film P (10) contains a photoacid generator, it is preferable to irradiate the surface protective film P (10) with light. Specifically, the light irradiation is UV irradiation, and the illuminance is preferably 5 mW / cm². ２ More than 9000mW / cm ２ Below is a description of a more comfortable illuminance of 5 mW / cm². ２ More than 8500mW / cm ２ More preferably, the illuminance is 5 mW / cm². ２ More than 8000mW / cm ２ The irradiation time is preferably 5 seconds to 250 seconds, more preferably 10 seconds to 200 seconds, and the integrated light intensity is preferably 200 mJ / cm². ２ More than 300J / cm ２ More preferably, 200 mJ / cm² ２ More than 250J / cm ２More preferably, 500 mJ / cm ２ More than 250J / cm ２ The following steps are carried out under ultraviolet conditions with a wavelength of preferably 200 nm to 420 nm, more preferably 250 nm to 380 nm. In addition to light irradiation, heating may also be performed on the surface protective film P(10). By adding heating to light irradiation, the cleanability can be further improved, and thus the residue originating from the surface protective film on the surface of the electronic component can be further reduced. The heating temperature is preferably 100°C to 200°C, more preferably 120°C to 180°C, and even more preferably 140°C to 160°C, from the viewpoint of further improving the dissolution rate of the surface protective film P(10). The heating time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 15 minutes. Light irradiation and heating may be performed simultaneously, or heating may be performed after light irradiation. Furthermore, if the acid generator (B) in the surface protective film P(10) contains a photoacid generator, it is more preferable to irradiate the surface protective film P(10) with light only.

[0066] If the acid generator (B) in the surface protective film P (10) contains a thermal acid generator, it is preferable to heat the surface protective film P (10). The heating temperature is preferably 100°C to 200°C, more preferably 120°C to 180°C, and even more preferably 140°C to 160°C. The heating time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 15 minutes.

[0067] As described above, it is preferable to heat, irradiate with light, or heat and irradiate the surface protective film P (10) and then clean the surface protective film P (10) and the electronic components (20) with a cleaning solution. The cleaning solution in cleaning step 1 (Figure 1(h)) preferably contains one or more selected from the group consisting of organic solvents and water, and more preferably contains water. The water used in the cleaning solution is preferably one or more selected from the group consisting of ion-exchanged water, pure water, purified water, and distilled water, from the viewpoint of suppressing damage to electronic components. The pH of the water used in the cleaning solution, measured in accordance with JIS Z 8802:2011, is preferably pH 5.0 to 9.0, more preferably 5.5 to 8.0, even more preferably 6.0 to 7.5, and even more preferably 6.0 to 7.0, from the viewpoint of suppressing damage to electronic components. The organic solvent includes, for example, one or more selected from the group consisting of ethanol, methanol, isopropanol, butanol, and propylene glycol monomethyl ether acetate. The organic solvent and water may be used individually or in combination of two or more.

[0068] The electronic component (20) to be cleaned in cleaning step 1 (Figure 1(h)) may be a fragmented electronic component (21) that has been fragmented by the DC step (Figure 1(e)) described later.

[0069] (Dicing (DC) Process) The manufacturing method of the electronic device of this embodiment may further include a DC process (Figure 1(e)) in which a structure R (200) comprising a dicing tape (50), a surface protective film P (10), and an electronic component (20) in this order is diced before the cleaning process 1 (Figure 1(h)). Dicing refers to the process of separating the electronic component (20) into individual pieces to produce individual electronic components (21), etc. In the DC process (Figure 1(e)), it is preferable to dice the electronic component (20) in the structure R (200) from the side opposite to the side on which the dicing tape (50) and surface protective film P (10) are provided. As the dicing method, a known method can be selected, and for example, one or more methods selected from the group consisting of plasma dicing, laser dicing, and blade dicing can be adopted. According to the manufacturing method of the electronic device of this embodiment, the surface protective film P(10) can be prevented from dissolving in water or peeling off from the electronic component (20) before at least one treatment selected from light irradiation and heating. Therefore, even when cutting water is used in the blade dicing method, for example, the surface protective film P(10) can perform its surface protective function on the electronic component (20). The dicing tape (50) and the surface protective film P(10) may be bonded together in advance to form an integrated tape. The structure R(200) may be formed by attaching the surface protective film P(10) side of this integrated tape to the electronic component (20).

