阅读说明：本技术 清洗剂组合物以及清洗方法 (Cleaning agent composition and cleaning method ) 是由 荻野浩司 奥野贵久 柄泽凉 新城彻也 于 2020-03-11 设计创作，主要内容包括：本发明提供一种清洗剂组合物,其用于去除粘接剂残留物,所述清洗剂组合物包含季铵盐和溶剂,上述溶剂仅由有机溶剂形成,上述有机溶剂包含N,N,N’,N’－四(烃)脲。(The present invention provides a detergent composition for removing adhesive residues, comprising a quaternary ammonium salt and a solvent, wherein the solvent is formed only by an organic solvent, and the organic solvent comprises N, N, N ', N' -tetra (hydrocarbon) urea.)

1. A cleaning composition for removing adhesive residues, comprising a quaternary ammonium salt and a solvent,

the solvent is formed only of an organic solvent,

the organic solvent comprises N, N' -tetra (hydrocarbon) urea.

2. The cleaning agent composition as claimed in claim 1,

the N, N, N ', N' -tetra (hydrocarbon) urea is N, N, N ', N' -tetraalkyl urea.

3. The cleaning agent composition as claimed in claim 2,

the four alkyl groups of the N, N, N ', N' -tetraalkyl urea are independently alkyl groups having 1-5 carbon atoms.

4. The cleaning agent composition according to claim 1,

the N, N ' -tetra (hydrocarbon) urea comprises at least one selected from the group consisting of N, N ' -tetramethylurea and N, N ' -tetraethylurea.

5. The cleaning agent composition according to any one of claims 1 to 4,

the cleaner composition also includes an organic solvent other than N, N, N ', N' -tetra (hydrocarbon) urea.

6. The cleaning agent composition according to claim 5,

the organic solvent other than N, N' -tetra (hydrocarbon) urea comprises an aprotic organic solvent.

7. The cleaning agent composition according to claim 6,

the aprotic organic solvent contains at least one selected from the group consisting of a glycol solvent, an ether solvent, an aromatic solvent and a lactam compound solvent.

8. The cleaning agent composition according to any one of claims 1 to 7, wherein,

the amount of N, N, N ', N' -tetra (hydrocarbon) urea is 10% by mass or more relative to the solvent.

9. The cleaning agent composition according to any one of claims 1 to 8,

the quaternary ammonium salt is halogen-containing quaternary ammonium salt.

10. The cleaning agent composition as claimed in claim 9,

the quaternary ammonium salt containing halogen is quaternary ammonium salt containing fluorine.

11. The cleaning agent composition as claimed in claim 10,

the fluorine-containing quaternary ammonium salt is ammonium tetra (hydrocarbon) fluoride.

12. The cleaning agent composition according to claim 11,

the tetra (hydrocarbon) ammonium fluoride comprises at least one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride.

13. A cleaning method is characterized in that the cleaning method comprises the following steps,

the cleaning agent composition according to any one of claims 1 to 12, wherein the adhesive residue remaining on the substrate is removed.

14. A method of manufacturing a processed semiconductor substrate, comprising:

a first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition;

a second step of processing the semiconductor substrate of the obtained laminate;

a third step of peeling off the semiconductor substrate after the processing; and

a fourth step of removing the adhesive residue remaining on the semiconductor substrate after the peeling by cleaning with the cleaning agent composition,

in the production method, the cleaning agent composition according to any one of claims 1 to 12 is used as the cleaning agent composition.

Technical Field

The present invention relates to a cleaning agent composition for removing adhesive residues after, for example, temporary adhesion and peeling of an adhesive layer formed on a semiconductor substrate using a polysiloxane adhesive, and a cleaning method.

Background

For the purpose of further integration of semiconductor wafers that have been integrated in a two-dimensional planar direction, a semiconductor integration technique is desired in which planes are integrated (stacked) in a three-dimensional direction. The three-dimensional lamination is a technique of integrating through-silicon via (TSV) into a plurality of layers while connecting them. When the integrated wafers are integrated into a multilayer, the integrated wafers are thinned by grinding on the side opposite to the circuit surface to be formed (i.e., the back surface), and the thinned semiconductor wafers are stacked.

The semiconductor wafer before thinning (also simply referred to as a wafer herein) is bonded to a support for polishing by a polishing apparatus. The bond at this time is called a temporary bond because it is necessary to be easily peeled off after polishing. The temporary bonding must be easily detached from the support, and when a large force is applied to the detachment, the thinned semiconductor wafer may be cut or deformed to prevent such easy detachment. However, in the back-side polishing of the semiconductor wafer, the support is not preferable because the support is detached or displaced by the polishing stress. The properties sought for temporary bonding are therefore: endures the stress during grinding and is easy to be disassembled after grinding. For example, the following properties are pursued: high stress (strong adhesion) is applied to the plane direction during polishing, and low stress (weak adhesion) is applied to the longitudinal direction during removal. In addition, the temperature may be high at 150 ℃ or higher in the processing step, and further, heat resistance is also required.

Under such circumstances, in the semiconductor field, a silicone adhesive having these properties is mainly used as a temporary adhesive. In addition, in the case of a polysiloxane-based adhesive using a polysiloxane-based adhesive, an adhesive residue often remains on the surface of a substrate after peeling off a thinned substrate, but in order to avoid a problem in a subsequent step, a cleaning agent composition for cleaning the surface of a semiconductor substrate by removing the residue has been developed (for example, patent documents 1 to 3), and there is a constant demand for a new cleaning agent composition in the recent semiconductor field. Patent document 1 discloses a silicone resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide, and patent document 2 discloses a cured resin remover containing an alkyl fluoride/ammonium, and further the appearance of an effective cleaning agent composition is desired. Further, patent document 3 discloses a cleaning agent composition using a urea derivative such as dimethyl urea, but since water is used as a solvent, there is a possibility that the substrate is corroded, and there is a problem that the use is inconvenient.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2014/092022

Patent document 2: specification of U.S. Pat. No. 6818608

Patent document 3: japanese laid-open patent publication No. 2007-243162

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a cleaning agent composition and a cleaning method, which can obtain good cleaning performance with respect to an adhesive residue obtained after temporary adhesion and peeling of an adhesive layer obtained using a polysiloxane-based adhesive, and can efficiently clean a substrate without corroding the substrate, for example, when a substrate such as a semiconductor substrate is cleaned.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that, for example, when a substrate such as a semiconductor substrate to which an adhesive residue after temporary adhesion peeling of an adhesive layer obtained using a silicone adhesive is attached is cleaned, the substrate can be cleaned efficiently and satisfactorily in a short time without corroding the substrate by using a cleaning agent composition containing a quaternary ammonium salt and a solvent composed of only an organic solvent containing N, N' -tetra (hydrocarbon) urea.

Patent document 3 does not describe the structure of the present invention and its inherent effects, and does not suggest or suggest them.

Namely, the present invention provides the following.

1. A cleaner composition for removing adhesive residues, the cleaner composition comprising a quaternary ammonium salt and a solvent, the solvent being formed solely from an organic solvent, the organic solvent comprising N, N' -tetra (hydrocarbon) urea.

2. The cleaning agent composition according to 1, characterized in that the N, N, N ', N' -tetra (hydrocarbon) urea is N, N, N ', N' -tetraalkylurea.

3. The cleaning agent composition according to claim 2, wherein the four alkyl groups of the N, N, N ', N' -tetraalkylurea are each independently an alkyl group having 1 to 5 carbon atoms.

4. The cleaning agent composition according to 1, wherein the N, N, N ', N' -tetra (hydrocarbon) urea comprises at least one selected from the group consisting of N, N, N ', N' -tetramethylurea and N, N, N ', N' -tetraethylurea.

5. The cleaning agent composition according to any one of claims 1 to 4, further comprising an organic solvent other than N, N, N ', N' -tetra (hydrocarbon) urea.

6. The cleaning agent composition according to 5, wherein the organic solvent other than N, N, N ', N' -tetra (hydrocarbon) urea comprises an aprotic organic solvent.

7. The cleaning agent composition according to claim 6, wherein the aprotic organic solvent comprises at least one selected from the group consisting of a glycol-based solvent, an ether-based solvent, an aromatic-based solvent and a lactam compound-based solvent.

