WO2024248021A1 - Film-forming composition, method for producing substrate, and method for producing film-forming composition - Google Patents

Abstract

A film-forming composition according to the present disclosure is used for forming a water-repellent film and comprises (I) a silylation agent, (II) a chlorine-containing silyl ester compound, and (III) an aprotic solvent.

Description

Film-forming composition, method for producing substrate, and method for producing film-forming composition

The present disclosure relates to a film-forming composition, a method for manufacturing a substrate, and a method for manufacturing a film-forming composition.

In recent years, there has been an increasing trend toward higher integration and miniaturization of semiconductor devices, and the miniaturization and high aspect ratio of resin patterns used as masks and inorganic patterns created by etching processes are progressing. However, at the same time, the problem of so-called pattern collapse has begun to occur. This pattern collapse is a phenomenon in which, when a large number of resin patterns or inorganic patterns are formed in parallel on a substrate, adjacent patterns lean against each other and, in some cases, the patterns break or peel off from their base. When such pattern collapse occurs, the desired product cannot be obtained, which leads to a decrease in product yield and reliability.
It is known that this pattern collapse occurs due to the surface tension of the cleaning liquid when the cleaning liquid dries during the cleaning process after pattern formation. In other words, when the cleaning liquid is removed during the drying process, stress based on the surface tension of the cleaning liquid acts between the patterns, causing the pattern collapse.
Therefore, chemicals that use a silylating agent to impart water repellency to the pattern surface and prevent pattern collapse are used at semiconductor manufacturing sites.
Patent Document 1 describes a surface treatment agent containing a silylating agent containing at least one compound having a disilazane structure and a solvent.

JP 2011-091349 A International Publication No. WO2011/155407

In order to further improve the water repellency provided by the silylating agent, a method of adding an accelerator to the chemical solution has been carried out. However, it has been found that chemical solutions using chlorine-containing accelerators have not been sufficiently studied.

As a result of intensive research conducted by the inventors in light of the above circumstances, they discovered a new chemical solution containing a chlorine-containing accelerator that can impart excellent water repellency to the substrate surface using a chemical solution containing a silylating agent, a chlorine-containing silyl ester compound, and an aprotic solvent, and thus completed the present disclosure.

According to one aspect of the present disclosure, the following film-forming composition, method for manufacturing a substrate, and method for manufacturing a film-forming composition are provided.

