Temporary adhesive residue cleaning composition and method for manufacturing processed semiconductor substrates

Abstract

A cleaning agent composition which is used for the purpose of removing an adhesive residue. This cleaning agent composition is characterized by containing a quaternary ammonium salt, a metal corrosion inhibitor and an organic solvent, and is also characterized in that the metal corrosion inhibitor is composed of an aliphatic saturated hydrocarbon compound monocarboxylic acid having from 7 to 40 carbon atoms, an aliphatic saturated hydrocarbon compound dicarboxylic acid having from 7 to 40 carbon atoms or an acid anhydride thereof, an aliphatic unsaturated hydrocarbon compound monocarboxylic acid having from 7 to 40 carbon atoms, or an aliphatic unsaturated hydrocarbon compound dicarboxylic acid having from 7 to 40 carbon atoms or an acid anhydride thereof.

Description

[Technical Field]

[0001] The present invention relates to a cleaning composition used to remove adhesive residue after peeling off a temporary adhesive layer formed on a semiconductor substrate using a polysiloxane adhesive, for example, and a method for producing processed semiconductor substrates. [Background technology]

[0002] Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but for the purpose of even greater integration, there is a demand for semiconductor integration technology that integrates (stacks) the plane in a three-dimensional direction. This three-dimensional stacking is a technology that integrates multiple layers while connecting them using through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the backside), and the thinned semiconductor wafers are stacked.

[0003] Semiconductor wafers (referred to simply as wafers here) before thinning are bonded to a support in preparation for polishing with a polishing machine. This bond is called a temporary bond because it must be easily removable after polishing. This temporary bond must be easily removed from the support; applying a large force during removal can cause the thinned semiconductor wafer to break or deform. Therefore, the temporary bond must be easily removed to prevent this. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during backside polishing. Therefore, the performance required for the temporary bond is to withstand the stress during polishing and be easily removed after polishing. For example, it must have high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the vertical direction during removal. Furthermore, heat resistance is also required, as temperatures can reach temperatures of over 150°C during the processing process.

[0004] Under these circumstances, polysiloxane adhesives that can provide these properties are mainly used as temporary adhesives in the semiconductor field. In polysiloxane-based adhesion using a polysiloxane adhesive, adhesive residue often remains on the substrate surface after the thinned substrate is peeled off. To avoid problems in subsequent processes, cleaning compositions have been developed to remove this residue and clean the semiconductor substrate surface (e.g., Patent Documents 1 and 2). In recent years, there has been a constant demand for new cleaning compositions in the semiconductor field. Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide, and Patent Document 2 discloses a hardened resin remover containing an alkyl ammonium fluoride, but the development of a more effective cleaning agent composition is desired. Incidentally, the semiconductor wafer is electrically connected to the semiconductor chip via bump balls made of a conductive material such as metal, and by using chips equipped with such bump balls, miniaturization of semiconductor packaging is being attempted. In this regard, bump balls made of metals such as copper and tin have poor corrosion resistance and are therefore subject to damage by cleaning compositions used to remove adhesive residues from supports and wafers (Patent Document 3). Therefore, one of the required properties of a cleaning composition is that it does not corrode bump balls. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2014 / 092022 [Patent Document 2] U.S. Patent No. 6,818,608 [Patent Document 3] Korean Patent Publication No. 2018-0066550 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a cleaning composition that, when cleaning a substrate such as a semiconductor substrate, exhibits good cleaning properties against adhesive residues after peeling off a temporary adhesive layer obtained using a polysiloxane adhesive, and that is suppressed from corrosive to metals such as bump balls, and a method for producing processed semiconductor substrates. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that when cleaning a substrate such as a semiconductor substrate to which adhesive residue remains after peeling off a temporary bond formed by, for example, an adhesive layer obtained using a polysiloxane adhesive, particularly an adhesive layer that is a cured film obtained from a siloxane adhesive containing a polysiloxane component that cures by a hydrosilylation reaction, a cleaning composition containing a quaternary ammonium salt, a metal corrosion inhibitor, and an organic solvent is used, and when the metal corrosion inhibitor is an aliphatic saturated hydrocarbon compound monocarboxylic acid, aliphatic saturated hydrocarbon compound dicarboxylic acid or an acid anhydride thereof, a C7-40 aliphatic unsaturated hydrocarbon compound monocarboxylic acid, or a C7-40 aliphatic unsaturated hydrocarbon compound dicarboxylic acid or an acid anhydride thereof, each having a carbon number equal to or greater than a predetermined value, the decrease in cleaning speed due to the addition of the metal corrosion inhibitor can be suppressed compared to when a carboxylic acid with a lower carbon number is used, and as a result, excellent cleaning ability can be achieved and corrosion of metals such as bump balls can be suppressed, thereby completing the present invention.

[0008] That is, the present invention is 1. A cleaning composition used to remove adhesive residues, comprising a quaternary ammonium salt, a metal corrosion inhibitor, and an organic solvent, wherein the metal corrosion inhibitor is selected from the group consisting of a saturated aliphatic hydrocarbon monocarboxylic acid having 7 to 40 carbon atoms, a saturated aliphatic hydrocarbon dicarboxylic acid having 7 to 40 carbon atoms or an acid anhydride thereof, an unsaturated aliphatic hydrocarbon monocarboxylic acid having 7 to 40 carbon atoms, and a unsaturated aliphatic hydrocarbon dicarboxylic acid having 7 to 40 carbon atoms or an acid anhydride thereof; 2. The cleaning composition according to 1, wherein the metal corrosion inhibitor contains a monocarboxylic acid saturated aliphatic hydrocarbon compound having 7 to 40 carbon atoms, a dicarboxylic anhydride saturated aliphatic hydrocarbon compound having 7 to 40 carbon atoms, or a dicarboxylic anhydride unsaturated aliphatic hydrocarbon compound having 7 to 40 carbon atoms. 3. The cleaning composition according to 2, wherein the metal corrosion inhibitor contains a saturated aliphatic hydrocarbon monocarboxylic acid having 7 to 40 carbon atoms or an unsaturated aliphatic hydrocarbon dicarboxylic acid anhydride having 7 to 40 carbon atoms. 4. The cleaning composition according to 1, wherein the metal corrosion inhibitor comprises lauric acid, dodecanoic diacid, or octadecenyl succinic anhydride. 5. The cleaning composition according to any one of 1 to 4, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt. 6. The cleaning composition according to 5, wherein the halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt. 7. The cleaning composition according to 6, wherein the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. 8. The cleaning composition of 7, 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. 9. The cleaning composition of any one of 1 to 8, wherein the adhesive residue is an adhesive residue from an adhesive layer obtained from an adhesive composition containing component (A) that cures by a hydrosilylation reaction. 10. A method for producing a processed semiconductor substrate, comprising: a first step of producing a laminate comprising a semiconductor substrate having bump balls, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate in the resulting laminate; a third step of peeling the semiconductor substrate after processing; and a fourth step of removing adhesive residue remaining on the peeled semiconductor substrate with a cleaning composition, wherein the cleaning composition is any one of the cleaning compositions 1 to 9. to provide. [Effects of the Invention]

[0009] The cleaning composition of the present invention makes it possible to quickly and easily clean substrates such as semiconductor substrates to which adhesive residue remains after peeling off a temporary bond formed by, for example, an adhesive layer obtained using a polysiloxane adhesive, particularly an adhesive layer that is a cured film obtained from a siloxane adhesive containing a polysiloxane component that cures by a hydrosilylation reaction, while suppressing corrosion of metals such as bump balls. Therefore, highly efficient production of good semiconductor devices can be expected. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in more detail below. The cleaning composition of 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 is used for this type of application. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, an anion paired with the quaternary ammonium cation is a hydroxide ion (OH - ); fluorine ion (F - ), chloride ions (Cl - ), bromide ion (Br - ), iodine ion (I - ) and other halogen ions; tetrafluoroborate ion (BF4 - ); Hexafluorophosphate ion (PF6 - ) and the like, but are not limited to these.

[0011] In the present invention, the quaternary ammonium salt is preferably 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 either the cation or the anion, but is preferably contained in the anion.

[0012] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.

[0013] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of hydrates. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride 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 detergent composition, but is usually 0.1 to 30% by mass relative to the detergent composition.

[0014] The cleaning agent composition of the present invention contains a metal corrosion inhibitor comprising a saturated aliphatic hydrocarbon compound monocarboxylic acid having 7 to 40 carbon atoms, a saturated aliphatic hydrocarbon compound dicarboxylic acid having 7 to 40 carbon atoms or an acid anhydride thereof, an unsaturated aliphatic hydrocarbon compound monocarboxylic acid having 7 to 40 carbon atoms, or an unsaturated aliphatic hydrocarbon compound dicarboxylic acid having 7 to 40 carbon atoms or an acid anhydride thereof. That is, the cleaning agent composition of the present invention contains, as a metal corrosion inhibitor, at least one selected from the group consisting of a monocarboxylic aliphatic saturated hydrocarbon compound having 7 to 40 carbon atoms, a dicarboxylic aliphatic saturated hydrocarbon compound having 7 to 40 carbon atoms, a dicarboxylic anhydride of a saturated aliphatic hydrocarbon compound having 7 to 40 carbon atoms, a monocarboxylic aliphatic unsaturated hydrocarbon compound having 7 to 40 carbon atoms, a dicarboxylic aliphatic unsaturated hydrocarbon compound having 7 to 40 carbon atoms, and a dicarboxylic anhydride of aliphatic unsaturated hydrocarbon compound having 7 to 40 carbon atoms. By using such a compound having a relatively long aliphatic hydrocarbon chain and one carboxy group (—COOH) or two carboxy groups, or an acid anhydride thereof, as a metal corrosion inhibitor, it is possible to achieve both excellent cleaning ability and excellent corrosion inhibition ability while controlling the deposition of the metal corrosion inhibitor by maintaining good solubility of the metal corrosion inhibitor in the organic solvent contained in the cleaning composition.

[0015] The monocarboxylic acid of an aliphatic saturated hydrocarbon compound having 7 to 40 carbon atoms is a compound in which one hydrogen atom of an aliphatic saturated hydrocarbon compound having 6 to 39 carbon atoms is replaced with a carboxy group, and may be linear, branched, or cyclic. From the viewpoint of achieving excellent cleaning ability and excellent corrosion inhibition ability with good reproducibility, linear or branched structures are preferred, and linear structures are more preferred. The aliphatic saturated hydrocarbon compound monocarboxylic acid having 7 to 40 carbon atoms can be used alone or in combination of two or more.