8. The cleaning agent composition according to any one of claims 1 to 7, wherein the amount of N, N, N ', N' -tetra (hydrocarbon) urea is 10% by mass or more relative to the solvent.

9. The cleaning agent composition according to any one of claims 1 to 8, characterized in that the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.

10. The cleaning agent composition according to claim 9, wherein the quaternary ammonium salt containing halogen is a quaternary ammonium salt containing fluorine.

11. The cleaning agent composition according to 10, wherein the quaternary ammonium salt containing fluorine is tetra (hydrocarbon) ammonium fluoride.

12. The cleaning agent composition according to 11, wherein the tetra (hydrocarbon) ammonium fluoride comprises at least one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride and tetrabutylammonium fluoride.

13. A cleaning method characterized by removing adhesive residues remaining on a substrate using the cleaning agent composition of any one of 1 to 12.

14. A method of manufacturing a processed semiconductor substrate, comprising: a first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of peeling off the semiconductor substrate after the processing; and a fourth step of cleaning and removing the adhesive residue remaining on the semiconductor substrate after the peeling with a cleaning agent composition, wherein the cleaning agent composition is any one of 1 to 12.

Effects of the invention

According to the cleaning agent composition of the present invention, for example, a substrate such as a semiconductor substrate to which an adhesive residue obtained by peeling off a temporary adhesion of an adhesive layer obtained using a silicone adhesive is attached can be cleaned easily in a short time.

Detailed Description

The present invention will be described in further detail below.

The detergent composition of the present invention is a detergent composition for removing adhesive residues, comprising a quaternary ammonium salt and a solvent, wherein the solvent is formed only of an organic solvent, and the organic solvent comprises N, N' -tetra (hydrocarbon) urea.

The cleaner composition of the present invention comprises a quaternary ammonium salt.

The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for such a purpose.

Typically, such a quaternary ammonium cation includes a tetra (hydrocarbon) ammonium cation. On the other hand, examples of anions paired therewith include: hydroxide ion (OH)^－) (ii) a Fluoride ion (F)^－) Chloride ion (Cl)^－) Bromine ion (Br)^－) Iodide ion (I)^－) A plasma of halogen ions; tetrafluoroboric acid ion (BF)₄ ^－) (ii) a Hexafluorophosphate ion (PF)₆ ^－) And the like, but is not limited thereto.

In the present invention, the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt.

In the quaternary ammonium salt, the halogen atom may be contained in a cation or an anion, but is preferably contained in an anion.

In a preferred embodiment, the quaternary ammonium salt containing fluorine is tetra (hydrocarbon) ammonium fluoride.

Specific examples of the hydrocarbon group in the tetra (hydrocarbon) ammonium fluoride include: an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like.

In a preferred embodiment of the present invention, the tetra (hydrocarbon) ammonium fluoride comprises tetraalkylammonium fluoride.

Specific examples of tetraalkylammonium fluorides include: tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride, and the like, but is not limited thereto. Among them, Tetrabutylammonium fluoride (also referred to as Tetrabutylammonium fluoride) is preferable.

The quaternary ammonium salt may also be a hydrate. The quaternary ammonium salts may be used singly or in combination of two or more.

The amount of the quaternary ammonium salt is not particularly limited as long as it is dissolved in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass based on the detergent composition.

The cleaning agent composition of the present invention comprises a solvent, wherein the solvent is formed only of an organic solvent, and the organic solvent comprises N, N' -tetra (hydrocarbon) urea.

In the present invention, by using only an organic solvent as a solvent contained in the cleaning agent composition, it is possible to reduce the occurrence of metal contamination, metal corrosion, and the like due to water, and to clean a substrate suitably with good reproducibility. Therefore, the cleaning agent composition of the present invention generally contains only an organic solvent as a solvent. The term "only organic solvent" means that only organic solvent is used as the solvent, and does not deny the presence of water contained in the organic solvent or other components.

In other words, the cleaning agent composition of the present invention is characterized by containing substantially no water. Here, the term "substantially free of water" means that water is not used, and as described above, a trace amount of water mixed with water or components of hydrates as other components is not excluded.

The cleaning agent composition of the present invention contains N, N' -tetra (hydrocarbon) urea as an organic solvent. Here, N, N, N ', N' -tetra (hydrocarbon) urea contained as the organic solvent in the present invention is at normal temperature (23 ℃) and normal pressure (1.013X 10)⁵Pa) is liquid.

The four hydrocarbon groups of the N, N, N ', N' -tetra (hydrocarbon) urea are independently a monovalent hydrocarbon group of 1 to 20 carbon atoms, preferably a monovalent aliphatic hydrocarbon group of 1 to 20 carbon atoms, and more preferably a monovalent aliphatic saturated hydrocarbon group of 1 to 20 carbon atoms.

The monovalent hydrocarbon group having 1 to 20 carbon atoms is typically an alkyl group having 1 to 20 carbon atoms, but is not limited thereto.

The alkyl group having 1 to 20 carbon atoms is derived from an alkane having 1 to 20 carbon atoms by removing one hydrogen atom, and may be any of a linear, branched, and cyclic alkyl group, but is preferably a linear or branched alkyl group having 10 or less carbon atoms, more preferably 5 or less carbon atoms, still more preferably 3 or less carbon atoms, and further preferably 1 or 2 carbon atoms.

In a preferred embodiment, the four hydrocarbyl groups of the N, N, N ', N' -tetra (hydrocarbon) urea are all the same group.

Specific examples of the linear or branched alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1, 2, 2-trimethyl-n-propyl, 1-methyl-n-butyl, 2, 3-methyl-n-butyl, 3-ethyl-n-butyl, 2-butyl, 1, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 2-butyl, 2-n-butyl, 2-n-butyl, 2-butyl, 3-butyl, 2-butyl, 3-butyl, 2-n-butyl, 3-butyl, 3-butyl, 3-n-butyl, 3-butyl, 3-butyl, 2-butyl, 3-n-butyl, 3-butyl, 3, or 2-butyl, 2, 2-butyl, 2-n-butyl, 2, 2-butyl, 2, 2-n-butyl, 2, 2-butyl, 2-n-butyl, 2-butyl, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, and the like, but are not limited thereto. Among them, methyl is preferred.

Specific examples of the cyclic alkyl group include: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1, 2-dimethyl-cyclopropyl, 2, 3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutyl, 1, 3-dimethyl-cyclobutyl, 2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2, 4-dimethyl-cyclobutyl, 3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, Examples of the alkyl group include, but are not limited to, a cycloalkyl group such as a 2-isopropyl-cyclopropyl group, a1, 2, 2-trimethyl-cyclopropyl group, a1, 2, 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, and a bicycloalkyl group such as a bicyclobutyl group, a bicyclopentyl group, a bicyclohexyl group, a bicycloheptyl group, a bicyclooctyl group, a bicyclononyl group, and a bicyclodecyl group.

Specific examples of the N, N ' -tetra (hydrocarbon) urea include, but are not limited to, N ' -tetramethylurea, N ' -tetraethylurea, and the like.

Among them, N' -tetramethylurea is preferable from the viewpoint of obtaining a cleaner composition having more excellent cleaning performance with good reproducibility.

The amount of the N, N '-tetra (hydrocarbon) urea is arbitrary, and is usually 10 mass% or more based on the total amount of the solvent contained in the cleaning agent composition, and an organic solvent other than N, N' -tetra (hydrocarbon) urea may be used as the remaining solvent, and for example, an aprotic organic solvent such as a glycol-based solvent, an ether-based solvent, an aromatic-based solvent, or a lactam compound-based solvent may be suitably used. These solvents may be used singly or in combination of two or more.

In one embodiment, the amount of the N, N' -tetra (hydrocarbon) urea is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on the total amount of the solvents contained in the detergent composition, from the viewpoint of obtaining a detergent composition having excellent detergency with good reproducibility.

Specific examples of the diol-based solvent include: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, xylene glycol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 2-pentanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, 2, 4-pentanediol, 2, 3-pentanediol, 1, 6-hexanediol, and the like, but is not limited thereto.

Examples of the ether solvent include: glycol ether solvents, glycol diether solvents, cyclic ether solvents, and the like, but are not limited thereto.