[0070] In the manufacturing method of the electronic device of this embodiment, the structure R (200) may further include a temporary fixing material (30) and a substrate Q (40) in this order on the side opposite to the surface protective film P (10) of the electronic component (20) (Figure 1(c)). Here, the substrate Q (40) is, for example, a glass plate or a stainless steel plate, and is a layer for supporting the electronic component (20) in the BG process described later (Figure 1(b)). The temporary fixing material (30) is a layer that comes into contact with and adheres to the side of the electronic component (20) opposite to the surface protective film P (10) when the substrate Q (40) is attached to the electronic component (20), and is a layer that is peeled off from the electronic component (20) together with the substrate Q (40) after the BG process described later (Figure 1(b)). Examples of the temporary fixing material (30) include a heat-peelable adhesive resin layer whose adhesive strength decreases with heating, and a radiation-peelable adhesive resin layer whose adhesive strength decreases with radiation.

[0071] (Peeling Process) The manufacturing method of the electronic device of this embodiment may further include a peeling process (Figure 1(d)) in which the temporary fixing material (30) and substrate Q (40) are peeled off from the structure R (200) before the DC process (Figure 1(e)). By peeling off the temporary fixing material (30) and substrate Q (40) from the structure R (200), the electronic components (20) are exposed, so that the electronic components (20) can be diced in the DC process (Figure 1(e)). The operation of peeling off the temporary fixing material (30) and substrate Q (40) from the structure R (200) may be performed manually, but it can generally be performed by a device called an automatic peeling machine.

[0072] Before or after the DC process (Figure 1(e)), a cleaning process (Figure 1(f)) may be performed as needed to clean the surface of the electronic component (20) after the temporary fixing material (30) and substrate Q (40) have been removed. Cleaning methods include wet cleaning such as water cleaning and solvent cleaning, and dry cleaning such as plasma cleaning. In the case of wet cleaning, ultrasonic cleaning may be used in combination. These cleaning methods can be appropriately selected depending on the degree of contamination of the surface of the electronic component (20). According to the manufacturing method of the electronic device of this embodiment, before performing at least one treatment selected from light irradiation and heating, it is possible to suppress the dissolution of the surface protective film P (10) by water or peeling off from the electronic component (20). Therefore, even if water or solvents are used in the cleaning process (Figure 1(f)), the surface protective film P (10) can perform its surface protective function on the electronic component (20).

[0073] Prior to the DC process (Figure 1(e)), the process may further include, if necessary, a step of cleaning the temporary fixing material (30) from the structure R (200) with an organic solvent. According to the manufacturing method of the electronic device of this embodiment, before performing at least one treatment selected from light irradiation and heating, it is possible to suppress the dissolution of the surface protective film P (10) by the organic solvent or peeling off from the electronic component (20), so that even when an organic solvent is used, the surface protective film P (10) can perform its surface protective function on the electronic component (20).

[0074] (Backgrinding (BG) process) In the method for manufacturing an electronic device according to this embodiment, the process may further include, before the DC process (Figure 1(e)), a step of preparing a structure S (100) comprising an electronic component (20), a temporary fixing material (30), and a substrate Q (40) in that order (Figure 1(a)), and a BG process (Figure 1(b)) of backgrinding the side of the structure S (100) opposite to the side of the electronic component (20) that is on the temporary fixing material (30). Such a structure S (100) can be manufactured, for example, by attaching the temporary fixing material (30) and the substrate Q (40) on top of the electronic component (20) in that order (Figure 1(a)).

[0075] Here, back grinding means thinning the electronic component (20) to a predetermined thickness without damaging it. For example, the structure S (100) is fixed to the chuck table of a grinding machine, and the back surface (non-circuit-formed surface) of the electronic component (20) is ground. The back grinding method is not particularly limited, but known grinding methods can be used. Each grinding can be performed while cooling the electronic component (20) and the grinding wheel with water. If necessary, a dry polishing process, which does not use grinding water, can be performed at the end of the grinding process. After back grinding is completed, chemical etching is performed as necessary. Chemical etching is performed by immersing the electronic component (20) in an etching solution selected from the group consisting of an acidic aqueous solution consisting of one or a mixture of hydrofluoric acid, nitric acid, sulfuric acid, acetic acid, etc., or an alkaline aqueous solution such as potassium hydroxide aqueous solution or sodium hydroxide aqueous solution. Etching is performed for purposes such as removing distortion on the back surface of the electronic component (20), further thinning the electronic component (20), removing oxide films, and pre-treatment when forming electrodes on the back surface. The etching solution is selected appropriately according to the above purposes.