1. A film-forming composition used to form a water-repellent film,
(I) a silylating agent;
(II) a silyl ester compound represented by the following general formula [2],
(III) an aprotic solvent,
A film-forming composition.
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
(In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms;
i is an integer from 1 to 3, h is an integer from 1 to 3, and i+h is an integer from 2 to 4.
2. The film-forming composition according to 1.,
The film-forming composition, wherein the silylating agent contains a silicon compound represented by the following general formula [1]:
R ¹ _a Si(H) _b X _4-ab [1]
(In the above general formula [1],
R ¹ is each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
Each X is independently a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, carbon, or halogen;
a is an integer from 1 to 3, b is an integer from 0 to 2, and the sum of a and b is 1 to 3.
3. The film-forming composition according to 1. or 2.,
The film-forming composition contains the silyl ester ^compound represented by -C _q Y _(2q+1-r) Cl _r (wherein each Y is independently a hydrogen atom or a fluorine atom bonded to carbon, Cl is a chlorine atom, q is an integer of 1 to 5, and r is 1 to 2q).
4. The film-forming composition according to any one of 1 to 3,
The aprotic solvent comprises one or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen atom-containing solvents, sulfoxide-based solvents, carbonate-based solvents, derivatives of polyhydric alcohols having no OH group, nitrogen atom-containing solvents having no N-H group, and silicone solvents.
5. The film-forming composition according to any one of 1 to 4,
The film-forming composition, wherein the content of the silylating agent is 0.1% by mass or more and 35% by mass or less, based on 100% by mass of the film-forming composition.
6. The film-forming composition according to any one of 1 to 5,
The film-forming composition, wherein the content of the silyl ester compound is 0.01% by mass or more and 10% by mass or less based on 100% by mass of the film-forming composition.
7. The film-forming composition according to any one of 1 to 6,
The film-forming composition has a water contact angle of 70° or more when the film is formed from the film-forming composition and measured in accordance with JIS R 3257:1999.
8. The film-forming composition according to any one of 1. to 7.,
A film-forming composition comprising the aprotic solvent (III) having polarity.
9. The film-forming composition according to any one of 1 to 8,
A film-forming composition which does not contain an amide compound represented by the following general formula [4], or the content of the amide compound is 0.1 mass % or less based on 100 mass % of the film-forming composition:
R ^b1 -C(=O)N(H)Z [4]
(In the above general formula [4],
R ^b1 is a hydrocarbon group having a Cl ₃ C moiety, a Cl ₂ HC moiety, or a Cl ₂ FC moiety;
Z is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms bonded to a nitrogen atom.
10. The film-forming composition according to 9.,
A film-forming composition comprising an amide compound having a structure in which, in the general formula [4], R ^b1 is a hydrocarbon group having no Cl ₃ C moiety, Cl ₂ HC moiety, or Cl ₂ FC moiety.
11. The film-forming composition according to any one of 1. to 10.,
A film-forming composition comprising one or more compounds selected from the group consisting of a silylamide compound represented by the following general formula [5] and an aminosilane compound represented by the following general formula [6]:
(R ^b2 -C(=O)N(H)) _j -Si(H) _4-j-t (R ^b3 ) _t [5]
(In the above general formula [5],
R ^b2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms,
R ^b3 each independently represents an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
j is an integer from 1 to 3, t is an integer from 1 to 3, and j+t is an integer from 2 to 4.
(R ^b4 ) _u Si(H) _v (NH ₂ ) _4-uv [6]
(In the above general formula [5],
R ^b4 each independently represents an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
u is an integer from 1 to 3, v is an integer from 0 to 2, and the sum of u and v is 1 to 3.
12. Preparing a substrate;
supplying a film-forming composition to the substrate to form a water-repellent film on at least a portion of a surface of the substrate,
The film forming composition,
(I) a silylating agent;
(II) a silyl ester compound represented by the following general formula [2],
(III) an aprotic solvent.
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
(In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms;
i is an integer from 1 to 3, h is an integer from 1 to 3, and i+h is an integer from 2 to 4.
13. A method for manufacturing a substrate according to 12., comprising the steps of:
A method for producing a substrate, comprising the step of cleaning the substrate before supplying the film-forming composition.
14. A method for producing a film-forming composition, comprising the step of mixing (I) a silylating agent, (II) a silyl ester compound, and (III) an aprotic solvent.
15. A method for producing a film-forming composition, comprising a reaction step of reacting (I) a silylating agent with a chlorocarboxylic acid compound containing at least one of a chlorocarboxylic acid and a chlorocarboxylic acid anhydride to obtain (II) a silyl ester compound.
16. A method for producing the film-forming composition according to 15.,
The chlorocarboxylic acid includes one or more compounds represented by the following general formula [7]:
The method for producing a film-forming composition, wherein the chlorocarboxylic anhydride contains one or more compounds represented by the following general formula [8]:
R ^C2 -C(=O)OH [7]
R ^C2 -C(=O)OC (=O)-R ^C2 [8]
(In the above general formulas [7] and [8],
R ^C2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced with chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced with fluorine atoms.
17. A method for producing the film-forming composition according to 15. or 16.,
The method for producing a film-forming composition includes the chlorocarboxylic acid compound, which contains at least one of the chlorocarboxylic acid having a pKa of -0.2 or more and 4.5 or less, and an anhydride thereof.
18. A method for producing the film-forming composition according to any one of 15. to 17., comprising the steps of:
The method for producing a film-forming composition, wherein the reaction step is carried out in an aprotic solvent (III).
19. A method for producing the film-forming composition according to any one of 15. to 18., comprising the steps of:
The method for producing a film-forming composition, wherein in the reaction step, the chlorocarboxylic acid compound contains the chlorocarboxylic acid and does not contain the chlorocarboxylic acid anhydride.
20. A method for producing the film-forming composition according to any one of 15. to 19., comprising the steps of:
The method for producing a film-forming composition, wherein the silylating agent (I) is other than a silazane compound.
21. A method for producing the film-forming composition according to any one of 15. to 20., comprising the steps of:
The method for producing a film-forming composition, wherein the reaction step is carried out under an inert atmosphere.