Examples of the glycol ether solvent include: (mono-, di-, tri-, poly) alkylene glycol monoalkyl ether, alkylene glycol monophenyl ether, etc., but are not limited thereto.

Examples of the alkylene glycol monoalkyl ether include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ethane, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and the like, but is not limited thereto.

Examples of the glycol diether solvent include: ethylene glycol dimethyl ether (also referred to as dimethoxyethane, hereinafter the same applies), ethylene glycol diethyl ether (diethoxyethane), ethylene glycol dipropylethane (dipropoxyethane), ethylene glycol dibutyl ether (dibutoxyethane), propylene glycol dimethyl ether (dimethoxypropane), propylene glycol diethyl ether (diethoxypropane), propylene glycol dipropyl ether (dipropoxypropane), and the like, but the present invention is not limited thereto.

The cyclic ether solvent is a compound in which at least one of carbon atoms constituting a ring of the cyclic hydrocarbon compound is substituted with an oxygen atom.

Typically, there may be mentioned: an epoxy compound obtained by epoxidizing a chain, branched or cyclic saturated hydrocarbon compound (that is, a compound obtained by forming a three-membered ring by two carbon atoms and an oxygen atom adjacent to each other) or a cyclic ether compound other than epoxy (except for an epoxy compound) obtained by substituting an oxygen atom for a carbon atom constituting a ring of a cyclic hydrocarbon compound having 4 or more carbon atoms (except for an aromatic hydrocarbon compound), and among these, a cyclic saturated hydrocarbon compound having 4 or more carbon atoms is preferable.

The number of carbon atoms of the epoxy compound is not particularly limited, but is usually 4 to 40, preferably 6 to 12.

The number of epoxy groups is not particularly limited, but is usually 1 to 4, preferably 1 or 2.

Specific examples of the epoxy compound include: epoxy chain or branched saturated hydrocarbon compounds such as 1, 2-epoxyn-butane, 1, 2-epoxyn-pentane, 1, 2-epoxyn-hexane, 1, 2-epoxyn-heptane, 1, 2-epoxyn-octane, 1, 2-epoxyn-nonane, 1, 2-epoxyn-decane and 1, 2-epoxyn-eicosane; epoxy cyclic saturated hydrocarbon compounds such as 1, 2-epoxycyclopentane, 1, 2-epoxycyclohexane, 1, 2-epoxycycloheptane, 1, 2-epoxycyclooctane, 1, 2-epoxycyclononane, 1, 2-epoxycyclodecane and 1, 2-epoxycycloeicosane, but are not limited thereto.

The number of carbon atoms of the cyclic ether compound other than epoxy is not particularly limited, but is usually 3 to 40, preferably 4 to 8.

The number of oxygen atoms (ether groups) is not particularly limited, but is usually 1 to 3, preferably 1 or 2.

Specific examples of the cyclic ether compound other than the epoxy compound include: oxetane saturated hydrocarbon compounds such as oxetane, oxolane (tetrahydrofuran), and oxolane (tetrahydropyran); and dioxane saturated hydrocarbon compounds such as 1, 3-dioxolane, 1, 3-dioxane (1, 3-dioxane), and 1, 4-dioxane (1, 4-dioxane), but the present invention is not limited thereto.

The cyclic alkyl chain alkyl ether compound is formed of a cyclic alkyl group, a chain alkyl group and an ether group connecting the two groups, and the number of carbon atoms is not particularly limited, but is usually 4 to 40, preferably 5 to 20.

The cyclic alkyl branched alkyl ether compound is formed of a cyclic alkyl group, a branched alkyl group and an ether group connecting the two groups, and the number of carbon atoms is not particularly limited, but is usually 6 to 40, preferably 5 to 20.

The di (cyclic alkyl) ether compound is formed of two cyclic alkyl groups and an ether group connecting the two groups, and the number of carbon atoms is not particularly limited, but is usually 6 to 40, preferably 10 to 20.

Among these, the cyclic ether compounds other than the epoxy compound are preferably cyclic alkyl chain alkyl ether compounds and cyclic alkyl branched alkyl ether compounds, and more preferably cyclic alkyl chain alkyl ether compounds.

The chain alkyl group is a group derived by removing a hydrogen atom at the end of a linear aliphatic hydrocarbon, and the number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 1 to 20.

Specific examples thereof include: methyl group, ethyl group, 1-n-propyl group, 1-n-butyl group, 1-n-pentyl group, 1-n-hexyl group, 1-n-heptyl group, 1-n-octyl group, 1-n-nonyl group, 1-n-decyl group and the like, but is not limited thereto.

The branched alkyl group is a group derived by removing a hydrogen atom of a linear or branched aliphatic hydrocarbon, and is a group other than a chain alkyl group, and the number of carbon atoms is not particularly limited, but is usually 3 to 40, preferably 3 to 40.

Specific examples thereof include: isopropyl, isobutyl, sec-butyl, tert-butyl, and the like, but are not limited thereto.

The cyclic alkyl group is a group derived by removing a hydrogen atom from a carbon atom constituting the ring of the cyclic aliphatic hydrocarbon, and the number of carbon atoms is not particularly limited, but is usually 3 to 40, preferably 5 to 20.

Specific examples thereof include: and a bicycloalkyl group such as a monocyclic alkyl group including a monocyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cycloheptyl group, a cyclohexyl group, etc., a bicyclo [2.2.1] heptan-1-yl group, a bicyclo [2.2.1] heptan-2-yl group, a bicyclo [2.2.1] heptan-7-yl group, a bicyclo [2.2.2] octan-1-yl group, a bicyclo [2.2.2] octan-2-yl group, a bicyclo [2.2.2] octan-7-yl group, etc., but the present invention is not limited thereto.

Specific examples of the cyclic alkyl chain alkyl ether compound include: cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether, cyclopentyl propyl ether, cyclopentyl butyl ether, cyclohexyl methyl ether, cyclohexyl ethyl ether, cyclohexyl propyl ether, cyclohexyl butyl ether, and the like, but is not limited thereto.

Specific examples of the cyclic alkyl branched alkyl ether compound include: cyclopentyl isopropyl ether, cyclopentyl tert-butyl ether, and the like, but are not limited thereto.

Specific examples of the di (cyclic alkyl) ether compound include: dicyclopentyl ether, dicyclohexyl ether, cyclopentyl cyclohexyl ether, and the like, but are not limited thereto.

The aromatic solvent includes, but is not limited to, aromatic compounds represented by formula (1).

(wherein s represents a substituent R substituted on the benzene ring¹⁰⁰The number of (2) or (3) s R¹⁰⁰Independently represent an alkyl group having 1 to 6 carbon atoms, and the total carbon number of the alkyl groups having 1 to 6 carbon atoms is 3 or more. )

In the formula (1), specific examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like, but is not limited thereto.

s represents a substituent R substituted on the benzene ring¹⁰⁰The number of (3) is 2 or 3.

In a preferred embodiment of the present invention, the aromatic compound represented by the formula (1) is an aromatic compound represented by the formula (1-1) or (1-2).

(in the formula, R¹⁰⁰Independently represents an alkyl group having 1 to 6 carbon atoms, and three R's in the formula (1-1)¹⁰⁰The total carbon number of the alkyl group having 1 to 6 carbon atoms of (A) is 3 or more, and two R in the formula (1-2)¹⁰⁰The total carbon number of the alkyl groups having 1 to 6 carbon atoms is 3 or more. )

Specific examples of the aromatic compound represented by the formula (1) include: 1, 2, 3-trimethylbenzene, 1, 2, 4-trimethylbenzene, 1, 2, 5-trimethylbenzene, 1, 3, 5-trimethylbenzene (mesitylene), 4-ethyltoluene, 4-n-propyltoluene, 4-isopropyltoluene, 4-n-butyltoluene, 4-sec-butyltoluene, 4-isobutyltoluene, 4-tert-butyltoluene and the like, but not limited thereto.

Among them, mesitylene and 4-tert-butyltoluene are preferable.

The lactam compound solvent includes, but is not limited to, lactam compounds represented by the following formula (2).

(in the formula, R¹⁰¹Represents an alkyl group having 1 to 6 carbon atoms, R¹⁰²Represents an alkylene group having 1 to 6 carbon atoms. )

In the formula (2), specific examples of the alkyl group having 1 to 6 carbon atoms include: examples of the alkylene group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited thereto.

