JP7299564B2 - Method for improving detergency of detergent composition, method for producing detergent composition, and detergent composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for improving the detergency of a detergent composition, a method for producing a detergent composition, and a detergent composition.

Semiconductor wafers, which have conventionally been integrated in a two-dimensional planar direction, are required to integrate (stack) a planar surface in a three-dimensional direction for the purpose of further integration (stacking). This three-dimensional lamination is a technique of integrating in multiple layers while connecting with a through silicon via (TSV). In multi-layer integration, each wafer to be integrated is thinned by polishing the side opposite to the circuit surface (that is, the back surface), and the thinned semiconductor wafers are stacked.

A semiconductor wafer (herein simply referred to as a wafer) prior to thinning is adhered to a support for polishing with a polishing apparatus. The adhesion at that time is called temporary adhesion because it must be easily peeled off after polishing. This temporary adhesion must be easily removed from the support, and if a large force is applied to the removal, the thinned semiconductor wafer may be cut or deformed. easily removed. However, it is not preferable that the back surface of the semiconductor wafer is removed or displaced due to polishing stress. Therefore, the performance required for the temporary adhesion is to withstand the stress during polishing and to be easily removed after polishing. For example, it is required to have high stress (strong adhesion) in the planar direction during polishing and low stress (weak adhesion) in the vertical direction during removal. In addition, high temperatures of 150° C. or higher may occur during processing, and heat resistance is also required.

Under such circumstances, in the field of semiconductors, polysiloxane-based adhesives that have these properties are mainly used as temporary adhesives. In polysiloxane bonding using a polysiloxane adhesive, adhesive residue often remains on the surface of the substrate after the thinned substrate is peeled off. In addition, a cleaning composition for removing this residue and cleaning the surface of a semiconductor substrate has been developed (for example, Patent Documents 1 and 2). There is always a demand for Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide, and Patent Document 2 discloses a cured resin remover containing an alkyl ammonium fluoride. However, further improvement in the detergency of detergent compositions is desired.

WO2014/092022 U.S. Pat. No. 6,818,608

The present invention has been made in view of the above circumstances, and a cleaning composition for removing adhesive residue on a semiconductor substrate after the temporary adhesion by an adhesive layer obtained using a siloxane-based adhesive has been peeled off. It is an object of the present invention to provide a method for improving the cleaning ability of objects, a method for producing a cleaning composition capable of favorably removing such substances, and such a cleaning composition.

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, the removal of adhesive residue on the semiconductor substrate after the temporary adhesion by the adhesive layer obtained by using, for example, a siloxane-based adhesive is peeled off. The inventors have found that the detergency can be improved by reducing the water content of a detergent composition containing a quaternary ammonium salt with a dehydrating agent, and completed the present invention.

That is, the present invention
1. 1. A method for improving the cleaning performance of a cleaning composition used to remove adhesive residue comprising a quaternary ammonium salt and an organic solvent, comprising:
A method for improving the detergency of a detergent composition, comprising the step of using a dehydrating agent to reduce the water content of the dehydrated detergent composition,
2. 1. A method for improving the detergency of a detergent composition, wherein the dehydrating agent comprises a physical desiccant;
3. 2. Method for improving detergency of a detergent composition, wherein the physical desiccant comprises at least one selected from the group consisting of silica gel, alumina and molecular sieves;
4. The method for improving the detergency of a detergent composition according to any one of 1 to 3, wherein the quaternary ammonium salt comprises a halogen-containing quaternary ammonium salt;
5. 4. The method for improving the detergency of the detergent composition, wherein the fluorine-containing quaternary ammonium salt contains tetra(hydrocarbon)ammonium fluoride;
6. A method for producing a cleaning composition used for removing adhesive residue, comprising the step of dehydrating a cleaning composition to be dewatered containing a quaternary ammonium salt and an organic solvent using a dehydrating agent;
7. 6. The method for producing a cleaning composition, wherein the dehydrating agent comprises a physical desiccant;
8. 7. The method for producing a cleaning composition according to 7, wherein the physical desiccant comprises at least one selected from the group consisting of silica gel, alumina and molecular sieves;
9. 8. The method for producing a cleaning composition according to any one of 6 to 8, wherein the quaternary ammonium salt comprises a halogen-containing quaternary ammonium salt;
10. 9. The method for producing a cleaning composition according to 9, wherein the halogen-containing quaternary ammonium salt comprises a fluorine-containing quaternary ammonium salt;
11. A cleaning composition used to remove adhesive residues, the cleaning composition comprising a quaternary ammonium salt and an organic solvent and having a water content of less than 0.5% by weight;
12. 11 cleaning compositions, wherein the quaternary ammonium salt comprises a halogen-containing quaternary ammonium salt;
13. The halogen-containing quaternary ammonium salt provides a detergent composition according to 11 or 12, wherein the fluorine-containing quaternary ammonium salt is included.

According to the present invention, the ability of cleaning compositions containing quaternary ammonium salts to remove adhesive residues can be enhanced by a simple treatment with a dehydrating agent.

The present invention will be described in more detail below.
The method for improving the cleaning performance of a cleaning composition of the present invention is a method for improving the cleaning performance of a cleaning composition used for removing adhesive residue containing a quaternary ammonium salt, comprising: reducing the water content of the dehydrated cleaning composition using
In the present invention, the dehydrated cleaning composition is a composition to be dehydrated using a dehydrating agent. The cleaning agent composition to be dewatered is usually a composition that has cleaning ability without being subjected to dehydration treatment and can be used to remove adhesive residue, but if dehydration treatment is performed, , its detergency is improved.

The dehydrating agent is not particularly limited as long as it does not impair the detergency of the detergent composition. is preferable.

In the present invention, the dehydrating agent is preferably a physical desiccant because it generally has little effect on the quaternary ammonium salt that expresses the detergency of the detergent composition and can improve the detergency with good reproducibility. A physical desiccant is one that does not undergo chemical changes due to moisture absorption, has porous pores, and develops dehydrating ability solely by adsorbing water.
The pores of such a physical desiccant are capable of removing water in the composition and retaining active ingredients derived from quaternary ammonium salts in the composition (e.g., fluorine anion of tetraalkylammonium fluoride). It is desirable not to remove it, and its effective radius is usually 1 nm or less, preferably 0.3 nm or less.

Physical desiccants typically include, but are not limited to, silica gel, alumina, molecular sieves, and the like.
Commercially available physical desiccants include, but are not limited to, Molecular Sieves 3A, Molecular Sieves 4A, Molecular Sieves 5A, Molecular Sieves 13X, and the like.