The present disclosure provides a film-forming composition that can produce a new chemical solution containing a chlorine-containing accelerator, a method for manufacturing a substrate using the same, and a method for manufacturing the film-forming composition.

FIG. 2 is a top view illustrating a schematic configuration of a substrate. FIG. 2 is a cross-sectional view illustrating a schematic configuration of a substrate. 1A to 1C are cross-sectional views illustrating process steps for manufacturing a substrate.

Below, an embodiment of the present disclosure will be described with reference to the drawings. Note that in all drawings, similar components are given similar reference symbols and descriptions will be omitted as appropriate. Also, the drawings are schematic diagrams and do not correspond to the actual dimensional ratios.

The film-forming composition of this embodiment will now be outlined.

The film-forming composition of the present embodiment contains (I) a silylation agent, (II) a silyl ester compound represented by the following general formula [2], and (III) an aprotic solvent.
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
(In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
i is an integer from 1 to 3, h is an integer from 1 to 3, and i+h is an integer from 2 to 4.

The inventors have found that a film-forming composition containing the above-mentioned silylating agent, a chlorine-containing silyl ester compound, and an aprotic solvent can impart excellent water repellency to the substrate surface.

The film-forming composition of the present embodiment is a surface-modifying chemical liquid used for forming a water-repellent film on at least a part of a substrate surface.
The water repellency can be defined using as an index the water contact angle measured by the coupon test described below.
The water-repellent film formed from the film-forming composition has a water contact angle, measured in accordance with JIS R 3257:1999, of, for example, 70° or more, preferably 75° or more, and more preferably 81° or more.
(Procedure for coupon testing)
A silicon wafer having no uneven pattern on its surface and a silicon oxide film with a thickness of 1 μm is cut to prepare coupons made of silicon substrates with dimensions of length, width and thickness of 4 cm, 1 cm and 0.75 mm.
The coupon is immersed in 1% by weight hydrofluoric acid at room temperature, then in water at room temperature, then in 2-propanol at room temperature, and then in propylene glycol monomethyl ether acetate at room temperature to wash it, where "room temperature" is 25°C.
An evaluation solution made of the film-forming composition was prepared, and the cleaned coupon was immersed in the evaluation solution at room temperature for 20 seconds.
The coupon is removed from the evaluation solution and washed by immersing it in 2-propanol at room temperature, and then the surface of the coupon is dried with nitrogen gas.
With the dried coupon placed on a horizontal surface, 2 μl of pure water is placed on the surface of the coupon on which the silicon oxide film is formed at room temperature, and the water contact angle (°) is measured in accordance with JIS R 3257:1999.

Patent Document 2 discloses a chemical solution for forming a water-repellent protective film on at least the recessed surface of a fine uneven pattern when cleaning a wafer having a fine uneven pattern on its surface, at least a part of which contains silicon elements, the chemical solution containing a silicon compound A of a predetermined structure and an acid A, the acid A being at least one selected from the group consisting of trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, and octyldimethylsilyl trifluoromethanesulfonate.
Patent Document 2 discloses that the use of a perfluoroalkyl derivative such as TMSTFA (trimethylsilyl trifluoroacetate) as an accelerator can provide excellent water repellency, but that the use of unsubstituted sulfuric acid, nitric acid, or acetic acid results in significantly inferior water repellency.
From this, it was predicted that compounds such as trimethylsilyl chlorodifluoroacetate (TMSCDA) and trimethylsilyl dichlorofluoroacetate (TMSDFA), in which at least a part of the fluorine atoms of a perfluoroalkyl derivative are replaced by chlorine atoms, would have insufficient electron-attracting properties of the chlorine atoms, and would impart less water repellency. However, when the above-mentioned compounds containing chlorine atoms are applied to accelerators, this is unexpectedly not the case, and water repellency equivalent to that of perfluoroalkyl derivatives such as TMSTFA can be achieved. Here, equivalent water repellency means that the water repellency is significantly superior to that of unsubstituted sulfuric acid, nitric acid or acetic acid, specifically, the water contact angle is 70° or more, which satisfies the water repellency standard.
According to this embodiment, by substituting at least a portion of the fluorine atoms of the perfluoroalkyl derivative with chlorine atoms, a film-forming composition having equivalent water repellency can be provided.
In addition, in view of the fact that natural fluorine resources are in a state of depletion, efforts to replace fluorine with chlorine in accelerators are preferable from the viewpoint of resource conservation.

