TW201932574A - Surface treatment agent and surface-treated body manufacturing method - Google Patents

Abstract

The present invention provides: a surface treatment agent that is capable of dissolving a raw material in a short period of time when preparing a solution and that is capable of exhibiting an excellent water repellency-imparting effect; and a surface-treated body manufacturing method that uses said surface treatment agent. The surface treatment agent according to the present invention is used for treating the surface of a to-be-treated body, and comprises: (I) at least one selected from silicon compounds represented by general formulas [1], [2], and [3]; (II) at least one selected from among nitrogen-containing heterocyclic compounds represented by general formula [4], nitrogen-containing heterocyclic compounds represented by general formula [5], and imidazole; and (III) an organic solvent. [1]: (R1)a(H)bSi[N(R2)C(=O)R3]4-a-b [2]: (R4)c(H)dSi[OC(=O)R5]4-c-d [3]: (R6)e(H)fSi[OC(R7)=NSi(R8)g(H)3-g]4-e-f [4] [5].

Description

Surface treatment agent and method of manufacturing surface treatment body

The present invention relates to a surface treatment agent and a method of producing a surface treatment body, and more particularly to a surface treatment agent and surface treatment which can be suitably applied to the surface treatment of a substrate to be processed, such as a substrate used in the manufacture of a semiconductor integrated circuit. The manufacturing method of the body.

In the manufacture of a semiconductor device or the like, a lithography technique is used before the substrate is subjected to etching or the like. In the lithography technique, a photosensitive resin layer is provided on a substrate using a photosensitive resin composition, and then selectively exposed by irradiation with active radiation, and selectively subjected to development treatment to selectively dissolve and remove photosensitivity. The resin layer forms a resin pattern on the substrate. Further, an inorganic pattern is formed on the substrate by performing etching treatment using the resin pattern as a mask.

In addition, in recent years, the tendency of the semiconductor device to be highly integrated and miniaturized has increased, and the resin pattern of the mask or the inorganic pattern produced by the etching process has been refined and the aspect ratio has been increasing. On the other hand, however, there is a problem of so-called pattern collapse. When the pattern collapses when a large number of resin patterns or inorganic patterns are formed in parallel on the substrate, the adjacent patterns approach each other in a manner of leaning against each other, and the pattern may be broken or peeled from the base as the case may be. If such a pattern collapses, the desired product cannot be obtained, resulting in a decrease in the yield or reliability of the product.

It can be seen that the pattern collapse is caused by the surface tension of the cleaning liquid when the cleaning liquid is dried during the cleaning process after the pattern formation. That is, when the cleaning liquid is removed during the drying process, the stress based on the surface tension of the cleaning liquid acts between the patterns to cause pattern collapse.

Therefore, in Patent Document 1, in order to prevent the pattern of the inorganic pattern or the resin pattern provided on the substrate from collapsing, it is disclosed that a surface treatment agent containing a sulfonating agent and a nitrogen-containing heterocyclic compound containing no ruthenium atom is used. The treatment body (pattern on the substrate) is subjected to surface treatment to impart water repellency.
[Previous Technical Literature]
[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2017-063179

[The problem that the invention wants to solve]

However, the inventors of the present invention have found that a surface treatment agent containing a sulfonating agent and a nitrogen-containing heterocyclic compound containing no ruthenium atom is present in a case where the raw material is dissolved at the time of preparation, or the water-repellent imparting effect is insufficient. Accordingly, it is an object of the present invention to provide a novel surface treatment agent that solves these problems.
[Technical means to solve the problem]

The present invention is a surface treatment agent for a surface treatment of a treated object, and comprises:
(I) at least one of the quinone compounds represented by the following general formulas [1], [2], and [3];
(II) at least one of a nitrogen-containing heterocyclic compound represented by the following formula [4], a nitrogen-containing heterocyclic compound represented by the following formula [5], and an imidazole;
(III) Organic solvent.
[Chemical 1]

[In the formula [1], R ^{1 is} , independently of each other, a part or all of hydrogen elements may be substituted with a fluorine element having a carbon number of from 1 to 18, and R ^{2 is} independently selected from a part or all of hydrogen. The element may be substituted with a group of a fluorine group having an alkyl group having 1 to 6 carbon atoms and a hydrogen group, and R ^{3 is} independently a part or all of the hydrogen element may be substituted with a carbon number of the fluorine element. Is an alkyl group of 1 to 6, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 1 to 3]
[Chemical 2]

[In the formula [2], R ^{4 is} , independently of each other, a part or all of hydrogen elements may be substituted with a fluorine element having a carbon number of from 1 to 18, and R ^{5 may} be a part or all of hydrogen independently of each other. The carbon number substituted with fluorine is 1 to 6 alkyl groups, c is an integer of 1 to 3, d is an integer of 0 to 2, and the total of c and d is 1 to 3]
[Chemical 3]

[In the formula [3], R ⁶ and R ⁸ are each independently a part or all of a hydrogen element may be substituted with a fluorine element having a carbon number of 1 to 18 one-valent hydrocarbon group, and R ^{7 is} independently selected from a part of each other. Or all hydrogen elements may be substituted with an alkyl group having a carbon number of 1 to 6 and a group of hydrogen elements, e is an integer of 1 to 3, and f is an integer of 0 to 2, and g is An integer from 1 to 3, the total of e and f is 1 to 3]
[Chemical 4]

[In the formula [4], R ⁹ and R ¹⁰ are each independently a divalent organic group containing a carbon element and/or a nitrogen element and a hydrogen element, and the total number of carbon atoms and nitrogen is 1 to 9, in the case of 2 or more. When there is a carbon element that does not form a ring]
[Chemical 5]

[In the formula [5], R ¹¹ is an alkyl group in which a part or all of the hydrogen element may be substituted with a fluorine element and having a carbon number of 1 to 6, and a part or all of the hydrogen element may be substituted with a fluorine element, and the carbon number is 1 to a trialkylsulfanyl group of 8 alkyl groups, a part or all of a hydrogen element may be substituted with an alkenyl group having 2 to 6 carbon atoms, and a part or all of hydrogen may be substituted with a fluorine element having a carbon number of 1 to An alkoxy group of 6 or an amine group, an alkylamino group having a part or all of a hydrogen element which may be substituted with an alkyl group having 1 to 6 carbon atoms of a fluorine element, and a part or all of hydrogen elements may be substituted with a fluorine element. a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a part or all of a hydrogen element may be substituted with an amino group having 1 to 6 carbon atoms, a nitro group, a nitro group, a phenyl group, a phenyl group or a benzyl group. Or a halogen group, R ¹² , R ¹³ and R ¹⁴ are each independently a part or all of a hydrogen element which may be substituted with a fluorine group having an alkyl group having 1 to 6 carbon atoms or a hydrogen group]

The concentration of (II) relative to the total amount of the above (I) to (III) is preferably 0.05 to 10% by mass.

When the above (II) is a liquid at 25 ° C and 1 atm, it is preferred from the viewpoint of solubility.

Further, if the above (II) is selected from 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]-7-undecene, 7-Methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene, N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, And at least one of the group consisting of trimethylsilyl imidazole is preferred from the viewpoint of solubility, wherein, if it is selected from 1,5-diazabicyclo[4.3.0]-5- Terpene, 1,8-diazabicyclo[5.4.0]-7-undecene, 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene, At least one of the group consisting of N-methylimidazole, N-ethylimidazole, N-propylimidazole, and N-butylimidazole is more preferable because it is easy to exhibit a more excellent water-repellent imparting effect. Especially if it is selected from 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]-7-undecene, and 7-methyl At least one of the groups consisting of -1,5,7-triazabicyclo[4.4.0]non-5-ene is more preferable because it is easy to exhibit an excellent water repellency imparting effect.

When the concentration of (I) in the total amount of the above (I) to (III) is 0.1 to 35% by mass, it is easy to form a protective film uniformly on the surface of the object to be treated, which is preferable. If it is less than 0.1% by mass, the water repellency imparting effect tends to be insufficient. Moreover, when it exceeds 35% by mass, the surface of the object to be treated is eroded or remains on the surface of the object to be treated as an impurity, and it is also inferior in terms of cost. Further, it is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, even more preferably from 1 to 9% by mass.

Further, the surface treatment agent contains at least one anthracene compound of the above formula [1] wherein a is 3, R ² is a methyl group, and R ³ is a fluorine-containing alkyl group having 1 to 6 carbon atoms as the above (I). Further, it is preferable that the water-repellent imparting effect is more excellent, and among them, the above (I) is preferably (CH ₃ ) ₃ SiN(CH ₃ )C(=O)CF ₃ .

When the ruthenium compound represented by the above formula [2] is used as the above (I), the above (II) is selected from 1,5-diazabicyclo[4.3.0]-5-pinene, 1 , in the group consisting of 8-diazabicyclo[5.4.0]-7-undecene and 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene At least one of them is particularly preferable because it is particularly excellent in the water repellency imparting effect.

In addition, when the surface treatment agent contains at least one ruthenium compound of the above formula [2] wherein c is 3 and R ⁵ is a fluorine-containing alkyl group having 1 to 6 carbon atoms, the above-mentioned (I) is easily dialed. It is more preferable because the water-based imparting effect is particularly excellent. However, when the above (I) is (CH ₃ ) ₃ SiOC(=O)CF ₃ , it is particularly preferable from the viewpoint of the water-repellent imparting effect.

Further, the surface treatment agent contains at least one ruthenium compound (I-1) in which a of the above formula [1] is 3, R ² is hydrogen, and R ³ is a fluorine-containing alkyl group having 1 to 6 carbon atoms. And at least one ruthenium compound (I-2) wherein c of the above formula [2] is 3 and R ⁵ is a fluorine-containing alkyl group having 1 to 6 carbon atoms, as the above (I), even if water is mixed thereinto In the case of the surface treatment agent, it is also preferable to stably maintain the water repellency imparting effect on the surface of the object to be treated, and it is more preferable that the above ruthenium compound (I-1) is (CH ₃ ) ₃ SiN (H). C(=O)CF ₃ , and the above hydrazine compound (I-2) is (CH ₃ ) ₃ SiOC(=O)CF ₃ .

Further, if the above (II) is selected from 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]-7-undecene, At least one of the group consisting of 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene is more preferable because it is particularly excellent in the water repellency imparting effect.

In addition, when the surface treatment agent contains at least one ruthenium compound of the above formula [3] wherein e and g are 3 and R ⁷ is a methyl group or a trifluoromethyl group, it is easy to be water-repellent. It is preferable that the effect is more excellent, and the above (I) is preferably (CH ₃ ) ₃ SiOC(CF ₃ )=NSi(CH ₃ ) ₃ .

When the ruthenium compound represented by the above formula [3] is used as the above (I), the above (II) is selected from 1,5-diazabicyclo[4.3.0]-5-nonene, 1 , in the group consisting of 8-diazabicyclo[5.4.0]-7-undecene and 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene At least one of them is preferred because it is excellent in water repellency imparting effect, and is preferably selected from the group consisting of 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diaza At least one of the group consisting of bicyclo [5.4.0]-7-undecene is particularly preferred because it is particularly excellent in the water repellency imparting effect.

The above organic solvent is preferably an aprotic solvent.

Moreover, the present invention is a method for producing a surface treated body in which the surface treatment agent according to any one of the above-mentioned items is brought into contact with the surface of the object to be treated, and the surface of the object to be treated is treated.
[Effects of the Invention]

According to the present invention, there is provided a surface treatment agent which does not have a concern of dissolving a raw material at the time of preparation or which has insufficient water-repellent imparting effect, and a method for producing a surface-treated body using the surface treatment agent.