[0016] Specific examples thereof include 1-heptanecarboxylic acid, 1-octanecarboxylic acid, 2-octanecarboxylic acid, 3-octanecarboxylic acid, 4-octanecarboxylic acid, 1-nonanecarboxylic acid, 2-nonanecarboxylic acid, 3-nonanecarboxylic acid, 4-nonanecarboxylic acid, 5-nonanecarboxylic acid, 1-decanecarboxylic acid, 2-decanecarboxylic acid, 3-decanecarboxylic acid, 4-decanecarboxylic acid, 5-decanecarboxylic acid, 1-undecanecarboxylic acid, 2-undecanecarboxylic acid, 3-undecanecarboxylic acid, 4-undecanecarboxylic acid, 5-undecanecarboxylic acid, 6-undecanecarboxylic acid, 7-undecanecarboxylic acid, 8-undecanecarboxylic acid, 9-undecanecarboxylic acid, 10-undecanecarboxylic acid, 11-undecanecarboxylic acid, 12-undecanecarboxylic acid, 13-undecanecarboxylic acid, 14-undecanecarboxylic acid, 15-undecanecarboxylic acid, 16-undecanecarboxylic acid, 17-undecanecarboxylic acid, 18-undecanecarboxylic acid, 19-undecanecarboxylic acid, 20-undecanecarboxylic acid, 21-undecanecarboxylic acid, 22-undecanecarboxylic acid, 23-undecanecarboxylic acid, 24-undecanecarboxylic acid, 25-undecanecarboxylic acid, 26-undecanecarboxylic acid, 27-undecanecarboxylic acid, 28-undecanecarboxylic acid, 29-undecanecarboxylic acid, 30-undecanecarboxylic acid, 31-undecanecarboxylic acid, 32-undecanecarboxylic acid, 33-undecanecarboxylic acid, 34-undecanecarboxylic acid, 35-undecanecarboxylic acid, 36-undecanecarboxylic acid, 37-undecanecarboxylic acid, 38-undecanecarboxylic acid, 39-undecanecarboxylic acid, Dodecanecarboxylic acid, 1-dodecanecarboxylic acid, 2-dodecanecarboxylic acid, 3-dodecanecarboxylic acid, 4-dodecanecarboxylic acid, 5-dodecanecarboxylic acid, 6-dodecanecarboxylic acid, 1-tridecanecarboxylic acid, 2-tridecanecarboxylic acid, 3-tridecanecarboxylic acid, 4-tridecanecarboxylic acid, 5-tridecanecarboxylic acid, 6-tridecanecarboxylic acid, 7-tridecanecarboxylic acid, 1-tetradecanecarboxylic acid, 2-tetradecanecarboxylic acid, 3-tetradecanecarboxylic acid, 4-tetradecanecarboxylic acid, 5-tetradecanecarboxylic acid, 6-tetradecane hexadecanecarboxylic acid, 7-tetradecanecarboxylic acid, 1-pentadecanecarboxylic acid, 2-pentadecanecarboxylic acid, 3-pentadecanecarboxylic acid, 4-pentadecanecarboxylic acid, 5-pentadecanecarboxylic acid, 6-pentadecanecarboxylic acid, 7-pentadecanecarboxylic acid, 8-pentadecanecarboxylic acid, 1-hexadecanecarboxylic acid, 2-hexadecanecarboxylic acid, 3-hexadecanecarboxylic acid, 4-hexadecanecarboxylic acid, 5-hexadecanecarboxylic acid, 6-hexadecanecarboxylic acid, 7-hexadecanecarboxylic acid, 8-hexadecanecarboxylic acid, 1-hexadecanecarboxylic acid Heptadecane carboxylic acid, 2-heptadecane carboxylic acid, 3-heptadecane carboxylic acid, 4-heptadecane carboxylic acid, 5-heptadecane carboxylic acid, 6-heptadecane carboxylic acid, 7-heptadecane carboxylic acid, 8-heptadecane carboxylic acid, 9-heptadecane carboxylic acid, 1-octadecane carboxylic acid, 2-octadecane carboxylic acid, 3-octadecane carboxylic acid, 4-octadecane carboxylic acid, 5-octadecane carboxylic acid, 6-octadecane carboxylic acid, 7-octadecane carboxylic acid, 8-octadecane carboxylic acid, 9-octadecane carboxylic acid,Examples of the carboxylic acid include, but are not limited to, 1-nonadecanecarboxylic acid, 2-nonadecanecarboxylic acid, 3-nonadecanecarboxylic acid, 4-nonadecanecarboxylic acid, 5-nonadecanecarboxylic acid, 6-nonadecanecarboxylic acid, 7-nonadecanecarboxylic acid, 8-nonadecanecarboxylic acid, 9-nonadecanecarboxylic acid, 10-nonadecanecarboxylic acid, 1-eicosanecarboxylic acid, 2-eicosanecarboxylic acid, 3-eicosanecarboxylic acid, 4-eicosanecarboxylic acid, 5-eicosanecarboxylic acid, 6-eicosanecarboxylic acid, 7-eicosanecarboxylic acid, 8-eicosanecarboxylic acid, 9-eicosanecarboxylic acid, and 10-eicosanecarboxylic acid.

[0017] The dicarboxylic acid of an aliphatic saturated hydrocarbon compound having 7 to 40 carbon atoms is obtained by replacing two hydrogen atoms of an aliphatic saturated hydrocarbon compound having 5 to 38 carbon atoms with a carboxy group, and may be linear, branched, or cyclic. From the viewpoint of reproducibly achieving excellent cleaning ability and excellent corrosion-inhibiting ability, linear or branched dicarboxylic acid is preferred, and linear dicarboxylic acid is more preferred. The aliphatic saturated hydrocarbon compound dicarboxylic acid having 7 to 40 carbon atoms can be used alone or in combination of two or more.

[0018] Specific examples thereof include 1,1-pentanedicarboxylic acid, 1,2-pentanedicarboxylic acid, 1,3-pentanedicarboxylic acid, 1,4-pentanedicarboxylic acid, 1,5-pentanedicarboxylic acid, 2,2-pentanedicarboxylic acid, 2,3-pentanedicarboxylic acid, 2,4-pentanedicarboxylic acid, 3,3-pentanedicarboxylic acid, 1,6-hexanedicarboxylic acid, 1,1-hexanedicarboxylic acid, 1,2-hexanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1,1-heptanedicarboxylic acid, 1, 2-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,1-octanedicarboxylic acid, 1,2-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,1-nonanedicarboxylic acid, 1,2-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (dodecanedioic acid), 1,1-decanedicarboxylic acid, 1,2-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,1-undecanedicarboxylic acid, 1,2-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,1-dodeca Dicarboxylic acid, 1,2-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,1-tridecanedicarboxylic acid, 1,2-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,1-tetradecanedicarboxylic acid, 1,2-tetradecanedicarboxylic acid, 1,15-pentadecanedicarboxylic acid, 1,1-pentadecanedicarboxylic acid, 1,2-pentadecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,1-hexadecanedicarboxylic acid, 1,2-hexadecanedicarboxylic acid Examples of the dicarboxylic acid include, but are not limited to, carboxylic acid, 1,17-heptadecadicarboxylic acid, 1,1-heptadecadicarboxylic acid, 1,2-heptadecadicarboxylic acid, 1,18-octadecanedicarboxylic acid, 1,1-octadecanedicarboxylic acid, 1,2-octadecanedicarboxylic acid, 1,19-nonadecanedicarboxylic acid, 1,1-nonadecanedicarboxylic acid, 1,2-nonadecanedicarboxylic acid, 1,20-eicosanedicarboxylic acid, 1,1-eicosanedicarboxylic acid, and 1,2-eicosanedicarboxylic acid.

[0019] The aliphatic saturated hydrocarbon compound dicarboxylic acid anhydride having 7 to 40 carbon atoms is an acid anhydride derived by intramolecular dehydration condensation of the above-mentioned aliphatic saturated hydrocarbon compound dicarboxylic acid, and may be linear, branched, or cyclic. From the viewpoint of reproducibly realizing excellent cleaning ability and excellent corrosion inhibiting ability, linear or branched anhydrides are preferred, and linear anhydrides are more preferred. The aliphatic saturated hydrocarbon compound dicarboxylic acid anhydride having 7 to 40 carbon atoms can be used alone or in combination of two or more.

[0020] Specific examples thereof include 1,1-pentanedicarboxylic anhydride, 1,2-pentanedicarboxylic anhydride, 1,6-hexanedicarboxylic anhydride, 1,1-hexanedicarboxylic anhydride, 1,2-hexanedicarboxylic anhydride, 1,7-heptanedicarboxylic anhydride, 1,1-heptanedicarboxylic anhydride, 1,2-heptanedicarboxylic anhydride, 1,8-octanedicarboxylic anhydride, 1,1-octanedicarboxylic anhydride, 1,2-octanedicarboxylic anhydride, 1,9-nonanedicarboxylic anhydride, 1,1- Nonanedicarboxylic anhydride, 1,2-nonanedicarboxylic anhydride, 1,10-decanedicarboxylic anhydride, 1,1-decanedicarboxylic anhydride, 1,2-decanedicarboxylic anhydride, 1,11-undecanedicarboxylic anhydride, 1,1-undecanedicarboxylic anhydride, 1,2-undecanedicarboxylic anhydride, 1,12-dodecanedicarboxylic anhydride, 1,1-dodecanedicarboxylic anhydride, 1,2-dodecanedicarboxylic anhydride, 1,13-tridecanedicarboxylic anhydride, 1,1-tridecanedicarboxylic acid Anhydride, 1,2-tridecanedicarboxylic anhydride, 1,14-tetradecanedicarboxylic anhydride, 1,1-tetradecanedicarboxylic anhydride, 1,2-tetradecanedicarboxylic anhydride, 1,15-pentadecanedicarboxylic anhydride, 1,1-pentadecanedicarboxylic anhydride, 1,2-pentadecanedicarboxylic anhydride, 1,16-hexadecanedicarboxylic anhydride, 1,1-hexadecanedicarboxylic anhydride, 1,2-hexadecanedicarboxylic anhydride, 1,17-heptadecadicarboxylic anhydride, 1,1- Examples of the dicarboxylic anhydride include, but are not limited to, heptadecadicarboxylic anhydride, 1,2-heptadecadicarboxylic anhydride, 1,18-octadecanedicarboxylic anhydride, 1,1-octadecanedicarboxylic anhydride, 1,2-octadecanedicarboxylic anhydride, 1,19-nonadecanedicarboxylic anhydride, 1,1-nonadecanedicarboxylic anhydride, 1,2-nonadecanedicarboxylic anhydride, 1,20-eicosanedicarboxylic anhydride, 1,1-eicosanedicarboxylic anhydride, and 1,2-eicosanedicarboxylic anhydride.

[0021] The aliphatic unsaturated hydrocarbon compound carboxylic acid having 7 to 40 carbon atoms is a compound in which one hydrogen atom of an aliphatic unsaturated hydrocarbon compound having 6 to 39 carbon atoms is replaced with a carboxy group, and may be linear, branched, or cyclic, and may be either an alkene or an alkyne. From the viewpoint of achieving excellent cleaning ability and excellent corrosion inhibition ability with good reproducibility, linear or branched alkene carboxylic acids are preferred, and linear alkene carboxylic acids are more preferred. The aliphatic unsaturated hydrocarbon compound carboxylic acid having 7 to 40 carbon atoms can be used alone or in combination of two or more.