[0076] (D2W Bonding Process) Before the cleaning process 1 (Figure 1(h)), the process may further include a step (Figure 1(g)) in which the side of the electronic component (20) (electronic component (21) after fragmentation) opposite to the side with the surface protective film P(10) is bonded to the substrate U(70). Here, it is preferable that the electronic component (20) (electronic component (21) after fragmentation) is directly bonded to the substrate U(70). Such a process is called the D2W bonding (die-to-wafer bonding) process. The substrate U(70) represents, for example, a semiconductor wafer. By directly laminating the electronic component (20) (electronic component (21) after fragmentation) and the substrate U(70), the electronic component (20) (electronic component (21) after fragmentation) and the substrate U(70) can be electrically connected by the through-electrode (22) described later. When the cleaning process described above (Figure 1(f)) is performed, the D2W bonding process (Figure 1(g)) is preferably performed after the cleaning process (Figure 1(f)), and it is preferable that the substrate U (70) is bonded to the cleaned surface of the electronic component (20) (electronic component (21) after fragmentation) in the cleaning process (Figure 1(f)).

[0077] Furthermore, the process may include a step (not shown) of peeling the dicing tape (50) from the surface protective film P (10) before the D2W bonding process (Figure 1(g)). This exposes the surface protective film P (10), allowing for smoother cleaning of the surface protective film P (10) in the cleaning process 1 (Figure 1(h)).

[0078] In the manufacturing method of the electronic device of this embodiment, the electronic component (20) may have a through electrode (22). A through electrode refers to, for example, a through hole formed vertically inside the substrate that is made conductive, and as will be described later, it is used to connect upper and lower electronic components when multiple electronic components are directly stacked. The through electrode (22) can be formed, for example, on the electronic component (20) of the structure S (100) before or after the BG process (Figure 1(b)), and can be manufactured by forming a through hole in the electronic component (20) and then making it conductive by copper plating or the like.

[0079] In the manufacturing method of the electronic device of this embodiment, after the cleaning step 1 (Figure 1(h)), a step (Figure 1(i)) of laminating another electronic component (80) onto the surface of the electronic component (20) (electronic component (21) after fragmentation) from which the surface protective film P (10) has been cleaned may be included. Here, it is preferable that the other electronic component (80) is directly laminated onto the electronic component (20) (electronic component (21) after fragmentation). By directly laminating the other electronic component (80) and the electronic component (20) (electronic component (21) after fragmentation), the electronic components can be electrically connected to each other by the through-electrode (22) described above. According to the manufacturing method of the electronic device of this embodiment, since the residue derived from the surface protective film on the surface of the electronic component (20) (electronic component (21) after fragmentation) can be reduced, connection failures can be further suppressed even when electronic components are directly laminated to each other.

[0080] (Second Embodiment) A second embodiment of the method for manufacturing an electronic device according to this embodiment will be described with reference to Figure 2. Figure 2 is a schematic cross-sectional view showing the method for manufacturing an electronic device according to the second embodiment of the present invention. In the second embodiment, the cleaning step 1 (Figure 2(h)), the DC step (Figure 2(e)), the D2W bonding step (Figure 2(g)), and the lamination step (Figure 2(i)) are carried out in accordance with the first embodiment.

[0081] In a second embodiment of the method for manufacturing an electronic device according to this embodiment, the structure R(200) may further include a surface protective film O(60) on the surface opposite to the surface protective film P(10) of the electronic component (20). If the structure R(200) further includes a surface protective film O(60), the surface protective film O(60) can function as a resist when performing ablation dicing or plasma dicing in the DC process (Figure 2(e)).

[0082] (Cleaning Step 2) After the DC step (Figure 2(e)), the process may further include a cleaning step 2 (Figure 2(f)) in which the surface protective film O(60) is cleaned after being subjected to at least one treatment selected from light irradiation and heating. In cleaning step 2 (Figure 2(f)), residue derived from the surface protective film O(60) on the electronic component (20) after dicing can be further reduced, so that even when the electronic component (20) (electronic component (21) after dicing) is directly bonded to the substrate U(70) in the subsequent D2W bonding step (Figure 2(g)), connection failures and the like can be further suppressed. Cleaning step 2 (Figure 2(f)) can be performed under conditions similar to those of cleaning step 1 (Figure 1(h)) described above, including light irradiation, heating, and cleaning.

[0083] If the structure R(200) includes a surface protective film O(60), the structure R(200) may further include a temporary fixing material (30) and a substrate Q(40) on the surface protective film O(60) in that order (Figure 2(c)). Details of the temporary fixing material (30) and the substrate Q(40) are described in the section on the first embodiment and are therefore omitted here. If the structure R(200) includes a surface protective film O(60), the structure R(200) can be manufactured, for example, by attaching the surface protective film O(60), temporary fixing material (30), and substrate Q(40) on an electronic component (20) in that order (Figure 2(a)).