In this specification, the term "water-repellent film" refers to both a compound having a silyl group derived from a silylating agent that is chemically bonded to the substrate surface, and a group of such compounds, regardless of whether or not the compounds interact with each other or are bonded to each other. The above bonds do not have to be direct bonds, and also include cases where the bonds are formed via other elements or substituents, etc.

The components of the film-forming composition of this embodiment are described in detail below.

(I) Silylation Agent)
As the silylating agent, a known silylating agent can be used.
The silylating agent may include, for example, a silicon compound represented by the following general formula [1]. These may be used alone or in combination of two or more kinds.

R ¹ _a Si(H) _b X _4-ab [1]

In the above general formula [1],
R ¹ is each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
Each X is independently a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, carbon, or halogen;
a is an integer of 1 to 3, b is an integer of 0 to 2, and the sum of a and b is 1 to 3.
The above-mentioned hydrocarbon groups are still referred to as hydrocarbon groups even when all of the hydrogen atoms are replaced with atoms other than hydrogen atoms.

R ¹ in the above general formula [1] may contain not only hydrogen, carbon, nitrogen, oxygen, a fluorine atom, or a chlorine atom, but also silicon, sulfur, a halogen atom (other than fluorine), etc. Furthermore, R ¹ in the above general formula [1] may contain an unsaturated bond, an aromatic ring, or a cyclic structure.

R ¹ in the above general formula [1] is independently at least one group selected from C _e H _2e+1 (e=1 to 18) and C _f F _2f+1 CH ₂ CH ₂ (f=1 to 8).

When R ¹ in the above general formula [1] contains a silicon atom, it may have a structure represented by the following general formula [1-1].
R ¹ _m X _3-m-n (H) _n Si-(CH ₂ ) _p -Si(H) _n X _3-m-n R ¹ _m [1-1]
In the above general formula [1-1], R ¹ (wherein R ¹ does not contain a silicon atom) and X are the same as those in the above general formula [1], m is an integer of 1 to 2, n is an integer of 0 to 1, the sum of m and n is 1 to 2, p is an integer of 1 to 18, and the methylene chain represented by -(CH ₂ ) _p - may be substituted with a halogen atom.

In the above general formula [1], X is a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, or carbon, and may contain not only hydrogen, carbon, nitrogen, and oxygen atoms, but also silicon, sulfur, halogen atoms, etc.