[0022] Specific examples thereof include cis-2-hexene-1-carboxylic acid, cis-2-hexene-4-carboxylic acid, cis-2-hexene-5-carboxylic acid, cis-2-hexene-6-carboxylic acid, trans-2-hexene-1-carboxylic acid, trans-2-hexene-4-carboxylic acid, trans-2-hexene-5-carboxylic acid, trans-2-hexene-6-carboxylic acid, 3-hexene-1-carboxylic acid, 3-hexene-2-carboxylic acid, cis-2-heptene-1-carboxylic acid, cis-4-heptene-1-carboxylic acid, cis-5-heptene-1-carboxylic acid, cis- cis-6-heptene-1-carboxylic acid, cis-7-heptene-1-carboxylic acid, trans-2-heptene-1-carboxylic acid, trans-4-heptene-1-carboxylic acid, trans-5-heptene-1-carboxylic acid, trans-6-heptene-1-carboxylic acid, trans-7-heptene-1-carboxylic acid, cis-3-heptene-1-carboxylic acid, cis-3-heptene-2-carboxylic acid, cis-3-heptene-5-carboxylic acid, cis-3-heptene-6-carboxylic acid, cis-3-heptene-7-carboxylic acid, trans-3-heptene-1-carboxylic acid, tra trans-3-heptene-2-carboxylic acid, trans-3-heptene-5-carboxylic acid, trans-3-heptene-6-carboxylic acid, trans-3-heptene-7-carboxylic acid, cis-2-octene-1-carboxylic acid, cis-2-octene-4-carboxylic acid, cis-2-octene-5-carboxylic acid, cis-2-octene-6-carboxylic acid, cis-2-octene-7-carboxylic acid, cis-2-octene-8-carboxylic acid, trans-2-octene-1-carboxylic acid, trans-2-octene-4-carboxylic acid, trans-2-octene-5-carboxylic acid, trans-2-octene-6-carboxylic acid, trans-2-octene-7-carboxylic acid, trans-2-octene-8-carboxylic acid, cis-3-octene-1-carboxylic acid, cis-3-octene-2-carboxylic acid, cis-3-octene-5-carboxylic acid, cis-3-octene-6-carboxylic acid, cis-3-octene-7-carboxylic acid, cis-3-octene-8-carboxylic acid, trans-3-octene-1-carboxylic acid, trans-3-octene-2-carboxylic acid, trans-3-octene-5-carboxylic acid, trans-3-octene-6-carboxylic acid,trans-3-octene-7-carboxylic acid, trans-3-octene-8-carboxylic acid, 4-octene-1-carboxylic acid, 4-octene-2-carboxylic acid, 4-octene-4-carboxylic acid, cis-2-nonene-1-carboxylic acid, cis-2-nonene-4-carboxylic acid, cis-2-nonene-5-carboxylic acid, cis-2-nonene-6-carboxylic acid, cis-2-nonene-7-carboxylic acid, cis-2-nonene-8-carboxylic acid, cis-2-nonene-9-carboxylic acid, trans-2-nonene-1-carboxylic acid, trans-2-nonene-4-carboxylic acid, trans-2- Nonene-5-carboxylic acid, trans-2-nonene-6-carboxylic acid, trans-2-nonene-7-carboxylic acid, trans-2-nonene-8-carboxylic acid, trans-2-nonene-9-carboxylic acid, cis-3-nonene-1-carboxylic acid, cis-3-nonene-2-carboxylic acid, cis-3-nonene-5-carboxylic acid, cis-3-nonene-6-carboxylic acid, cis-3-nonene-7-carboxylic acid, cis-3-nonene-8-carboxylic acid, cis-3-nonene-9-carboxylic acid, trans-3-nonene-1-carboxylic acid, trans-3-nonene-2-carboxylic acid, trans -3-nonene-5-carboxylic acid, trans-3-nonene-6-carboxylic acid, trans-3-nonene-7-carboxylic acid, trans-3-nonene-8-carboxylic acid, trans-3-nonene-9-carboxylic acid, cis-4-nonene-1-carboxylic acid, cis-4-nonene-2-carboxylic acid, cis-4-nonene-3-carboxylic acid, cis-4-nonene-6-carboxylic acid, cis-4-nonene-7-carboxylic acid, cis-4-nonene-8-carboxylic acid, cis-4-nonene-9-carboxylic acid, trans-4-nonene-1-carboxylic acid, trans-4-nonene-2-carboxylic acid, trans-4-nonene-3-carboxylic acid, trans-4-nonene-6-carboxylic acid, trans-4-nonene-7-carboxylic acid, trans-4-nonene-8-carboxylic acid, trans-4-nonene-9-carboxylic acid, cis-2-denene-1-carboxylic acid, cis-2-denene-4-carboxylic acid, cis-2-denene-5-carboxylic acid, cis-2-denene-6-carboxylic acid, cis-2-denene-7-carboxylic acid, cis-2-denene-8-carboxylic acid, cis-2-denene-9-carboxylic acid, cis-2-denene-10-carboxylic acid, trans-2-denene-1-carboxylic acid,trans-2-denene-4-carboxylic acid, trans-2-denene-5-carboxylic acid, trans-2-denene-6-carboxylic acid, trans-2-denene-7-carboxylic acid, trans-2-denene-8-carboxylic acid, trans-2-denene-9-carboxylic acid, trans-2-denene-10-carboxylic acid, cis-3-denene-1-carboxylic acid, cis-3-denene-2-carboxylic acid, cis-3-denene-5-carboxylic acid, cis-3-denene-6-carboxylic acid Carboxylic acid, cis-3-denene-7-carboxylic acid, cis-3-denene-8-carboxylic acid, cis-3-denene-9-carboxylic acid, cis-3-denene-10-carboxylic acid, trans-3-denene-1-carboxylic acid, trans-3-denene-2-carboxylic acid, trans-3-denene-5-carboxylic acid, trans-3-denene-6-carboxylic acid, trans-3-denene-7-carboxylic acid, trans-3-denene-8-carboxylic acid, trans-3-denene cis-4-denene-9-carboxylic acid, trans-3-denene-10-carboxylic acid, cis-4-denene-1-carboxylic acid, cis-4-denene-2-carboxylic acid, cis-4-denene-3-carboxylic acid, cis-4-denene-6-carboxylic acid, cis-4-denene-7-carboxylic acid, cis-4-denene-8-carboxylic acid, cis-4-denene-9-carboxylic acid, cis-4-denene-10-carboxylic acid, trans-4-denene-1-carboxylic acid, trans-4-denene- Examples of the carboxylic acid include, but are not limited to, trans-4-denene-2-carboxylic acid, trans-4-denene-3-carboxylic acid, trans-4-denene-6-carboxylic acid, trans-4-denene-7-carboxylic acid, trans-4-denene-8-carboxylic acid, trans-4-denene-9-carboxylic acid, trans-4-denene-10-carboxylic acid, 5-denene-1-carboxylic acid, 5-denene-2-carboxylic acid, 5-denene-3-carboxylic acid, and 5-denene-4-carboxylic acid.

[0023] The aliphatic unsaturated hydrocarbon dicarboxylic acid having 7 to 40 carbon atoms is an aliphatic unsaturated hydrocarbon compound having 5 to 38 carbon atoms in which two hydrogen atoms have been replaced by carboxy groups, and may be linear, branched, or cyclic, and may be either an alkene or an alkyne. From the viewpoint of reproducibly achieving excellent cleaning ability and excellent corrosion-inhibiting ability, linear or branched alkene dicarboxylic acids are preferred, and linear alkene dicarboxylic acids are more preferred. The aliphatic unsaturated hydrocarbon compound dicarboxylic acid having 7 to 40 carbon atoms can be used alone or in combination of two or more.

[0024] Specific examples thereof include cis-2-pentene-1,1-dicarboxylic acid, cis-2-pentene-1,5-dicarboxylic acid, cis-2-hexene-1,1-dicarboxylic acid, trans-2-hexene-1,1-dicarboxylic acid, cis-2-hexene-1,6-dicarboxylic acid, trans-2-hexene-1,6-dicarboxylic acid, cis-3-hexene-1,1-dicarboxylic acid, trans-3-hexene-1,1-dicarboxylic acid, cis-3-hexene-1,2-dicarboxylic acid, trans-3-hexene-1,2-dicarboxylic acid, cis-3-hexene-1,6-dicarboxylic acid, trans-3-hexene-1,6-dicarboxylic acid, cis-2-heptene-1,1-dicarboxylic acid, trans-2-heptene-1,1-dicarboxylic acid, cis-2-heptene-1,7-dicarboxylic acid, trans-2-heptene-1,7-dicarboxylic acid, cis-3-heptene-1,1-dicarboxylic acid, trans-3-heptene-1,1-dicarboxylic acid, cis-3-heptene-1,2-dicarboxylic acid, trans-3-heptene-1,2-dicarboxylic acid, cis-3-heptene-1,7-dicarboxylic acid, trans-3-heptene-1,7-dicarboxylic acid, cis-2-octene trans-2-octene-1,1-dicarboxylic acid, trans-2-octene-1,8-dicarboxylic acid, trans-2-octene-1,8-dicarboxylic acid, cis-3-octene-1,1-dicarboxylic acid, trans-3-octene-1,1-dicarboxylic acid, cis-3-octene-1,2-dicarboxylic acid, trans-3-octene-1,2-dicarboxylic acid, cis-3-octene-1,8-dicarboxylic acid, trans-3-octene-1,8-dicarboxylic acid, cis-2-nonene-1,1-dicarboxylic acid, trans-2-nonene-1,1-dicarboxylic acid Carboxylic acid, cis-2-nonene-1,9-dicarboxylic acid, trans-2-nonene-1,9-dicarboxylic acid, cis-3-nonene-1,1-dicarboxylic acid, trans-3-nonene-1,1-dicarboxylic acid, cis-3-nonene-1,2-dicarboxylic acid, trans-3-nonene-1,2-dicarboxylic acid, cis-3-nonene-1,9-dicarboxylic acid, trans-3-nonene-1,9-dicarboxylic acid, cis-2-decene-1,1-dicarboxylic acid, trans-2-decene-1,1-dicarboxylic acid, cis-2-decene-1,10-dicarboxylic acid, trans-2-decene-1,10-dicarboxylic acid, cis-3-decene-1,1-dicarboxylic acid, trans-3-decene-1,1-dicarboxylic acid, cis-3-decene-1,2-dicarboxylic acid, trans-3-decene-1,2-dicarboxylic acid, cis-3-decene-1,10-dicarboxylic acid, trans-3-decene-1,10-dicarboxylic acid, cis-2-undecene-1,1-dicarboxylic acid, trans-2-undecene-1,1-dicarboxylic acid, cis-2-undecene-1,11-dicarboxylic acid, trans-2-undecene-1,11-dicarboxylic acid, cis-3-undecene-1,1- Dicarboxylic acid, trans-3-undecene-1,1-dicarboxylic acid, cis-3-undecene-1,2-dicarboxylic acid, trans-3-undecene-1,2-dicarboxylic acid, cis-3-undecene-1,11-dicarboxylic acid, trans-3-undecene-1,11-dicarboxylic acid, cis-2-dodecene-1,1-dicarboxylic acid, trans-2-dodecene-1,1-dicarboxylic acid, cis-2-dodecene-1,12-dicarboxylic acid, trans-2-dodecene-1,12-dicarboxylic acid, cis-3-dodecene-1,1-dicarboxylic acid, trans-3-dodecene- 1,1-dicarboxylic acid, cis-3-dodecene-1,2-dicarboxylic acid, trans-3-dodecene-1,2-dicarboxylic acid, cis-3-dodecene-1,12-dicarboxylic acid, trans-3-dodecene-1,12-dicarboxylic acid, cis-2-tridecene-1,1-dicarboxylic acid, trans-2-tridecene-1,13-dicarboxylic acid, trans-2-tridecene-1,13-dicarboxylic acid, cis-3-tridecene-1,1-dicarboxylic acid, trans-3-tridecene-1,1-dicarboxylic acid, cis-3-tridecene-1,1-dicarboxylic acid Tridecene-1,2-dicarboxylic acid, trans-3-tridecene-1,2-dicarboxylic acid, cis-3-tridecene-1,13-dicarboxylic acid, trans-3-tridecene-1,13-dicarboxylic acid, cis-2-tetradecene-1,1-dicarboxylic acid, trans-2-tetradecene-1,1-dicarboxylic acid, cis-2-tetradecene-1,14-dicarboxylic acid, trans-2-tetradecene-1,14-dicarboxylic acid, cis-3-tetradecene-1,1-dicarboxylic acid, trans-3-tetradecene-1,1-dicarboxylic acid, cis-3-tetradecene-1,2-dicarboxylic acid, trans-3-tetradecene-1,2-dicarboxylic acid, cis-3-tetradecene-1,14-dicarboxylic acid, trans-3-tetradecene-1,14-dicarboxylic acid, cis-2-pentadecene-1,1-dicarboxylic acid, trans-2-pentadecene-1,1-dicarboxylic acid, cis-2-pentadecene-1,15-dicarboxylic acid, trans-2-pentadecene-1,15-dicarboxylic acid, cis-3-pentadecene-1,1-dicarboxylic acid, trans-3-pentadecene-1,1-dicarboxylic acid, cis-3-pentadecene-1,2 -dicarboxylic acid, trans-3-pentaladecene-1,2-dicarboxylic acid, cis-3-pentadecene-1,15-dicarboxylic acid, trans-3-pentaladecene-1,15-dicarboxylic acid, cis-2-hexadecene-1,1-dicarboxylic acid, trans-2-hexadecene-1,1-dicarboxylic acid, cis-2-hexadecene-1,16-dicarboxylic acid, trans-2-hexadecene-1,16-dicarboxylic acid, cis-3-hexadecene-1,1-dicarboxylic acid, trans-3-hexadecene-1,1-dicarboxylic acid, cis-3-hexadecene-1, 2-dicarboxylic acid, trans-3-hexaladecene-1,2-dicarboxylic acid, cis-3-hexadecene-1,16-dicarboxylic acid, trans-3-hexaladecene-1,16-dicarboxylic acid, cis-2-heptadecene-1,1-dicarboxylic acid, trans-2-heptadecene-1,1-dicarboxylic acid, cis-2-heptadecene-1,17-dicarboxylic acid, trans-2-heptadecene-1,17-dicarboxylic acid, cis-3-heptadecene-1,1-dicarboxylic acid, trans-3-heptadecene-1,1-dicarboxylic acid, cis-3-heptadecene-1 ,2-dicarboxylic acid, trans-3-heptadecene-1,2-dicarboxylic acid, cis-3-heptadecene-1,17-dicarboxylic acid, trans-3-heptadecene-1,17-dicarboxylic acid, cis-2-octadecene-1,1-dicarboxylic acid, trans-2-octadecene-1,1-dicarboxylic acid, cis-2-octadecene-1,18-dicarboxylic acid, trans-2-octadecene-1,18-dicarboxylic acid, cis-3-octadecene-1,1-dicarboxylic acid, trans-3-octadecene-1,1-dicarboxylic acid, cis-3-octadecene-1,2-dicarboxylic acid, trans-3-octadecene-1,2-dicarboxylic acid, cis-3-octadecene-1,18-dicarboxylic acid, trans-3-octadecene-1,18-dicarboxylic acid, cis-2-nonadecene-1,1-dicarboxylic acid, trans-2-nonadecene-1,1-dicarboxylic acid, cis-2-nonadecene-1,19-dicarboxylic acid, trans-2-nonadecene-1,19-dicarboxylic acid, cis-3-nonadecene-1,1-dicarboxylic acid, trans-3-nonadecene-1,1-dicarboxylic acid, cis-3-nonadecene-1,2-dicarboxylic acid, trans-3-nonadecene-1,2-dicarboxylic acid, cis-3-nonadecene-1,1 Examples of the cis-eicosene-1,20-dicarboxylic acid include, but are not limited to, cis-3-eicosene-1,1-dicarboxylic acid, cis-2-eicosene-1,1-dicarboxylic acid, cis-2-eicosene-1,20-dicarboxylic acid, cis-3-eicosene-1,1-dicarboxylic acid, trans-3-eicosene-1,1-dicarboxylic acid, cis-3-eicosene-1,2-dicarboxylic acid, trans-3-eicosene-1,2-dicarboxylic acid, cis-3-eicosene-1,20-dicarboxylic acid, and trans-3-eicosene-1,20-dicarboxylic acid.