The dewatered detergent composition used in the present invention contains 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 can be used for this type of application.

Such quaternary ammonium cations typically include tetra(hydrocarbon)ammonium cations. On the other hand, as the anions that ^{form a} pair with it ^, there are hydroxide ions (OH ⁻ ) ^; tetrafluoroborate ion (BF ₄ ⁻ ); hexafluorophosphate ion (PF ₆ ⁻ ), etc., but not limited thereto.

In the present invention, the quaternary ammonium salt preferably includes a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.
In the quaternary ammonium salt, the halogen atom may be contained in the cation or the anion, preferably the anion.

In a preferred embodiment, the fluorine-containing quaternary ammonium salt comprises tetra(hydrocarbon)ammonium fluoride (ie, 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, and an alkynyl group having 6 to 20 carbon atoms. Specific examples of such alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, including aryl groups such as those described below, are the same as those described below.

In one preferred embodiment of the invention, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride (ie, a tetraalkylammonium fluoride).
Specific examples of tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride. Among them, tetrabutylammonium fluoride (tetrabutylammonium fluoride (TBAF)) is preferred.

Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used as hydrates. Further, quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride and hydrates thereof 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 dissolves in the solvent contained in the cleaning agent composition to be dehydrated. is.

The dehydrated cleaning agent composition used in the present invention contains an organic solvent.
Such an organic solvent is not particularly limited as long as it is used for this type of application, and examples thereof include amide compounds.
More specifically, a preferred example is an acid amide derivative represented by formula (Z).

In the formula, R ⁰ represents an ethyl group, a propyl group or an isopropyl group, preferably an ethyl group. R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms. Alkyl groups having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, Examples include s-butyl group, t-butyl group, cyclobutyl group and the like. Among these, R ^A and R ^B are preferably methyl or ethyl groups.

Acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N, N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc., but are limited to these. not. An acid amide derivative can be used individually by 1 type or in combination of 2 or more types.
Among these, N,N-dimethylpropionamide is particularly preferred.

The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

The dehydrated cleaning agent composition of the present invention may contain one or more organic solvents different from the amide compounds described above.
Such other organic solvent is used for this type of application, and is particularly limited as long as it dissolves the quaternary ammonium salt and is compatible with the above-described amide compound. not a thing

An example of another preferred organic solvent is alkylene glycol dialkyl ether.

Specific examples of alkylene glycol dialkyl ether include ethylene glycol dimethyl ether (1,2-dimethoxyethane), ethylene glycol diethyl ether (1,2-diethoxyethane), ethylene glycol dipropyl ether , ethylene glycol dibutyl ether, propylene glycol dimethyl ether. , propylene glycol diethyl ether, propylene glycol dipropyl ether, and the like, but are not limited to these.
An alkylene glycol dialkyl ether can be used individually by 1 type or in combination of 2 or more types.

Another preferable example of the organic solvent is an aromatic hydrocarbon compound, and a specific example thereof is an aromatic hydrocarbon compound represented by formula (1).

In the above formula (1), specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl, s-butyl, t-butyl and the like. .
s represents the number of substituents R ¹⁰⁰ substituted on the benzene ring, and is 2 or 3;

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

Each R ¹⁰⁰ independently represents an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms of the three R ¹⁰⁰ alkyl groups having 1 to 5 carbon atoms in formula (1-1) is 3 or more. and the total number of carbon atoms of the two R ¹⁰⁰ alkyl groups having 1 to 6 carbon atoms in formula (1-2) is 3 or more.

Specific examples of the aromatic hydrocarbon compound represented by 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-s-butyltoluene, 4-isobutyltoluene, 4-t-butyl Examples include, but are not limited to, toluene.
Among them, mesitylene and 4-t-butyltoluene are preferred.

Another preferred example of the organic solvent is a cyclic structure-containing ether compound. The cyclic structure-containing ether compounds include cyclic ether compounds, cyclic alkyl chain alkyl ether compounds, cyclic alkyl branched alkyl ether compounds, and di(cyclic alkyl) ether compounds. The cyclic structure-containing ether compounds can be used singly or in combination of two or more.
A cyclic ether compound is a cyclic hydrocarbon compound in which at least one carbon atom constituting a ring is substituted with an oxygen atom.
Typically, an epoxy compound obtained by epoxidizing a linear, branched or cyclic saturated hydrocarbon compound (that is, two carbon atoms and an oxygen atom adjacent to each other form a three-membered ring) or , cyclic ether compounds other than epoxy in which carbon atoms constituting the ring of cyclic hydrocarbon compounds having 4 or more carbon atoms (excluding aromatic hydrocarbon compounds) are substituted with oxygen atoms (epoxy compounds are excluded). The same applies hereinafter.) Among others, as such a cyclic hydrocarbon compound having 4 or more carbon atoms, a saturated cyclic hydrocarbon compound having 4 or more carbon atoms is preferable.

Although the number of carbon atoms in the epoxy compound is not particularly limited, it is usually 4-40, preferably 6-12.
Although the number of epoxy groups is not particularly limited, it is usually 1 to 4, preferably 1 or 2.

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

The carbon number of the cyclic ether compound other than epoxy is not particularly limited, but is usually 3-40, preferably 4-8.
Although the number of oxygen atoms (ether groups) is not particularly limited, it is usually 1 to 3, preferably 1 or 2.

Specific examples of cyclic ether compounds other than the epoxy include oxacyclobutane (oxetane), oxacyclopentane (tetrahydrofuran), oxacyclic saturated hydrocarbon compounds such as oxacyclohexane, 1,3-dioxacyclopentane, 1,3- Dioxa cyclic saturated hydrocarbon compounds such as dioxacyclohexane (1,3-dioxane), 1,4-dioxacyclohexane (1,4-dioxane), and the like, but not limited thereto.

The cyclic alkyl chain alkyl ether compound consists of a cyclic alkyl group, a chain alkyl group, and an ether group connecting the two, and the number of carbon atoms thereof is not particularly limited, but is usually 4 to 40. Yes, preferably 5-20.
The cyclic alkyl branched alkyl ether compound consists of a cyclic alkyl group, a branched alkyl group, and an ether group connecting the two, and the number of carbon atoms thereof is not particularly limited, but is usually 6 to 40. Yes, preferably 5-20.
The di(cyclic alkyl) ether compound consists of two cyclic alkyl groups and an ether group connecting the two, and the number of carbon atoms thereof is not particularly limited, but is usually 6 to 40, It is preferably 10-20.
Among them, as the cyclic ether compound other than epoxy, a cyclic alkyl chain alkyl ether compound and a cyclic alkyl branched alkyl ether compound are preferable, and a cyclic alkyl chain alkyl ether compound is more preferable.