1. Surface Treatment Agent The surface treatment agent of the present invention is used when the surface of the object to be treated is decanolated, and comprises: (I) an anthracene compound represented by the above formulas [1], [2] and [3] At least one of them;
(II) at least one of the nitrogen-containing heterocyclic compound represented by the above formula [4], the nitrogen-containing heterocyclic compound represented by the above formula [5], and imidazole;
(III) Organic solvent.

The type of the object to be treated treated by the surface treatment agent of the present invention is not particularly limited. The object to be processed is preferably a "substrate". Here, as the "substrate" to be subjected to the sulfonation treatment, a substrate for forming a semiconductor device, the surface of the substrate, and the inorganic pattern and the resin pattern provided on the substrate can be exemplified except for the surface of the substrate itself. The surface, as well as the surface of the inorganic layer and the organic layer that are not patterned.

As the inorganic pattern provided on the substrate, a pattern formed by performing an etching treatment on the surface of the inorganic layer existing on the substrate by a photoresist method and then performing an etching treatment can be exemplified. In addition to the substrate itself, an oxide film constituting an element of the substrate, a film or layer of an inorganic material such as tantalum nitride, titanium nitride or tungsten formed on the surface of the substrate may be exemplified. The film or layer is not particularly limited, and examples thereof include a film or layer of an inorganic substance formed in the process of producing a semiconductor device.

As the resin pattern provided on the substrate, a resin pattern formed on the substrate by a photoresist method can be exemplified. Such a resin pattern is formed, for example, by forming an organic layer as a film of a photoresist on a substrate, and exposing the organic layer through a photomask to perform development. The organic layer may be provided on the surface of the laminated film provided on the surface of the substrate, or the like, in addition to the surface of the substrate itself. The organic layer is not particularly limited, and examples thereof include a film of an organic material provided to form an etching mask during the fabrication of the semiconductor device.

The solution type surface treatment agent obtained by dissolving the above (I) and (II) in the organic solvent of the above (III) is applied to a substrate to be processed, for example, by a spin coating method or a dipping method. The surface is contacted to allow surface treatment. In addition, for example, the solution-type surface treatment agent is vaporized, and the vapor is supplied to the surface of the object to be treated such as a substrate, and the surface of the object to be processed is aggregated and held in a liquid state to be contacted. This can also be surface treated.

Hereinafter, each component will be described.

(I) A ruthenium compound The R ¹ group of the above formula [1], the R ⁴ group of the above formula [2], and the R ⁶ group of the above formula [3] are water-repellent functional groups. Further, the -N(R ² )C(=O)R ³ group of the above formula [1], the -OC(=O)R ⁵ group of the above formula [2], and the above-mentioned formula [3] OC(R ⁷ )=NSi(R ⁸ ) _g (H) The _3-g group reacts with the surface of the object to be treated, and the site having the functional group having the above water repellency is fixed to the object to be treated, whereby The treatment body forms a water-repellent protective film (hereinafter, it may be described as a "water-repellent protective film" or simply as a "protective film"). Further, it is more preferable that the base which reacts with the surface of the object to be treated is a structure which further improves the water repellency of the protective film. When the hydrazine compound and the component (II) are used, the ruthenium compound reacts rapidly with the surface of the object to be treated, and a water repellency imparting effect can be obtained.

Specific examples of the ruthenium compound of the above formula [1] include CH ₃ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₂ H ₅ Si[N(CH ₃ )C(= O)CF ₃ ] ₃ , C ₃ H ₇ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₄ H ₉ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₅ H ₁₁ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₆ H ₁₃ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₇ H ₁₅ Si[N(CH ₃ ) C(=O)CF ₃ ] ₃ , C ₈ H ₁₇ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₉ H ₁₉ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₀ H ₂₁ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₁ H ₂₃ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₂ H ₂₅ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₃ H ₂₇ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₄ H ₂₉ Si[N(CH ₃ )C (=O)CF ₃ ] ₃ , C ₁₅ H ₃₁ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₆ H ₃₃ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₇ H ₃₅ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₁₈ H ₃₇ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , (CH ₃ ) ₂ Si[ N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₂ H ₅ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , (C ₂ H ₅ ) ₂ Si[N (CH ₃ )C(=O)CF ₃ ] ₂ , C ₃ H ₇ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , (C ₃ H ₇ ) ₂ Si[N( CH ₃ )C(=O)CF ₃ ] ₂ , C ₄ H ₉ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , (C ₄ H ₉ ) ₂ Si[N(CH ₃ ) C(=O)CF ₃ ] ₂ , C ₅ H ₁₁ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₆ H ₁₃ Si(CH ₃ )[N(CH ₃ ) C(=O)CF ₃ ] ₂ , C ₇ H ₁₅ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₈ H ₁₇ Si(CH ₃ )[N(CH ₃ ) C(=O)CF ₃ ] ₂ , C ₉ H ₁₉ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₁₀ H ₂₁ Si(CH ₃ )[N(CH ₃ ) C(=O)CF ₃ ] ₂ , C ₁₁ H ₂₃ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₁₂ H ₂₅ Si(CH ₃ )[N(CH ₃ ) C(=O)CF ₃ ] ₂ , C ₁₃ H ₂₇ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₁₄ H ₂₉ Si(CH ₃ )[N(CH ₃ ) C(=O)CF ₃ ] ₂ , C ₁₅ H ₃₁ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₁₆ H ₃₃ Si(CH ₃ )[N(CH ₃ ) C(=O)CF ₃ ] ₂ , C ₁₇ H ₃₅ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₁₈ H ₃₇ Si(CH ₃ )[N(CH ₃ ) C(=O)CF ₃ ] ₂ , (CH ₃ ) ₃ SiN(CH ₃ )C(=O)CF ₃ , C ₂ H ₅ Si(CH ₃ ) ₂ N(CH ₃ )C(=O) CF ₃ , (C ₂ H ₅ ) ₂ Si(CH ₃ )N(CH ₃ )C(=O)CF ₃ , (C ₂ H ₅ ) ₃ SiN(CH ₃ )C(=O)CF ₃ , C ₃ H ₇ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , (C ₃ H ₇ ) ₂ Si(CH ₃ )N(CH ₃ )C(=O)CF ₃ , (C ₃ H ₇ ) ₃ SiN(CH ₃ )C(=O)CF ₃ , C ₄ H ₉ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , (C ₄ H ₉ ) ₃ SiN(CH ₃ ) C(=O)CF ₃ , C ₅ H ₁₁ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₆ H ₁₃ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₇ H ₁₅ Si( CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₈ H ₁₇ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₉ H ₁₉ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₁₀ H ₂₁ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₁₁ H ₂₃ Si(CH ₃ ) ₂ N(CH ₃ C(=O)CF ₃ , C ₁₂ H ₂₅ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₁₃ H ₂₇ Si(CH ₃ ) ₂ N(CH ₃ )C(= O) CF ₃ , C ₁₄ H ₂₉ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₁₅ H ₃₁ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₁₆ H ₃₃ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₁₇ H ₃₅ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₁₈ H ₃₇ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , (CH ₃ ) ₂ Si(H)N(CH ₃ )C(=O)CF ₃ ,CH ₃ Si(H) ₂ N (CH ₃ )C(=O)CF ₃ , (C ₂ H ₅ ) ₂ Si(H)N(CH ₃ )C(=O)CF ₃ , C ₂ H ₅ Si(H) ₂ N(CH ₃ ) C(=O)CF ₃ , C ₂ H ₅ Si(CH ₃ )(H)N(CH ₃ )C(=O)CF ₃ , (C ₃ H ₇ ) ₂ Si(H)N(CH ₃ )C (=O)CF ₃ , C ₃ H ₇ Si(H) ₂ N(CH ₃ )C(=O)CF ₃ , CF ₃ CH ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₂ F ₅ CH ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₃ F ₇ CH ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₄ F ₉ C H ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si[N(CH ₃ )C(=O)CF ₃ ] ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ )[N(CH ₃ )C(=O CF ₃ ] ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )[N (CH ₃ )C(=O)CF ₃ ] ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )[N(CH ₃ )C(=O)CF ₃ ] ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ N(CH ₃ )C(=O) CF ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ N(CH ₃ )C (=O)CF ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ N( CH ₃ )C(=O)CF ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)C F ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ N(CH ₃ )C(=O)CF ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H)N(CH ₃ )C (=O) N-methyl-N-alkyldecyltrifluoroacetamide such as CF ₃ or the above-N-methyl-N-alkyldecyltrifluoroacetamide-N(CH ₃ ) C (= O) CF ₃ group substituted with -N (CH ₃₎ except for _{-N (CH 3) C (=} O) CF 3 group of ^{C (= O) R 3 (} R 3 is a hydrogen elements may be partially or entirely A compound obtained by substituting a fluorine atom with an alkyl group having 1 to 6 carbon atoms. Further, a methyl moiety of -N(CH ₃ )C(=O)R ³ of the above compound may be substituted with a hydrogen group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, a pentafluoroethyl group, or a seventh group. A compound formed from fluoropropyl or nonafluorobutyl. Further, as the hydrazine compound of the above formula [1], a commercially available one can be used. For example, as long as it is N-methyl-N-trimethyldecyltrifluoroacetamide [(CH ₃ ) ₃ SiN(CH ₃ )C(=O)CF ₃ ], Tokyo Chemical Industry Co., Ltd. can be used. maker.

From the viewpoint of the water-repellent imparting effect, the R ² group of the above formula [1] is preferably a part or all of a hydrogen element which may be substituted with a fluorine atom having an alkyl group having 1 to 4 carbon atoms or a hydrogen group. It is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen group, and particularly preferably a methyl group.

From the viewpoint of the water-repellent imparting effect, the R ³ group of the above formula [1] is preferably an alkyl group in which all hydrogen elements are substituted with a fluorine element, and the carbon number of the alkyl group is more preferably from 1 to 4, and the number of carbon atoms Especially good is 1.

Further, in the above formula [1], when the number of the -N(R ² )C(=O)R ³ groups represented by 4-a-b is 1, the protective film can be formed homogeneously, and thus good.

Further, in the above formula [1], when b is 0, the water repellency is easily maintained during the cleaning after the formation of the protective film described below, which is preferable.

Further, when the R ¹ group of the above formula [1] is a combination of two methyl groups and one linear alkyl group, the protective film can be formed homogeneously, which is more preferable. Further, the R ¹ group is preferably three methyl groups.