[0025] The aliphatic unsaturated hydrocarbon compound dicarboxylic acid anhydride having 7 to 40 carbon atoms is an acid anhydride derived by intramolecular dehydration condensation of the above-mentioned aliphatic unsaturated hydrocarbon compound dicarboxylic acid, and may be any of linear, branched, or cyclic, and may be any of an alkene or an alkyne. From the viewpoint of achieving excellent cleaning ability and excellent corrosion inhibition ability with good reproducibility, etc., linear or branched alkene dicarboxylic acid anhydride is preferred, and linear alkene dicarboxylic acid anhydride is more preferred. The aliphatic unsaturated hydrocarbon compound dicarboxylic acid anhydride having 7 to 40 carbon atoms can be used alone or in combination of two or more.

[0026] Specific examples thereof include cis-2-butene-1,1-dicarboxylic anhydride, cis-2-butene-1,4-dicarboxylic anhydride, trans-2-butene-1,1-dicarboxylic anhydride, trans-2-butene-1,4-dicarboxylic anhydride, cis-2-pentene-1,1-dicarboxylic anhydride, cis-2-pentene-1,5-dicarboxylic anhydride, cis-2-hexene-1,1-dicarboxylic anhydride, trans-2-hexene-1,1-dicarboxylic anhydride, cis-2-hexene-1,6-dicarboxylic anhydride, and trans-2-hexene-1,6-dicarboxylic anhydride. carboxylic anhydride, cis-3-hexene-1,1-dicarboxylic anhydride, trans-3-hexene-1,1-dicarboxylic anhydride, cis-3-hexene-1,2-dicarboxylic anhydride, trans-3-hexene-1,2-dicarboxylic anhydride, cis-3-hexene-1,6-dicarboxylic anhydride, trans-3-hexene-1,6-dicarboxylic anhydride, cis-2-heptene-1,1-dicarboxylic anhydride, trans-2-heptene-1,1-dicarboxylic anhydride, cis-2-heptene-1,7-dicarboxylic anhydride, trans-2-heptene-1,7- Dicarboxylic acid anhydrides, cis-3-heptene-1,1-dicarboxylic anhydride, trans-3-heptene-1,1-dicarboxylic anhydride, cis-3-heptene-1,2-dicarboxylic anhydride, trans-3-heptene-1,2-dicarboxylic anhydride, cis-3-heptene-1,7-dicarboxylic anhydride, trans-3-heptene-1,7-dicarboxylic anhydride, cis-2-octene-1,1-dicarboxylic anhydride, trans-2-octene-1,1-dicarboxylic anhydride, cis-2-octene-1,8-dicarboxylic anhydride, trans-2-octene-1 ,8-dicarboxylic anhydride, cis-3-octene-1,1-dicarboxylic anhydride, trans-3-octene-1,1-dicarboxylic anhydride, cis-3-octene-1,2-dicarboxylic anhydride, trans-3-octene-1,2-dicarboxylic anhydride, cis-3-octene-1,8-dicarboxylic anhydride, trans-3-octene-1,8-dicarboxylic anhydride, cis-2-nonene-1,1-dicarboxylic anhydride, trans-2-nonene-1,1-dicarboxylic anhydride, cis-2-nonene-1,9-dicarboxylic anhydride, trans-2-nonene-1,9-dicarboxylic anhydride, cis-3-nonene-1,1-dicarboxylic anhydride, trans-3-nonene-1,1-dicarboxylic anhydride, cis-3-nonene-1,2-dicarboxylic anhydride, trans-3-nonene-1,2-dicarboxylic anhydride, cis-3-nonene-1,9-dicarboxylic anhydride, trans-3-nonene-1,9-dicarboxylic anhydride, cis-2-decene-1,1-dicarboxylic anhydride, trans-2-decene-1,10-dicarboxylic anhydride, trans-2-decene-1,10-dicarboxylic anhydride Carboxylic acid anhydrides, cis-3-decene-1,1-dicarboxylic anhydride, trans-3-decene-1,1-dicarboxylic anhydride, cis-3-decene-1,2-dicarboxylic anhydride, trans-3-decene-1,2-dicarboxylic anhydride, cis-3-decene-1,10-dicarboxylic anhydride, trans-3-decene-1,10-dicarboxylic anhydride, cis-2-undecene-1,1-dicarboxylic anhydride, trans-2-undecene-1,1-dicarboxylic anhydride, cis-2-undecene-1,11-dicarboxylic anhydride, trans-2-undecene- 1,11-dicarboxylic anhydride, cis-3-undecene-1,1-dicarboxylic anhydride, trans-3-undecene-1,1-dicarboxylic anhydride, cis-3-undecene-1,2-dicarboxylic anhydride, trans-3-undecene-1,2-dicarboxylic anhydride, cis-3-undecene-1,11-dicarboxylic anhydride, trans-3-undecene-1,11-dicarboxylic anhydride, cis-2-dodecene-1,1-dicarboxylic anhydride, trans-2-dodecene-1,1-dicarboxylic anhydride, cis-2-dodecene-1,12-dicarboxylic anhydride trans-2-dodecene-1,12-dicarboxylic anhydride, cis-3-dodecene-1,1-dicarboxylic anhydride, trans-3-dodecene-1,1-dicarboxylic anhydride, cis-3-dodecene-1,2-dicarboxylic anhydride, trans-3-dodecene-1,2-dicarboxylic anhydride, cis-3-dodecene-1,12-dicarboxylic anhydride, trans-3-dodecene-1,12-dicarboxylic anhydride, cis-2-tridecene-1,1-dicarboxylic anhydride, trans-2-tridecene-1,1-dicarboxylic anhydride, cis-2-tridecene-1,13-dicarboxylic anhydride, trans-2-tridecene-1,13-dicarboxylic anhydride, cis-3-tridecene-1,1-dicarboxylic anhydride, trans-3-tridecene-1,1-dicarboxylic anhydride, cis-3-tridecene-1,2-dicarboxylic anhydride, trans-3-tridecene-1,2-dicarboxylic anhydride, cis-3-tridecene-1,13-dicarboxylic anhydride, trans-3-tridecene-1,13-dicarboxylic anhydride, cis-2-tetradecene-1,1-dicarboxylic anhydride, trans-2-tetradecene-1,1-dicarboxylic anhydride carboxylic anhydride, cis-2-tetradecene-1,14-dicarboxylic anhydride, trans-2-tetradecene-1,14-dicarboxylic anhydride, cis-3-tetradecene-1,1-dicarboxylic anhydride, trans-3-tetradecene-1,1-dicarboxylic anhydride, cis-3-tetradecene-1,2-dicarboxylic anhydride, trans-3-tetradecene-1,2-dicarboxylic anhydride, cis-3-tetradecene-1,14-dicarboxylic anhydride, trans-3-tetradecene-1,14-dicarboxylic anhydride, cis-2-pentadecene-1,1-dicarboxylic anhydride carboxylic anhydride, trans-2-pentadecene-1,1-dicarboxylic anhydride, cis-2-pentadecene-1,15-dicarboxylic anhydride, trans-2-pentadecene-1,15-dicarboxylic anhydride, cis-3-pentadecene-1,1-dicarboxylic anhydride, trans-3-pentadecene-1,1-dicarboxylic anhydride, cis-3-pentadecene-1,2-dicarboxylic anhydride, trans-3-pentadecene-1,2-dicarboxylic anhydride, cis-3-pentadecene-1,15-dicarboxylic anhydride, trans-3-pentadecene-1,1 5-dicarboxylic anhydride, cis-2-hexadecene-1,1-dicarboxylic anhydride, trans-2-hexadecene-1,1-dicarboxylic anhydride, cis-2-hexadecene-1,16-dicarboxylic anhydride, trans-2-hexadecene-1,16-dicarboxylic anhydride, cis-3-hexadecene-1,1-dicarboxylic anhydride, trans-3-hexadecene-1,1-dicarboxylic anhydride, cis-3-hexadecene-1,2-dicarboxylic anhydride, trans-3-hexadecene-1,2-dicarboxylic anhydride, cis-3-hexadecene-1,16-dicarboxylic anhydride, trans-3-hexaladecene-1,16-dicarboxylic anhydride, cis-2-heptadecene-1,1-dicarboxylic anhydride, trans-2-heptadecene-1,1-dicarboxylic anhydride, cis-2-heptadecene-1,17-dicarboxylic anhydride, trans-2-heptadecene-1,17-dicarboxylic anhydride, cis-3-heptadecene-1,1-dicarboxylic anhydride, trans-3-heptadecene-1,1-dicarboxylic anhydride, cis-3-heptadecene-1,2-dicarboxylic anhydride, trans-3-heptadecene 1,2-octadecene-1,1-dicarboxylic anhydride, cis-3-heptadecene-1,17-dicarboxylic anhydride, trans-3-heptadecene-1,17-dicarboxylic anhydride, cis-2-octadecene-1,1-dicarboxylic anhydride, trans-2-octadecene-1,1-dicarboxylic anhydride, cis-2-octadecene-1,18-dicarboxylic anhydride, trans-2-octadecene-1,18-dicarboxylic anhydride, cis-3-octadecene-1,1-dicarboxylic anhydride, trans-3-octadecene-1,1-dicarboxylic anhydride, cis-3- Octadecene-1,2-dicarboxylic anhydride, trans-3-octadecene-1,2-dicarboxylic anhydride, cis-3-octadecene-1,18-dicarboxylic anhydride, trans-3-octadecene-1,18-dicarboxylic anhydride, cis-2-nonadecene-1,1-dicarboxylic anhydride, trans-2-nonadecene-1,1-dicarboxylic anhydride, cis-2-nonadecene-1,19-dicarboxylic anhydride, trans-2-nonadecene-1,19-dicarboxylic anhydride, cis-3-nonadecene-1,1-dicarboxylic anhydride, trans-3- Nonadecene-1,1-dicarboxylic anhydride, cis-3-nonadecene-1,2-dicarboxylic anhydride, trans-3-nonadecene-1,2-dicarboxylic anhydride, cis-3-nonadecene-1,19-dicarboxylic anhydride, trans-3-nonadecene-1,19-dicarboxylic anhydride, cis-2-eicosene-1,1-dicarboxylic anhydride, trans-2-eicosene-1,1-dicarboxylic anhydride, cis-2-eicosene-1,20-dicarboxylic anhydride, trans-2-eicosene-1,20-dicarboxylic anhydride, cis-3-eicosene-1,Examples of the dicarboxylic acid anhydride include, but are not limited to, trans-3-eicosene-1,1-dicarboxylic acid anhydride, cis-3-eicosene-1,2-dicarboxylic acid anhydride, trans-3-eicosene-1,2-dicarboxylic acid anhydride, cis-3-eicosene-1,20-dicarboxylic acid anhydride, and trans-3-eicosene-1,20-dicarboxylic acid anhydride.