Specific examples of the lactam compound represented by the above formula (2) include: α -lactam compounds, β -lactam compounds, γ -lactam compounds, δ -lactam compounds, and the like, and these may be used singly or in combination of two or more.

In a preferred embodiment of the present invention, the lactam compound represented by the above formula (2) comprises 1-alkyl-2-pyrrolidone (N-alkyl- γ -butyrolactam), in a more preferred embodiment, N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a still more preferred embodiment, N-methylpyrrolidone (NMP).

The detergent composition of the present invention is obtained by mixing the quaternary ammonium salt, N' -tetra (hydrocarbon) urea and, if necessary, other components, and the order of mixing the components may be arbitrarily selected as long as the problems such as precipitation and separation of liquid, which are not intended to achieve the object of the present invention, do not occur. That is, a part of all the components of the cleaning agent composition may be mixed in advance, and then the remaining components may be mixed, or all the components may be mixed at once. If necessary, the cleaning agent composition may be filtered, or the supernatant liquid may be recovered by avoiding insoluble components after mixing and used as a cleaning agent. In addition, when the component used has hygroscopicity and deliquescence, for example, all or a part of the preparation of the cleaning agent composition may be performed under an inert gas atmosphere.

The cleaning agent composition of the present invention described above has good cleaning properties with respect to an adhesive such as a silicone adhesive, and is excellent in both cleaning speed and cleaning durability.

Specifically, as for the cleaning speed, when the adhesive layer obtained from the adhesive composition is brought into contact with the cleaning agent composition of the present invention for 5 minutes at room temperature (23 ℃), the film thickness is measured to decrease before and after the contact, and the etching rate [ μm/min ] calculated by dividing the amount of decrease by the cleaning time is usually 5.0[ μm/min ] or more, in a preferred embodiment 7.0[ μm/min ] or more, in a still more preferred embodiment 8.0[ μm/min ] or more, and in a still more preferred embodiment 9.0[ μm/min ] or more.

Further, regarding the cleaning duration, when 1g of the adhesive solid obtained from the adhesive composition is brought into contact with 2g of the cleaning agent composition of the present invention at room temperature (23 ℃), the cleaning agent composition of the present invention usually dissolves most of the adhesive solid within 12 to 24 hours, preferably dissolves the adhesive solid within 2 to 12 hours, and more preferably dissolves the adhesive solid within 1 to 2 hours.

According to the present invention, by using the cleaning agent composition, for example, a silicone adhesive remaining on a substrate such as a semiconductor substrate is cleaned and removed, and the substrate can be cleaned in a short time, and the substrate such as a semiconductor substrate can be cleaned efficiently and satisfactorily.

The cleaning agent composition of the present invention is used for cleaning the surface of various substrates such as semiconductor substrates, and the object to be cleaned is not limited to silicon semiconductor substrates, and for example, the cleaning agent composition includes: various substrates such as a germanium substrate, a gallium-arsenic substrate, a gallium-phosphorus substrate, a gallium-arsenic-aluminum substrate, an aluminum-plated silicon substrate, a copper-plated silicon substrate, a silver-plated silicon substrate, a gold-plated silicon substrate, a titanium-plated silicon substrate, a silicon nitride film-forming silicon substrate, a silicon oxide film-forming silicon substrate, a polyimide film-forming silicon substrate, a glass substrate, a quartz substrate, a liquid crystal substrate, and an organic EL substrate.

A preferred method of using the cleaning agent composition of the present invention in a semiconductor process includes a method of manufacturing a thinned substrate used in a semiconductor packaging technology such as TSV.

Specifically, a method of manufacture comprising: a first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of peeling off the semiconductor substrate after the processing; and a fourth step of removing the adhesive residue remaining on the semiconductor substrate after the peeling by cleaning with a cleaning agent composition, wherein the cleaning agent composition of the present invention is used as the cleaning agent composition.

As the adhesive composition for forming the adhesive layer in the first step, typically, at least one adhesive selected from the group consisting of silicone-based, acrylic-based, epoxy-based, polyamide-based, polystyrene-based, polyimide-based, and phenol-based adhesives can be used, and in particular, it is effective to use the cleaning agent composition of the present invention for cleaning the silicone-based adhesive, wherein the cleaning agent composition of the present invention is effective for cleaning and removing the adhesive residue of the silicone-based adhesive containing the component (a) that is cured by the hydrosilylation reaction.

Therefore, a method for manufacturing a thinned substrate using a polysiloxane adhesive (adhesive composition) containing the component (a) that is cured by a hydrosilylation reaction and the cleaning agent composition of the present invention will be described below, but the present invention is not limited thereto.

First, a first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described.

The component (a) which is contained in the adhesive composition and is cured by the hydrosilylation reaction contains, for example, polysiloxane (a1) and platinum group metal-based catalyst (a2), and the polysiloxane (a1) contains a compound selected from the group consisting of SiO₂Siloxane units (Q units), R¹R²R³SiO_1/2Siloxane units (M units), R⁴R⁵SiO_2/2Siloxane units (D units) and R⁶SiO_3/2The polysiloxane (A1) comprises a polyorganosiloxane (a1) and a polyorganosiloxane (a2), and the polyorganosiloxane (a1) comprises one or more units selected from the group consisting of siloxane units (T units)₂Siloxane units (Q' units), R¹’R²’R³’SiO_1/2Siloxane units (M' units), R⁴’R⁵’SiO_2/2Siloxane units (D' units) and R⁶’SiO_3/2One or two or more units selected from the group consisting of the siloxane units (T 'units) and at least one selected from the group consisting of the M' units, the D 'units and the T' units, and the polyorganosiloxane (a2) comprises a polyorganosiloxane selected from the group consisting of SiO₂Siloxane units (Q' units), R¹”R²”R³”SiO_1/2Siloxane units (M' units), R⁴”R⁵”SiO_2/2Siloxane units (D' units) and R⁶”SiO_3/2One or two or more units selected from the group consisting of the siloxane units (T "units) shown, and at least one selected from the group consisting of the M" units, D "units, and T" units described above.

R¹～R⁶Is a group or atom bonded to a silicon atom, and independently represents an alkyl group, an alkenyl group or a hydrogen atom.

R¹’～R⁶' is a group bonded to a silicon atom, independently of each otherDenotes alkyl or alkenyl, but R¹’～R⁶At least one of' is alkenyl.

R¹”～R⁶"is a group or atom bonded to a silicon atom, independently of one another represents an alkyl group or a hydrogen atom, with the proviso that R¹”～R⁶At least one of "is a hydrogen atom.

The alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group, and the number of carbon atoms thereof is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less.

Specific examples of the linear or branched alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1-dimethyl-n-propyl, 1, 2-dimethyl-n-propyl, 2, 2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1, 2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, and the like, but is not limited thereto.

Among them, methyl is preferred.

Specific examples of the cyclic alkyl group include: cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1, 2-dimethylcyclopropyl, 2, 3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1, 2-dimethylcyclobutyl, 1, 3-dimethylcyclobutyl, 2, 2-dimethylcyclobutyl, 2, 3-dimethylcyclobutyl, 2, 4-dimethylcyclobutyl, 3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1, 2, 2-trimethylcyclopropyl, 1-methylcyclobutyl, 2-dimethylcyclopropyl, 2-ethylcyclopropyl, 2-isopropylcyclopropyl, 1, 2, 2-trimethylcyclopropyl, 2-methylcyclobutyl, 3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-cyclopropyl, 2-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2-methyl-propyl, 2-methyl-butyl, 2-propyl, 2, 2-methyl-propyl, 2, 2-methyl-propyl, 2, 2-methyl, 2, examples of the alkyl group include, but are not limited to, a cycloalkyl group such as 1, 2, 3-trimethylcyclopropyl group, 2, 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group, and a bicycloalkyl group such as a dicyclobutyl group, dicyclopentyl group, dicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

The alkenyl group may be either linear or branched, and the number of carbon atoms is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less.