[0084] (Peeling process) Before the DC process (Figure 2(e)), a peeling process (Figure 2(d)) may be further included to peel the temporary fixing material (30) and the substrate Q (40) from the structure R (200). The peeling process (Figure 2(d)) can be carried out in accordance with the peeling process (Figure 1(d)) in the first embodiment. In the second embodiment, the structure R (200) has a surface protective film O (60) between the electronic component (20) and the temporary fixing material (30). After peeling the temporary fixing material (30) and the substrate Q (40) from the structure R (200), the residue of the temporary fixing material (30) remains on the surface protective film O (60). Since the surface protective film O (60) is cleaned in the cleaning process 2 (Figure 2(f)), it is preferable in that no residue of the temporary fixing material (30) remains on the electronic component (20) compared to the case where there is no surface protective film O (60).

[0085] (Backgrinding (BG) process) The process may further include a step (Figure 2(a)) of preparing a structure T (300) comprising an electronic component (20), a surface protective film O (60), a temporary fixing material (30), and a substrate Q (40) in that order, prior to the DC process (Figure 2(e)), and a BG process (Figure 2(b)) of backgrinding the side of the structure T (300) opposite to the side of the electronic component (20) with the surface protective film O (60). Such a structure T (300) can be manufactured, for example, by attaching the surface protective film O (60), temporary fixing material (30), and substrate Q (40) on top of the electronic component (20) in that order (Figure 2(a)). The BG process (Figure 2(b)) can be carried out by a method similar to the BG process (Figure 1(b)) in the first embodiment.

[0086] The manufacturing method for electronic devices of this embodiment can reduce residue derived from the surface protective film on the surface of electronic components (20) during the manufacturing process of the electronic device. Examples of electronic components include semiconductor chips, semiconductor panels, semiconductor packages, and semiconductor wafers. Furthermore, the electronic device of this embodiment includes, for example, a single electronic component, a package of electronic components, a combination of multiple electronic components, and an electronic device with electronic components or a packaged electronic device mounted on a substrate. Among these, the manufacturing method for electronic devices of this embodiment is preferably used in the manufacture of electronic devices (e.g., semiconductor packages) that are directly stacked and connected to each other without the use of bumps, etc., known as hybrid bonding. More specifically, it is preferably used in electronic devices (e.g., HBM (High Bandwidth Memory)) that have stacked electronic components (e.g., DRAM) equipped with through-electrodes (e.g., through-silicon electrodes (TSVs)). In such electronic devices, electronic components are directly stacked and connected via through electrodes, making connection failures prone to occur due to fine residue (particles) left after tape removal, such as surface protective films, during bonding. According to the manufacturing method of the electronic device of this embodiment, the surface protective film can be cleaned, thereby reducing fine residue on the surface of electronic components and further suppressing connection failures in the electronic device.

[0087] The material and composition of the surface protective film O(60) are not particularly limited, but the surface protective film O(60) can also be made of the same material and has the same composition as the surface protective film P(10).

[0088] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted.

[0089] It should be noted that the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that can achieve the objectives of the present invention are included in the present invention.

[0090] This embodiment will be described in detail below with reference to examples and comparative examples. However, this embodiment is not limited in any way to the descriptions in these examples.

[0091] <Raw Materials> The raw materials used in the examples and comparative examples are as follows: (Polymer (A)) (Structural Unit (a)) ・Structural Unit (a-1): 1-Ethoxyethyl Methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) ・Structural Unit (a-2): (2-Methyl-2-ethyl-1,3-Dioxolan-4-yl)Methyl Acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., MEDOL-10) (Structural Unit (b)) ・Structural Unit (b-1): Acrylic Acid (manufactured by Fujifilm Wako Pure Chemical Corporation) ・Structural Unit (b-2): Methacrylic Acid (manufactured by Fujifilm Wako Pure Chemical Corporation) ・Structural Unit (b-3): 2-(Acetoacetyloxy)ethyl Methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0092] (Acid Generator (B)) ・Acid Generator (B-1): Nonionic photoacid generator: Bis(tert-butylsulfonyl)diazomethane, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., WPAG-170 ・Acid Generator (B-2): Sulfonium salt type photoacid generator: manufactured by Sunapro Co., Ltd., CPI-100B

[0093] (Crosslinking agent (C)) ・Crosslinking agent (C-1): Diethylene glycol divinyl ether (manufactured by Tokyo Chemical Industries, Ltd.) ・Crosslinking agent (C-2): Triethylene glycol divinyl ether (manufactured by Tokyo Chemical Industries, Ltd.) ・Crosslinking agent (C-3): Adiposihydrazide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・Crosslinking agent (C-4): Ethylenediamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0094] <Synthesis of Polymer (A)> Polymer solutions for each example were synthesized according to the formulations in Table 1 using the following method.