[0027] When the aliphatic unsaturated hydrocarbon compound carboxylic acid or aliphatic unsaturated hydrocarbon compound dicarboxylic acid or its acid anhydride used as the metal corrosion inhibitor in the present invention has cis-trans isomers, the metal corrosion inhibitor may be a mixture of these isomers.

[0028] The acid anhydride as the metal corrosion inhibitor preferably has a succinic anhydride structure. When the metal corrosion inhibitor contains such a structure, a cleaning composition that exhibits both excellent cleaning ability and excellent corrosion inhibition ability can be obtained with even better reproducibility. In addition, in a dicarboxylic acid having a carboxy group on each of two adjacent carbon atoms, these two carboxy groups undergo dehydration condensation within the molecule to form a five-membered ring, giving a succinic anhydride structure.

[0029] The carbon number of each of the aliphatic saturated hydrocarbon compound monocarboxylic acid, aliphatic saturated hydrocarbon compound dicarboxylic acid and its acid anhydride, aliphatic unsaturated hydrocarbon compound monocarboxylic acid, and aliphatic unsaturated hydrocarbon compound dicarboxylic acid and its acid anhydride, which are metal corrosion inhibitors, is preferably 35 or less, more preferably 30 or less, even more preferably 25 or less, and still more preferably 20 or less, from the viewpoint of ensuring solubility in an organic solvent contained in the cleaning composition and suppressing precipitation of the metal corrosion inhibitor. From the viewpoint of reproducibly obtaining a cleaning composition with excellent detergency, the carbon number is preferably 8 or more, more preferably 9 or more, and even more preferably 10 or more.

[0030] Among these, as the metal corrosion inhibitor, a saturated aliphatic hydrocarbon monocarboxylic acid having 7 to 40 carbon atoms, a saturated aliphatic hydrocarbon dicarboxylic acid anhydride having 7 to 40 carbon atoms, or an unsaturated aliphatic hydrocarbon dicarboxylic acid anhydride having 7 to 40 carbon atoms is preferred, a saturated aliphatic hydrocarbon monocarboxylic acid having 7 to 40 carbon atoms, or an unsaturated aliphatic hydrocarbon dicarboxylic acid anhydride having 7 to 40 carbon atoms is more preferred, and lauric acid, dodecanoic diacid, or octadecenyl succinic anhydride is even more preferred.

[0031] The amount of the metal corrosion inhibitor is not particularly limited as long as it dissolves in the organic solvent contained in the cleaning composition, but is usually 0.01 to 10% by mass relative to the cleaning composition.

[0032] The cleaning agent composition of the present invention may contain a metal corrosion inhibitor other than the metal corrosion inhibitor composed of any one of a saturated aliphatic hydrocarbon compound monocarboxylic acid having 7 to 40 carbon atoms, a saturated aliphatic hydrocarbon compound dicarboxylic acid having 7 to 40 carbon atoms and its acid anhydride, an unsaturated aliphatic hydrocarbon compound monocarboxylic acid having 7 to 40 carbon atoms, and an unsaturated aliphatic hydrocarbon compound dicarboxylic acid having 7 to 40 carbon atoms and its acid anhydride.

[0033] The cleaning composition of 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 dissolves the quaternary ammonium salt and the metal corrosion inhibitor. However, from the viewpoint of reproducibly obtaining a cleaning composition having excellent detergency and from the viewpoint of obtaining a cleaning composition that dissolves the quaternary ammonium salt and the metal corrosion inhibitor well and has excellent uniformity, the organic solvent preferably contains one or more amide solvents.

[0034] An example of a preferred amide solvent is an acid amide derivative represented by formula (Z).

[0035] [ka]

[0036] In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. A and R B are each independently an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R A and R B As for each of the groups, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

[0037] Examples of the acid amide derivative 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. In particular, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are preferred, and N,N-dimethylpropionamide is more preferred.

[0038] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between the corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0039] Another example of a preferred amide solvent is a lactam compound represented by formula (Y).

[0040] [ka]

[0041] In the above formula (Y), specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc., and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., but are not limited to these.

[0042] Specific examples of the lactam compound represented by the above formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used alone or in combination of two or more.

[0043] In a preferred embodiment of the present invention, the lactam compound represented by the above formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it comprises N-methylpyrrolidone (NMP).

[0044] The cleaning composition of the present invention may contain one or more other organic solvents different from the above-mentioned amide compound. Such other organic solvents are not particularly limited as long as they are used for this type of application and are compatible with the above-mentioned amide compounds.

[0045] An example of a preferred other solvent is alkylene glycol dialkyl ether. Specific examples of alkylene glycol dialkyl ethers include ethylene glycol dimethyl ether (also called dimethoxyethane, the same applies below), ethylene glycol diethyl ether (diethoxyethane), ethylene glycol dipropyl ethane (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 are not limited to these. The alkylene glycol dialkyl ethers can be used alone or in combination of two or more.

[0046] Another example of a preferable other solvent is an aromatic hydrocarbon compound, and a specific example thereof is an aromatic hydrocarbon compound represented by formula (1).

[0047] [ka]

[0048] In the above formula (1), specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. s is a substituent R substituted on the benzene ring 100 represents the number of digits, and is either 2 or 3.

[0049] 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).

[0050] [ka]

[0051] R 100are each independently an alkyl group having 1 to 6 carbon atoms, and the three R 100 The total number of carbon atoms in the alkyl groups having 1 to 6 carbon atoms is 3 or more, and the two R 100 The total number of carbon atoms in the alkyl groups having 1 to 6 carbon atoms is 3 or more.

[0052] Specific examples of the aromatic hydrocarbon compound represented by formula (1) include, but are not limited to, 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, and 4-t-butyltoluene. Among these, mesitylene and 4-t-butyltoluene are preferred.

[0053] Another example of a preferred other solvent is a cyclic structure-containing ether compound. Examples of the cyclic structure-containing ether include a cyclic ether compound, a cyclic alkyl chain alkyl ether compound, a cyclic alkyl branched alkyl ether compound, and a di(cyclic alkyl) ether compound.

[0054] A cyclic ether compound is a cyclic hydrocarbon compound in which at least one of the carbon atoms constituting the ring is substituted with an oxygen atom. Typical examples include epoxy compounds in which a linear, branched, or cyclic saturated hydrocarbon compound is epoxidized (i.e., two adjacent carbon atoms and an oxygen atom form a three-membered ring), and cyclic ether compounds other than epoxy in which a carbon atom forming a ring of a cyclic hydrocarbon compound (excluding aromatic hydrocarbon compounds) having 4 or more carbon atoms is substituted with an oxygen atom (epoxy compounds are excluded; the same applies hereinafter). Among these, as such cyclic hydrocarbon compounds having 4 or more carbon atoms, cyclic saturated hydrocarbon compounds having 4 or more carbon atoms are preferred.

[0055] The number of carbon atoms in the epoxy compound is not particularly limited, but is usually 4 to 40, and preferably 6 to 12. The number of epoxy groups is not particularly limited, but is usually 1 to 4, and preferably 1 or 2.

[0056] Specific examples of the epoxy compound include, but are not limited to, epoxy linear or branched saturated hydrocarbon compounds such as 1,2-epoxy-n-butane, 1,2-epoxy-n-pentane, 1,2-epoxy-n-hexane, 1,2-epoxy-n-heptane, 1,2-epoxy-n-octane, 1,2-epoxy-n-nonane, 1,2-epoxy-n-decane, and 1,2-epoxy-n-eicosane; and 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.

[0057] The number of carbon atoms in the cyclic ether compound other than epoxy is not particularly limited, but is usually 3 to 40, and preferably 4 to 8. The number of oxygen atoms (ether groups) is not particularly limited, but is usually 1 to 3, and preferably 1 or 2.

[0058] Specific examples of the cyclic ether compound other than epoxy include oxacyclic saturated hydrocarbon compounds such as oxacyclobutane (oxetane), oxacyclopentane (tetrahydrofuran), and oxacyclohexane, and dioxacyclic saturated hydrocarbon compounds such as 1,3-dioxacyclopentane, 1,3-dioxacyclohexane (1,3-dioxane), and 1,4-dioxacyclohexane (1,4-dioxane), but are not limited to these.