Specific examples of the ruthenium compound of the above formula [2] include CH ₃ Si(OC(=O)CF ₃ ) ₃ , C ₂ H ₅ Si(OC(=O)CF ₃ ) ₃ , C ₃ H ₇ Si(OC(=O)CF ₃ ) ₃ , C ₄ H ₉ Si(OC(=O)CF ₃ ) ₃ , C ₅ H ₁₁ Si(OC(=O)CF ₃ ) ₃ , C ₆ H ₁₃ Si (OC(=O)CF ₃ ) ₃ , C ₇ H ₁₅ Si(OC(=O)CF ₃ ) ₃ , C ₈ H ₁₇ Si(OC(=O)CF ₃ ) ₃ , C ₉ H ₁₉ Si(OC (=O)CF ₃ ) ₃ , C ₁₀ H ₂₁ Si(OC(=O)CF ₃ ) ₃ , C ₁₁ H ₂₃ Si(OC(=O)CF ₃ ) ₃ , C ₁₂ H ₂₅ Si(OC(= O)CF ₃ ) ₃ , C ₁₃ H ₂₇ Si(OC(=O)CF ₃ ) ₃ , C ₁₄ H ₂₉ Si(OC(=O)CF ₃ ) ₃ , C ₁₅ H ₃₁ Si(OC(=O) CF ₃ ) ₃ , C ₁₆ H ₃₃ Si(OC(=O)CF ₃ ) ₃ , C ₁₇ H ₃₅ Si(OC(=O)CF ₃ ) ₃ , C ₁₈ H ₃₇ Si(OC(=O)CF _{3 3} , (CH ₃ ) ₂ Si(OC(=O)CF ₃ ) ₂ , C ₂ H ₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si(OC (=O)CF ₃ ) ₂ , C ₃ H ₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (C ₃ H ₇ ) ₂ Si(OC(=O)CF ₃ ) ₂ , C ₄ H ₉ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (C ₄ H ₉ ) ₂ Si(OC(=O)CF ₃ ) ₂ , C ₅ H ₁₁ Si(CH ₃ )(OC(= O)CF ₃ ) ₂ , C ₆ H ₁₃ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₇ H ₁₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₈ H ₁₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₉ H ₁₉ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₀ H ₂₁ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₁ H ₂₃ Si(CH ₃ )(OC(= O)CF ₃ ) ₂ , C ₁₂ H ₂₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₃ H ₂₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₄ H ₂₉ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₅ H ₃₁ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₆ H ₃₃ Si(CH ₃ )(OC(= O)CF ₃ ) ₂ , C ₁₇ H ₃₅ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₁₈ H ₃₇ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , (CH _{3 3} SiOC(=O)CF ₃ , C ₂ H ₅ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (C ₂ H ₅ ) ₂ Si(CH ₃ )OC(=O)CF ₃ , (C ₂ H ₅ ) ₃ SiOC(=O)CF ₃ , C ₃ H ₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (C ₃ H ₇ ) ₂ Si(CH ₃ )OC(=O)CF ₃ , (C ₃ H ₇ ) ₃ SiOC(=O)CF ₃ , C ₄ H ₉ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (C ₄ H ₉ ) ₃ SiOC(=O)CF ₃ , C ₅ H ₁₁ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₆ H ₁₃ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₇ H ₁₅ Si(CH ₃ ) ₂ OC(=O) CF ₃ , C ₈ H ₁₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₉ H ₁₉ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₀ H ₂₁ Si(CH ₃ ) ₂ OC (=O)CF ₃ , C ₁₁ H ₂₃ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₂ H ₂₅ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₃ H ₂₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₄ H ₂₉ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₅ H ₃₁ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₆ H ₃₃ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₇ H ₃₅ Si( CH ₃ ) ₂ OC(=O)CF ₃ , C ₁₈ H ₃₇ Si(CH ₃ ) ₂ OC(=O)CF ₃ , (CH ₃ ) ₂ Si(H)OC(=O)CF ₃ ,CH ₃ Si (H) ₂ OC(=O)CF ₃ , (C ₂ H ₅ ) ₂ Si(H)OC(=O)CF ₃ , C ₂ H ₅ Si(H) ₂ OC(=O)CF ₃ , C ₂ H ₅ Si(CH ₃ )(H)OC(=O)CF ₃ , (C ₃ H ₇ ) ₂ Si(H)OC(=O)CF ₃ , C ₃ H ₇ Si(H) ₂ OC(=O CF ₃ , CF ₃ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(OC(=O)CF ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )(OC( =O)CF ₃ ) ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ )(OC(=O) ) CF ₃ ) ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF _{3 2} , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )(OC(=O)CF ₃ ) ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₄ F ₉ CH ₂ CH ₂ Si (CH ₃ ) ₂ OC(=O)CF ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC (=O)CF ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(=O)CF ₃ , trifluoroacetoxy decane such as CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H)OC(=O)CF ₃ or -OC(=O)CF _{3 of the} above trifluoroethoxy decane The group is substituted by -OC(=O)R ⁵ other than the -OC(=O)CF ₃ group (R ⁵ is an alkyl group having a carbon number of 1 to 6 which may be substituted with a fluorine element or a fluorine element) Adults and so on. Further, as the hydrazine compound of the above formula [2], a commercially available one can be used. For example, as long as it is trimethyldecyltrifluoroacetate [(CH ₃ ) ₃ Si-OC(=O)CF ₃ ], a manufacturer of Tokyo Chemical Industry Co., Ltd. can be used.

Imparting water repellency to the viewpoint of the effect, the above -OC (= O) R ⁵ R ⁵ is preferably a group of elements are all hydrogen fluorine substituted alkyl group, the carbon number of the alkyl group of 1 to 4, more preferably The carbon number is especially good at 1.

Further, when the number of the -OC(=O)R ⁵ groups represented by 4-c-d in the above formula [2] is 1, the protective film can be formed homogeneously, which is more preferable.

In addition, when d in the above formula [2] is 0, the water repellency is easily maintained during the cleaning after the formation of the protective film described below, which is preferable.

Further, when R ⁴ of the above formula [2] is a combination of two methyl groups and one linear alkyl group, the protective film can be formed homogeneously, which is more preferable. Further, the R ⁴ group is preferably three methyl groups.

Specific examples of the ruthenium compound of the above formula [3] include CH ₃ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₂ H ₅ Si[OC(CH ₃ )=NSi( CH ₃ ) ₃ ] ₃ , C ₃ H ₇ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₄ H ₉ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₅ H ₁₁ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₆ H ₁₃ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₇ H ₁₅ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₈ H ₁₇ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₉ H ₁₉ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₀ H ₂₁ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₁ H ₂₃ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₂ H ₂₅ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₃ H ₂₇ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₄ H ₂₉ Si[OC(CH ₃ )= NSi(CH ₃ ) ₃ ] ₃ , C ₁₅ H ₃₁ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₆ H ₃₃ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₇ H ₃₅ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₁₈ H ₃₇ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , (CH ₃ ) ₂ Si[ OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₂ H ₅ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , (C ₂ H ₅ ) ₂ Si[OC (CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₃ H ₇ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , (C ₃ H ₇ ) ₂ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₄ H ₉ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , (C ₄ H ₉ ) ₂ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₅ H ₁₁ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₆ H ₁₃ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₇ H ₁₅ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₈ H ₁₇ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₉ H ₁₉ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₀ H ₂₁ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₁ H ₂₃ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₂ H ₂₅ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₃ H ₂₇ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₄ H ₂₉ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₅ H ₃₁ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₆ H ₃₃ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₇ H ₃₅ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₁₈ H ₃₇ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , (CH ₃ ) ₃ SiOC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₂ H ₅ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , (C ₂ H ₅ ) ₂ Si(CH ₃ )OC(CH ₃ )=NSi(CH ₃ ) ₃ , (C ₂ H ₅ ) ₃ SiOC( CH ₃ )=NS i(CH ₃ ) ₃ , C ₃ H ₇ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , (C ₃ H ₇ ) ₂ Si(CH ₃ )OC(CH ₃ )=NSi( CH ₃ ) ₃ , (C ₃ H ₇ ) ₃ SiOC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₄ H ₉ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , (C ₄ H ₉ ) ₃ SiOC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₅ H ₁₁ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₆ H ₁₃ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₇ H ₁₅ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₈ H ₁₇ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₉ H ₁₉ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₀ H ₂₁ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi (CH ₃ ) ₃ , C ₁₁ H ₂₃ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₂ H ₂₅ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₃ H ₂₇ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₄ H ₂₉ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₅ H ₃₁ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₆ H ₃₃ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₇ H ₃₅ Si( CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₁₈ H ₃₇ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , (CH ₃ ) ₂ Si(H)OC (CH ₃ )=NSi(CH ₃ ) ₃ , CH ₃ Si(H) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , (C ₂ H ₅ ) ₂ Si(H OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₂ H ₅ Si(H) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₂ H ₅ Si(CH ₃ )(H)OC( CH ₃ )=NSi(CH ₃ ) ₃ , (C ₃ H ₇ ) ₂ Si(H)OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₃ H ₇ Si(H) ₂ OC(CH ₃ )= NSi(CH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₂ F ₅ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH _{3 3} ] ₃ , C ₃ F ₇ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₄ F ₉ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH _{3 3} ] ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH _{3 3} ] ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si[OC(CH ₃ )=NSi(CH _{3 3} ] ₃ , CF ₃ CH ₂ CH ₂ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )[OC(CH _{3 )} )=NSi(CH ₃ ) ₃ ] ₂ , C ₃ F ₇ CH ₂ CH ₂ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₄ F ₉ CH ₂ CH ₂ Si( CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ )[OC(CH ₃ )=NSi( CH ₃ ) ₃ ] ₂ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ )[OC(CH ₃ )=NSi(CH ₃ ) ₃ ] ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC( CH ₃ )=NSi(CH ₃ ) ₃ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₃ F ₇ CH ₂ CH ₂ Si(CH _{3 2} OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₄ F ₉ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₅ F ₁₁ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₆ F ₁₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , C ₈ F ₁₇ CH ₂ CH ₂ Si(CH ₃ ) ₂ OC(CH ₃ )=NSi(CH ₃ ) ₃ , a compound such as CF ₃ CH ₂ CH ₂ Si(CH ₃ )(H)OC(CH ₃ )=NSi(CH ₃ ) ₃ or a compound of the above compound substituted with —OC(CH ₃ )=NSi(CH ₃ ) ₃ -OC(CH ₃ )=NSi(CH ₃ ) ₃ group other than -OC(CH ₃ )=NSi(R ⁸ ) _g (H) _3-g group (R ⁸ is a part or all of hydrogen element can be substituted The number of carbon atoms of the fluorine element is 1 to 18 one-valent hydrocarbon groups). Further, a methyl moiety of -OC(CH ₃ )=NSi(R ⁸ ) _g (H) _3-g group of the above compound may be substituted with a hydrogen group, an ethyl group, a propyl group, a butyl group or a trifluoromethyl group. , a compound such as pentafluoroethyl, heptafluoropropyl or nonafluorobutyl. Further, as the hydrazine compound of the above formula [3], a commercially available one can be used. For example, as long as it is N,O-bis(trimethyldecyl)trifluoroacetamide [(CH ₃ ) ₃ SiOC(CF ₃ )=NSi(CH ₃ ) ₃ ], Tokyo Chemical Industry Co., Ltd. can be used. maker.

From the viewpoint of the water-repellent imparting effect, the R ⁷ group of the above formula [3] is preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group, which may be substituted with a fluorine element. Or a trifluoromethyl group, particularly preferably a trifluoromethyl group.

Further, from the viewpoint of the water-repellent imparting effect, the R ⁸ group of the above formula [3] is preferably three methyl groups.

Further, in the above formula [3], the number of -OC(R ⁷ )=NSi(R ⁸ ) _g (H) _3-g groups represented by 4-ef is 1, and the above protection can be uniformly formed. The film is therefore better.

In addition, when f is 0 in the above formula [3], it is preferred to maintain water repellency during washing after formation of the protective film described below.

Further, when the R ⁶ group of the above formula [3] is a combination of two methyl groups and one linear alkyl group, the protective film can be formed homogeneously, which is more preferable. Further, the R ⁶ group is preferably three methyl groups.

In addition, the surface treatment agent contains at least one ruthenium compound (I-1) in which a of the above formula [1] is 3, R ² is a hydrogen element, and R ³ is a fluorine-containing alkyl group having 1 to 6 carbon atoms. And at least one ruthenium compound (I-2) wherein c of the above formula [2] is 3 and R ⁵ is a fluorine-containing alkyl group having 1 to 6 carbon atoms, as the above (I), even if water is mixed thereinto In the case of the surface treatment agent, it is also preferable to stably maintain the water repellency imparting effect on the surface of the object to be treated.

The surface treatment agent may be obtained by dissolving the ruthenium compound (I-1) prepared as a raw material separately from the ruthenium compound (I-2) and the above (II) in the above (III), or may be obtained by The mixture obtained by the reaction to form a raw material of the hydrazine compound (I-1) and the hydrazine compound (I-2).
For example, if 1,1,1,3,3,3-hexamethyldioxane and trifluoroacetic anhydride are used as a raw material, N-trimethylnonane as the above hydrazine compound (I-1) can be produced. a trifluoroacetamide, and a trimethylsulfonyltrifluoroacetate as the above hydrazine compound (I-2) can be produced, so that the hydrazine compound (I-1) and the hydrazine compound can be obtained by the reaction. Surface treatment agent of I-2).