（上記一般式［１－２］中、Ｒ^５は、それぞれ独立して、一部又は全ての水素原子がフッ素原子に置き換えられていてもよい炭素数が１～８の２価の炭化水素基である。）、－Ｎ＝Ｃ（ＮＲ^６ _２）_２、－Ｎ＝Ｃ（ＮＲ^６ _２）Ｒ^６（ここで、Ｒ^６は、それぞれ独立して、水素基、－Ｃ≡Ｎ基、－ＮＯ_２基、及び、一部又は全ての水素原子がフッ素原子に置き換えられていてもよい炭化水素基から選択され、上記炭化水素基は酸素原子及び／又は窒素原子を有していてもよい。）、－Ｎ（Ｒ^ａ１）（Ｒ^ａ２）（ここで、上記Ｒ^ａ１は水素原子、又は飽和若しくは不飽和アルキル基を示し、Ｒ^ａ２は飽和若しくは不飽和アルキル基、飽和若しくは不飽和シクロアルキル基、又は飽和若しくは不飽和ヘテロシクロアルキル基を示す。Ｒ^ａ１及びＲ^ａ２は互いに結合して窒素原子を有する飽和又は不飽和ヘテロシクロアルキル基を形成してもよい。）、－Ｎ（Ｒ^ａ３）－Ｓｉ（Ｒ^ａ４）（Ｒ^ａ５）（Ｒ^ａ６）（ここで、上記Ｒ^ａ３は水素原子、炭素数が１～４の炭化水素基、トリメチルシリル基、又はジメチルシリル基を示し、上記Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６はそれぞれ独立に水素原子又は有機基を表し、Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６に含まれる炭素原子の合計の個数は１個以上である。）、－Ｎ（Ｒ^ａ７）－Ｃ（＝Ｏ）Ｒ^ａ８（ここで、上記Ｒ^ａ７は、水素原子、メチル基、トリメチルシリル基、またはジメチルシリル基を示し、Ｒ^ａ８は、水素原子、飽和若しくは不飽和アルキル基、含フッ素アルキル基、又はトリアルキルシリルアミノ基を示す。）、などがある。 In X in the above general formula [1], examples of monovalent groups in which the atom bonded to the Si atom is nitrogen include, for example, an isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an azide group, an acetamide group, -NHC(=O) _CF3 , -N( _CH3 )C(=O) _CH3 , -N( _CH3 )C(=O) _CF3 , -N=C( _CH3 )OSi( _CH3 ) ₃ , -N=C( _CF3 )OSi( _CH3 ) ₃ , -NHC(=O)-OSi( _CH3 ) ₃ , -NHC(=O)-NH-Si( _CH3 ) ₃ , an imidazole ring, a triazole ring, a tetrazole ring, an oxazolidinone ring, a morpholine ring, and -NH-C(=O)-Si( _CH3 ) _3. , -N(S(=O) ₂ R ⁴ ) ₂ (wherein R ⁴ is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and a fluorine atom), and a substituent having a structure of the following general formula [1-2]:

(In the above general formula [1-2], R ⁵ is each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms.), -N=C(NR ⁶ ₂ ) ₂ , -N=C(NR ⁶ ₂ )R ⁶ (wherein R ⁶ is each independently selected from a hydrogen group, a -C≡N group, a -NO ₂ group, and a hydrocarbon group in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon group may have an oxygen atom and/or a nitrogen atom.), -N(R ^a1 )(R ^a2 ) (wherein R ^a1 is a hydrogen atom, or a saturated or unsaturated alkyl group, and R ^a2 is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group. ^{R a1} and R ^a2 may be bonded to each other to form a saturated or unsaturated heterocycloalkyl group having a nitrogen atom.), -N(R ^a3 )-Si(R ^a4 )(R ^a5 )(R ^a6 ) (wherein R ^a3 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group, or a dimethylsilyl group, and R ^a4 , R ^a5 , and R ^a6 each independently represent a hydrogen atom or an organic group, and the total number of carbon atoms contained in R ^a4 , R ^a5, and R ^a6 is 1 or more; -N(R ^a7 )-C(═O)R ^a8 (wherein R ^a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, and R ^a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group); and the like.