[0059] The cyclic alkyl chain alkyl ether compound comprises a cyclic alkyl group, a chain alkyl group, and an ether group connecting the two, and the number of carbon atoms is not particularly limited, but is usually 4 to 40, and preferably 5 to 20. The cyclic alkyl branched alkyl ether compound comprises a cyclic alkyl group, a branched alkyl group, and an ether group connecting the two, and the number of carbon atoms is not particularly limited, but is usually 6 to 40, and preferably 5 to 20. A di(cyclic alkyl) ether compound consists of two cyclic alkyl groups and an ether group connecting them, and although the number of carbon atoms is not particularly limited, it is usually 6 to 40, and preferably 10 to 20. Among these, as the cyclic ether compounds other than epoxy, cyclic alkyl chain alkyl ether compounds and cyclic alkyl branched alkyl ether compounds are preferred, and cyclic alkyl chain alkyl ether compounds are more preferred.

[0060] A chain alkyl group is a group derived by removing a hydrogen atom from the terminal of a straight-chain aliphatic hydrocarbon, and although there are no particular limitations on the number of carbon atoms, it is usually 1 to 40, and preferably 1 to 20. Specific examples thereof include, but are not limited to, 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, a 1-n-octyl group, a 1-n-nonyl group, and a 1-n-decyl group.

[0061] 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 therein is not particularly limited, but is usually 3 to 40, and preferably 3 to 20. Specific examples thereof include, but are not limited to, an isopropyl group, an isobutyl group, a s-butyl group, a t-butyl group, and the like.

[0062] A cyclic alkyl group is a group derived by removing a hydrogen atom from a carbon atom constituting a ring of a cyclic aliphatic hydrocarbon, and the number of carbon atoms therein is not particularly limited, but is usually 3 to 40, and preferably 5 to 20. Specific examples thereof include monocycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, and cyclohexyl; and bicycloalkyl groups such as bicyclo[2.2.1]heptan-1-yl, bicyclo[2.2.1]heptan-2-yl, bicyclo[2.2.1]heptan-7-yl, bicyclo[2.2.2]octan-1-yl, bicyclo[2.2.2]octan-2-yl, and bicyclo[2.2.2]octan-7-yl, but are not limited to these.

[0063] Specific examples of the cyclic alkyl chain alkyl ether compound include, but are not limited to, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether, cyclopentyl propyl ether, cyclopentyl butyl ether, cyclohexyl methyl ether, cyclohexyl ethyl ether, cyclohexyl propyl ether, and cyclohexyl butyl ether. Specific examples of the cyclic alkyl branched alkyl ether compound include, but are not limited to, cyclopentyl isopropyl ether and cyclopentyl t-butyl ether. Specific examples of the di(cyclic alkyl) ether compound include, but are not limited to, dicyclopentyl ether, dicyclohexyl ether, cyclopentyl cyclohexyl ether, and the like.

[0064] The amount of the organic solvent other than the above-mentioned amide compound is usually determined appropriately so as to be 95 mass% or less of the solvent contained in the cleaning composition, as long as the components contained in the cleaning composition, such as the quaternary ammonium salt and the metal corrosion inhibitor, do not precipitate or separate and are uniformly mixed with the above-mentioned amide compound.

[0065] In the present invention, the cleaning composition contains only an organic solvent as the solvent, thereby reducing the occurrence of water-induced metal contamination, metal corrosion, and the like, and enabling substrates to be cleaned reproducibly and suitably. Therefore, the cleaning composition of the present invention usually contains only an organic solvent as the solvent. Note that "only an organic solvent" means that only the organic solvent is intentionally used as the solvent, and does not exclude the presence of water contained in the organic solvent or other components. In other words, the cleaning composition of the present invention is characterized by being substantially free of water. Here, "substantially free of water" means that water is not blended, and does not exclude water as hydrates of other components or trace amounts of water mixed in with the components, as described above. When the cleaning composition of the present invention is prepared using only an organic solvent as the solvent, the water content of the resulting cleaning composition cannot be generally defined because it varies depending on factors such as whether the organic solvent used has been dehydrated in advance, whether the organic solvent or solids used are highly hygroscopic, and whether the quaternary ammonium salt used is a hydrate. However, the water content is usually less than 5% by mass, preferably less than 4% by mass, and more preferably less than 3% by mass. The water content can be calculated, for example, by the Karl Fischer method using a trace moisture analyzer, Model CA-200 (manufactured by Mitsubishi Chemical Analytech Corporation).

[0066] The cleaning composition of the present invention can be obtained by mixing the quaternary ammonium salt, the metal corrosion inhibitor, the organic solvent, and other components as necessary. The components can be mixed in any order as long as problems such as precipitation or liquid separation that would prevent the achievement of the object of the present invention do not occur. That is, some of the components of the cleaning composition may be mixed in advance, and then the remaining components may be mixed, or all of the components may be mixed at once. If necessary, the cleaning composition may be filtered, or the supernatant may be recovered after mixing, avoiding insoluble components, and used as the cleaning composition. Furthermore, if the components used are, for example, hygroscopic or deliquescent, all or part of the steps for preparing the cleaning composition may be performed under an inert gas.

[0067] By using the cleaning composition of the present invention as described above, polysiloxane-based adhesives remaining on semiconductor substrates such as silicon wafers can be effectively removed. This not only enables the semiconductor substrate to be cleaned in a short time, but also makes it possible to suppress damage to metals such as bumps on the semiconductor substrate, which is expected to enable the efficient production of good semiconductor elements. Specifically, with regard to the cleaning speed, when an adhesive layer obtained from the adhesive composition is brought into contact with the cleaning composition of the present invention for 5 minutes at room temperature (23°C), the decrease in film thickness is measured before and after the contact, and the etching rate [μm / min] calculated by dividing the decrease by the cleaning time is usually 4.5 [μm / min] or more, in a preferred embodiment 5.0 [μm / min] or more, in a more preferred embodiment 5.5 [μm / min] or more, in an even more preferred embodiment 6.0 [μm / min] or more, and in an even more preferred embodiment 6.5 [μm / min] or more. Regarding cleaning durability, when 1 g of an adhesive solid obtained from the adhesive composition is brought into contact with 2 g of the cleaning composition of the present invention at room temperature (23°C), the cleaning composition of the present invention usually dissolves most of the adhesive solid within 12 to 24 hours, and in a preferred embodiment, completely dissolves the adhesive solid within 2 to 12 hours, and in a more preferred embodiment, completely dissolves the adhesive solid within 1 to 2 hours.

[0068] Use of the cleaning composition of the present invention as described above makes it possible to effectively remove polysiloxane adhesives remaining on substrates such as semiconductor substrates. As a result, not only can the substrate be cleaned in a short time, but also, when the substrate has bump balls, corrosion of the bump balls can be avoided or reduced, thereby enabling highly efficient and reliable substrate cleaning.

[0069] The cleaning composition of the present invention can be used to clean the surfaces of various substrates such as semiconductor substrates. The objects to be cleaned are not limited to silicon semiconductor substrates, but also include various substrates such as germanium substrates, gallium-arsenic substrates, gallium-phosphorus substrates, gallium-arsenic-aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon nitride film-formed silicon substrates, silicon oxide film-formed silicon substrates, polyimide film-formed silicon substrates, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.

[0070] For example, examples of the use of the cleaning composition of the present invention in semiconductor processes include use in a method for producing processed semiconductor substrates, such as thinned ones, used in semiconductor packaging techniques such as TSV. Specifically, the cleaning composition of the present invention is used as the cleaning composition in a production method including: a first step of producing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from the adhesive composition; a second step of processing the semiconductor substrate in the obtained laminate; a third step of peeling off the semiconductor substrate after processing; and a fourth step of removing adhesive residue remaining on the peeled semiconductor substrate with the cleaning composition.

[0071] The adhesive composition used to form the adhesive layer in the first step may be any of the various adhesive compositions described above. However, the detergent composition of the present invention is effective for removing an adhesive layer obtained from a polysiloxane adhesive, and is even more effective for removing an adhesive layer obtained from a polysiloxane adhesive containing component (A) that cures via a hydrosilylation reaction. Therefore, an example will be described below in which an adhesive layer obtained using a polysiloxane adhesive (adhesive composition) is removed using the cleaning composition of the present invention when a semiconductor substrate is manufactured using the adhesive layer, but the present invention is not limited thereto.

[0072] First, the first step of producing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described.

[0073] In one embodiment, the first step includes a step of applying an adhesive composition to the surface of a semiconductor substrate or a support substrate to form an adhesive coating layer, and a step of joining the semiconductor substrate and the support substrate together via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring them into close contact while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate. In another embodiment, the first step includes, for example, a step of applying an adhesive composition to the surface of a semiconductor substrate and heating it to form an adhesive coating layer, a step of applying a release agent composition to the surface of a support substrate and heating it to form a release agent coating layer, and a step of applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate into close contact while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate. Note that, although the procedure of applying the adhesive composition to the semiconductor substrate and the release agent composition to the support substrate and then heating has been described, the application and heating of the adhesive composition and the release agent composition may be performed sequentially on either substrate. In each of the above embodiments, the treatment conditions to be adopted, such as heat treatment, reduced pressure treatment, or a combination of both, are determined in consideration of various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the film obtained from both compositions, the film thickness, and the desired adhesive strength.

[0074] Here, for example, the semiconductor substrate is a wafer and the support substrate is a support body, and the adhesive composition may be applied to either or both of the semiconductor substrate and the support substrate.

[0075] Examples of wafers include, but are not limited to, silicon wafers and glass wafers with a diameter of about 300 mm and a thickness of about 770 μm. In particular, the cleaning composition of the present invention can effectively clean a semiconductor substrate having bumps thereon while suppressing damage to the bumps by a cleaning method using the same. Specific examples of such semiconductor substrates with bumps include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps, which are usually selected appropriately from the following conditions: bump height of about 1 to 200 μm, bump diameter of 1 to 200 μm, and bump pitch of 1 to 500 μm. Specific examples of plated bumps include, but are not limited to, alloy plating mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps.

[0076] The support (carrier) is not particularly limited, but may be, for example, a silicon wafer with a diameter of about 300 mm and a thickness of about 700 μm, but is not limited to this.

[0077] In a preferred embodiment, the polysiloxane adhesive (adhesive composition) contains, as an adhesive component, a polyorganosiloxane component (A) that cures by a hydrosilylation reaction. In a more preferred embodiment, the polyorganosiloxane component (A) that cures by a hydrosilylation reaction contains a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 Siloxane unit (M unit) represented by R 4 R 5 SiO 2 / 2 Siloxane units (D units) represented by the formula 6 SiO 3 / 2 and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (Q' units) represented by SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 Siloxane unit (M' unit) represented by R 4 'R 5 'SiO 2 / 2 Siloxane units (D' units) represented by the formula: and R 6 'SiO 3 / 2and a polyorganosiloxane (a1) containing at least one unit selected from the group consisting of siloxane units (T' units) represented by the following formula: 1 "R 2 "R 3 "SiO 1 / 2 Siloxane unit (M" unit) represented by R 4 "R 5 "SiO 2 / 2 Siloxane units (D" units) represented by and R 6 "SiO 3 / 2 and a polyorganosiloxane (a2) containing one or more units selected from the group consisting of siloxane units (T" units) represented by the following formula: and containing at least one unit selected from the group consisting of the M" units, D" units and T" units.