When the concentration of (I) is from 0.1 to 35% by mass based on 100% by mass of the total of the above (I) to (III), it is easy to form a protective film uniformly on the surface of the object to be treated, which is preferable. If it is less than 0.1% by mass, the water repellency imparting effect tends to be insufficient. Moreover, when it exceeds 35% by mass, the surface of the object to be treated is eroded or remains on the surface of the object to be treated as an impurity, and it is also inferior in terms of cost. Further, it is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, even more preferably from 1 to 9% by mass.

(II) component The nitrogen-containing heterocyclic compound represented by the above formula [4], the nitrogen-containing heterocyclic compound represented by the above formula [5], and the imidazole-promoted -N(R) of the above formula [1] ² ) a C(=O)R ³ group, an -OC(=O)R ⁵ group of the above formula [2], and -OC(R ⁷ )=NSi(R ⁸ ) _{g of the} above formula [3] H) The reaction of the _3-g group with the surface of the object to be treated may itself be part of the formation of a protective film.

The nitrogen-containing heterocyclic compound represented by the above formula [4] is preferably a divalent hydrocarbon group wherein R ⁹ is a carbon number 3, and R ¹⁰ contains a carbon element and/or a nitrogen element and a hydrogen element, and the carbon number and the nitrogen number are The total amount is 3 to 5, and a divalent organic group which does not constitute a carbon element of the ring may be present, and it is preferably a liquid at 25 ° C and 1 atm from the viewpoint that it is less likely to cause insoluble matter after preparation. Specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]-7-undecene, 7- Methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene and the like.

As the nitrogen-containing heterocyclic compound represented by the above formula [4], a commercially available one can be used, and from the viewpoint of relatively easy availability, 1,5-diazabicyclo[4.3.0]-5-fluorene can be used. Alkene (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), 1,8-diazabicyclo[5.4.0]-7-undecene (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), 7-methyl-1, 5,7-Triazabicyclo[4.4.0]non-5-ene (for example, manufactured by Tokyo Chemical Industry Co., Ltd.).

The above general formula [5] of the nitrogen-containing heterocyclic compound represented by R ¹¹ is preferably an alkyl group having 1 to 4 carbon atoms, the alkyl group or trimethyl silicon, and R ^12, R ¹³ and R ¹⁴ is a hydrogen group, as Specific examples thereof include N-methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, and trimethyldecyl imidazole.

In addition, it is preferred that the nitrogen-containing heterocyclic compound represented by the above formula [5] is a liquid at 25 ° C and 1 atm, and is preferably N, from the viewpoint that the insoluble matter is less likely to be formed after the preparation. - methylimidazole, N-ethylimidazole, N-propylimidazole, N-butylimidazole, trimethyldecyl imidazole, and the like.

As a nitrogen-containing heterocyclic compound represented by the above-mentioned general formula [5], and an imidazole, a commercially available product can be used, and imidazole (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), N- can be used from the viewpoint of relatively easy availability. Methylimidazole (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), N-ethylimidazole (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), N-propylimidazole (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), N-butyl Imidazole (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), trimethylsilyl imidazole (for example, manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

The concentration of (II) is preferably 0.05 to 10% by mass based on 100% by mass of the total of the above (I) to (III). When it is 0.05% by mass or more, the reaction promoting effect (and the water repellency imparting effect) is easily exhibited, which is preferable. When it is 10% by mass or less, it is less likely to corrode the surface of the object to be treated, and it is less likely to remain as an impurity on the surface of the object to be treated, which is preferable. Moreover, it is also difficult to produce a surface treatment agent which is insoluble in an organic solvent and is inhomogeneous, and therefore it is preferable. The concentration is more preferably 0.07 to 5% by mass, still more preferably 0.1 to 2% by mass.

(III) Organic Solvent In the above surface treatment agent, the above (I) and (II) are dissolved in the (III) organic solvent. The surface treatment agent contains an organic solvent, and the surface treatment of the object to be processed by a spin coating method, a dipping method, or the like is facilitated.

The organic solvent is not particularly limited as long as it can dissolve the above (I) and (II) and has less damage to the surface of the object to be processed (for example, the surface of the substrate (inorganic pattern, resin pattern, etc.)). Previously known organic solvents can be used.

The organic solvent can be suitably used, for example, in a hydrocarbon, an ester, an ether, a ketone, a halogen-containing solvent, an anthraquinone solvent, an anthraquinone solvent, a lactone solvent, a carbonate solvent, or a derivative of a polyol. An aprotic solvent such as a solvent which does not have an OH group, a nitrogen-containing element which does not have an NH group, a polyoxo-oxygen solvent, a terpene-based solvent, a mercaptan, or a mixture thereof. When a hydrocarbon, an ester, an ether, a halogen-containing solvent, or a derivative of a polyhydric alcohol, which does not have an OH group, or a mixture thereof, is used, water repellency can be formed in the object to be treated in a short time. The protective film is therefore better. Further, in view of the solubility of the above (I) and (II), the content of the nonpolar solvent is preferably as the organic solvent, and it is more preferable to use a nonpolar solvent as the organic solvent.

Examples of the above hydrocarbons include n-hexane, n-heptane, n-octane, n-decane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, and n-eighteen An alkane, n-icosane, and a branched hydrocarbon corresponding to the carbon number (for example, isododecane, 2,2,4,4,6,8,8-heptamethylnonane, etc.) , cyclohexane, methylcyclohexane, decahydronaphthalene, benzene, toluene, xylene, (o-, m-, or p-) diethylbenzene, 1,3,5-trimethylbenzene, naphthalene As an example of the above esters, there are ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, and acetic acid. Heptyl ester, n-octyl acetate, n-amyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl n-octanoate, decanoic acid Ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, dimethyl adipate, 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propyl propionate, ethyl ethoxyacetate, etc., as examples of the above ethers, there are di-n-propyl ether, ethyl n-butyl ether, di-n-butyl ether, ethyl n-pentyl ether, di-n-pentyl ether, and B. a hexyl hexyl ether, di-n-hexyl ether, di-n-octyl ether, and a branched hydrocarbon group such as diisopropyl ether or diisoamyl ether corresponding to the carbon number, dimethyl ether, diethyl ether, and Ethyl ether, methylcyclopentyl ether, diphenyl ether, tetrahydrofuran, dioxane, methyl perfluoropropyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, methyl perfluorohexyl ether, ethyl all Examples of the ketones include fluorohexyl ether and the like, and acetone, ethyl acetonide, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-octanone, 3-octanone, and cyclohexanone. , isophorone, etc., as examples of the halogen-containing solvent, perfluorooctane, perfluorodecane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene, etc., perfluorocarbon, 1,1, 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, Zeorora H (manufactured by Zeon, Japan), hydrofluorocarbon, methyl perfluoroisobutyl ether, methyl Perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, Asah Iclin AE-3000 (made by Asahi Glass), Novec 7100, Novec 7200, Novec 7300, Novec 7600 (all manufactured by 3M), such as hydrofluoroether, chlorocarbon such as tetrachloromethane, chloroform such as chloroform, and chlorofluorocarbon such as dichlorodifluoromethane. 1,1-Dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3 a hydrochlorofluorocarbon such as 3-trifluoropropene or 1,2-dichloro-3,3,3-trifluoropropene, a perfluoroether or a perfluoropolyether, and the like, as an example of the above-mentioned anthraquinone solvent, Examples of the above-mentioned oxime-based solvent include dimethyl hydrazine, diethyl hydrazine, bis(2-hydroxyethyl) fluorene, tetramethylene hydrazine, etc., and examples of the above-mentioned lactone-based solvent. , β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-octanolactone, γ-caprolactone, γ-decalactone, γ-decalactone, Γ-undecalactone, γ-dodecanolactone, δ-valerolactone, δ-caprolactone, δ-octanolactone, δ-decalactone, δ-decalactone, δ-undecalactone And δ-dodecanolide, ε-caprolactone, etc., and examples of the carbonate-based solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, and the like. Examples of the derivatives which do not have an OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether. Acid ester, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl Ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol diacetate , triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate Ester, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol single Methyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, Propylene glycol monomethyl ether acetate, propylene Alcohol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether Acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether Acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, Butanediol dimethyl ether, butanediol monomethyl ether acetate, butanediol diacetate, triacetin, 3-methoxybutyl acetate, 3-methyl-3-methyl Examples of the solvent of the nitrogen-containing element having no NH group, such as oxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc., are N,N-dimethylformamidine. Amine, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl -2-pyrrolidine , 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, triethylamine, pyridine As an example of the polyoxyl solvent, there are hexamethyldioxane, octamethyltrioxane, decamethyltetraoxane, dodecamethylpentaoxane, etc. as a terpene solvent. Examples thereof include p-menthane, diphenyl menthane, limonene, terpinene, decane, norbornane, decane, etc., and examples of the above-mentioned mercaptans include 1-hexyl mercaptan and 2-methyl group. -1-pentyl mercaptan, 3-methyl-1-pentyl mercaptan, 4-methyl-1-pentyl mercaptan, 2,2-dimethyl-1-butanethiol, 3,3-dimethyl 1-butanol, 2-ethyl-1-butanethiol, 1-octylmercaptan, benzyl mercaptan, 1-octyl mercaptan, 2-ethyl-1-hexyl mercaptan, 1-sulfonium sulfur Alcohol, 1-decyl mercaptan, 1-undecyl mercaptan, 1-dodecanethiol, 1-tridecyl mercaptan, and the like.

Further, in view of the solubility of the above (I) and (II), the organic solvent is preferably one in which no derivative of the polyol has an OH group. Specific examples of the above-mentioned polyols which do not have an OH group include the above-exemplified compounds, and among them, propylene glycol monoalkyl ether acetate is preferred from the viewpoint of a small environmental load. It is propylene glycol monomethyl ether acetate.

In order to further improve the stability, the surface treatment agent of the present invention may contain an additive such as a polymerization inhibitor or a chain transfer agent, an antioxidant, or the like.

Further, the total amount of water in the starting material of the surface treating agent is preferably 2,000 ppm by mass or less based on the total amount of the raw material. When the total amount of water exceeds 2000 ppm by mass, the effect of the above-mentioned antimony compound or (II) component is lowered, and it is not easy to form the above protective film in a short time. Therefore, the total amount of the water content in the raw material of the surface treatment agent is preferably as small as possible, and is preferably 500 ppm by mass or less, and more preferably 200 ppm by mass or less. Further, when the amount of water is large, the storage stability of the surface treatment agent is likely to be lowered. Therefore, the amount of water is preferably small, preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less. Further, the amount of the water is preferably as small as possible, but in the above content range, the amount of water in the raw material of the surface treatment agent may be 0.1 ppm by mass or more. Therefore, the ruthenium compound, the component (II), and the organic solvent contained in the surface treatment agent are preferably those which do not contain a large amount of water.