Specific examples of alkenyl groups include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1-isopropylvinyl, 2-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1-isopropylvinyl, 2-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-propenyl, 1-methyl-1-butenyl, 1-methyl-butenyl, 1-3-butenyl, 1-methyl-butenyl, 1-2-butenyl, 1-methyl-2-butenyl, 1-propenyl, 1-2-methyl-2-butenyl, 2-methyl-2-butenyl, 2-methyl-2-propenyl, 2-methyl-propenyl, 2-propenyl, 2-isopropylvinyl, 2-propenyl, 2-methyl-propenyl, 2-methyl-2-butyl, 2-methyl-butyl, 2-2, 2-methyl-propenyl, 2-2, 2-butyl, 2, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1-dimethyl-2-butenyl, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 1-isobutyl vinyl, 2-dimethyl-3-butenyl, 2, 3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-2-propenyl, 1, 2-methyl-2-butenyl, 1-butyl, 2, 3-dimethyl-3-butenyl, 2-butyl, 2-isobutyl-2-butenyl, 2-butyl, 2-ethyl-butyl, 2-butyl, 2-butyl, 2-ethyl-butyl, 2-butyl, 2-butyl, 2-ethyl-3, 2-butyl, 2-butyl, 2-2, 2-butyl, 2-ethyl-3, 2-butyl, 2-3, 2-butyl, 2-2, 2-butyl, 2-butyl, 2-2, 2-butyl, 2-butyl, 2-butyl, 2-butyl, 2-butyl, 2-, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl and the like, but not limited thereto.

Among them, vinyl and 2-propenyl are preferable.

As described above, the polysiloxane (a1) includes the polyorganosiloxane (a1) and the polyorganosiloxane (a2), and the alkenyl group contained in the polyorganosiloxane (a1) and the hydrogen atom (Si — H group) contained in the polyorganosiloxane (a2) form a crosslinked structure through a hydrosilylation reaction based on the platinum group metal-based catalyst (a2) and cure.

The polyorganosiloxane (a1) contains one or two or more units selected from the group consisting of a Q ' unit, an M ' unit, a D ' unit and a T ' unit, and at least one selected from the group consisting of the M ' unit, the D ' unit and the T ' unit. As the polyorganosiloxane (a1), two or more kinds of polyorganosiloxanes satisfying such conditions may be used in combination.

Preferred combinations of two or more selected from the group consisting of Q ', M', D ', and T' units include: (Q ' unit and M ' unit), (D ' unit and M ' unit), (T ' unit and M ' unit), (Q ' unit, T ' unit, and M ' unit), but is not limited thereto.

In the case where two or more kinds of polyorganosiloxanes (a1) are contained, a combination of (Q ' unit and M ' unit) and (D ' unit and M ' unit), (T ' unit and M ' unit) and (D ' unit and M ' unit), (Q ' unit, T ' unit and M ' unit) and (T ' unit and M ' unit) are preferable, but the present invention is not limited thereto.

The polyorganosiloxane (a2) contains one or more units selected from the group consisting of a Q "unit, an M" unit, a D "unit, and a T" unit, and at least one selected from the group consisting of the M "unit, the D" unit, and the T "unit. As the polyorganosiloxane (a2), two or more kinds of polyorganosiloxanes satisfying such conditions may be used in combination.

Preferred combinations of two or more selected from the group consisting of Q "unit, M" unit, D "unit, and T" unit include: (M "unit and D" unit), (Q "unit and M" unit), (Q "unit, T" unit, and M "unit), but is not limited thereto.

The polyorganosiloxane (a1) is composed of siloxane units in which an alkyl group and/or an alkenyl group is bonded to a silicon atom, R¹’～R⁶The proportion of alkenyl groups in all the substituents represented by' is preferably from 0.1 to 50.0 mol%, more preferably from 0.5 to 30.0 mol%, and the remainder R is¹’～R⁶' may be provided as an alkyl group.

The polyorganosiloxane (a2) is composed of siloxane units in which alkyl groups and/or hydrogen atoms are bonded to silicon atoms, R¹”～R⁶"the hydrogen atom ratio in all the substituents and the substituent atoms represented by" is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the rest R¹”～R⁶"may be an alkyl group.

The polysiloxane (a1) comprises polyorganosiloxane (a1) and polyorganosiloxane (a2), but in a preferred embodiment of the present invention, the molar ratio of alkenyl groups contained in polyorganosiloxane (a1) to hydrogen atoms constituting Si — H bonds contained in polyorganosiloxane (a2) is in the range of 1.0: 0.5-1.0: in the range of 0.66.

The weight average molecular weights of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are usually 500 to 1000000, preferably 5000 to 50000, respectively.

The weight average molecular weight can be measured, for example, using a GPC apparatus (EcoSec, HLC-8320 GPC, manufactured by Tosoh corporation) and a GPC column (Shodex (registered trademark), KF-803L, KF-802, and KF-801, manufactured by Showa Denko K.K.), with the column temperature being 40 ℃, tetrahydrofuran being used as an eluent (elution solvent), the flow rate (flow rate) being 1.0 mL/min, and polystyrene (manufactured by Sigma-Aldrich Co.) being used as a standard sample.

The polyorganosiloxane (a1) and the polyorganosiloxane (a2) contained in the adhesive composition react with each other by a hydrosilylation reaction, thereby forming a cured film. Therefore, the mechanism of this curing is different from that of, for example, via a silanol group, and therefore, it is not necessary for any siloxane to contain a functional group capable of forming a silanol group by hydrolysis, such as a silanol group or an alkyloxy group.

The component (A) contains a platinum group metal-based catalyst (A2).

Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction of the alkenyl group of polyorganosiloxane (a1) and the Si — H group of polyorganosiloxane (a 2).

Specific examples of the platinum-based metal catalyst include: platinum group catalysts such as platinum black, platinum chloride, chloroplatinic acid, a reactant of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, and platinum bisacetoacetate, but are not limited thereto.

Examples of the complex of platinum and olefins include, but are not limited to, a complex of divinyltetramethyldisiloxane and platinum.

Usually, the amount of the platinum group metal-based catalyst (a2) is in the range of 1.0 to 50.0ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a 2).

The component (a) may also contain a polymerization inhibitor (a 3). That is, by including the polymerization inhibitor in the adhesive composition, curing by heating at the time of bonding can be appropriately controlled, and the adhesive composition providing the adhesive layer excellent in adhesiveness and releasability can be obtained with good reproducibility.

The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include: and alkynylalkyl alcohols optionally substituted with an aryl group, such as 1-ethynyl-1-cyclohexanol and 1, 1-diphenyl-2-propyn-1-ol, but not limited thereto.

The amount of the polymerization inhibitor is usually 1000.0ppm or more relative to the polyorganosiloxane (a1) and the polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

The adhesive composition may also include: and (B) at least one member selected from the group consisting of a member containing an epoxy-modified polyorganosiloxane, a member containing a methyl group-containing polyorganosiloxane, and a member containing a phenyl group-containing polyorganosiloxane. By including such a component (B) in the adhesive composition, the obtained adhesive layer can be appropriately peeled with good reproducibility.

Examples of the epoxy-modified polyorganosiloxane include R¹¹R¹²SiO_2/2Siloxane units (D) shown¹⁰A cell).

R¹¹Is a group bonded to a silicon atom, represents an alkyl group, R¹²The group bonded to a silicon atom represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include those described above.

The epoxy group in the epoxy group-containing organic group may be an epoxy group independent of other rings without being condensed, or an epoxy group having a condensed ring with other rings, such as 1, 2-epoxycyclohexyl group.

Specific examples of the organic group containing an epoxy group include: 3-glycidoxypropyl group and 2- (3, 4-epoxycyclohexyl) ethyl group, but the present invention is not limited thereto.

In the present invention, a preferable example of the epoxy-modified polyorganosiloxane is epoxy-modified polydimethylsiloxane, but the epoxy-modified polyorganosiloxane is not limited thereto.

The epoxy-modified polyorganosiloxane contains the above-mentioned siloxane unit (D)¹⁰Unit) except for D¹⁰The unit may include the Q unit, the M unit, and/or the T unit.