（上記一般式［１－２］中、Ｒ^５は上述したとおりである。例えば、Ｎ－（トリメチルシリル）Ｎ，Ｎ－ジフルオロメタン－１，３－ビス（スルホニル）イミド等）、－Ｎ＝Ｃ（ＮＲ^６ _２）_２、－Ｎ＝Ｃ（ＮＲ^６ _２）Ｒ^６（Ｒ^６は上述したとおりである。例えば、２－トリメチルシリル－１，１，３，３－テトラメチルグアニジン等）、－Ｎ（Ｒ^ａ１）Ｒ^ａ２（Ｒ^ａ１、Ｒ^ａ２は上述したとおりである。）、－Ｎ（Ｒ^ａ３）－Ｓｉ（Ｒ^ａ４）（Ｒ^ａ５）（Ｒ^ａ６）（Ｒ^ａ３、Ｒ^ａ４、Ｒ^ａ５及びＲ^ａ６は上述したとおりである。例えば、ヘキサメチルジシラザン、Ｎ－メチルヘキサメチルジシラザン、１，１，３，３－テトラメチルジシラザン、１，３－ジメチルジシラザン、１，３－ジ－Ｎ－オクチルテトラメチルジシラザン、１，３－ジビニルテトラメチルジシラザン、ヘプタメチルジシラザン、Ｎ－アリル－Ｎ，Ｎ－ビス（トリメチルシリル）アミン、１，３－ジフェニルテトラメチルジシラザン、１，１，３，３－テトラフェニル－１，３－ジメチルジシラザン、ノナメチルトリシラザン、ペンタメチルエチルジシラザン、ペンタメチルビニルジシラザン、ペンタメチルプロピルジシラザン、ペンタメチルエチルジシラザン、ペンタメチル－ｔ－ブチルジシラザン、ペンタメチルフェニルジシラザン、トリメチルトリエチルジシラザン等。）、－Ｎ（Ｒ^ａ７）－Ｃ（＝Ｏ）Ｒ^ａ８（Ｒ^ａ７、Ｒ^ａ８は上述したとおりである。例えば、Ｎ－トリメチルシリルアセトアミド、Ｎ－トリメチルシリルトリフルオロアセトアミド、Ｎ－メチル－Ｎ－トリメチルシリルアセトアミド、Ｎ－メチル－Ｎ－トリメチルシリルトリフルオロアセトアミド、ビス（トリメチルシリル）アセトアミド、ビス（トリメチルシリル）トリフルオロアセトアミド等。）に置き換えたものなどが挙げられる。 Examples of the silylating agent in which X in the above general formula [1] is a monovalent group in which the atom bonded to the Si atom is nitrogen include _CH3Si ( _{NH2 ) 3} , _C2H5Si ( _NH2 ) ₃ , _{C3H7Si ( NH2 ) 3} , _C4H9Si ( _NH2 ) ₃ , C5H11Si _{( NH2} ) ₃ , _C6H13Si ( _NH2 ) _{3 , C7H15Si ( NH2} ) _{3 , C8H17Si ( NH2} ) _{3 , C9H19Si} ( _NH2 ) _{3 , C10H21Si} ( _NH2 ) ₃ , _{and C11H23} Si( _{NH2 ) 3} , C12H25Si(NH2) _{3 , C13H27Si} ( _NH2 ) _{3 , C14H29Si ( NH2} ) _{3 , C15H31Si ( NH2 ) 3} , _C16H33 Si( _NH2 ) ₃ , C17H35Si(NH2) ₃ , _{C18H37Si (} NH2 _{) 3} , _{( CH3} ) _{2Si ( NH2} ) _{2 , C2H5Si ( CH3 )} ( _NH2 ) ₂ , ( _{C2H 5} ) _2Si ( _{NH2 ) 2} , _C3H7 Si( _CH3 )( _NH2 ) ₂ , ( _{C3H7 ) 2Si ( NH2} ) _{2 , C4H9Si} ( _CH3 )( _NH2 ) ₂ , _{( C4H9 ) 2Si} ( _NH2 )2, _C5H11Si ( _{CH3) )} ( _NH2 ) ₂ , _{C6H13Si ( CH3} )( _NH2 ) ₂ , _C7H15Si ( _{CH3 )} ( _NH2 ) _{2 ,} C8H17Si _{( CH3} )( _NH2 ) ₂ , _C9H19Si ( _CH3 )( _NH2 ) _{2 , C10H21Si} ( _CH3 )( _NH2 ) _{2 , C11H23Si} ( _CH3 )( _NH2 )2, _C12H25Si ( _{CH3 )} ( _NH2 ) _{2 , C13H27Si ( CH3 )} ( _NH2 ) ₂ , _C14H29 Si( _CH3 )( _NH2 ) _{2 , C15H31Si ( CH3 )} ( _NH2 ) ₂ , _C16H33Si ( _CH3 )( _NH2 ) _{2 , C17H35Si} ( _CH3 )( _NH2 ) ₂ , _{C18H 37} Si( _CH3 )( _NH2 ) ₂ , ( _CH3 ) _{3 SiNH2} , _C2H5Si (CH3) _{2NH2 , ( C2H5 ) 2Si ( CH3} ) _{NH2 , ( C2H5} ) _{3SiNH2 , C3H7Si} ( _{CH3 )2NH2 ,} ( _{C3H 7} ) _2Si ( _{CH3 ) NH2,} ( _{C3H7 ) 3SiNH2 , C4H9Si} ( _CH3 ) _{2NH2 ,} ( _{C4H9 ) 3SiNH2 , C5H11Si ( CH3} ) _{2NH2 ,} C ₆ H ₁₃ Si(CH ₃ ) ₂ NH ₂ , C _{7 H15Si} ( _CH3 ) _{2NH2 , C8H17Si ( CH3 ) 2NH2 , C9H19Si ( CH3} ) _2NH2 , _{C10H21Si ( CH3 ) 2NH2 , C11H23 Si ( CH3} ) _{2NH2 ,} C12H25Si _{( CH3 ) 2NH2 , C13H27Si ( CH3} ) _2NH2 , _{C14H29Si ( CH3 ) 2NH2} , _C15H31Si (CH _{3 ) 2NH2} , _C16H33Si ( _{CH3 ) 2 NH2} , _C17H35Si ( _CH3 ) _2NH2 , _{C18H37Si (} CH3) _{2NH2 , ( CH3} ) _2Si (H _{) NH2} , _CH3Si ( _{H )2NH2 ,} ( _{C2H5 ) 2} Si(H) _{NH2 , C2H5Si} ( _{H ) 2NH2 , C2H5Si(CH3} )(H) _NH2 , _{( C3H7 ) 2Si} (H _{) NH2 , C3H7Si} (H) _2NH2 , _{CF3CH2CH 2Si ( NH2 ) 3} , _{C2F5CH2 CH2Si ( NH2} ) _{3 , C3F7CH2CH2Si ( NH2 ) 3, C4F9CH2CH2Si ( NH2 ) 3 , C5F11CH2CH2Si ( NH2 ) 3 , C6 F13CH2CH2Si ( NH2 ) 3 , C7F15CH2CH2Si ( NH2 ) 3 , C8F17CH2CH2Si ( NH2 ) 3 , CF3CH2CH2Si} ( _{CH3 )} )(NH ₂ ) ₂ , C ₂ F ₅ CH ₂ CH ₂ Si(CH ₃ )(NH _{2 ) 2} , _{C3F7CH2CH2Si ( CH3} ) _{( NH2 ) 2 , C4F9CH2CH2Si(CH3 ) ( NH2 ) 2 , C5F11CH2CH2Si ( CH3} )( _{NH2 ) 2} , _{C6F13CH2CH2Si ( CH3} ) _{( NH2 ) 2 , C7F15CH2CH2Si ( CH3} )( _NH2 ) _{2 , C8F17CH2CH2Si ( CH3 )} ( _NH2 ) ₂ , CF ₃ CH ₂ CH ₂ Si(CH ₃ ) ₂ NH ₂ , C _{2F5CH2CH2Si ( CH3 ) 2NH2 , C3F7CH2CH2Si ( CH3 ) 2NH2 , C4F9CH2CH2Si ( CH3 ) 2NH2 , C5F11 ​ ​ ​ ​ CH2CH2Si ( CH3 ) 2NH2 , C6F13CH2CH2Si ( CH3 ) 2NH2 , C7F15CH2CH2Si ( CH3 ) 2NH2 , C8F17CH2 ​ ​ ​ CH2Si ( CH3 ) 2NH2 , CF3CH2CH2Si} ( _CH3 )(H)NH ₂ , aminosilanes such as aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, and aminodimethyl-t-butylsilane, or the amino group (-NH ₂ group) of the aminosilanes is substituted with -N=C=O, dialkylamino groups (-N(CH ₃ ) ₂ , -N(C ₂ H ₅ ) ₂ , etc.), t-butylamino groups, allylamino groups, -N=C=S, -N ₃ , -NHC(=O)CH ₃ , -NHC(=O)CF ₃ , -N(CH ₃ )C(=O)CH ₃ , -N(CH ₃ )C(=O)CF ₃ , -N=C(CH ₃ )OSi(CH ₃ ) ₃ , -N=C(CF ₃ )OSi(CH ₃ ) ₃ , -NHC(=O)-OSi(CH ₃ ) ₃ , -NHC(=O)-NH-Si(CH ₃ ) ₃ (for example, N,N'-bis(trimethylsilyl)urea, etc.), imidazole ring (for example, N-trimethylsilylimidazole, etc.), triazole ring (for example, N-trimethylsilyltriazole, etc.), tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH ₃ ) ₃ , -N(S(=O) ₂ R ⁴ ) ₂ (R ⁴ is as described above. For example, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc.), and substituents having the structure of the above general formula [1-2].