Further, it is preferable that the number of particles larger than 0.2 μm in the particle measurement by the light scattering type liquid particle detector in the liquid phase in the surface treatment agent is 100 or less per 1 mL of the surface treatment agent. If the amount of the particles larger than 0.2 μm is more than 100 per 1 mL of the surface treatment agent, the object to be treated may be damaged by the particles, thereby causing a decrease in the yield of the device and a decrease in reliability. Poor. Further, when the amount of the particles larger than 0.2 μm is 100 or less per 1 mL of the surface treatment agent, it is preferable to omit or reduce the washing with a solvent or water after the formation of the protective film. Further, the smaller the number of the particles larger than 0.2 μm, the more preferable, but if it is within the above content range, the surface treatment agent may be one or more per 1 mL.
Further, in the surface treatment agent of the present invention, the measurement of the fine particles in the liquid phase is carried out by using a commercially available measuring device in the method of measuring the particle size in a light scattering type liquid using a laser as a light source. Refers to the light scattering equivalent diameter of the standard particle reference of PSL (polystyrene latex).
Here, the above-mentioned fine particles are particles, such as dust, dust, organic solids, and inorganic solids, which are contained as impurities in the raw material, or dust, dust, and organic solids which are mixed as contaminants in the preparation of the surface treatment agent. Particles such as inorganic solids and the like are equivalent to being insoluble in the surface treatment agent and present in the form of particles.

Further, it is preferable that the content of each element (metal impurity) of Na, Mg, K, Ca, Mn, Fe, Cu, Li, Al, Cr, Ni, Zn, and Ag in the surface treatment agent is relative to the surface treatment The total amount of the agent is 0.1 mass ppb or less. When the content of the metal impurities exceeds 0.1 mass ppb with respect to the total amount of the surface treatment agent, there is a possibility that the junction leakage current of the device is increased, which causes a decrease in the yield of the device and a decrease in reliability, which is not preferable. In addition, when the content of the metal impurities is 0.1 mass ppb or less with respect to the total amount of the surface treatment agent, the surface of the object to be treated which is treated with a solvent or water after the protective film is formed on the surface of the object to be treated can be omitted or reduced ( It is preferred to wash the surface of the protective film. Therefore, the content of the metal impurities is preferably as small as possible, but within the above content range, each element may be 0.001 mass ppb or more with respect to the total amount of the surface treatment agent.

2. Method for Producing Surface Treatment Body The method for producing a surface treatment body according to the present invention is to treat the surface of the object to be treated by contacting the surface treatment agent of the present invention with the surface of the object to be treated.

In the surface treatment method of the present invention, the surface of the substrate to be treated refers to the surface of the inorganic pattern and the resin pattern provided on the substrate, and the surface of the inorganic layer and the organic layer which are not patterned, except for the surface of the substrate itself. .

The method for producing a surface-treated body of the present invention is obtained by subjecting the surface of the object to be subjected to a decane treatment to obtain a surface-treated body, and the purpose of the treatment may be any, and a representative example of the object of the treatment may be mentioned (1) Hydrophobicizing the surface of the object to be processed such as a substrate to improve the adhesion to a resin pattern such as a photoresist or the like; (2) preventing the substrate from being washed on the surface of the substrate to be processed as a substrate The pattern of the inorganic pattern or the resin pattern on the surface collapses.

In the above (1), as a method of bringing the surface treatment agent of the present invention into contact with the surface of the object to be treated, a conventionally known method can be used without particular limitation, and for example, the surface treatment agent of the present invention can be used. A method of bringing the vapor into contact with the surface of the object to be treated, a method of bringing the surface treating agent of the present invention into contact with the surface of the object to be processed, or the like by a spin coating method or a dipping method.
In the case where the substrate used in the formation of the organic layer as the film of the photoresist is the object to be processed, the contact of the surface treatment agent is preferably performed before the formation of the organic layer.
By such an operation, the surface of the object to be treated is decanolated, and the hydrophobicity of the surface of the object to be treated is improved. When the substrate to be processed is a substrate and a substrate treated with a surface treatment agent is used, the surface of the substrate is hydrophobized, for example, the adhesion of the substrate to the photoresist or the like is improved.

In the above (2), the surface treatment agent of the present invention may be brought into contact with the surface of the substrate of the object to be processed before the cleaning operation after the formation of the inorganic pattern or the resin pattern.

Usually, after the inorganic pattern is formed on the surface of the substrate, the surface of the pattern is usually washed with an aqueous cleaning solution such as SPM (sulfuric acid, hydrogen peroxide) or APM (ammonia or hydrogen peroxide). In addition, after the cleaning, the aqueous cleaning liquid held on the surface of the substrate may be replaced with a cleaning liquid different from the aqueous cleaning liquid (hereinafter referred to as "cleaning liquid A"), and further washed. . The above-mentioned cleaning liquid A is an organic solvent, a mixture of the organic solvent and the aqueous cleaning solution, and a cleaning liquid in which at least one of an acid, a base, and a surfactant is mixed.
Further, usually, after a resin pattern is formed on the surface of the substrate, the development residue or the developer is removed by washing with a washing solution such as water or an active agent washing liquid.

The cleaning method (surface treatment) of the substrate is not particularly limited as long as a cleaning device for the surface treatment agent or the cleaning liquid which can maintain a liquid state on the surface of the substrate is used. For example, a single-piece method in which a substrate is held at a substantially horizontal level and rotated, and a cleaning method of a rotary cleaning device that supplies a liquid toward the vicinity of a rotation center and washes the substrate one by one is representative; or In a batch method, a cleaning apparatus in which a plurality of substrates are washed in a immersion cleaning tank is used. In addition, the surface treatment agent or the cleaning liquid in the case where the surface treatment agent or the cleaning liquid in a liquid state is supplied to the surface of the substrate is not particularly limited as long as it is liquid when held on the surface of the substrate. For example, there are liquids, vapors, and the like.

Examples of the organic solvent which is one of preferable examples of the cleaning solution A include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfonium-based solvents, lactone-based solvents, and carbonate-based solvents. Alcohols, derivatives of polyhydric alcohols, solvents containing nitrogen elements, and the like.

The surface treatment agent in a liquid state of the present invention is used by replacing the aqueous cleaning solution or the cleaning solution A with the surface treatment agent. In addition, the surface treatment agent to be replaced may be replaced with a cleaning liquid different from the surface treatment agent (hereinafter referred to as "cleaning liquid B").

After washing with the aqueous cleaning solution or the cleaning solution A as described above, the cleaning liquid is replaced with a surface treatment agent in a liquid state, and the surface treatment agent is held on the substrate while the surface treatment agent is held on the substrate surface. The above protective film is formed. The protective film of the present invention may not necessarily be formed continuously, or may not necessarily be uniformly formed. However, since it is more excellent in water repellency, it is more preferably continuously and uniformly formed. Further, the time for holding the surface treatment agent on the substrate is preferably from 1 to 120 seconds.

When the surface treatment agent is raised in temperature, it is easy to form the above protective film in a shorter period of time. The temperature at which the homogeneous protective film is easily formed is 10 ° C or more and does not reach the boiling point of the surface treatment agent, and is preferably maintained at 15 ° C or higher and at a temperature lower than the boiling point of the surface treatment agent by 10 ° C or lower. The temperature of the surface treatment agent is preferably maintained at this temperature while being held on the substrate. In addition, the boiling point of the surface treatment agent means the boiling point of the component which is the most measured by the mass ratio among the components contained in the surface treatment agent.

After the protective film is formed as described above, the surface treatment agent in a liquid state remaining on the surface of the substrate can be replaced with the cleaning liquid B, and then transferred to a drying step. Examples of the cleaning solution B include a mixture of an aqueous cleaning solution, an organic solvent, an aqueous cleaning solution, and an organic solvent, or at least one of an acid, a base, and a surfactant mixed therein. And mixtures of such surface treatment agents and the like. From the viewpoint of removing particulates or metal impurities, the above-mentioned cleaning liquid B is more preferably water, an organic solvent, or a mixture of water and an organic solvent.

Examples of the organic solvent which is one of preferable examples of the cleaning liquid B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, anthraquinone solvents, alcohols, and derivatives of polyhydric alcohols. A solvent containing a nitrogen element or the like.

Further, when the protective film formed on the surface of the substrate by the surface treatment agent of the present invention is used as the organic solvent, the cleaning liquid B is not easily reduced in water repellency by the cleaning of the cleaning liquid B.

Water repellency is achieved by forming the above protective film on the surface of the substrate. Moreover, the protective film is also held on the surface of the substrate when the liquid is removed from the surface of the substrate.

When the protective film is formed on the surface of the substrate, if the contact angle when the water is held on the surface is 85 to 130°, the adhesion of the resin pattern or the like including the photoresist or the like is hard to be produced. From the viewpoint of collapse, it is more preferably 90 to 130°.

Next, the liquid held on the surface of the substrate on which the protective film is formed by the surface treatment agent is removed from the surface of the substrate by drying. At this time, the liquid held on the surface of the substrate may be the above surface treatment agent, the above-mentioned cleaning liquid B, or a mixed liquid thereof. The mixed liquid is mixed with the surface treatment agent and the cleaning liquid B, or the component contained in the surface treatment agent is contained in a concentration lower than the surface treatment agent, and the mixed liquid may be the surface treatment agent. The liquid which is replaced in the middle of the cleaning liquid B may be a mixed liquid obtained by mixing the above (I) to (III) in the cleaning liquid B in advance. From the viewpoint of the cleanliness of the surface of the substrate, water, an organic solvent, or a mixture of water and an organic solvent is preferred. Further, after the liquid is temporarily removed from the surface of the substrate, the cleaning liquid B may be held on the surface of the substrate, and then dried.

Further, when the cleaning film B is used for cleaning after the formation of the protective film, the cleaning time, that is, the time during which the cleaning liquid B is held, removes the particles or impurities on the surface of the substrate, Good for 1 to 60 seconds. From the viewpoint of the effect of maintaining the water repellency of the protective film formed on the surface of the substrate, when an organic solvent is used as the cleaning liquid B, the water repellency of the surface of the substrate tends to be maintained even if the cleaning is performed.

The liquid held on the surface of the substrate is removed by the above drying. The drying is preferably carried out by a known drying method such as spin drying, IPA (2-propanol) vapor drying, mazonic drying, heat drying, warm air drying, air drying, and vacuum drying.

After the above drying, the protective film can be further removed. In the case of removing the water-repellent protective film, it is effective to cut off the C-C bond and the C-F bond in the water-repellent protective film. The method is not particularly limited as long as the bond can be cut. For example, the surface of the substrate is irradiated with light, the substrate is heated, the substrate is exposed to ozone, and the surface of the substrate is plasma-irradiated. The surface of the substrate is subjected to corona discharge or the like.

In the case where the protective film is removed by light irradiation, it is preferable that the irradiation is shorter than the energy of 83 kcal/mol and 116 kcal/mol which is equivalent to the bonding energy of the CC bond and the CF bond in the protective film. Ultraviolet light at wavelengths of 340 nm and 240 nm. As the light source, a metal halide lamp, a low pressure mercury lamp, a high pressure mercury lamp, an excimer lamp, a carbon arc or the like can be used. In the case of a metal halide lamp, for example, an illuminance meter (U.S. illuminance meter UM-10 manufactured by Konica Minolta Sensing) and a light receiving unit UM-360 (peak sensitivity wavelength: 365 nm, measurement wavelength range: 310 to 400) The measured value of nm]) is preferably 100 mW/cm ² or more, and more preferably 200 mW/cm ² or more. Further, if the irradiation intensity is less than 100 mW/cm ² , it takes a long time to remove the protective film. Further, in the case of a low-pressure mercury lamp, ultraviolet rays having a shorter wavelength are irradiated, so that the protective film can be removed in a short time even if the irradiation intensity is low, which is preferable.

In addition, when the protective film is removed by light irradiation, ozone is generated by decomposing the constituent components of the protective film by ultraviolet rays, and when the constituent components of the protective film are oxidized and volatilized by the ozone, the processing time is shortened, which is preferable. . As the light source, a low pressure mercury lamp, an excimer lamp or the like can be used. Further, it is possible to perform light irradiation while heating the substrate.