In a preferred embodiment, specific examples of the epoxy-modified polyorganosiloxane include: by D only¹⁰Polyorganosiloxane of unit composition comprising D¹⁰Polyorganosiloxane unit and Q unit, comprising D¹⁰Polyorganosiloxane of units and M units, comprising D¹⁰Polyorganosiloxane unit and T unit, containing D¹⁰Polyorganosiloxane unit, Q unit and M unit, containing D¹⁰Polyorganosiloxane unit, polyorganosiloxane unit of M unit and polyorganosiloxane unit of T unit, and polyorganosiloxane composition containing D unit¹⁰Polyorganosiloxane units, Q units, M units, and T units.

The epoxy-modified polyorganosiloxane is preferably an epoxy-modified polydimethylsiloxane having an epoxy value of 0.1 to 5, and the weight average molecular weight thereof is usually 1500 to 500000, but from the viewpoint of suppressing precipitation in the adhesive composition, the weight average molecular weight thereof is preferably 100000 or less.

Specific examples of the epoxy-modified polyorganosiloxane include: trade name CMS-227 (manufactured BY Gelest Co., Ltd., weight average molecular weight 27000) represented BY formula (A-1), trade name ECMS-327 (manufactured BY Gelest Co., Ltd., weight average molecular weight 28800) represented BY formula (A-2), trade name KF-101 (manufactured BY shin-Etsu chemical industries, Ltd., weight average molecular weight 31800) represented BY formula (A-4), trade name KF-1001 (manufactured BY shin-Etsu chemical industries, Ltd., weight average molecular weight 55600) represented BY formula (A-4), trade name KF-1005 (manufactured BY shin-Etsu chemical industries, Ltd., weight average molecular weight 11500) represented BY formula (A-5), trade name X-22-343 (manufactured BY shin-Etsu chemical industries, Ltd., weight average molecular weight 2400) represented BY formula (A-6), trade name 16-839 (manufactured BY Dow Corg Co., weight average molecular weight 51700) represented BY formula (A-7), and trade name MS-327 (manufactured BY Gelest Co., Ltd., ECst, weight average molecular weight 28800), etc., but is not limited thereto.

(m and n are the number of repeating units, respectively.)

(m and n are the number of repeating units, respectively.)

(m and n are the number of repeating units, R is an alkylene group having 1 to 10 carbon atoms.)

(m and n are the number of repeating units, R is an alkylene group having 1 to 10 carbon atoms.)

(m, n and o each represents the number of repeating units, R represents an alkylene group having 1 to 10 carbon atoms.)

(m and n are the number of repeating units, R is an alkylene group having 1 to 10 carbon atoms.)

(m and n are the number of repeating units, R is an alkylene group having 1 to 10 carbon atoms.)

(m and n are the number of repeating units, respectively.)

Examples of the methyl group-containing polyorganosiloxane include polyorganosiloxanes containing R²¹⁰R²²⁰SiO_2/2Siloxane units (D) shown²⁰⁰Units) of polyorganosiloxane, preferably containing R²¹R²¹SiO_2/2Siloxane units (D) shown²⁰Units) of a polyorganosiloxane.

R²¹⁰And R²²⁰The groups bonded to the silicon atom independently represent alkyl groups, at least one of which is methyl, and specific examples of the alkyl groups include those described above.

R²¹The group bonded to a silicon atom represents an alkyl group, and specific examples of the alkyl group include those described above.Wherein, as R²¹Preferably methyl.

The methyl group-containing polyorganosiloxane is preferably exemplified by polydimethylsiloxane, but is not limited thereto.

The methyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D)²⁰⁰Unit or D²⁰Unit) but other than D²⁰⁰Unit and D²⁰In addition to the units, the Q unit, M unit and/or T unit may be optionally contained.

In one embodiment, specific examples of the methyl group-containing polyorganosiloxane include: by D only²⁰⁰Polyorganosiloxane of unit composition comprising D²⁰⁰Polyorganosiloxane unit and Q unit, comprising D²⁰⁰Polyorganosiloxane of units and M units, comprising D²⁰⁰Polyorganosiloxane unit and T unit, containing D²⁰⁰Polyorganosiloxane unit, Q unit and M unit, containing D²⁰⁰Polyorganosiloxane unit, polyorganosiloxane unit of M unit and polyorganosiloxane unit of T unit, and polyorganosiloxane composition containing D unit²⁰⁰A unit, a Q unit, an M unit and a T unit.

In a preferred embodiment, specific examples of the methyl group-containing polyorganosiloxane include: by D only²⁰Polyorganosiloxane of unit composition comprising D²⁰Polyorganosiloxane unit and Q unit, comprising D²⁰Polyorganosiloxane of units and M units, comprising D²⁰Polyorganosiloxane unit and T unit, containing D²⁰Polyorganosiloxane unit, Q unit and M unit, containing D²⁰Polyorganosiloxane unit, polyorganosiloxane unit of M unit and polyorganosiloxane unit of T unit, and polyorganosiloxane composition containing D unit²⁰A unit, a Q unit, an M unit and a T unit.

The methyl group-containing polyorganosiloxane usually has a viscosity of 1000 to 2000000mm²(ii) s, but preferably 10000 to 1000000mm²And s. The methyl group-containing polyorganosiloxane is typically a dimethylsilicone Oil (Silicone Oil) composed of polydimethylsiloxane. The viscosity is expressed as kinematic viscosity, centistokes (cSt)mm²And s. The kinematic viscosity can be measured using a kinematic viscometer.

Further, the viscosity (mPas) may be divided by the density (g/cm)³) To obtain the final product. That is, the viscosity and density can be determined from the viscosity and density measured at 25 ℃ with an E-type rotational viscometer. Can be based on kinematic viscosity (mm)²Viscosity (mPa · s)/density (g/cm) ═ s³) This equation is calculated.

Specific examples of the methyl group-containing polyorganosiloxane include: WACKER (registered trademark SILICONE FLUID AK series, manufactured by shin-Etsu chemical Co., Ltd.) made by Wacker corporation, dimethyl SILICONE oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl SILICONE oil (KF-995), and the like, but the invention is not limited thereto.

As the phenyl group-containing polyorganosiloxane, for example, a polyorganosiloxane containing R³¹R³²SiO_2/2Siloxane units (D) shown³⁰Units) of a phenyl-containing polyorganosiloxane.

R³¹Is a group bonded to the silicon atom and represents phenyl or alkyl, R³²The group bonded to a silicon atom represents a phenyl group, and specific examples of the alkyl group include those described above, but a methyl group is preferable.

The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D)³⁰Unit) but other than D³⁰The unit may include the Q unit, the M unit, and/or the T unit.

In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include: by D only³⁰Polyorganosiloxane of unit composition comprising D³⁰Polyorganosiloxane unit and Q unit, comprising D³⁰Polyorganosiloxane of units and M units, comprising D³⁰Polyorganosiloxane unit and T unit, containing D³⁰Polyorganosiloxane unit, Q unit and M unit, containing D³⁰Polyorganosiloxane unit, polyorganosiloxane unit of M unit and polyorganosiloxane unit of T unit, and polyorganosiloxane composition containing D unit³⁰A unit, a Q unit, an M unit and a T unit.

The weight average molecular weight of the phenyl group-containing polyorganosiloxane is usually 1500 to 500000, but is preferably 100000 or less from the viewpoint of suppressing precipitation in the adhesive composition.

Specific examples of the phenyl group-containing polyorganosiloxane include: a trade name PMM-1043 (manufactured by Gelest, Inc. having a weight-average molecular weight of 67000 and a viscosity of 30000 mm) represented by the formula (C-1)²(s) and a trade name PMM-1025 represented by the formula (C-2) (manufactured by Gelest, Inc., having a weight-average molecular weight of 25200 and a viscosity of 500mm²(s) KF 50-3000 CS (manufactured by shin-Etsu chemical Co., Ltd.) having a trade name represented by the formula (C-3), a weight average molecular weight of 39400, and a viscosity of 3000mm²(s) TSF431 (manufactured by MOMENTIVE Inc., having a weight-average molecular weight of 1800 and a viscosity of 100 mm) represented by the formula (C-4)²(s) trade name TSF433 (manufactured by MOMENTIVE corporation, weight average molecular weight 3000, viscosity 450 mm) represented by the formula (C-5)²(s) and (C-6) a trade name PDM-0421 (manufactured by Gelest, Inc., having a weight-average molecular weight of 6200 and a viscosity of 100mm²(s) and a trade name PDM-0821 (manufactured by Gelest, Inc. having a weight average molecular weight of 8600 and a viscosity of 125 mm) represented by the formula (C-7)²And/s), but not limited thereto.