[0078] R 1 ~R 6 are groups or atoms bonded to the silicon atom, and each independently represents an alkyl group, an alkenyl group, or a hydrogen atom.

[0079] R 1 '~R 6 R ' are groups bonded to silicon atoms, and each independently represents an alkyl group or an alkenyl group. 1 '~R 6 At least one of the groups is an alkenyl group.

[0080] R 1 ”~R 6 " are groups or atoms bonded to the silicon atom, and independently represent alkyl groups or hydrogen atoms, but R 1 ”~R 6 At least one of " is a hydrogen atom.

[0081] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0082] Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, and a 3-methyl-n-pentyl group. Examples of the alkyl group include, but are not limited to, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Among these, a methyl group is preferred. Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl cycloalkyl groups such as 1-n-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-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these.

[0083] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0084] Specific examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 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, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl, 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 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- Examples of the alkyl group include, but are not limited to, a 2-propenyl group, a 1-methyl-2-cyclopentenyl group, a 1-methyl-3-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a 2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, a 2-methyl-4-cyclopentenyl group, a 2-methyl-5-cyclopentenyl group, a 2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group. Of these, an ethenyl group and a 2-propenyl group are preferred.

[0085] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1) and the polyorganosiloxane (a2), and the alkenyl groups contained in the polyorganosiloxane (a1) and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2) undergo a hydrosilylation reaction in the presence of a platinum group metal catalyst (A2) to form a crosslinked structure and cure.

[0086] The polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. As the polyorganosiloxane (a1), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0087] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).

[0088] Furthermore, when the polyorganosiloxane (a1) contains two or more types of polyorganosiloxane, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units 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 are not limited to these.

[0089] The polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q″ units, M″ units, D″ units, and T″ units, and also contains at least one unit selected from the group consisting of M″ units, D″ units, and T″ units. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0090] Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units and M" units).

[0091] The polyorganosiloxane (a1) is composed of siloxane units in which alkyl and / or alkenyl groups are bonded to the silicon atoms thereof, and R1 '~R 6 The proportion of alkenyl groups in all the substituents represented by R 1 '~R 6 ' can be an alkyl group.

[0092] The polyorganosiloxane (a2) is composed of siloxane units in which alkyl groups and / or hydrogen atoms are bonded to the silicon atoms. 1 ”~R 6 The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R is preferably 0.1 mol % to 50.0 mol %, more preferably 10.0 mol % to 40.0 mol %, and the remaining R 1 ”~R 6 " can be an alkyl group.

[0093] The polysiloxane (A1) contains a polyorganosiloxane (a1) and a polyorganosiloxane (a2). In a preferred embodiment, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0094] The weight average molecular weight of each of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 500 to 1,000,000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. The weight-average molecular weight, number-average molecular weight, and dispersity in the present invention can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), at a column temperature of 40°C, using tetrahydrofuran as an eluent (elution solvent), at a flow rate (flow rate) of 0.35 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0095] The viscosity of each of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 10 to 1,000,000 (mPa·s), but from the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 50 to 10,000 (mPa·s). Note that the viscosity in the present invention is a value measured at 25°C using an E-type rotational viscometer.

[0096] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film by hydrosilylation, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0097] In a preferred embodiment, the adhesive component (S) contains the above-mentioned polysiloxane (A1) and a platinum group metal catalyst (A2). 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).

[0098] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum. The amount of the platinum group metal catalyst (A2) is usually in the range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0099] The polyorganosiloxane component (A) may contain a polymerization inhibitor (A3) for the purpose of inhibiting the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. The amount of the polymerization inhibitor is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

[0100] The adhesive composition of the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition of the present invention, the resulting adhesive layer can be suitably peeled off with good reproducibility. A typical example of such a release agent component (B) is a polyorganosiloxane, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

[0101] The weight-average molecular weight of the polyorganosiloxane that is the release agent component (B) is usually 100,000 to 2,000,000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000, and its dispersity is usually 1.0 to 10.0, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured by the methods described above.

[0102] Examples of epoxy group-containing polyorganosiloxanes include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing units.

[0103] R 11 is a group bonded to a silicon atom and represents an alkyl group, and 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 include those listed above.

[0104] Furthermore, the epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with other rings, or may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.

[0105] Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

[0106] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 10 units), but D 10In addition to the units, the above Q units, M units and / or T units may be contained.

[0107] In a preferred embodiment, specific examples of the epoxy group-containing polyorganosiloxane include D 10 Polyorganosiloxane consisting of only units, D 10 polyorganosiloxanes containing D units and Q units; 10 Polyorganosiloxanes containing D units and M units, 10 Polyorganosiloxanes containing D units and T units, 10 polyorganosiloxanes containing units, Q units and M units, D 10 Polyorganosiloxanes containing units, M units and T units, D 10 Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0108] 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, but from the viewpoint of suppressing precipitation in the adhesive composition, it is preferably 100,000 or less.

[0109] Specific examples of epoxy group-containing polyorganosiloxanes include CMS-227 (manufactured by Gelest Co., Ltd., weight average molecular weight 27,000) represented by formula (A-1), ECMS-327 (manufactured by Gelest Co., Ltd., weight average molecular weight 28,800) represented by formula (A-2), KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 31,800) represented by formula (A-3), and KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 55,600) represented by formula (A-4). ), trade name KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd., weight-average molecular weight 11,500) represented by formula (A-5), trade name X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd., weight-average molecular weight 2,400) represented by formula (A-6), trade name BY16-839 (manufactured by Dow Corning Corporation, weight-average molecular weight 51,700) represented by formula (A-7), trade name ECMS-327 (manufactured by Gelest Pharmaceuticals, weight-average molecular weight 28,800) represented by formula (A-8), but are not limited to these.

[0110] [ka] (m and n are the numbers of repeating units, respectively.)

[0111] [ka] (m and n are the numbers of repeating units, respectively.)

[0112] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0113] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0114] [ka] (m, n, and o each represent the number of repeating units. R represents an alkylene group having 1 to 10 carbon atoms.)

[0115] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0116] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0117] [ka] (m and n are the numbers of repeating units, respectively.)

[0118] Examples of the methyl group-containing polyorganosiloxane include R 210 R 220 SiO 2 / 2 The siloxane unit (D 200 units), preferably R 21 R 21 SiO 2 / 2 The siloxane unit (D 20 Examples include those containing units.

[0119] R 210 and R 220 are groups bonded to a silicon atom, and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those listed above. R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include those listed above. 21 As the alkyl group, a methyl group is preferred. A preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited to this.

[0120] The methyl group-containing polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D 200 Unit or D 20 units), but D 200 Units and D 20 In addition to the units, the above Q units, M units and / or T units may be contained.

[0121] In one embodiment, specific examples of the methyl group-containing polyorganosiloxane include D 200 Polyorganosiloxane consisting of only units, D 200 polyorganosiloxanes containing D units and Q units; 200 Polyorganosiloxanes containing D units and M units, 200 Polyorganosiloxanes containing D units and T units, 200 polyorganosiloxanes containing units, Q units and M units, D 200 Polyorganosiloxanes containing units, M units and T units, D 200 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0122] In a preferred embodiment, specific examples of the methyl group-containing polyorganosiloxane include D 20 Polyorganosiloxane consisting of only units, D 20 polyorganosiloxanes containing D units and Q units; 20 Polyorganosiloxanes containing D units and M units, 20 Polyorganosiloxanes containing D units and T units, 20 polyorganosiloxanes containing units, Q units and M units, D 20 Polyorganosiloxanes containing units, M units and T units, D 20 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0123] The viscosity of methyl group-containing polyorganosiloxane is usually 1,000 to 2,000,000 mm 2 / s, but preferably 10,000 to 1,000,000 mm 2 / s. The methyl group-containing polyorganosiloxane is typically a dimethyl silicone oil made of polydimethylsiloxane. The viscosity value is expressed as kinematic viscosity, and is expressed in centistokes (cSt) = mm 2 / s. Kinematic viscosity can be measured using a kinematic viscometer. Viscosity (mPa s) can also be converted to density (g / cm 3 ) can also be calculated by dividing by the viscosity measured at 25°C using an E-type rotational viscometer and the density. 2 / s)=viscosity (mPa s) / density (g / cm 3 ) can be calculated from the formula:

[0124] Specific examples of methyl group-containing polyorganosiloxanes include the WACKERSILICONE FLUID AK series manufactured by Wacker Chemie, dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) manufactured by Shin-Etsu Chemical Co., Ltd., and cyclic dimethyl silicone oil (KF-995), but are not limited to these.

[0125] Examples of the phenyl group-containing polyorganosiloxane include R 31 R 32 SiO 2 / 2 The siloxane unit (D 30 Examples include those containing units.

[0126] 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. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0127] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 units), but D 30 In addition to the units, the above Q units, M units and / or T units may be contained.

[0128] In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include D 30 Polyorganosiloxane consisting of only units, D 30 polyorganosiloxanes containing D units and Q units; 30 Polyorganosiloxanes containing D units and M units, 30 Polyorganosiloxanes containing D units and T units, 30 polyorganosiloxanes containing units, Q units and M units, D 30 Polyorganosiloxanes containing units, M units and T units, D 30 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0129] The weight average molecular weight of the phenyl group-containing polyorganosiloxane is usually 1,500 to 500,000, but from the viewpoint of suppressing precipitation in the adhesive composition, it is preferably 100,000 or less.

[0130] A specific example of the phenyl group-containing polyorganosiloxane is PMM-1043 (trade name, manufactured by Gelest, Inc., weight average molecular weight 67,000, viscosity 30,000 mm), represented by formula (C-1). 2 / s), and PMM-1025 (trade name, manufactured by Gelest, Inc., weight average molecular weight 25,200, viscosity 500 mm 2 / s), and the trade name KF50-3000CS (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 39,400, viscosity 3000 mm represented by formula (C-3). 2 / s), and the product name TSF431 (manufactured by MOMENTIVE Co., Ltd., weight average molecular weight 1,800, viscosity 100 mm 2 / s), and the product name TSF433 (manufactured by MOMENTIVE Co., Ltd., weight average molecular weight 3,000, viscosity 450 mm2 / s), and PDM-0421 (trade name, manufactured by Gelest, Inc., weight average molecular weight 6,200, viscosity 100 mm) represented by formula (C-6). 2 / s), and PDM-0821 (trade name, manufactured by Gelest, Inc., weight average molecular weight 8,600, viscosity 125 mm 2 / s), but are not limited to these.

[0131] [ka] (m and n represent the number of repeating units.)

[0132] [ka] (m and n represent the number of repeating units.)

[0133] [ka] (m and n represent the number of repeating units.)

[0134] [ka] (m and n represent the number of repeating units.)

[0135] [ka] (m and n represent the number of repeating units.)

[0136] [ka] (m and n represent the number of repeating units.)

[0137] [ka] (m and n represent the number of repeating units.)

[0138] In a preferred embodiment, the adhesive composition of the present invention contains a release agent component (B) together with a polyorganosiloxane component (A) that cures via a hydrosilylation reaction, and in a more preferred embodiment, the release agent component (B) contains a polyorganosiloxane.

[0139] The adhesive composition of the present invention can contain the adhesive component (S) and the release agent component (B) in any ratio. However, in consideration of the balance between adhesion and releasability, the mass ratio of component (S) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25. That is, when a polyorganosiloxane component (A) that cures via a hydrosilylation reaction is contained, the mass ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0140] The adhesive composition of the present invention may contain a solvent for the purpose of adjusting viscosity, etc., and specific examples of such a solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0141] More specific examples include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. These solvents can be used alone or in combination of two or more.