[0095] (Preparation of Polymer (A) Solution 1) 8.0 g of 1-ethoxyethyl methacrylate, 1.2 g of acrylic acid, and 18 g of ethyl acetate were mixed to obtain monomer solution 1. In addition, 0.37 g of 2,2'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., AIBN) was dissolved in 7.4 g of ethyl acetate to obtain an initiator solution. Next, 2.1 mL of the initiator solution was added to the monomer solution 1, which had been heated to 65°C under a nitrogen atmosphere. After heating under a nitrogen atmosphere for 1 hour with stirring, another 2.1 mL of the initiator solution was added and the mixture was heated for a further 7 hours. After allowing it to cool to room temperature and stand for 14 hours or more, it was heated again under a nitrogen atmosphere with stirring at 65°C for 7 hours to obtain polymer (A) solution 1.

[0096] (Preparation of Polymer (A) Solution 2) Polymer (A) Solution 2 was obtained in the same manner as Polymer (A) Solution 1, except that the acrylic acid in monomer solution 1 was replaced with 1.5 g of methacrylic acid and the amount of initiator solution added was changed to 2.3 mL each.

[0097] (Preparation of Polymer (A) Solution 3) 10 g of 1-ethoxyethyl methacrylate, 2.7 g of methacrylic acid, and 25 g of ethyl acetate were mixed to obtain monomer solution 3. In addition, 0.37 g of 2,2'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., AIBN) was dissolved in 7.4 g of ethyl acetate to obtain an initiator solution. Next, 3.0 mL of the initiator solution was added to the monomer solution 3, which had been heated to 65°C under a nitrogen atmosphere. After heating under a nitrogen atmosphere for 1 hour with stirring, another 3.0 mL of the initiator solution was added and the mixture was heated for a further 7 hours. After cooling to room temperature and standing for 14 hours or more, the mixture was heated again under a nitrogen atmosphere at 65°C for 5 hours with stirring, and then heated at 80°C for 2 hours to obtain polymer (A) solution 3.

[0098] (Preparation of Polymer (A) Solution 4) 5.0 g of 1-ethoxyethyl methacrylate, 1.1 g of methacrylic acid, 1.1 g of MEDOL-10, and 14 g of ethyl acetate were mixed to obtain monomer solution 4. In addition, 0.37 g of 2,2'-azobis(isobutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., AIBN) was dissolved in 7.4 g of ethyl acetate to obtain an initiator solution. Next, 1.7 mL of the initiator solution was added to the monomer solution 4, which had been heated to 65°C under a nitrogen atmosphere. After heating under a nitrogen atmosphere for 1 hour with stirring, another 1.7 mL of the initiator solution was added and heated for a further 7 hours. After cooling to room temperature and standing for 14 hours or more, it was heated again under a nitrogen atmosphere at 65°C for 5 hours with stirring, and then heated at 80°C for 2 hours to obtain polymer (A) solution 4.

[0099] (Preparation of Polymer (A) Solution 5) Polymer (A) Solution 5 was obtained in the same manner as Polymer (A) Solution 1, except that the amount of 1-ethoxyethyl methacrylate in monomer solution 1 was changed to 13 g, the acrylic acid was changed to 2.0 g of 2-(acetoacetyloxy)ethyl methacrylate, the ethyl acetate was changed to 29 g, and the amount of initiator solution added was changed to 3.5 mL each.

[0100] (Preparation of Polymer (A) Solution 6) Polymer (A) Solution 6 was obtained in the same manner as Polymer (A) Solution 1, except that the amount of 1-ethoxyethyl methacrylate in monomer solution 1 was changed to 5.0 g, the acrylic acid was changed to 0.75 g of 2-(acetoacetyloxy)ethyl methacrylate, the ethyl acetate was changed to 21 g, and the amount of initiator solution added was changed to 1.3 mL each.

[0101] (Preparation of Polymer (A) Solution 7) Polymer (A) Solution 7 was obtained in the same manner as Polymer (A) Solution 1, except that the amount of 1-ethoxyethyl methacrylate in monomer solution 1 was changed to 5.0 g, the acrylic acid was changed to 0.38 g of 2-(acetoacetyloxy)ethyl methacrylate, the ethyl acetate was changed to 10 g, and the amount of initiator solution added was changed to 1.3 mL each.