In the case of heating the substrate, it is preferred to heat the substrate at 400 to 1000 ° C, preferably 500 to 900 ° C. The heating time is preferably carried out for 10 seconds to 60 minutes, preferably 30 seconds to 10 minutes. Further, in this step, ozone exposure, plasma irradiation, corona discharge, or the like may be used in combination. Further, light can be irradiated while being heated toward the substrate.

The method of removing the protective film by heating includes a method of bringing the heat source into contact with the substrate, a method of placing the substrate in a heated atmosphere such as a heat treatment furnace, and the like. Furthermore, the method of placing the substrate in a heated atmosphere facilitates the uniform application of the energy for removing the protective film to the surface of the substrate even when the plurality of substrates are processed. Therefore, the operation is relatively simple and short-time. The processing is completed within, and the processing capacity is higher than that of the industrial method.

In the case where the substrate is exposed to ozone, it is preferable to supply ozone generated by ultraviolet irradiation using a low-pressure mercury lamp or the like or low-temperature discharge using a high voltage to the surface of the substrate. The substrate may be exposed to light while exposed to ozone, or may be heated while facing the substrate for ozone exposure.

By combining the above-described light irradiation, heating, ozone exposure, plasma irradiation, and corona discharge, the protective film on the surface of the substrate can be efficiently removed.
[Examples]

Hereinafter, an experimental example in which an embodiment of the present invention is disclosed will be more specifically disclosed. Furthermore, the present invention is not limited to the experimental examples.

In the present invention, the ease of solubility of the raw material at the time of preparation of the surface treatment agent and the water repellency imparting effect when the surface treatment agent is surface-treated with the surface treatment agent (hereinafter also referred to as "wafer") are evaluated. . Further, in the examples and the comparative examples, water which is a representative of the aqueous cleaning solution was used as the liquid which was in contact with the surface of the wafer at the time of evaluating the contact angle.

However, in the case of a wafer having a fine uneven pattern on the surface, the contact angle of the protective film itself formed on the surface of the uneven pattern cannot be accurately evaluated.
The contact angle of the water droplets is evaluated in the same manner as in JIS R 3257 "Test method for wettability of the surface of the substrate glass", and a few μl of water droplets are dropped on the surface of the sample (substrate), and the water droplets and the substrate are measured. The angle formed by the surface is carried out. However, in the case of a patterned wafer, the contact angle becomes very large. The reason for this is that the contact angle is affected by the surface shape (roughness) of the substrate due to the effect of the Wenzel effect or the Cassie effect, and the contact angle of the apparent water droplet is increased.

Therefore, in the examples and the comparative examples, the surface treatment agent is applied to a wafer having a smooth surface, and a protective film is formed on the surface of the wafer, and the protective film is regarded as a crystal having a fine concavo-convex pattern formed on the surface. A protective film formed on the surface of the circle was subjected to various evaluations. Further, in the examples and the comparative examples, a "wafer with SiO ₂ film" having a SiO ₂ layer on a silicon wafer having a smooth surface was used as a wafer having a smooth surface.

Hereinafter, the evaluation method, the preparation of the surface treatment agent, the method of producing the surface treatment body using the surface treatment agent, and the evaluation results will be described.

[Evaluation method]
(A) The dissolution time of the raw material at the time of preparation was mixed with the raw material of the surface treatment agent while maintaining the liquid temperature at 25 ° C, and the time (dissolution time) at which the entire amount of the raw material was dissolved was visually observed to be stirred. Of course, the shorter the dissolution time, the easier the raw material dissolves, so that it is preferred.
Therefore, the case where the raw material was dissolved within 30 seconds of stirring at 25 ° C was evaluated as acceptable. In addition, in the following table, the case where the raw material was stirred for more than 5 seconds and 30 seconds was described as ○, and the case where the raw material was dissolved within 5 seconds of stirring was evaluated as "the result of particularly excellent solubility" and was expressed as ◎.
On the other hand, when stirring was continued, the raw material was dissolved, but the stirring required to be more than 30 seconds was expressed as Δ, and the case where the total amount of the raw materials could not be dissolved even if the stirring was continued for more than 1 hour was expressed as ×, and was evaluated as unacceptable.

(B) Evaluation of the contact angle of the protective film formed on the surface of the wafer (evaluation of the water-repellent imparting effect)
About 2 μl of pure water was placed on the surface of the wafer on which the protective film was formed, and the angle (contact angle) between the water droplet and the surface of the wafer was measured by a contact angle meter (manufactured by Kyowa Interface Science: CA-X type). ° The above evaluation is acceptable.

[Example 1]
(1) Preparation of surface treatment agent (I) N-methyl-N-trimethylnonane which is a raw material of the surface treatment agent while maintaining the liquid temperature at 25 ° C in such a manner as to have the content shown in Table 1 Trifluoroacetamide [(CH ₃ ) ₃ SiN(CH ₃ )C(=O)CF ₃ ] (manufactured by Tokyo Chemical Industry Co., Ltd., sometimes referred to as "MSTFA"), (II) Imidazole (Tokyo Manufactured by Kasei Kogyo Co., Ltd., hereinafter referred to as "Im") and (III) propylene glycol monomethyl ether acetate as an organic solvent (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "PGMEA") The mixing was carried out, and as a result, a surface treatment agent in a state in which the entire amount of the raw material was dissolved under stirring for about 15 seconds was obtained.

(2) Cleaning of the wafer After the pattern of the etching treatment is formed, the wafer of the object to be treated with a smooth thermal oxide film (the Si crystal having a thermal oxide film layer having a thickness of 1 μm on the surface) is formed. The circle was immersed in a 1% by mass aqueous solution of hydrofluoric acid at room temperature for 10 minutes, immersed in pure water at room temperature for 1 minute, and immersed in 2-propanol (iPA) at room temperature for 1 minute.

(3) Surface treatment using a surface treatment agent for ruthenium wafer The immersed ruthenium wafer is immersed in a surface treatment agent prepared in the above "(1) Preparation of a surface treatment agent", and immersed at room temperature for 20 seconds. Immerse in iPA at room temperature for 1 minute. Finally, the wafer is removed from the iPA and air is blown to remove the iPA from the surface.

The evaluation was carried out by the method described in the above (B). As a result, as shown in Table 1, the contact angle after the surface treatment was 86°, and a good water repellency imparting effect was exhibited.

[Table 1]

[Table 2]

[Examples 2 to 19, Comparative Examples 1 to 89]
The surface treatment of the wafer was carried out in the same manner as in Example 1 except that the concentration of the type (I) or (II) of the raw material of the surface treatment agent was changed as shown in Tables 1 and 2. Evaluation.
Furthermore, in the table,
"N-MeIm" means N-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"N-EtIm" means N-ethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"N-BuIm" means N-butylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.),
"DBN" means 1,5-diazabicyclo[4.3.0]-5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.),
"DBU" means 1,8-diazabicyclo [5.4.0]-7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.),
"MTBD" means 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene (manufactured by Tokyo Chemical Industry Co., Ltd.).
"TMS-Im" means N-trimethyldecyl imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"TMS-TFA" means trimethyldecyl trifluoroacetate [(CH ₃ ) ₃ Si-OC(=O)CF ₃ ] (manufactured by Tokyo Chemical Industry Co., Ltd.),
"BSTFA" means N,O-bis(trimethyldecyl)trifluoroacetamide [(CH ₃ ) ₃ SiOC(CF ₃ )=NSi(CH ₃ ) ₃ ] (manufactured by Tokyo Chemical Industry Co., Ltd.) ,
"Tet" means 1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-MeTet" means 5-methyltetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"Tri" means 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.),
"BzoTri" means 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.),
"Pyr" means pyrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"2-MeIm" means 2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"4-MeIm" means 4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"TFAcIm" means 1-(trifluoroacetamidine)imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"3-Mer-1,2,4-Tri" means 3-mercapto-1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-MeBzoTri" means 5-methyl-1H-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-AminoTet" means 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"Tet-1-AcOH" means 1H-tetrazole-1-acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
"Tet-5-AcOH" means 1H-tetrazole-5-acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-Mer-1-MeTet" means 5-mercapto-1-methyltetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-BnTet" means 5-benzyl-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-PhTet" means 5-phenyltetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-pTolTet" means 5-(p-tolyl)-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.),
"5-Mer-1-PhTet" means 5-mercapto-1-phenyl-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.).
"5-MeThiTet" means 5-(methylthio)-1H-tetrazole (manufactured by Sigma-Aldrich Co., Ltd.).
"Sac" means o-sulfonylbenzamide (saccharin) (manufactured by Tokyo Chemical Industry Co., Ltd.),
"iOx" means isoxazole (manufactured by Tokyo Chemical Industry Co., Ltd.),
"TMS-DMA" means N-(trimethyldecyl)dimethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.).
"HMDS" means 1,1,1,3,3,3-hexamethyldioxane (manufactured by Tokyo Chemical Industry Co., Ltd.),
"TDACP" means 2,2,5,5-tetramethyl-2,5-diin-1-azetane (manufactured by Gelest),
"HMCTS" means 2,2,4,4,6,6-hexamethylcyclotriazane (manufactured by Tokyo Chemical Industry Co., Ltd.).

In the examples 1 to 19, the dissolution time of the surface treatment agent was 30 seconds or less, and if the surface treatment agent obtained was used, the surface of the object to be treated (wafer) was excellently dialed. Water-based.

On the other hand, in the composition of Comparative Examples 1 to 63 in which the component (II) is different from the surface treatment agent of the present invention, the insoluble component was not dissolved if the stirring was not continued for more than 30 seconds after mixing the raw materials (Comparative Example 1) 2, 4, 6, 7, 9, 10, 12 to 16, 18 to 20, 22, 23, 25, 27, 28, 30, 31, 33, 35 to 37, 39 to 41, 43 to 46, 48, 49, 52, 54, 56 to 58, 60 to 62); or after the mixing of the raw materials for 1 hour, the insoluble components remaining in the dissolution were visually confirmed (Comparative Examples 3, 11, 17, 24, 32, 34) , 38, 51, 53, 55, 59); or the dissolution time is shorter than 30 seconds, but the water-repellent effect is poor (Comparative Examples 5, 8, 21, 26, 29, 42, 47, 50) , 63), which is inferior to the surface treatment agent of the present invention.

Further, the composition of Comparative Examples 64 to 68 in which the component (I) is different from the surface treatment agent of the present invention (the surface treatment agent of Examples 1 to 9, 22, and 23 of JP-A-2017-063179, respectively) In the corresponding composition, the dissolution time was shorter than 30 seconds, but the water-repellent imparting effect was inferior (Comparative Examples 64 to 68), which was inferior to the surface treatment agent of the present invention.

Further, the composition of Comparative Examples 69 to 89 in which both the component (I) and the component (II) are different from the surface treatment agent of the present invention (Examples 15, 16, 19 to JP-A-2017-063179, respectively) In the composition corresponding to the surface treatment agent of 21, 34, 35, and 38 to 51, if it is not continuously stirred for more than 30 seconds after mixing the raw materials, it is not dissolved (Comparative Examples 72, 73, 75, 77, 78, 83) After continuously stirring for 1 hour after mixing the raw materials, the insoluble components remaining in the dissolution were confirmed by visual observation (Comparative Examples 69 to 71, 74, 79 to 82, and 84 to 88); or the dissolution time was short, but the water repellency was imparted. The result of the poor effect (Comparative Examples 76 and 89) was inferior to the surface treatment agent of the present invention.