A chain alkyl group is a group derived by removing a terminal hydrogen atom from a linear aliphatic hydrocarbon, and the number of carbon atoms thereof is not particularly limited, but is usually 1 to 40, preferably is 1-20.
Specific examples include a methyl group, an ethyl group, a 1-n-propyl group, a 1-n-butyl group, a 1-n-pentyl group, a 1-n-hexyl group, a 1-n-heptyl group, and a 1-n -octyl group, 1-n-nonyl group, 1-n-decyl group and the like, but are not limited thereto.

A branched alkyl group is a group derived by removing a hydrogen atom from a linear or branched aliphatic hydrocarbon, other than a chain alkyl group, and the number of carbon atoms thereof is particularly limited. but usually 3-40, preferably 3-40.
Specific examples thereof include, but are not limited to, isopropyl group, isobutyl group, s-butyl group, t-butyl group and the like.

A cyclic alkyl group is a group derived by removing a hydrogen atom on a carbon atom constituting a ring of a cyclic aliphatic hydrocarbon, and the number of carbon atoms thereof is not particularly limited, but usually 3 to 40. Yes, preferably 5-20.
Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cycloheptyl group, a monocycloalkyl group such as cyclohexyl, a bicyclo[2.2.1]heptan-1-yl group, and a bicyclo[2.2.1 ] heptane-2-yl group, bicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octane-2- yl group, bicycloalkyl group such as bicyclo[2.2.2]octan-7-yl group, and the like, but are not limited thereto.

Specific examples of cyclic alkyl chain alkyl ether compounds 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. It can be, but is not limited to.
Specific examples of cyclic alkyl branched alkyl ether compounds include, but are not limited to, cyclopentyl isopropyl ether, cyclopentyl t-butyl ether, and the like.
Specific examples of the di(cyclic alkyl) ether compound include, but are not limited to, dicyclopentyl ether, dicyclohexyl ether, cyclopentylcyclohexyl ether, and the like.

The amount of the other organic solvent different from the above-mentioned amide compound is limited to the extent that the solid content contained in the cleaning agent composition to be dewatered does not precipitate and is uniformly mixed with the amide compound. It is appropriately determined in the range of 5 to 95% by mass in the solvent contained in the substance.

The dehydrated detergent composition used in the present invention is obtained by mixing the above quaternary ammonium salt or its hydrate, the above organic solvent and, if necessary, other ingredients. Such hydrates include, but are not limited to, tetrabutylammonium fluoride trihydrate and the like.
The components of the dewatered cleaning agent composition can be mixed in any order as long as problems such as precipitation and separation of the composition do not occur.
That is, of all the components of the cleaning agent composition to be dewatered, a part 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 to be dewatered may be filtered, or the supernatant may be collected while avoiding the insoluble components after mixing, and used as the cleaning agent composition to be dewatered. Further, when the components used are hygroscopic or deliquescent, for example, all or part of the preparation of the dehydrated cleaning agent composition may be carried out under inert gas.

The procedure for reducing the water content of the dehydrated cleaning composition using a dehydrating agent is not particularly limited, but an example is the following method.
The cleaning agent composition to be dewatered is put into a suitable container, and the dehydrating agent is further added thereto, or the dehydrating agent is put into a suitable container, the cleaning agent composition to be dewatered is further added thereto, and the resulting mixture is The dehydrating agent is removed after the dehydration treatment is carried out by allowing to stand for an appropriate time while stirring if necessary. By doing so, it is possible to obtain a detergent composition with improved detergency. In addition, filtration, centrifugation, etc. are mentioned as the method of removing a dehydrating agent.

The amount of the dehydrating agent is usually 5% by mass or more, preferably 10% by mass or more, with respect to the dewatering cleaning agent composition, from the viewpoint of improving the cleaning ability with good reproducibility by reliable dehydration. From the viewpoint of avoiding loss due to adsorption of the composition, the content is usually 50% by mass or less, preferably 40% by mass or less.
The dehydration treatment time is not particularly limited as long as dehydration is performed, but from the viewpoint of improving the detergency with good reproducibility by reliable dehydration, it is usually 6 hours or more, preferably 12 hours or more, more preferably 12 hours or more. It is 16 hours or more, more preferably 20 hours or more, and still more preferably 24 hours or more, and from the viewpoint of avoiding losses due to adsorption of the composition to the dehydrating agent, unnecessary side reactions, etc., it is usually 96 hours or less, preferably 96 hours or more. It is 72 hours or less, more preferably 48 hours or less, still more preferably 36 hours or less.

Moreover, the following method is mentioned as another example of the dehydration method.
A column tube is filled with a dehydrating agent, or a funnel is filled with the dehydrating agent, and the cleaning agent composition to be dehydrated is allowed to flow through the dehydration agent, after which the composition is recovered. By doing so, it is possible to obtain a detergent composition with improved detergency.

According to the method for improving the cleaning ability of the cleaning composition of the present invention described above, it is possible to realize a cleaning composition having improved cleaning ability for polysiloxane adhesives.
Specifically, regarding the cleaning speed, when the adhesive layer obtained from the adhesive composition was brought into contact with the cleaning composition for 5 minutes at room temperature (23°C), the film thickness reduction was measured before and after the contact, and the reduction was With respect to the etching rate [μm/min] calculated by dividing the amount of cleaning time by the cleaning time, the etching rate of the cleaning composition, which is the composition after dehydration treatment using the dehydrating agent, is It is usually 0.2 [μm/min] or more, and in a preferred embodiment, 0.3 [μm/min] or more, more preferably than the value of the etching rate of the dehydrated cleaning composition, which is the composition before treatment. It is as high as 0.4 [μm/min] or more in a preferred embodiment, 0.5 [μm/min] or more in a more preferred embodiment, and 0.6 [μm/min] or more in a further preferred embodiment.

In the present invention, the water content of the cleaning composition obtained after the step of reducing the water content of the cleaning composition to be dehydrated using a dehydrating agent is usually less than 0.50% by mass, preferably less than 0.40% by mass. %, even more preferably less than 0.30 wt%, even more preferably less than 0.20 wt%, even more preferably less than 0.15 wt%. By setting the water content in such a range, excellent detergency is exhibited. The reason for such excellent detergency is not clear, but water in the composition has an adverse effect on the active ingredient derived from the quaternary ammonium salt, and in particular, water is the active ingredient derived from the tetraalkylammonium fluoride. It is presumed that the fluorine anion is adversely affected, and as a result, the function as a detergent composition is impaired. In the present invention, the water content can be calculated, for example, by the Karl Fischer method using a trace water content analyzer CA-200 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).
Among them, a dehydrated detergent composition prepared using a quaternary ammonium salt hydrate always contains water derived from the hydrate even when only an organic solvent is used as a solvent. There is concern about the adverse effects of water on
Therefore, according to the present invention, a dewatered cleaning agent prepared using a quaternary ammonium salt hydrate, in particular a tetra(hydrocarbon)ammonium fluoride hydrate such as tetrabutylammonium fluoride hydrate, When the composition is used, the improvement in detergency appears more remarkably.