[0102] (Preparation of Polymer (A) Solution 8) Polymer (A) Solution 8 was obtained in the same manner as Polymer (A) Solution 1, except that the amount of 1-ethoxyethyl methacrylate in monomer solution 1 was changed to 4.0 g, the acrylic acid was changed to 0.45 g of 2-(acetoacetyloxy)ethyl methacrylate, the ethyl acetate was changed to 8.6 g, and the amount of initiator solution added was changed to 1.0 mL each.

[0103] (Preparation of Polymer (A) Solution 9) Polymer (A) Solution 9 was obtained in the same manner as Polymer (A) Solution 4, except that the amount of 1-ethoxyethyl methacrylate in monomer solution 4 was changed to 4.0 g, the methacrylic acid was changed to 0.53 g of 2-(acetoacetyloxy)ethyl methacrylate, the MEDOL-10 was changed to 0.84 g, the ethyl acetate was changed to 10 g, and the amount of initiator solution added was changed to 1.3 mL each.

[0104] <Weight-average molecular weight (Mw), number-average molecular weight (Mn), and Mw / Mn> For each example polymer (A), the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions. (Conditions) ・Automatic injection device: Waters Japan, 717plus ・Pump: Fromm, KP-22-13S dual pump ・Column: Agilent Technologies, PLgel 10μ MIXED-B, inner diameter 7.5 mm x 300 mm (3 columns) ・Differential refractive index detector: Resonac Corporation, Shodex RI-101 ・Column calibration: Agilent Technologies, EasiCal PS-1 polystyrene ・Eluent: Fujifilm Wako Pure Chemical Industries, HPLC tetrahydrofuran ・Column temperature: 40℃ ・Flow rate: 1.0 mL / min In addition, Mw / Mn was calculated from the obtained values. The results are shown in Table 1.

[0105]

[0106] <Method for producing surface protection composition> The obtained polymer (A), acid generator (B), crosslinking agent (C), and solvents are acetone, ethyl acetate, propylene carbonate (PC), H ２O,1-methoxy-2-propanol (MP) and isopropyl alcohol (IPA) were mixed using a mixing rotor in the formulations shown in Tables 2 to 4 until homogeneous to obtain each example of surface protection composition.

[0107] <Coating Conditions> The surface protection composition for each example was applied to a substrate of glass (water slide glass, manufactured by Matsunami Glass Industry Co., Ltd., S7213) or silicon wafer (manufactured by Seiren KST Co., Ltd., 3 cm × 4.5-7.5 cm) using a non-wire bar coater OSP-80-L60 (film thickness 80 μm / wet), dried on a hot plate at 120°C for 10 minutes, then cured in an oven at 50°C for 48 hours (hereinafter referred to as heating condition A), or dried on a hot plate at 130°C for 5 minutes (hereinafter referred to as heating condition B), or dried on a hot plate at 120°C for 10 minutes (hereinafter referred to as heating condition C) to obtain a coated film on the substrate. The thickness of the film after drying was within the range of 5 ± 5 μm. The substrates used in each example and the drying conditions (heating conditions) of the film are shown in Table 5.

[0108] <Evaluation of Solvent Resistance> One drop of propylene glycol monomethyl ether acetate (PGMEA) was applied to the above film using a plastic dropper and left for 2 minutes. After wiping off the PGMEA with a cloth, the condition of the substrate and the above film was observed, and the solvent resistance was evaluated according to the following (criteria). A to C are considered acceptable. The results are shown in Table 5. (Criteria) A: The film did not dissolve, or only traces of solvent remained. B: The film swelled. C: The film became thinner, but the film remained on the surface of the substrate. D: The film dissolved, and the substrate was exposed.

[0109] <Evaluation of Water Resistance> The substrate and film were immersed in purified water (pH 6.5) for 10 minutes. After removing the substrate and film from the water, their condition was observed, and their water resistance was evaluated according to the following criteria. A is considered a pass. The results are shown in Table 5. (Criteria) A: The film did not dissolve and remained in close contact with the substrate. B: The film peeled off from the substrate. C: The film became cloudy or dissolved.