Further, Examples 2 to 8 in which N-MeIm, N-EtIm, N-BuIm, DBN, DBU, MTBD, and TMS-Im which are liquid at 25 ° C and 1 atm are used as (II) (Examples) The surface treatment agent of 10 to 16) has a dissolution time of less than 5 seconds as compared with the surface treatment agent of Example 1 (Example 9) which is solid at 25 ° C and 1 atm. It is very short and is superior in terms of shortening of the dissolution time of the raw material. Further, from the viewpoint of the water-repellent imparting effect, it has been confirmed that at least one selected from the group consisting of DBN, DBU, MTBD, N-MeIm, N-EtIm, and N-BuIm is preferably used as (II). (Examples 2 to 7, 13 to 15), and it is more preferable to use at least one selected from the group consisting of DBN, DBU, and MTBD as (II) (Examples 5 to 7, 13 to 15) .
Further, regarding the use of BSTFA as the above (I) and the use of DBN, DBU, or MTBD as Examples 17 to 19 of the above (II), the water-repellent imparting effect and the dissolution time of the raw material are shortened. Excellent.

[Example A-1]
(1) Preparation of the surface treatment agent The N-three of the (I) bismuth compound (I-1) which is the raw material of the surface treatment agent while maintaining the liquid temperature at 25 ° C in such a manner as to be the content shown in Table 3 Methyl decyl trifluoroacetamide (manufactured by Karl Bucher) [(CH ₃ ) ₃ SiN(H)C(=O)CF ₃ ] (hereinafter sometimes referred to as "TMS-TFAcA") and anthracene compound (I) -2) TMS-TFA, (II) Im, and (III) PGMEA were mixed, and as a result, a surface treatment agent in a state in which the entire amount of the raw material was dissolved under stirring for about 15 seconds was obtained.

(2) Evaluation of contact angle retention rate after surface treatment Using the above surface treatment agent, the ruthenium wafer was washed and surface-treated in the same manner as in Example 1, and evaluation was carried out by the method described in the above (B). As a result, as shown in Table 3, the contact angle after the surface treatment was 88°, showing a good water repellency imparting effect. The contact angle evaluation after the surface treatment was taken as the reference contact angle when water (0.00% by mass of water added) was not added.
Then, a surface treatment agent obtained by adding 0.01% by mass and 0.02% by mass of water to the total amount of the surface treatment agent to the total amount of the surface treatment agent and stirring at 25° C. for 1 minute is used in the same manner as described above. The surface treatment of the wafer and the contact angle evaluation after surface treatment. The relative value (contact angle maintenance ratio after surface treatment) when the contact angle is set to 100 is shown in Table 3 and FIG.

[table 3]

[Example A-2]
(1) The surface treatment agent is prepared by maintaining the liquid temperature at 25 ° C while HMDS as a raw material of (I) and trifluoroacetic anhydride [CF ₃ C(=O)-OC(=O)CF ₃ ] ( Manufactured by Tokyo Chemical Industry Co., Ltd., the following may be described as "TFAA"), (II) Im, and (III) PGMEA, and HMDS and TFAA are reacted as shown in the following reaction formula to form a ruthenium compound (I). -1) of TMS-TFAcA, and TMS-TFA as the above-mentioned hydrazine compound (I-2), thereby obtaining a surface treatment agent containing the (I) hydrazine compound (I-1) in the content shown in Table 3 TMS-TFAcA and TMS-TFA, (II) Im, and (III) PGMEA of the oxime compound (I-2). Further, a surface treatment agent in a state in which the entire amount of the raw material has been dissolved under stirring for about 15 seconds can be obtained.
[Chemical 6]

(2) Evaluation of contact angle maintenance ratio after surface treatment The contact angle maintenance ratio after the surface treatment was evaluated in the same manner as in Example A-1. The results are shown in Table 3 and Figure 1.

Further, as a reference, a surface treatment agent of Example 9 using only TMS-TFA as (I), that is, a combination of the ruthenium compound (I-1) and the ruthenium compound (I-2) was used, and the examples were Evaluation of contact angle maintenance rate after surface treatment in the same order of A-1. The results are shown in Table 3 and Figure 1.

According to the above results, it is clear that the surface treatment agent of the present invention contains at least one of the above formula [1] wherein a is 3, R ² is hydrogen, and R ³ is a fluorine-containing alkyl group having 1 to 6 carbon atoms. The compound (I-1) and at least one ruthenium compound (I-2) wherein c of the above formula [2] is 3 and R ⁵ is a fluorine-containing alkyl group having 1 to 6 carbon atoms is the above (I). In the case where water is mixed into the surface treatment agent, it is easy to stably maintain the water repellency imparting effect on the surface of the object to be treated, which is preferable.

[Examples A-3, A-4, 10]
The surface treatment agent was prepared in the same manner as in the above Examples A-1 and A-2 except that N-MeIm was used as the (II), and the contact angle maintenance ratio after the surface treatment was evaluated.
Further, as a reference, a surface treatment agent of Example 10 using only TMS-TFA as (I), that is, a combination of the ruthenium compound (I-1) and the ruthenium compound (I-2) was used, and the examples were Evaluation of contact angle maintenance rate after surface treatment in the same order of A-1. The results are shown in Table 3 and Figure 2.

[Examples A-5, A-6, 13]
The surface treatment agent was prepared in the same manner as in the above Examples A-1 and A-2 except that the DBN was used as the (II), and the contact angle maintenance ratio after the surface treatment was evaluated.
Further, as a reference, a surface treatment agent of Example 13 using only TMS-TFA as (I), that is, a combination of the ruthenium compound (I-1) and the ruthenium compound (I-2) was used, and the examples were Evaluation of contact angle maintenance rate after surface treatment in the same order of A-1. The results are shown in Table 3 and Figure 3.

According to the above results, it is clear that the surface treatment agent of the present invention contains the above-mentioned general formula [1], a is 3, R ² is hydrogen, and R ³ is a carbon number, even when the type of the type (II) is changed. At least one ruthenium compound (I-1) of the fluoroalkyl group of ～6, and at least one ruthenium compound of the above formula [2], wherein c is 3 and R ⁵ is a fluorine-containing alkyl group having 1 to 6 carbon atoms; (I-2) As the above (I), even when water is mixed into the surface treatment agent, it is easy to stably maintain the water repellency imparting effect on the surface of the object to be treated, which is preferable.

[Examples 2-1, 2-2]
As shown in Table 4, the same as in Example 2 except that the concentration of (II) was changed to 15.0 mmol/100 g and 97.4 mmol/100 g, respectively, with respect to the total amount of (I) to (III). The surface of the wafer is processed and evaluated. The results are shown in Table 4 and Figure 4.

[Table 4]

[Examples 5-1, 5-2]
As shown in Table 4, the same as in Example 5 except that the concentration of (II) was changed to 15.0 mmol/100 g and 97.4 mmol/100 g, respectively, with respect to the total amount of (I) to (III). The surface of the wafer is processed and evaluated. The results are shown in Table 4 and Figure 4.

[Comparative Examples 6-1, 6-2]
As shown in Table 4, in the same manner as in Comparative Example 6, except that the concentration of (II) was changed to 15.0 mmol/100 g and 97.4 mmol/100 g, respectively, with respect to the total amount of (I) to (III). The surface of the wafer is processed and evaluated. The results are shown in Table 4 and Figure 4.

[Comparative Examples 7-1, 7-2]
As shown in Table 4, the same as Comparative Example 7 except that the concentration of (II) was changed to 15.0 mmol/100 g and 97.4 mmol/100 g, respectively, with respect to the total amount of (I) to (III). The surface of the wafer is processed and evaluated. The results are shown in Table 4 and Figure 4.

In Examples 2, 2-1, and 2-2 using N-MeIm as (II), the concentration of (II) relative to the total amount of (I) to (III) was increased to 2.4 mmol/100 g. 15.0 mmol/100 g, 97.4 mmol/100 g, and the contact angles were 94°, 97°, and 99°, showing a tendency to increase. Further, regardless of the increase in the concentration of the above (II), the dissolution time was ◎ and was a good result. Furthermore, the results of the dissolution time are shown in parentheses in the vicinity of each graph in FIG.

Similarly, in Examples 5, 5-1, and 5-2 in which DBN was used as (II), the concentration of (II) relative to the total amount of (I) to (III) was increased to 2.4 mmol/100. g, 15.0 mmol/100 g, 97.4 mmol/100 g, and contact angles of 93°, 96°, and 98° showed a tendency to increase. Further, regardless of the increase in the concentration of the above (II), the dissolution time was ◎ and was a good result.

On the other hand, in Comparative Examples 6, 6-1, and 6-2 using 2-MeIm as (II), the concentration of (II) relative to the total amount of (I) to (III) was increased to 2.4. Ment/100 g, 15.0 mmol/100 g, 97.4 mmol/100 g, contact angles of 72°, 79°, 78° showed a tendency to increase, but the dissolution times were △, △, ×, respectively. The tendency of the concentration to deteriorate.

In Comparative Examples 7, 7-1, and 7-2 using (II) 4-MeIm as (II), the concentration of (II) relative to the total amount of (I) to (III) was also increased to 2.4. Ment/100 g, 15.0 mmol/100 g, 97.4 mmol/100 g, contact angles of 85°, 89°, 84° showed a slight increase, but the dissolution time was Δ (dissolution time: about 3 minutes) Δ (dissolution time: about 10 minutes) and Δ (dissolution time: about 30 minutes) tend to deteriorate as the concentration of (II) increases.

From the above results, it was confirmed that the surface treatment agent of the present invention can exert an excellent water repellency imparting effect in a wide range of the concentration of (II) relative to the total amount of (I) to (III), and at the time of preparation. The raw material can be dissolved in a short time. Therefore, in the surface treatment agent of the present invention, the concentration of (II) can be freely selected, and in particular, in the case of the reaction-promoting effect (and the water-repellent imparting effect), a suitable range of 0.05% by mass or more can be selected, which is difficult. From the viewpoint of corroding the surface of the object to be treated and the like, it is not easy to remain as an impurity on the surface of the object to be processed, and an appropriate range of 10.0% by mass or less can be selected.

On the other hand, when a nitrogen-containing heterocyclic compound which does not satisfy the component (II) of the present invention is used, the solubility is inferior, and as the concentration of the nitrogen-containing heterocyclic compound increases, the solubility deteriorates.

[Embodiment 2D, 2D-1, 2D-2]
In the same manner as in Examples 2, 2-1, and 2-2, except that the organic solvent was changed to n-decane/TPGDME (tripropylene glycol dimethyl ether)-43 as shown in Table 5, respectively. The surface treatment of the wafer was carried out and evaluated. The results are shown in Table 5 and Figure 5. Here, n-decane/TPGDME-43 means that the concentration of tripropylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., sometimes referred to as "TPGDME") relative to the total amount of (I) to (III) is 43. A mixed solvent of mass % of n-decane (manufactured by Tokyo Chemical Industry Co., Ltd.) and TPGDME.

[table 5]

[Examples 5D, 5D-1, 5D-2]
As shown in Table 5, the surface treatment of the wafer was carried out in the same manner as in Examples 5, 5-1, and 5-2, except that the organic solvent was changed to n-decane/TPGDME-43. . The results are shown in Table 5 and Figure 5.

[Comparative Examples 6D, 6D-1, 6D-2]
As shown in Table 5, the surface treatment of the wafer was carried out in the same manner as in Comparative Examples 6, 6-1, and 6-2, except that the organic solvent was changed to n-decane/TPGDME-43. . The results are shown in Table 5 and Figure 5.

[Comparative Examples 7D, 7D-1, 7D-2]
The surface treatment of the wafer was carried out in the same manner as in Comparative Examples 7, 7-1, and 7-2, except that the organic solvent was changed to n-decane/TPGDME-43, and the evaluation was performed. . The results are shown in Table 5 and Figure 5.