The method for producing a cleaning composition of the present invention is a method for producing a cleaning composition used for removing adhesive residue, the cleaning composition to be dehydrated containing a quaternary ammonium salt and an organic solvent. It includes the step of dehydrating the object using a dehydrating agent.
The cleaning composition to be dewatered, the dehydrating agent, the dewatering method, related conditions, preferred embodiments, and the like are the same as those described above.

The cleaning composition of the present invention can be obtained, for example, by the method for producing the cleaning composition of the present invention described above. .
Specifically, the cleaning rate was measured by contacting the adhesive layer obtained from the adhesive composition with the cleaning composition for 5 minutes at room temperature (23° C.), measuring the film thickness reduction before and after the contact, The cleaning composition of the present invention has an etching rate [μm/min] calculated by dividing the decreased amount by the cleaning time, and is usually 9.1 [μm/min] or more. 2 [μm/min] or more, in a more preferred embodiment it is 9.3 [μm/min] or more, in a still more preferable embodiment it is 9.4 [μm/min] or more, and in a still more preferable embodiment it is 9 .5 [μm/min] or more.
Further, regarding the cleaning durability, when 1 g of the adhesive solid obtained from the adhesive composition is brought into contact with 2 g of the cleaning composition at room temperature (23° C.), the cleaning composition of the present invention usually has a cleaning power of 12%. It takes about 24 hours to dissolve most of the adhesive solids, preferably 2 to 12 hours to completely dissolve the adhesive solids, and in a more preferred embodiment 1 to 2 hours to completely dissolve the adhesive solids.

According to the present invention, it is possible to clean the substrate in a short time by cleaning and removing the polysiloxane-based adhesive remaining on the substrate, such as a semiconductor substrate, using the cleaning composition. It is possible to clean substrates such as semiconductor substrates with high efficiency.
The cleaning 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. , gallium-arsenide substrate, gallium-phosphorus substrate, gallium-arsenic-aluminum substrate, aluminized silicon substrate, copper-plated silicon substrate, silver-plated silicon substrate, gold-plated silicon substrate, titanium-plated silicon substrate, silicon nitride film-formed silicon substrate, oxidation Various substrates such as a silicon film-formed silicon substrate, a polyimide film-formed silicon substrate, a glass substrate, a quartz substrate, a liquid crystal substrate and an organic EL substrate are also included.

Suitable methods for using the cleaning composition of the present invention in semiconductor processes include use in methods for manufacturing processed substrates such as thinned substrates used in semiconductor package technology such as TSV.
Specifically, a first step of manufacturing a laminate comprising 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, and processing A method for manufacturing a processed substrate, comprising a third step of subsequently peeling off the semiconductor substrate, and a fourth step of washing and removing adhesive residue remaining on the peeled semiconductor substrate with a detergent composition, as a detergent composition A cleaning composition of the present invention is used.

The adhesive composition used for forming the adhesive layer in the first step typically includes silicone-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, and polystyrene-based adhesives. At least one adhesive selected from the group consisting of adhesives, polyimide adhesives, and phenolic resin adhesives may be used, but the cleaning composition of the present invention is used particularly for cleaning polysiloxane adhesives. It is effective to employ the cleaning composition of the present invention, and among others, the cleaning composition of the present invention is effective for cleaning and removing adhesive residue of a polysiloxane adhesive containing a component (A) that cures by a hydrosilylation reaction.
Therefore, a method for producing a processed substrate using a polysiloxane-based adhesive (adhesive composition) containing a component (A) that cures by a hydrosilylation reaction (adhesive composition) and the cleaning composition of the present invention will be described below. The invention is not so limited.

First, the 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) contained in the adhesive composition and cured by a hydrosilylation reaction is, for ^{example, a siloxane unit (Q unit) represented by SiO2} _, ^a siloxane unit represented by ^R1R2R3SiO1 _/2 ( M units), siloxane units represented by R ⁴ R ⁵ SiO _2/2 (D units), and siloxane units represented by R ⁶ SiO _3/2 (T units). A polysiloxane (A1) containing the above units and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) is a siloxane unit (Q' unit) represented by SiO ₂ , R ¹ 'R Siloxane units represented by ^{2′R 3′SiO} _1/2 (M′ units), siloxane units represented by R ^{4′R 5′SiO} _2/2 (D′ units) and R ^6′SiO _3/2 Contains one or more units selected from the group consisting of siloxane units (T' units) represented by, and at least one selected from the group consisting of the above M' units, D' units and T' units A polyorganosiloxane (a1) containing a siloxane unit (Q" unit) represented by SiO ₂ , a siloxane unit (M" unit) represented by R ¹ ″R ² ″R ³ ″SiO _1/2 , and R ¹ or 2 selected from the group consisting of siloxane units represented by 4 ″R ⁵ ″SiO _2/2 (D″ units) and siloxane units represented by R ⁶ ″SiO _3/2 (T″ units) A polyorganosiloxane (a2) containing the above units and at least one selected from the group consisting of the above M″ units, D″ units and T″ units.

R ¹ to R ⁶ are groups or atoms bonded to a silicon atom and each independently represents an alkyl group, an alkenyl group or a hydrogen atom.
R ¹ ' to R ⁶ ' are groups bonded to a silicon atom and independently represent an alkyl group or an alkenyl group, and at least one of R ¹ ' to R ⁶ ' is an alkenyl group.
R ¹ ″ to R ⁶ ″ are groups or atoms bonded to a silicon atom and independently represent an alkyl group or a hydrogen atom, but at least one of R ¹ ″ to R ⁶ ″ is a hydrogen atom .

The alkyl group may be linear, branched or cyclic, but is preferably a linear or branched alkyl group. Yes, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group. , n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl- n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl -n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1 , 1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group etc., but not limited to these.
Among them, a methyl group is preferred.

Specific examples of cyclic alkyl groups 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 group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3- dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group , 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl -cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclo Cycloalkyl groups such as propyl , 2-ethyl-3-methyl-cyclopropyl, bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl Examples include, but are not limited to, alkyl groups and the like.