[0110] <Evaluation of Cleanability> The obtained film was irradiated with light according to the following light irradiation conditions A or B. (Light Irradiation Condition A) The substrate with the film was placed on a stainless steel stand, and the illuminance was 7705 mW / cm². ２ Irradiation time 30 seconds, cumulative light intensity 231 J / cm² ２ Under these conditions, ultraviolet light with a wavelength of 365 nm was irradiated onto the film-side surface of the substrate. Using a radiation thermometer, the temperature of the film surface on the SUS stand during light irradiation was measured to be approximately 30°C. (Light irradiation condition B) The substrate with the obtained film was placed on the SUS stand, and the irradiance was 20 mW / cm². ２ Irradiation time 150 seconds, integrated light intensity 3000 mJ / cm² ２ Under these conditions, ultraviolet light including a wavelength of 365 nm was irradiated onto the film-side surface of the substrate using a high-pressure mercury lamp (manufactured by Technovision Co., Ltd., product name: UVC-408).

[0111] Next, the substrate and the film were immersed in purified water (pH 6.5), and the time until all of the film dissolved or peeled off in the water (dissolution time (minutes) or peeling time (minutes)) was measured. Furthermore, the cleanability was evaluated according to the following criteria. A is considered a pass. The results are shown in Table 5. (Criteria) A: The film dissolved or peeled off completely within 30 minutes. B: The film neither dissolved nor peeled off within 30 minutes.

[0112]

[0113]

[0114]

[0115] In Tables 2-4, PC stands for propylene carbonate, MP for 1-methoxy-2-propanol, and IPA for isopropyl alcohol.

[0116]

[0117] This application claims priority based on Japanese Patent Application No. 2024-230843, filed on 26 December 2024, and incorporates all of its disclosures herein.

[0118] 10 Surface protective film P 20 Electronic component 21 Electronic component after fragmentation 22 Through electrode 30 Temporary fixing material 40 Substrate Q 50 Dicing tape 60 Surface protective film O 70 Substrate U 80 Other electronic components 100 Structure S 200 Structure R 300 Structure T

Claims

1. A surface protection composition capable of forming a water-washable protective film after at least one treatment selected from light irradiation and heating, comprising: a polymer (A) having crosslinkable groups; an acid generator (B) comprising at least one selected from a photoacid generator and a thermoacid generator; and an acid-degradable crosslinking agent (C) capable of reacting with the crosslinkable groups of the polymer (A) and forming an acid-degradable crosslinked structure.

2. The surface protection composition according to claim 1, wherein the polymer (A) comprises one or more selected from the group consisting of a poly(meth)acrylic polymer having a crosslinkable group, a polyvinyl alcohol polymer having a crosslinkable group, a polyvinylpyrrolidone polymer having a crosslinkable group, and a polyethylene oxide polymer having a crosslinkable group.

3. The surface protective composition according to claim 1 or 2, wherein the crosslinkable group comprises one or more selected from the group consisting of a carboxyl group, a ketone group, a hydroxyl group, an amino group, and a vinyl ether group.

4. The surface protective composition according to any one of claims 1 to 3, wherein the polymer (A) further has an acid-degradable group.

5. The surface protective composition according to claim 4, wherein the functional group protected by the acid-degradable group comprises at least one selected from the group consisting of carboxyl groups and hydroxyl groups.

6. The surface protective composition according to claim 4 or 5, wherein the acid-degradable group comprises at least one selected from the group consisting of a group containing an ether bond, a group containing an ester bond, and an alkyl group.

7. The surface protection composition according to claim 6, wherein the group containing the ether bond contains an alkyl group having 1 to 8 carbon atoms.

8. The surface protective composition according to any one of claims 1 to 7, wherein the acid-degradable crosslinking agent (C) contains two or more crosslinkable groups selected from the group consisting of vinyl ether groups, amino groups, carboxyl groups, ketone groups, and hydroxyl groups within its molecule.

9. The surface protection composition according to any one of claims 1 to 8, wherein the acid-degradable crosslinking agent (C) comprises one or more selected from the group consisting of polyvinyl ether compounds and polyamine compounds.

10. The surface protection composition according to any one of claims 1 to 9, wherein the acid-degradable crosslinking agent (C) has a structure derived from (poly)alkylene glycol.

11. The surface protective composition according to any one of claims 1 to 10, wherein the acid-degradable crosslinked structure formed by the polymer (A) and the acid-degradable crosslinking agent (C) includes at least one selected from the group consisting of a group containing an ether bond, a group containing an ester bond, and a group containing an imine bond.

12. The surface protective composition according to any one of claims 1 to 11, wherein the weight-average molecular weight (Mw) of the polymer (A), measured by gel permeation chromatography, is 5,000 or more and 10,000,000 or less on a polystyrene basis.

13. The surface protection composition according to any one of claims 1 to 12, wherein the acid generator (B) comprises a photoacid generator.

14. The surface protection composition according to claim 13, wherein the photoacid generator comprises one or more selected from sulfonium salt type photoacid generators, iodonium salt type photoacid generators, and nonionic type photoacid generators.