(m and n represent the number of repeating units.)

(m and n represent the number of repeating units.)

(m and n represent the number of repeating units.)

(m and n represent the number of repeating units.)

(m and n represent the number of repeating units.)

(m and n represent the number of repeating units.)

(m and n represent the number of repeating units.)

The silicone adhesive composition may contain the component (a) and the component (B) at an arbitrary ratio, but in consideration of the balance between adhesiveness and releasability, the ratio of the component (a) to the component (B) is preferably 99.995: 0.005-30: 70, more preferably 99.9: 0.1-75: 25.

the adhesive composition may contain a solvent for the purpose of adjusting the viscosity, and specific examples thereof include: aliphatic carbonated water, aromatic hydrocarbons, ketones, and the like, but are not limited thereto.

More specifically, there may be mentioned: hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene (mesitylene), cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, and the like, but is not limited thereto. Such solvents may be used singly or in combination of two or more.

When the adhesive composition contains a solvent, the content thereof is appropriately set in consideration of the viscosity of the adhesive composition to be expected, the coating method to be used, the thickness of the film to be produced, and the like, but the content is in the range of about 10 to 90 mass% with respect to the entire adhesive composition.

The viscosity of the adhesive composition is usually 500 to 20000 mPas, preferably 1000 to 5000 mPas at 25 ℃, and can be adjusted by changing the kind of the organic solvent used, the ratio thereof, the concentration of the film-constituting component, and the like, in consideration of various factors such as the coating method used, the desired film thickness, and the like. Here, the film-constituting component means a component other than a solvent.

The adhesive composition used in the present invention can be produced by mixing the film-forming component with a solvent. However, when the adhesive composition used in the present invention does not contain a solvent, the adhesive composition can be produced by mixing the film-forming components.

Specifically, the first step includes: a pre-step of applying the adhesive composition to a surface of a semiconductor substrate or a support substrate to form an adhesive coating layer; and a post-step of laminating the semiconductor substrate and the support substrate with the adhesive coating layer interposed therebetween, applying a load in a thickness direction of the semiconductor substrate and the support substrate while applying at least one of a heating treatment and a pressure reduction treatment, thereby bringing the semiconductor substrate, the adhesive coating layer, and the support substrate into close contact with each other, and then performing a post-heating treatment. The adhesive coating layer is finally cured as appropriate by post-heat treatment in the subsequent step to form an adhesive layer, thereby producing a laminate.

Here, the semiconductor substrate is a wafer, and the support substrate is a support. The adhesive composition may be applied to either or both of the semiconductor substrate and the supporting substrate.

Examples of the wafer include a silicon wafer having a diameter of 300mm and a thickness of about 770 μm, and a glass wafer, but the wafer is not limited thereto.

The support (carrier) is not particularly limited, and examples thereof include, but are not limited to, a silicon wafer having a diameter of 300mm and a thickness of about 700 μm.

The adhesive coating layer has a film thickness of usually 5 to 500 μm, but the film thickness is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more from the viewpoint of maintaining the film strength, and the film thickness is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 120 μm or less, and still more preferably 70 μm or less from the viewpoint of avoiding unevenness due to a thick film.

The coating method is not particularly limited, but spin coating is generally used. A method of separately forming a coating film by a spin coating method or the like and attaching the sheet-like coating film may be employed, and this is also referred to as coating or coating film.

The temperature of the heat treatment is usually 80 ℃ or higher, and is preferably 150 ℃ or lower from the viewpoint of preventing excessive curing. The time for the heat treatment is usually 30 seconds or more, preferably 1 minute or more from the viewpoint of reliably exhibiting the temporary adhesion performance, and the time for the heat treatment is usually 10 minutes or less, preferably 5 minutes or less from the viewpoint of suppressing the deterioration of the adhesive layer and other members.

The pressure reduction treatment may be carried out by exposing the two substrates and the adhesive coating layer therebetween to an air pressure of 10 to 10000 Pa. The time for the pressure reduction treatment is usually 1 to 30 minutes.

In a preferred embodiment of the present invention, the two substrates and the layer therebetween are preferably bonded by heat treatment, more preferably by using both heat treatment and reduced pressure treatment.

The load in the thickness direction of the semiconductor substrate and the supporting substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the supporting substrate, and the layers therebetween and can firmly adhere them to each other, but is usually within a range of 10 to 1000N.

The post-heating temperature is preferably 120 ℃ or higher from the viewpoint of obtaining a sufficient curing rate, and is preferably 260 ℃ or lower from the viewpoint of preventing deterioration of the substrate and the adhesive. The heating time is usually 1 minute or more from the viewpoint of achieving appropriate bonding of the cured wafers, and is preferably 5 minutes or more from the viewpoint of stabilization of physical properties of the adhesive, and the heating time is usually 180 minutes or less, and preferably 120 minutes or less from the viewpoint of avoiding adverse effects on the adhesive layer due to excessive heating, and the like. Heating may be performed using a hot plate, an oven, or the like. One of the purposes of the post-heat treatment is to cure the component (a) more appropriately.

Next, a second step of processing the semiconductor substrate of the obtained laminate by the method described above will be described.

As an example of the processing performed on the laminate used in the present invention, processing of the back surface opposite to the circuit surface of the front surface of the semiconductor substrate, typically, thinning of the wafer by polishing of the back surface of the wafer, may be mentioned. Using such a thinned wafer, formation of through-silicon vias (TSVs) and the like is performed, and then the thinned wafer is peeled off from the support to form a stacked body of wafers, thereby achieving three-dimensional mounting. Further, formation of a wafer back surface electrode and the like is also performed before and after three-dimensional mounting. In the thinning of the wafer and the TSV process, heat of 250-350 ℃ is applied in a state of being adhered to the support, but the adhesive layer included in the laminate used in the present invention has heat resistance to the heat.

For example, a wafer having a diameter of 300mm and a thickness of about 770 μm can be thinned to a thickness of about 80 μm to 4 μm by polishing the back surface opposite to the circuit surface on the front surface.

Next, a third step of peeling off the semiconductor substrate formed of the semiconductor substrate after the processing will be described.

Examples of the method for peeling off the laminate used in the present invention include: solvent peeling, laser peeling, mechanical peeling using a tool having a sharp portion, peeling between the support and the wafer, and the like, but is not limited thereto. Generally, peeling is performed after processing such as thinning.

In the third step, the adhesive does not necessarily adhere to the support substrate side completely and is peeled off, and a part of the adhesive may remain on the processed substrate. Therefore, in the fourth step, by cleaning the surface of the substrate to which the residual adhesive is attached with the above-described detergent composition of the present invention, the adhesive on the substrate can be sufficiently cleaned and removed.

Finally, a fourth step of cleaning and removing the adhesive residue remaining on the semiconductor substrate composed of the peeled semiconductor substrate with the cleaning agent composition will be described.

The fourth step is a step of removing the adhesive residue remaining on the peeled substrate by cleaning with the cleaning agent composition of the present invention, and specifically, for example, the thinned substrate remaining on the adhesive is immersed in the cleaning agent composition of the present invention, and if necessary, the adhesive residue may be removed by cleaning with a method such as ultrasonic cleaning.

In the case of ultrasonic cleaning, conditions are appropriately determined in consideration of the state of the surface of the substrate, and the adhesive residue remaining on the substrate can be sufficiently removed by performing cleaning treatment under conditions of 20kHz to 5MHz and 10 seconds to 30 minutes in general.

The method for manufacturing a thinned substrate according to the present invention includes the first to fourth steps described above, and may include steps other than these steps. For example, in the fourth step, before the cleaning with the cleaning agent composition of the present invention, the substrate may be immersed in various solvents or tape stripping (tape stripping) may be performed to remove the adhesive residue, as necessary.

In addition, various modifications may be made to the constituent elements and method elements related to the first to fourth steps without departing from the scope of the present invention.

The present invention will be described below by way of examples and comparative examples, but the present invention is not limited to the following examples. The apparatus used in the present invention is as follows.

(1) Stirrer (revolution and rotation stirrer): a rotation and revolution agitator ARE-500 manufactured by THINKY.