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

Specific examples of alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1 -propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group , 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group , 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl- 3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclo pentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1 -methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group , 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3- methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl- 2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3 -dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2, 3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group , 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group , 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1 -methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2 -methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl- 3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group etc., but not limited to these.
Among them, an ethenyl group and a 2-propenyl group are preferred.

As described above, polysiloxane (A1) includes polyorganosiloxane (a1) and polyorganosiloxane (a2), but alkenyl groups contained in polyorganosiloxane (a1) and polyorganosiloxane (a2) contain Hydrogen atoms (Si—H groups) form a crosslinked structure through a hydrosilylation reaction by the platinum group metal-based catalyst (A2) and are cured.

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

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

Further, when two or more types of polyorganosiloxanes included in the polyorganosiloxane (a1) are included, (Q' unit and M' unit) and (D' unit and M' unit) combination, (T' unit and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but these is not limited to

Polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q″ units, M″ units, D″ units and T″ units, and the M″ units, D″ units and It contains at least one selected from the group consisting of T″ units. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

Preferred combinations of two or more selected from the group consisting of Q″ units, M″ units, D″ units and T″ units include (M″ units and D″ units), (Q″ units and M″ units), (Q" units and T" units and M" units).

Polyorganosiloxane (a1) is composed of siloxane units in which alkyl groups and/or alkenyl groups ^are bonded to silicon atoms thereof, and ^alkenyl The proportion of the group is preferably 0.1 mol % to 50.0 mol %, more preferably 0.5 mol % to 30.0 mol %, and the remaining R ¹ ' to R ⁶ ' are alkyl groups. be able to.

Polyorganosiloxane (a2) is composed of siloxane units in which alkyl groups and/or hydrogen atoms are bonded to silicon atoms thereof, and all substituents and substituents represented by R ¹ '' to R ⁶ '' The proportion of hydrogen atoms in the atoms is preferably 0.1 mol% to 50.0 mol%, more preferably 10.0 mol% to 40.0 mol%, and the remaining R ¹ ″ to R ⁶ ″ are It can be an alkyl group.

Polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2). In a preferred embodiment of the present invention, the alkenyl group contained in polyorganosiloxane (a1) and polyorganosiloxane The molar ratio with hydrogen atoms constituting Si—H bonds contained in (a2) is in the range of 1.0:0.5 to 1.0:0.66.

The weight average molecular weights of polyorganosiloxane (a1) and polyorganosiloxane (a2) are usually 500 to 1,000,000, preferably 5,000 to 50,000.

Incidentally, the weight average molecular weight, for example, GPC apparatus (Tosoh Corporation EcoSEC, HLC-8320GPC) and GPC column (Showa Denko Co., Ltd. Shodex (registered trademark), KF-803L, KF-802 and KF-801 ), the column temperature is 40 ° C., tetrahydrofuran is used as the eluent (elution solvent), the flow rate (flow rate) is 1.0 mL / min, and polystyrene (manufactured by Sigma-Aldrich) is used as a standard sample for measurement. be able to.

Polyorganosiloxane (a1) and polyorganosiloxane (a2) contained in such an adhesive composition react with each other through a hydrosilylation reaction to form a cured film. Therefore, the curing mechanism differs from that via, for example, silanol groups, and therefore all siloxanes contain silanol groups and functional groups that can form silanol groups by hydrolysis, such as alkyloxy groups. need not be included.

Component (A) contains a platinum group metal-based catalyst (A2) together with the polysiloxane (A1) described above.
Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si—H groups of the polyorganosiloxane (a2).

Specific examples of platinum-based metal catalysts include platinum black, platinum chloride, chloroplatinic acid, reactants of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, and the like. platinum-based catalysts including, but not limited to:
Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.

The amount of platinum group metal-based catalyst (A2) is usually in the range of 1.0 to 50.0 ppm with respect to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2).

Component (A) may contain a polymerization inhibitor (A3). By including a polymerization inhibitor in the adhesive composition, it becomes possible to suitably control curing by heating during lamination, and an adhesive composition that provides an adhesive layer having excellent adhesiveness and peelability can be obtained with good reproducibility. .

The polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction. alkynyl alkyl alcohols such as ols, but are not limited thereto.

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

Such an adhesive composition contains a component (B ) may be included. By including the component (B) in the adhesive composition, the resulting adhesive layer can be suitably peeled off with good reproducibility.

Examples of epoxy group-containing polyorganosiloxanes include those containing siloxane units ( ^D10 units) represented by R ¹¹ R ¹² SiO _2/2 .

R ¹¹ is a group bonded to a silicon atom and represents an alkyl group, R ¹² is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group are , the above examples can be mentioned.

In addition, the epoxy group in the organic group containing an epoxy group may be an independent epoxy group without being condensed with other rings, such as 1,2-epoxycyclohexyl group, other rings and condensed rings It may be an epoxy group that has been formed.

Specific examples of organic groups containing epoxy groups include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
In the present invention, a preferable example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but the present invention is not limited thereto.

The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units ( ^D10 units), but may contain the above Q units, M units and/or T units in addition to the ^D10 units.

In a preferred embodiment, specific examples of the epoxy group-containing polyorganosiloxane include polyorganosiloxane consisting only of ^D10 units, polyorganosiloxane containing ^D10 units and Q units, and ^D10 units and M units. Polyorganosiloxane, D Polyorganosiloxane containing ¹⁰ units and T units, D Polyorganosiloxane containing ¹⁰ units, Q units and M units, D Polyorganosiloxane containing ¹⁰ units, M units and T units, D Examples include polyorganosiloxanes containing ¹⁰ units, Q units, M units, and T units.

The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5, and its weight average molecular weight is usually 1,500 to 500,000. From the viewpoint of suppressing precipitation at , it is preferably 100,000 or less.

Specific examples of the epoxy group-containing polyorganosiloxane include CMS-227 (trade name, manufactured by Gelest Co., Ltd., weight average molecular weight: 27,000) represented by formula (A-1), represented by formula (A-2). Trade name ECMS-327 (manufactured by Gelest, weight average molecular weight 28,800), trade name KF-101 represented by formula (A-3) (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 31,800), Trade name KF-1001 represented by formula (A-4) (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 55,600), trade name KF-1005 represented by formula (A-5) (Shin-Etsu Chemical Kogyo Co., Ltd., weight average molecular weight 11,500), trade name X-22-343 represented by formula (A-6) (Shin-Etsu Chemical Co., Ltd., weight average molecular weight 2,400), formula ( A-7) represented by the trade name BY16-839 (manufactured by Dow Corning, weight average molecular weight 51,700), trade name represented by the formula (A-8) ECMS-327 (manufactured by Gelest, weight average molecular weight 28,800) and the like, but are not limited to these.