In Examples 2D, 2D-1, and 2D-2 using N-MeIm as (II), the concentration of (II) relative to the total amount of (I) to (III) was increased to 2.4 mmol/100 g. 15.0 mmol/100 g, 97.4 mmol/100 g, and the contact angles were 94°, 95°, and 96°, showing a tendency to increase. Further, regardless of the increase in the concentration of the above (II), the dissolution time was ◎ and was a good result. Furthermore, the results of the dissolution time are shown in parentheses in the vicinity of each graph in FIG.

In Examples 5D, 5D-1, and 5D-2 using DBN as (II), the concentration of (II) relative to the total amount of (I) to (III) was increased to 2.4 mmol/100 g, 15.0. Mold/100 g, 97.4 mmol/100 g, and contact angles of 93°, 94°, and 95° showed a tendency to increase. Further, regardless of the increase in the concentration of the above (II), the dissolution time was ◎ and was a good result.

On the other hand, in Comparative Examples 6D, 6D-1, and 6D-2 using 2-MeIm as (II), the concentration of (II) relative to the total amount of (I) to (III) was increased to 2.4. Ment/100 g, 15.0 mmol/100 g, 97.4 mmol/100 g, contact angles of 75°, 79°, 83° showed a tendency to increase, but the dissolution times were △, ×, ×, respectively. The tendency of the concentration to deteriorate.

In Comparative Examples 7D, 7D-1, and 7D-2 using (II) 4-MeIm as (II), the concentration of (II) relative to the total amount of (I) to (III) was also increased to 2.4. Ment/100 g, 15.0 mmol/100 g, 97.4 mmol/100 g, contact angles of 82°, 84°, 87° showed a tendency to increase, but the dissolution time was Δ (dissolution time: about 5 minutes), Δ (dissolution time: about 15 minutes) and Δ (dissolution time: about 50 minutes) tend to deteriorate as the concentration of (II) increases.
Further, as compared with the case of the above Comparative Examples 7, 7-1, and 7-2 using PGMEA as the organic solvent, it was found that "decane/TPGDME-43 was used as an organic solvent using n-decane containing a nonpolar solvent as an organic solvent. In the case of Comparative Examples 7D, 7D-1, and 7D-2, the dissolution time was longer. Therefore, from the viewpoint of the solubility of the above (I) and (II), it is considered that the content of the nonpolar solvent is preferably as the organic solvent. The above tends to be confirmed in other examples and comparative examples.

When a nitrogen-containing heterocyclic compound which does not satisfy the component (II) of the present invention is used, the solubility in the case of "decane/TPGDME-43" using n-decane containing a non-polar solvent as an organic solvent is also poor. As the concentration of the nitrogen-containing heterocyclic compound increases, the solubility deteriorates. Further, according to the comparison between Table 4 and Table 5, and the comparison between FIG. 4 and FIG. 5, it was confirmed that the organic solvent was changed from the PGMEA of the polar solvent to the "decane/TPGDME-43" of the non-polar solvent n-decane. Then, the solubility tends to deteriorate further.

On the other hand, it has been confirmed that the surface treatment agent of the present invention can be used in (II) relative to (I) even in the case of using "nonane/TPGDME-43" which is a non-polar solvent of n-decane as an organic solvent. The concentration of the total amount of ~(III) exhibits an excellent water-repellent imparting effect in a wide range, and the raw material can be dissolved in a short time during preparation. Therefore, in the surface treatment agent of the present invention, the concentration of (II) can be freely selected, and in particular, a suitable range of 0.05% by mass or more can be selected from the viewpoint of the reaction-promoting effect (and further the water-repellent imparting effect). From the viewpoint of not easily corroding the surface of the object to be processed and the like, and it is difficult to remain as an impurity on the surface of the object to be processed, a suitable range of 10.0% by mass or less can be selected.

As described above, the surface treatment agent of the present invention does not greatly depend on the polarity of the organic solvent, and exhibits an excellent water-repellent imparting effect, and can dissolve the raw material in a short time during preparation.

Fig. 1 is a graph showing the contact angle maintenance ratio after surface treatment with respect to the amount of water added (Examples A-1, A-2, and 9).

Fig. 2 is a graph showing the contact angle maintenance ratio after surface treatment with respect to the amount of water added (Examples A-3, A-4, and 10).

Fig. 3 is a graph showing the contact angle maintenance ratio after surface treatment with respect to the amount of water added (Examples A-5, A-6, and 13).

Fig. 4 is a graph showing the relationship between the contact angle after surface treatment and the tendency of dissolution time (PGMEA solvent) with respect to the concentration of (II).

Fig. 5 is a graph showing the relationship between the contact angle after surface treatment and the tendency of dissolution time (n-decane, TPGDME mixed solvent) with respect to the concentration of (II).

Claims (20)

A surface treatment agent for use in a surface treatment of a target object, comprising: (I) at least one of the ruthenium compounds represented by the following general formulas [1], [2], and [3]; II) at least one of a nitrogen-containing heterocyclic compound represented by the following formula [4], a nitrogen-containing heterocyclic compound represented by the following formula [5], and an imidazole; and (III) an organic solvent; [In the formula [1], R ^{1 is} , independently of each other, a part or all of hydrogen elements may be substituted with a fluorine element having a carbon number of from 1 to 18, and R ^{2 is} independently selected from a part or all of hydrogen. The element may be substituted with a group of a fluorine group having an alkyl group having 1 to 6 carbon atoms and a hydrogen group, and R ^{3 is} independently a part or all of the hydrogen element may be substituted with a carbon number of the fluorine element. Is an alkyl group of 1 to 6, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 1 to 3] [In the formula [2], R ^{4 is} , independently of each other, a part or all of hydrogen elements may be substituted with a fluorine element having a carbon number of from 1 to 18, and R ^{5 may} be a part or all of hydrogen independently of each other. The carbon number substituted with fluorine is 1 to 6 alkyl groups, c is an integer of 1 to 3, d is an integer of 0 to 2, and the total of c and d is 1 to 3] [In the formula [3], R ⁶ and R ⁸ are each independently a part or all of a hydrogen element may be substituted with a fluorine element having a carbon number of 1 to 18 one-valent hydrocarbon group, and R ^{7 is} independently selected from a part of each other. Or all hydrogen elements may be substituted with an alkyl group having a carbon number of 1 to 6 and a group of hydrogen elements, e is an integer of 1 to 3, and f is an integer of 0 to 2, and g is An integer from 1 to 3, the total of e and f is 1 to 3] [In the formula [4], R ⁹ and R ¹⁰ are each independently a divalent organic group containing a carbon element and/or a nitrogen element and a hydrogen element, and the total number of carbon atoms and nitrogen is 1 to 9, in the case of 2 or more. When there is a carbon element that does not form a ring] [In the formula [5], R ¹¹ is an alkyl group in which a part or all of the hydrogen element may be substituted with a fluorine element and having a carbon number of 1 to 6, and a part or all of the hydrogen element may be substituted with a fluorine element, and the carbon number is 1 to a trialkylsulfanyl group of 8 alkyl groups, a part or all of a hydrogen element may be substituted with an alkenyl group having 2 to 6 carbon atoms, and a part or all of hydrogen may be substituted with a fluorine element having a carbon number of 1 to An alkoxy group of 6 or an amine group, an alkylamino group having a part or all of a hydrogen element which may be substituted with an alkyl group having 1 to 6 carbon atoms of a fluorine element, and a part or all of hydrogen elements may be substituted with a fluorine element. a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a part or all of a hydrogen element may be substituted with an amino group having 1 to 6 carbon atoms, a nitro group, a nitro group, a phenyl group, a phenyl group or a benzyl group. Or a halogen group, and R ¹² , R ¹³ and R ¹⁴ are each independently a part or all of a hydrogen element which may be substituted with a fluorine group having an alkyl group having 1 to 6 carbon atoms or a hydrogen group]. The surface treatment agent of claim 1, wherein the concentration of (II) relative to the total amount of the above (I) to (III) is 0.05 to 10% by mass. The surface treatment agent of claim 1, wherein the above (II) is a liquid at 25 ° C and 1 atm. The surface treatment agent of claim 1, wherein R ¹¹ of the above formula [5] is an alkyl group having 1 to 4 carbon atoms or a trimethylsulfanyl group, and R ¹² , R ¹³ and R ¹⁴ are a hydrogen group. The surface treatment agent of claim 1, wherein the above (II) is selected from the group consisting of 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]- 7-undecene, 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene, N-methylimidazole, N-ethylimidazole, N-propylimidazole At least one of the group consisting of N-butylimidazole and trimethyldecyl imidazole. The surface treatment agent of claim 1, wherein the concentration of (I) relative to the total amount of the above (I) to (III) is 0.1 to 35% by mass. The surface treatment agent according to claim 1, which comprises at least one anthracene compound of the above formula [1] wherein a is 3, R ² is a methyl group, and R ³ is a fluorine-containing alkyl group having 1 to 6 carbon atoms as the above ( I). The surface treatment agent of claim 1, wherein the above (I) is (CH ₃ ) ₃ SiN(CH ₃ )C(=O)CF ₃ . The surface treatment agent of claim 1, which contains the hydrazine compound represented by the above formula [2] as the above (I), and The above (II) is selected from the group consisting of 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]-7-undecene, 7-A At least one of the group consisting of keto-1,5,7-triazabicyclo[4.4.0]non-5-ene. The surface treatment agent of claim 1, which contains at least one hydrazine compound of the above formula [2] wherein c is 3 and R ⁵ is a fluorine-containing alkyl group having 1 to 6 carbon atoms as the above (I). The surface treatment agent of claim 1, wherein the above (I) is (CH ₃ ) ₃ SiOC(=O)CF ₃ . The surface treatment agent of claim 11, wherein the concentration of the above (CH ₃ ) ₃ SiOC(=O)CF ₃ relative to the total amount of the above (I) to (III) is 1 to 20% by mass. The surface treatment agent according to claim 1, which comprises at least one anthracene compound of the above formula [1] wherein a is 3 and R ² is hydrogen and R ³ is a fluorine-containing alkyl group having 1 to 6 carbon atoms (I- 1) and at least one hydrazine compound (I-2) wherein c of the above formula [2] is 3 and R ⁵ is a fluorine-containing alkyl group having 1 to 6 carbon atoms is the above (I). The surface treatment agent of claim 13, wherein the above ruthenium compound (I-1) is (CH ₃ ) ₃ SiN(H)C(=O)CF ₃ , and the above ruthenium compound (I-2) is (CH ₃ ) ₃ SiOC(=O)CF ₃ . The surface treatment agent of claim 10, wherein the above (II) is selected from the group consisting of 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]- At least one of the group consisting of 7-undecene and 7-methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene. The surface treatment agent according to claim 1, which comprises at least one hydrazine compound wherein e and g of the above formula [3] are 3 and R ⁷ is a methyl group or a trifluoromethyl group as the above (I). The surface treatment agent of claim 1, wherein the above (I) is (CH ₃ ) ₃ SiOC(CF ₃ )=NSi(CH ₃ ) ₃ . The surface treatment agent of claim 1, which comprises the above-described (I) compound represented by the above formula [3], and Containing a compound selected from 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]-7-undecene, 7-methyl-1, At least one of the groups consisting of 5,7-triazabicyclo[4.4.0]non-5-ene is as the above (II). The surface treatment agent according to any one of claims 1 to 18, wherein the organic solvent is an aprotic solvent. A method of producing a surface treatment body, wherein the surface treatment agent according to any one of claims 1 to 19 is brought into contact with a surface of the object to be treated, and the surface of the object to be treated is treated.