(2) Viscometer: a rotational viscometer TVE-22H manufactured by Toyobo industries, Ltd.

(3) The stirrer: mix Rotor Variable 1-1186-12 manufactured by AS ONE.

(4) And (3) a stirrer H: AS ONE, heating type Rocking Mixer (rock Mixer) HRM-1.

(5) Contact type film thickness meter: a thickness measuring apparatus WT-425 for a precision wafer manufactured in Tokyo, Ltd.

[1] Preparation of adhesive composition

[ preparation example 1]

To a 600mL stirring vessel exclusive for use in a rotation and revolution stirrer were added 150g of a base polymer (Wacker Chemie) composed of a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPas as (a1) and a vinyl group-containing MQ resin, 15.81g of an SiH group-containing linear polydimethylsiloxane (Wacker Chemie) having a viscosity of 100 mPas as (a2) and 0.17g of 1-ethynyl-1-cyclohexanol (Wacker Chemie) as (A3), and the mixture was stirred for 5 minutes in the rotation and revolution stirrer.

To the obtained mixture, 0.33g of a platinum catalyst (product of Wacker Chemie) as (a2) and 9.98g of a vinyl group-containing linear polydimethylsiloxane (product of Wacker Chemie) having a viscosity of 1000mPa · s as (a1) were added, and the mixture was stirred in a 50mL screw tube for 5 minutes in a rotation and revolution stirrer to obtain 0.52g of a mixture, and the mixture was stirred in the rotation and revolution stirrer for 5 minutes, and the obtained mixture was filtered with a nylon filter 300 mesh to obtain an adhesive composition. The viscosity of the adhesive composition measured with a rotational viscometer was 9900mPa · s.

[ preparation example 2]

To a 600mL stirring vessel exclusive for use in a rotation and revolution stirrer, 95g of a vinyl group-containing MQ resin (Wacker Chemie corporation) as (a1), 93.4g of p-menthane (manufactured by Nippon Terpene Chemicals) as a solvent, and 0.41g of 1, 1-diphenyl-2-propyn-1-ol (manufactured by tokyo chemical industries, ltd.) were added, and stirred in the rotation and revolution stirrer for 5 minutes.

To the resulting mixture were added 29.5g of SiH group-containing linear polydimethylsiloxane (Wacker Chemie) having a viscosity of 100 mPas as (a2), and vinyl group-containing linear polydimethylsiloxane (Wacker Chemie) having a viscosity of 200 mPas as (a1), as (B)Viscosity of 1000000mm²0.41g of polyorganosiloxane (product name: AK1000000, manufactured by Wacker Chemie) and 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as (A3) were further stirred for 5 minutes in a rotary and rotary stirrer.

Then, to the obtained mixture were added 14.9g of a mixture obtained by stirring 0.20g of the platinum catalyst (Wacker Chemie) as (a2) and 17.7g of a vinyl group-containing linear polydimethylsiloxane (Wacker Chemie) having a viscosity of 1000mPa · s as (a1) in a 50mL screw tube for 5 minutes in a rotation and revolution stirrer, followed by stirring for 5 minutes in the rotation and revolution stirrer and filtering the obtained mixture with a nylon filter 300 mesh to obtain an adhesive composition. The viscosity of the adhesive composition measured with a rotary viscometer was 4600mPa · s.

[2] Preparation of detergent composition

[ example 1]

To 5g of tetrabutylammonium fluoride trihydrate (manufactured by kanto chemical corporation), 95g of N, N' -tetramethylurea as a solvent was added and stirred to obtain a cleaning agent composition.

[ example 2]

A cleaning agent composition was obtained in the same manner as in example 1, except that N, N '-tetraethylurea was used instead of N, N' -tetramethylurea.

[ example 3]

A cleaning agent composition was obtained in the same manner as in example 1 except that 47.5g of N, N, N ', N' -tetramethylurea and 47.5g of 1, 2-diethoxyethane were used as solvents.

[ example 4]

A cleaning agent composition was obtained in the same manner as in example 1 except that 47.5g of N, N, N ', N' -tetramethylurea and 47.5g of mesitylene were used as solvents.

[ example 5]

A cleaning agent composition was obtained in the same manner as in example 1 except that 47.5g of N, N, N ', N' -tetramethylurea and 47.5g of tetrahydrofuran were used as solvents.

[ example 6]

A cleaning agent composition was obtained in the same manner as in example 1 except that 47.5g of N, N, N ', N' -tetramethylurea and 47.5g of cyclopentylmethyl ether were used as solvents.

[ example 7]

A cleaning agent composition was obtained in the same manner as in example 1 except that 47.5g of N, N, N ', N' -tetramethylurea and 47.5g of tetrahydropyran were used as solvents.

Comparative example 1

A cleaning agent composition was obtained in the same manner as in example 1, except that 1, 3-dimethyl-2-imidazolidinone was used instead of N, N' -tetramethylurea.

[3] Evaluation of Performance of cleaning agent composition

The following evaluations were made because a high cleaning speed at which the adhesive residue is dissolved immediately after contact with the cleaning agent composition and an excellent cleaning power for maintaining the cleaning were required for the excellent cleaning agent composition. By combining a higher cleaning speed and a higher cleaning durability, more effective cleaning can be expected.

[ 3-1 ] measurement of etching Rate

The etching rate was measured in order to measure the cleaning rate of the obtained cleaning agent composition. The adhesive composition obtained in preparation example 1 was applied to a 12-inch silicon wafer by a spin coater to a thickness of 100 μm, and cured at 150 ℃/15 minutes and 190 ℃/10 minutes. The wafer after film formation was cut into 4cm square pieces, and the film thickness was measured using a contact film thickness meter. Then, the piece was placed in a stainless steel dish having a diameter of 9cm, 7mL of the resulting detergent composition was added thereto, and the lid was closed, and then the mixture was placed in a stirrer H and stirred/washed at 23 ℃ for 5 minutes. After cleaning, the wafer was taken out, cleaned with isopropyl alcohol and pure water, subjected to dry baking (dry cake) at 150 ℃ for 1 minute, and then the film thickness was measured again by a contact film thickness meter, the decrease in film thickness was measured before and after cleaning, and the etching rate [ μm/min ] was calculated as an index of cleaning power by dividing the amount of decrease by the cleaning time. The results are shown in Table 1.

[ 3-2 ] evaluation of solubility

In order to measure the cleaning durability of the obtained cleaning agent composition, a dissolution test of the adhesive was performed. The adhesive composition obtained in preparation example 2 was applied to a 12-inch silicon wafer by means of a spin coater, and cured at 120 ℃/1.5 minutes followed by 200 ℃/10 minutes. Then, the cured product of the adhesive composition was scraped off from the 12-inch wafer using the blade of the cutter. 1g of a cured product of the adhesive composition was weighed into a 9mL screw tube, and 2g of the obtained cleaning agent composition was added to confirm the dissolution state of the cured product at 23 ℃. The case where the cured product was completely dissolved within 1 to 2 hours was regarded as "excellent", the case where the cured product was completely dissolved within 2 to 12 hours was regarded as "excellent", the case where most of the cured product was dissolved within 12 to 24 hours was regarded as "good", and the case where most of the cured product remained dissolved even with time was regarded as "poor". The results are shown in Table 1.

[ Table 1]

	Etching Rate [ mu m/min]	Dissolution test
			Example 1	10.0	Good taste
Example 2	5.5	Is very good
			Example 3	11.1	Is very good
Example 4	9.1	Is very good
			Example 5	12.53	Is very good
Example 6	11.9	Is very good
			Example 7	10.5	Is very good
Comparative example 1	4.0	Difference (D)

As shown in table 1, the cleaning agent composition of the present invention using N, N '-tetramethylurea as N, N' -tetra (hydrocarbon) urea together with tetrabutylammonium fluoride as a quaternary ammonium salt exhibited not only a high etching rate, i.e., an excellent cleaning rate, but also an excellent solubility to an adhesive as compared with the cleaning agent of the comparative example.

[ 3-3 ] evaluation of corrosiveness

The silicon wafer was immersed in each of the cleaning agent compositions obtained in examples 1 to 7 for 5 minutes, and as a result, no corrosion of the silicon wafer was observed in any of the cases where any of the compositions was used.