（ｍ及びｎはそれぞれ繰り返し単位の数である。）

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

（ｍ及びｎはそれぞれ繰り返し単位の数である。）

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

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

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

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

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

（ｍ、ｎ及びｏはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

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

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

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

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

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

（ｍ及びｎはそれぞれ繰り返し単位の数である。）

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

As the methyl group-containing polyorganosiloxane, for example, a siloxane unit represented by R ²¹⁰ R ²²⁰ SiO _2/2 (D ²⁰⁰ unit), preferably a siloxane unit represented by R ²¹ R ²¹ SiO _2/2 (D ²⁰ unit).

R ²¹⁰ and R ²²⁰ are groups bonded to a silicon atom and each independently represent an alkyl group, at least one of which is a methyl group. can.
R ²¹ is a group bonded to a silicon atom and represents an alkyl group, and specific examples of the alkyl group include those mentioned above. Among them, R ²¹ is preferably a methyl group.
A preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but the present invention is not limited thereto.

Methyl group-containing polyorganosiloxane contains the above-described siloxane units (D ²⁰⁰ or D ²⁰ units), but in addition to D ²⁰⁰ and D ²⁰ units, even if it contains the above Q units, M units and / or T units good.

In one aspect, specific examples of the methyl group-containing polyorganosiloxane include a polyorganosiloxane consisting only of D ²⁰⁰ units, a polyorganosiloxane containing D ²⁰⁰ units and Q units, and D ²⁰⁰ units and M units. Polyorganosiloxane, D Polyorganosiloxane containing ²⁰⁰ units and T units, D Polyorganosiloxane containing ²⁰⁰ units, Q units and M units, D Polyorganosiloxane containing ²⁰⁰ units, M units and T units, D Polyorganosiloxanes containing ²⁰⁰ units, Q units, M units and T units are mentioned.

In a preferred embodiment, specific examples of the methyl group-containing polyorganosiloxane include a polyorganosiloxane consisting only of ^D20 units, a polyorganosiloxane containing ^D20 units and Q units, and ^D20 units and M units. Polyorganosiloxane, D Polyorganosiloxane containing ²⁰ units and T units, D Polyorganosiloxane containing ²⁰ units, Q units and M units, D Polyorganosiloxane containing ²⁰ units, M units and T units, D Polyorganosiloxanes containing ²⁰ units, Q units, M units and T units are mentioned.

The viscosity of the methyl group-containing polyorganosiloxane is usually 1,000 to 2,000,000 mm ² /s, preferably 10,000 to 1,000,000 mm ² /s. The methyl group-containing polyorganosiloxane is typically dimethylsilicone oil made of polydimethylsiloxane. This viscosity value is expressed in kinematic viscosity, centistokes (cSt) = mm ² /s. Kinematic viscosity can be measured with a kinematic viscometer. It can also be obtained by dividing the viscosity (mPa·s) by the density (g/cm ³ ). That is, it can be obtained from the viscosity and density measured by an E-type rotational viscometer at 25°C. It can be calculated from the formula kinematic viscosity (mm ² /s)=viscosity (mPa·s)/density (g/cm ³ ).

Specific examples of the methyl group-containing polyorganosiloxane include WACKER (registered trademark SILICONE FLUID AK series manufactured by Wacker) and 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 are not limited thereto.

Examples of phenyl group-containing polyorganosiloxanes include those containing siloxane units represented by R ³¹ R ³² SiO _2/2 (D ³⁰ units).
R ³¹ is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R ³² is a group bonded to a silicon atom and represents a phenyl group; can be mentioned, but a methyl group is preferred.

The phenyl group-containing polyorganosiloxane contains the siloxane units ( ^D30 units) described above, but may contain the above Q units, M units and/or T units in addition to the ^D30 units.

In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include a polyorganosiloxane consisting only of ^D30 units, a polyorganosiloxane containing ^D30 units and Q units, and ^D30 units and M units. Polyorganosiloxane, D Polyorganosiloxane containing ³⁰ units and T units, D Polyorganosiloxane containing ³⁰ units, Q units and M units, D Polyorganosiloxane containing ³⁰ units, M units and T units, D Polyorganosiloxanes containing ³⁰ units, Q units, M units and T units are mentioned.

The weight average molecular weight of the phenyl group-containing polyorganosiloxane is generally 1,500 to 500,000, but preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive composition.

Specific examples of the phenyl group-containing polyorganosiloxane include PMM-1043 (manufactured by Gelest, Inc., weight average molecular weight 67,000, viscosity 30,000 mm ² /s) represented by the formula (C-1), Product name PMM-1025 (manufactured by Gelest, Inc., weight average molecular weight 25,200, viscosity 500 mm ² /s) represented by formula (C-2), product name KF50- represented by formula (C-3) 3000CS (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 39,400, viscosity 3000 mm ² /s), trade name TSF431 represented by formula (C-4) (manufactured by MOMENTIVE, weight average molecular weight 1,800, viscosity 100 mm ² /s), trade name represented by formula (C-5) TSF433 (manufactured by MOMENTIVE, weight average molecular weight 3,000, viscosity 450 mm ² / s), trade name represented by formula (C-6) PDM-0421 (manufactured by Gelest, Inc., weight average molecular weight 6,200, viscosity 100 mm ² /s), trade name PDM-0821 (manufactured by Gelest, Inc., weight average molecular weight 8 , 600 and a viscosity of 125 mm ² /s), but are not limited thereto.

（ｍ及びｎは繰り返し単位の数を示す。）

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

（ｍ及びｎは繰り返し単位の数を示す。）

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

（ｍ及びｎは繰り返し単位の数を示す。）

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

（ｍ及びｎは繰り返し単位の数を示す。）

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

（ｍ及びｎは繰り返し単位の数を示す。）

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

（ｍ及びｎは繰り返し単位の数を示す。）

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

（ｍ及びｎは繰り返し単位の数を示す。）

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

Such an adhesive composition may contain component (A) and component (B) in any ratio, but considering the balance between adhesiveness and peelability, the ratio of component (A) to component (B) is , in mass ratio, preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

Such an adhesive composition may contain a solvent for the purpose of viscosity adjustment, etc. Specific examples thereof include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, and the like. .