[0142] When the adhesive composition of the present invention contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the thin film to be produced, etc., but is in the range of about 10 to 90 mass % of the entire composition.

[0143] The viscosity of the adhesive composition of the present invention is typically 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s, at 25° C. The viscosity of the adhesive composition of the present invention can be adjusted by changing the types and ratios of organic solvents used, the concentrations of film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness. In the present invention, the film constituent components refer to components other than the solvent contained in the composition.

[0144] The adhesive composition of the present invention can be prepared by mixing the adhesive component (S) with the release agent component (B), if used, and a solvent. The order of mixing is not particularly limited, but examples of methods that can easily and reproducibly produce an adhesive composition include, but are not limited to, a method of dissolving the adhesive component (S) and the release agent component (B) in a solvent, or a method of dissolving part of the adhesive component (S) and part of the release agent component (B) in a solvent and the rest in a solvent, and then mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause the components to decompose or deteriorate. In the present invention, for the purpose of removing foreign matter, the adhesive composition may be filtered using a submicrometer filter or the like during production or after all components have been mixed.

[0145] Stripping compositions include compositions containing stripping components used in this type of application.

[0146] The coating method is not particularly limited, but is usually a spin coating method. Note that a method of forming a coating film by a separate spin coating method or the like and then attaching a sheet-like coating film may also be employed, and this method is also referred to as coating or coating film.

[0147] The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the desired thickness of the adhesive layer, etc., but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0148] The heating temperature of the applied release agent composition cannot be generally specified because it differs depending on the types and amounts of crosslinking agent, acid generator, acid, etc., whether a solvent is included, the desired thickness of the release layer, etc., but is preferably 120°C or higher from the viewpoint of achieving suitable curing, and is preferably 260°C or lower from the viewpoint of preventing excessive curing, and the heating time is usually 1 to 10 minutes. Heating can be carried out using a hot plate, an oven, or the like.

[0149] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually 5 to 500 μm.

[0150] The thickness of the release agent coating layer obtained by applying the release agent composition and heating it is usually 5 to 500 μm.

[0151] The heating temperature is generally determined appropriately within the range of 20 to 150°C, taking into consideration the need to soften the adhesive coating layer to achieve favorable bonding with the release agent coating layer, the need to achieve favorable curing of the release agent coating layer, etc. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component or release agent component, the heating temperature is preferably 130°C or lower, more preferably 90°C or lower, and from the viewpoint of reliably exhibiting adhesive ability and release ability, the heating time is generally 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of suppressing deterioration of the adhesive layer and other members, but is generally 10 minutes or shorter, preferably 5 minutes or shorter.

[0152] The reduced pressure treatment can be carried out by exposing the semiconductor substrate, adhesive coating layer, and support substrate, or the semiconductor substrate, adhesive coating layer, release agent coating layer, and support substrate, to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0153] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are bonded together, preferably by a reduced pressure treatment, more preferably by a combination of a heat treatment and a reduced pressure treatment.

[0154] 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, the support substrate, and the layers therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 1000 N.

[0155] The post-heating temperature for the post-heating treatment 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, adhesive components, release agent components, etc. The heating time is usually 1 minute or longer from the viewpoint of achieving suitable wafer bonding by curing, and preferably 5 minutes or longer from the viewpoint of stabilizing the physical properties of the adhesive, and is usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of avoiding adverse effects on the adhesive layer due to excessive heating. Heating can be carried out using a hot plate, oven, etc. One purpose of the post-heat treatment is to more suitably cure the adhesive component (S).

[0156] Next, the second step of processing the semiconductor substrate of the laminate will be described. One example of processing applied to the laminate is processing the back surface of the semiconductor substrate, which is the surface opposite to the circuit surface. Typically, the wafer is thinned by polishing the back surface. Using such a thinned wafer, through-silicon vias (TSVs) and other structures are formed. The thinned wafer is then peeled off from the support to form a wafer stack, which is then used for three-dimensional packaging. Also, before or after this, electrodes and other structures are formed on the back surface of the wafer. During the wafer thinning and TSV processes, heat of 250 to 350°C is applied while the wafer is attached to the support, and the adhesive layer contained in the laminate used in the present invention is usually heat-resistant to this heat. 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 4 to 80 μm by polishing the back surface opposite the circuit surface on the front surface.

[0157] Next, the third step of peeling off the semiconductor substrate after processing will be described. The method for peeling off the laminate includes, but is not limited to, solvent peeling, laser peeling, mechanical peeling using a tool with a sharp part, peeling by peeling off between a support and a wafer, and the like. Usually, peeling is performed after processing such as thinning. In the third step, the adhesive (adhesive layer) is not necessarily completely adhered to the support substrate and peeled off, and some of it may be left behind on the processed semiconductor substrate. Therefore, in the fourth step, the surface of the semiconductor substrate to which the remaining adhesive is attached is cleaned with the cleaning composition of the present invention, thereby allowing the adhesive residue on the substrate to be sufficiently removed.

[0158] Finally, the fourth step of removing adhesive residue remaining on the peeled semiconductor substrate with a cleaning composition will be described. The fourth step is a step of removing adhesive residue remaining on the semiconductor substrate after peeling using the cleaning composition of the present invention. Specifically, for example, the thinned substrate on which the adhesive remains is immersed in the cleaning composition of the present invention, and if necessary, ultrasonic cleaning or other means are also used to remove the adhesive residue. When ultrasonic cleaning is used, the conditions are determined appropriately taking into consideration the state of the surface of the substrate. Generally, cleaning at 20 kHz to 5 MHz for 10 seconds to 30 minutes can sufficiently remove adhesive residue remaining on the substrate.

[0159] The method for producing a processed substrate of the present invention includes the above-mentioned steps 1 to 4, but may also include steps other than these. For example, in step 4, before cleaning with the cleaning composition of the present invention, adhesive residue may be removed by immersing the substrate in various solvents or by tape peeling, as necessary. Furthermore, the above-mentioned components and methodological elements related to steps 1 to 4 may be variously modified without departing from the spirit and scope of the present invention. [Example]

[0160] 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) Agitator (rotating / revolving mixer): Thinky Corporation Rotating / revolving mixer ARE-500 (2) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd. (3) Mixer: AS ONE Mix Rotor Variable 1-1186-12 (4) Mixer H: AS ONE heated rocking mixer HRM-1 (5) Contact film thickness meter: Tokyo Seimitsu Co., Ltd. Wafer thickness measuring device WT-425

[0161] [1] Preparation of adhesive composition [Preparation Example 1] A 600 mL stirring vessel designed specifically for use with a planetary centrifugal mixer was charged with 150 g of (a1) a base polymer (manufactured by Wacker Chemie) consisting of a vinyl-containing linear polydimethylsiloxane with a viscosity of 200 mPa·s and a vinyl-containing MQ resin, 15.81 g of (a2) a SiH-containing linear polydimethylsiloxane with a viscosity of 100 mPa·s (manufactured by Wacker Chemie), and 0.17 g of (A3) 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie), and the mixture was stirred for 5 minutes using the planetary centrifugal mixer. To the resulting mixture, 0.33 g of a platinum catalyst (A2) (manufactured by Wacker Chemie) and 9.98 g of a vinyl-containing linear polydimethylsiloxane (a1) with a viscosity of 1000 mPa·s (manufactured by Wacker Chemie) were stirred for 5 minutes in a planetary centrifugal mixer, and 0.52 g of a mixture obtained separately was added. The mixture was stirred for 5 minutes in a planetary centrifugal mixer, and the final mixture was filtered through a 300-mesh nylon filter to obtain an adhesive composition.

[0162] [2] Preparation of cleaning composition [Example 1] To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.), 0.5 g of octadecenylsuccinic anhydride and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a detergent composition.

[0163] [Example 2] To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.), 0.5 g of dodecanoic diacid and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a detergent composition.

[0164] [Example 3] To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.), 0.5 g of lauric acid and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a detergent composition.

[0165] [Comparative Example 1] To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.), 0.5 g of succinic anhydride and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a detergent composition.

[0166] Comparative Example 2 A cleaning composition was obtained by adding 0.5 g of adipic acid and 95 g of N,N-dimethylpropionamide to 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.) and stirring the mixture.

[0167] Comparative Example 3 To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.), 0.5 g of glutaric acid and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a detergent composition.

[0168] [3] Performance evaluation of cleaning agent compositions A good cleaning composition needs to have a high cleaning speed that dissolves adhesive residue immediately after contacting it, so the following evaluation was carried out. A higher cleaning speed is expected to result in more effective cleaning. The etching rate was measured to evaluate the cleaning speed of the resulting cleaning composition. The adhesive composition obtained in Preparation Example 1 was applied to a 12-inch silicon wafer using a spin coater, and heated at 150°C for 15 minutes and then at 190°C for 10 minutes to form an adhesive layer (thickness 100 μm). The wafer with the film (adhesive layer) was then cut into 4 cm square chips, and the film thickness was measured using a contact film thickness meter. The chips were then placed in a 9 cm diameter stainless steel dish, 7 mL of the resulting cleaning composition added, and the dish was capped. The dish was then placed on a stirrer H and stirred and washed at 23°C for 5 minutes. After washing, the chips were removed, washed with isopropanol and pure water, dried at 150°C for 1 minute, and the film thickness was measured again using a contact film thickness meter. The film thickness reduction before and after washing was calculated, and the etching rate [μm / min] was calculated by dividing the reduction by the washing time, which was used as an index of cleaning power. The results are shown in Table 1.

[0169] [Table 1]

[0170] By using the metal corrosion inhibitor of the present invention, an excellent cleaning speed was achieved despite the presence of the metal corrosion inhibitor in the cleaning composition. On the other hand, the cleaning compositions of the comparative examples did not exhibit the same cleaning speed as the cleaning compositions of the present invention. Use of the cleaning composition of the present invention is expected to enable the suitable removal of adhesive residues on semiconductor substrates while suppressing or avoiding corrosion of bump balls.

Claims

1. A temporary adhesive residue cleaner composition for removing temporary adhesive residue used in producing processed semiconductor substrates, comprising: the temporary adhesive residue is a temporary adhesive residue of an adhesive layer obtained from an adhesive composition containing a component (A) that cures by a hydrosilylation reaction, a quaternary ammonium salt, a metal corrosion inhibitor, and an organic solvent; the quaternary ammonium salt is a halogen-containing quaternary ammonium salt, the metal corrosion inhibitor comprises lauric acid, dodecanoic diacid, or octadecenyl succinic anhydride; The temporary adhesive residue cleaner composition, characterized in that the organic solvent contains an amide solvent, and the amount of the metal corrosion inhibitor is 0.01 to 10 mass % based on the temporary adhesive residue cleaner composition.

2. 2. The temporary adhesive residue cleaner composition according to claim 1, wherein said halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt.

3. 3. A temporary adhesive residue cleaner composition according to claim 2, wherein said fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.

4. 4. The temporary adhesive residue cleaning composition according to claim 3, 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.

5. A method for producing a processed semiconductor substrate, comprising: a first step of producing a laminate comprising a semiconductor substrate having bump balls, a support substrate, and a temporary adhesive layer obtained from the temporary adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of peeling off the semiconductor substrate after processing; and a fourth step of removing temporary adhesive residue remaining on the peeled semiconductor substrate with a temporary adhesive residue cleaning composition, wherein the temporary adhesive residue cleaning composition is the temporary adhesive residue cleaning composition according to any one of claims 1 to 4.

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