15. The surface protection composition according to any one of claims 1 to 14, wherein the content of the acid generator (B) in the surface protection composition is 0.5 parts by mass or more and 50.0 parts by mass or less per 100 parts by mass of the polymer (A).

16. The surface protective composition according to any one of claims 1 to 15, wherein when the following <Method 1> is performed, the film made of the surface protective composition satisfies at least one of the following conditions: (1) it does not dissolve in propylene glycol monomethyl ether acetate, (2) only the adhesion marks of propylene glycol monomethyl ether acetate remain, (3) it swells, and (4) it becomes a thin film but the film remains on the substrate surface. <Method 1> A film with a thickness of 5 ± 5 μm made of the surface protective composition containing an acid-degradable crosslinked structure is formed on a substrate. Then, one drop of propylene glycol monomethyl ether acetate (PGMEA) is applied to the film and left for 2 minutes, after which the PGMEA is wiped off and the state of the film is observed.

17. The surface protective composition according to any one of claims 1 to 16, wherein when the following Method 2 is performed, the film made of the surface protective composition does not dissolve in water and adheres closely to the substrate. Method 2 A film with a thickness of 5 ± 5 μm made of the surface protective composition containing an acid-degradable crosslinked structure is formed on a substrate. Next, the laminate consisting of the substrate and the film is immersed in purified water for 10 minutes, and then the laminate is removed from the purified water and the state of the film is observed.

18. The surface protective composition according to any one of claims 1 to 17, wherein the dissolution time or peeling time of the surface protective composition when the following Method 3 is performed is 30 minutes or less. Method 3 A film with a thickness of 5 ± 5 μm made of the surface protective composition containing an acid-degradable crosslinked structure is formed on a substrate. Next, the laminate consisting of the substrate and the film is irradiated with ultraviolet light from the film side under conditions that decompose the acid-degradable crosslinked structure. Next, the laminate consisting of the substrate and the film is immersed in purified water, and the time until the entire film dissolves or peels off in the purified water (dissolution time or peeling time (minutes)) is measured.

19. The surface protection composition according to any one of claims 1 to 18, wherein the pH of the water used for the water washing, as measured in accordance with JIS Z 8802:2011, is 5.0 or more and 9.0 or less.

20. A surface protection composition according to any one of claims 1 to 19, used to form a surface protection film that protects the surface of an electronic component.

21. The surface protective composition according to claim 20, wherein the surface protective film is a surface protective film that protects the surface of an electronic component and is ultimately removed.

22. A surface protective film comprising a film formed by the surface protective composition according to any one of claims 1 to 21.

23. A method for manufacturing an electronic device, comprising a cleaning step 1 in which an electronic component having a surface protective film P formed with a surface protective composition according to any one of claims 1 to 21 is subjected to at least one treatment selected from light irradiation and heating, and then the surface protective film P is cleaned.

24. The method for manufacturing an electronic device according to claim 23, further comprising the step of bonding the side of the electronic component opposite to the side with the surface protective film P to the substrate U before the cleaning step 1.

25. A method for manufacturing an electronic device according to claim 23 or 24, further comprising a DC step of dicing a structure R comprising, in this order, a dicing tape, the surface protective film P, and the electronic component, before the cleaning step 1.

26. The method for manufacturing an electronic device according to claim 25, wherein the structure R further comprises a temporary fixing material and a substrate Q in this order on the side of the electronic component opposite to the surface protective film P.

27. The method for manufacturing an electronic device according to claim 26, further comprising a peeling step of peeling the temporary fixing material and the substrate Q from the structure R before the DC step.

28. The method for manufacturing an electronic device according to claim 26 or 27, further comprising the step of cleaning the temporary fixing material from the structure R with an organic solvent before the DC step.

29. A method for manufacturing an electronic device according to any one of claims 26 to 28, further comprising, before the DC step, a step of preparing a structure S comprising the electronic component, the temporary fixing material, and the substrate Q in that order, and a BG step of back-grinding the surface of the electronic component in the structure S that is opposite to the surface facing the temporary fixing material.

30. A method for manufacturing an electronic device according to any one of claims 23 to 29, comprising the step of laminating another electronic component onto the surface of the electronic component whose surface protective film P has been cleaned after the cleaning step 1.

31. The method for manufacturing an electronic device according to any one of claims 23 to 30, wherein the cleaning solution in the cleaning step 1 comprises one or more selected from the group consisting of organic solvents and water.

32. The method for manufacturing an electronic device according to any one of claims 23 to 31, wherein the electronic component has a through electrode.

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