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

When such an adhesive composition contains a solvent, the content thereof is appropriately set in consideration of the desired viscosity of the adhesive composition, the coating method to be employed, the thickness of the thin film to be produced, etc. It is in the range of about 10 to 90% by mass with respect to the entire agent composition.
The viscosity of the adhesive composition is usually 1,000 to 20,000 mPa·s at 25° C. Considering various factors such as the coating method to be used and the desired film thickness, the type of organic solvent to be used and their It can be adjusted by changing the ratio, the film constituent concentration, and the like.

The above adhesive composition can be produced by mixing the film-constituting components and a solvent. However, if the solvent is not included, the above adhesive composition can be produced by mixing the membrane constituents.
The order of mixing is not particularly limited, but examples of a method for easily and reproducibly producing an adhesive composition include, for example, a method of dissolving all film constituents in a solvent, a method of A method of dissolving part of the components in a solvent, dissolving the rest of the membrane constituent components in the solvent, and mixing the resulting solutions can be mentioned. In this case, if necessary, a part of the solvent or membrane constituents with excellent solubility can be added at the end.
In the preparation of the composition, the composition may be appropriately heated as long as the components do not decompose or deteriorate. In addition, for the purpose of removing foreign substances in the composition, the composition may be filtered using a submicrometer order filter or the like during the production of the composition or after all the components are mixed.

More specifically, the first step of the above-described process substrate manufacturing method includes a pre-step of applying the adhesive composition to the surface of a semiconductor substrate or a supporting substrate to form an adhesive coating layer; and the support substrate through the adhesive coating layer, and applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a depressurization treatment. and a post-process in which the adhesive coating layer and the support substrate are brought into close contact with each other, and then a post-heating treatment is performed. By the post-heating treatment in the post-process, the adhesive coating layer is finally suitably cured to become the adhesive layer, and the laminate is manufactured.

Here, for example, the semiconductor substrate is a wafer, and the support substrate is a support. The object to which the adhesive composition is applied may be either or both of the semiconductor substrate and the support substrate.
Examples of wafers include, but are not limited to, silicon wafers and glass wafers having a diameter of about 300 mm and a thickness of about 770 μm.
The support (carrier) is not particularly limited, but may be, for example, a silicon wafer having a diameter of about 300 mm and a thickness of about 700 mm, but is not limited to this.

The film thickness of the adhesive coating layer is usually 5 to 500 μm, but from the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more. From the viewpoint of avoiding nonuniformity, the thickness is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 120 μm or less, and even more preferably 70 μm or less.

Although the coating method is not particularly limited, it is usually a spin coating method. A method of separately forming a coating film by a spin coating method or the like and attaching a sheet-like coating film may be adopted, and this is also referred to as coating or coating film.

The temperature of the heat treatment is usually 80° C. or higher, and preferably 150° C. or lower from the viewpoint of preventing excessive curing. The heat treatment time is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of ensuring that the temporary bonding ability is exhibited. It is preferably 5 minutes or less.

The reduced pressure treatment may be performed by exposing the two substrates and the adhesive coating layer therebetween to an atmospheric pressure of 10 to 10,000 Pa. The time for decompression treatment is usually 1 to 30 minutes.

In a preferred embodiment of the present invention, the two substrates and the layer therebetween are preferably laminated by heat treatment, more preferably by a combination of heat treatment and vacuum treatment.

The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the layers therebetween and can firmly adhere them together. not required, but usually in the range of 10 to 1,000N.

The post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing rate, and preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate or adhesive. The heating time is usually 1 minute or more from the viewpoint of achieving suitable bonding of the wafers by curing, and is preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive. From the viewpoint of avoiding adverse effects on the body, the time is usually 180 minutes or less, preferably 120 minutes or less. Heating can be performed using a hot plate, an oven, or the like. One purpose of the post-heat treatment is to cure the component (A) more favorably.

Next, the second step of processing the semiconductor substrate of the laminate obtained by the method described above will be described.
An example of the processing applied to the laminate used in the present invention includes processing of the back surface of the front surface of the semiconductor substrate opposite to the circuit surface, typically thinning the wafer by polishing the back surface of the wafer. be done. Using such a thinned wafer, through-silicon vias (TSVs) and the like are formed, and then the thinned wafer is separated from the support to form a wafer stack, which is three-dimensionally mounted. Before or after that, the formation of the wafer rear surface electrode and the like is also performed. In the wafer thinning and TSV process, heat of 250 to 350° C. is applied while the wafer is adhered to the support. there is
For example, a wafer with a diameter of 300 mm 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, the third step of peeling off the semiconductor substrate after processing will be described.
The peeling method of the laminate used in the present invention includes, but is not limited to, solvent peeling, laser peeling, mechanical peeling using a material having a sharp portion, peeling between the support and the wafer, and the like. Peeling is usually performed after processing such as thinning.
In the third step, the adhesive is not necessarily completely adhered to the supporting substrate and peeled off, and may be partially left on the processed substrate. Therefore, in the fourth step, the surface of the substrate to which the remaining adhesive has adhered is washed with the above-described cleaning composition of the present invention, so that the adhesive on the substrate can be sufficiently washed off.

Finally, the fourth step of cleaning and removing adhesive residue remaining on the peeled semiconductor substrate with a cleaning composition will be described.
The fourth step is a step of cleaning and removing the adhesive residue remaining on the surface of the semiconductor substrate after peeling with the cleaning composition of the present invention. The substrate is immersed in the cleaning agent composition of the present invention, and if necessary, ultrasonic cleaning or the like is also used in combination to remove the adhesive residue by cleaning.
When ultrasonic cleaning is used, the conditions are appropriately determined in consideration of the state of the surface of the substrate. Adhesive residue remaining on top can be sufficiently removed.

The method of manufacturing a processed substrate such as a thinned substrate of the present invention includes the first to fourth steps described above, but may include steps other than these steps. For example, in the fourth step, before cleaning with the cleaning composition of the present invention, if necessary, the substrate is immersed in various solvents or subjected to tape peeling to remove adhesive residue. may

Various changes may be made to the above structural and methodological elements relating to the first to fourth steps without departing from the gist of the present invention.

EXAMPLES The present invention will be described below with reference to 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 (rotation/revolution mixer): Rotation/revolution mixer ARE-500 manufactured by Thinky Co., Ltd.
(2) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.
(3) Stirrer: AS ONE mix rotor variable 1-1186-12
(4) Stirrer H: Heating type rocking mixer HRM-1 manufactured by AS ONE
(5) Contact-type film thickness gauge: Wafer thickness measuring device WT-425 manufactured by Tokyo Seimitsu Co., Ltd.
(6) Moisture content measurement (Karl Fischer method): Trace moisture measuring device CA-200 type manufactured by Mitsubishi Chemical Analytech Co., Ltd.

[1] Preparation of adhesive composition [Preparation Example 1]
In a 600 mL stirring vessel dedicated to the rotation and revolution mixer, 150 g of a base polymer (manufactured by Wacker Chemi Co., Ltd.) consisting of a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa s and a vinyl group-containing MQ resin as (a1), and viscosity as (a2) 15.81 g of 100 mPa s SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi Co.) and 0.17 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemi Co.) as (A3) were added and mixed with a rotation-revolution mixer. Stir for 5 minutes.
To the resulting mixture, 0.33 g of a platinum catalyst (manufactured by Wacker Chemi Co., Ltd.) as (A2) and a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi Co., Ltd.) having a viscosity of 1000 mPa s as (a1) were added to a 50 mL screw tube. 9.98 g is stirred for 5 minutes with a rotation and revolution mixer, 0.52 g is added from the separately obtained mixture, stirred for 5 minutes with a rotation and revolution mixer, the resulting mixture is filtered through a nylon filter 300 mesh, and the adhesive composition got stuff The viscosity of the adhesive composition measured using a rotational viscometer was 9900 mPa·s.

[Preparation Example 2]
In a 600 mL stirring vessel dedicated to the rotation/revolution mixer, 95 g of a base polymer (manufactured by Wacker Chemi Co., Ltd.) made of a vinyl group-containing MQ resin as (a1), 93.4 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent and (A3 ), 0.41 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added and stirred for 5 minutes with a rotation-revolution mixer.
To the resulting mixture, (a2) a SiH group-containing linear polydimethylsiloxane having a viscosity of 100 mPa s (manufactured by Wacker Chemie) and (a1) a vinyl group-containing linear polydimethylsiloxane having a viscosity of 200 mPa s (Wacker Chemie) were added. 29.5 g of polydimethylsiloxane as component (B), polyorganosiloxane having a viscosity of 1000000 mm ² /s (manufactured by Wacker Chemi Co., trade name AK1000000), and 1-ethynyl-1-cyclohexanol (Wacker Chemi Co., Ltd.) as (A3). 0.41 g (manufactured by Co., Ltd.) was added, and the mixture was further stirred for 5 minutes using a rotation/revolution mixer.
Then, 0.20 g of a platinum catalyst (manufactured by Wacker Chemi Co., Ltd.) as (A2) and vinyl group-containing linear polydimethylsiloxane (Wacker Chemi Co., Ltd.) having a viscosity of 1000 mPa s as (a1) were added to the resulting mixture in a screw tube of 50 mL. ) is stirred for 5 minutes with a rotation and revolution mixer, 14.9 g is added from the separately obtained mixture, stirred for another 5 minutes with a rotation and revolution mixer, and the resulting mixture is filtered through a nylon filter 300 mesh, An adhesive composition was obtained. The viscosity of the adhesive composition measured using a rotational viscometer was 4600 mPa·s.

[2] Preparation of detergent composition [Example 1]
To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.), 95 g of N,N-dimethylpropionamide was added and stirred, and the resulting composition was added with molecular sieves 3A (manufactured by Kanto Chemical Co., Ltd.) ) was added and dehydrated by standing for 24 hours with occasional stirring. After that, the molecular sieves were removed to obtain a detergent composition. The water content of the cleaning composition obtained was 0.09%.

[Comparative Example 1]
95 g of N,N-dimethylpropionamide was added to 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and stirred to obtain a detergent composition. In addition, the water content of the obtained detergent composition was 0.65%.

[3] Performance Evaluation of Cleaning Composition An excellent cleaning composition requires a high cleaning rate to dissolve the adhesive residue immediately after it comes into contact with it, so the following evaluation was performed.

[3-1] Measurement of Etching Rate Etching rate was measured in order to evaluate the cleaning rate of the obtained cleaning composition. The adhesive composition obtained in Preparation Example 1 was applied to a 12-inch silicon wafer with a spin coater so as to have a thickness of 100 μm, and was thermally cured at 150° C./15 minutes and 190° C./10 minutes. After the film formation, the wafer was cut into chips of 4 cm square, and the film thickness was measured using a contact film thickness meter. After that, the chip was placed in a stainless petri dish with a diameter of 9 cm, 7 mL of the resulting detergent composition was added, and the chip was capped. After washing, the chip was taken out, washed with isopropanol and pure water, and dry-baked at 150°C for 1 minute. Then, the etching rate [μm/min] was calculated by dividing the decreased amount by the cleaning time and used as an index of the cleaning power. Results are shown in Table 1.

As shown in Table 1, it was possible to improve the detergency by reducing the water content of the detergent composition containing the quaternary ammonium salt and the organic solvent.

Claims (6)

1. A method for improving the cleaning performance of a cleaning composition used to remove adhesive residue comprising a quaternary ammonium salt and an organic solvent, comprising:
The quaternary ammonium salt comprises tetra(hydrocarbon)ammonium fluoride,
The content of the quaternary ammonium salt in the cleaning composition is 0.1 to 30% by mass, and the water content of the cleaning composition to be dehydrated is reduced by using a dehydrating agent so that the water content is 0.1% by mass. Improving the detergency of the detergent composition, comprising a step of making the detergent composition less than 50% by mass, wherein the dehydrating agent contains a physical drying agent, and the effective radius of the pores is 1 nm or less. Method. 2. The method for improving detergency of a detergent composition according to claim 1 , wherein said physical desiccant comprises at least one selected from the group consisting of silica gel, alumina and molecular sieves. A dehydrated cleaning agent composition containing a quaternary ammonium salt with a content of 0.1 to 30% by mass and an organic solvent is dehydrated using a dehydrating agent so that the water content is less than 0.50% by mass. comprising a step of forming an agent composition,
The quaternary ammonium salt comprises tetra(hydrocarbon)ammonium fluoride,
A method for producing a cleaning composition used for removing adhesive residue, wherein the dehydrating agent comprises a physical drying agent, the effective radius of pores of which is 1 nm or less . 4. The method for producing a cleaning composition according to claim 3 , wherein said dehydrating agent comprises a physical drying agent. 5. The method for producing a cleaning composition according to claim 4 , wherein said physical desiccant comprises at least one selected from the group consisting of silica gel, alumina and molecular sieves. A cleaning composition used for removing adhesive residue, comprising a quaternary ammonium salt with a content of 0.1 to 30% by weight and an organic solvent,
A cleaning composition , wherein the quaternary ammonium salt comprises tetra(hydrocarbon)ammonium fluoride and has a water content of less than 0.15% by mass.