(In the above general formula [1-2], R ⁵ is as described above. For example, N-(trimethylsilyl)N,N-difluoromethane-1,3-bis(sulfonyl)imide, etc.), -N=C(NR ⁶ ₂ ) ₂ , -N=C(NR ⁶ ₂ )R ⁶ (R ⁶ is as described above. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, etc.), -N(R ^a1 )R ^a2 (R ^a1 and R ^a2 are as described above), -N(R ^a3 )-Si(R ^a4 )(R ^a5 )(R ^a6 ) (R ^a3 , R ^a4 , R ^a5 and R ^a6 is as described above. For example, hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-dimethyldisilazane, 1,3-di-N-octyltetramethyldisilazane, 1,3-divinyltetramethyldisilazane, heptamethyldisilazane, N-allyl-N,N-bis(trimethylsilyl)amine, 1,3-diphenyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, nonamethyltrisilazane, pentamethylethyldisilazane, pentamethylvinyldisilazane, pentamethylpropyldisilazane, pentamethylethyldisilazane, pentamethyl-t-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane, etc.), -N(R ^a7 )-C(=O)R ^a8 (R ^a7 and R ^a8 are as described above. For example, N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, etc.) are exemplified.

Examples of silylating agents in which X in the above general formula [1] is a monovalent group in which the atom bonded to the Si atom is oxygen include those in which the amino group ( _-NH2 group) of the above aminosilane is substituted with -O-C(=A)R ^a9 (wherein A represents O, CHR ^a10 , CHOR ^a10 , CR ^a10 R ^a10 , or NR ^a11 , R ^a9 and R ^a10 each independently represent a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorine-containing alkyl group, a chlorine-containing alkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenylethyl group, or an acetyl group, and R ^a11 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. For example, trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl trifluoroacetate, dimethylsilyl trifluoroacetate, monomethylsilyl trifluoroacetate, trimethylsilyl trichloroacetate, trimethylsilyl propionate, trimethylsilyl butyrate, etc.), -O-C(R ^a12 )=N(R ^a13 ) (wherein R ^a12 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group, and R ^a13 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group), -O-C(R ^a14 )=CH-C(=O)R ^a15 (wherein R ^a14 and R ^a15 each independently represents a hydrogen atom or an organic group. For example, trimethylsilyloxy-3-penten-2-one, 2-trimethylsiloxypent-2-en-4-one, etc.), -OR ^a16 (wherein R ^a16 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a fluorine-containing alkyl group. For example, CH ₃ Si(OCH ₃ ) ₃ , C ₂ H ₅ Si(OCH ₃ ) ₃ , C ₃ H ₇ Si(OCH ₃ ) ₃ , C ₄ H ₉ Si(OCH ₃ ) ₃ , C ₅ H ₁₁ Si(OCH ₃ ) ₃ , C ₆ H ₁₃ Si(OCH ₃ ) ₃ , C ₇ H ₁₅ Si(OCH ₃ ) ₃ , C ₈ H ₁₇ Si(OCH ₃ ) _{3 , C9H21Si} ( _{OCH3 ) 3 ,} C10H21Si _{( OCH3} ) _{3 , C11H23Si} ( _OCH3 ) ₃ , _C12H25Si ( _{OCH3 ) 3} , _C13H27Si (OCH ₃ ) _{3 ,} C14H29Si( _{OCH3 ) 3} , C15H31Si _{(OCH3)3 , C16H33Si ( OCH3 ) 3} , _{C17H35Si ( OCH3 ) 3 , C18H37} Si( _OCH3 ) ₃ , ( _CH3 ) _2Si ( _OCH3 ) ₂ , _{C2H5Si(CH3)(OCH3 ) 2 , (C2H5)2Si(OCH3)2 , C3H7Si ( CH3 ) ( OCH3 ) 2 , ( C3H7} ) _2Si ( _OCH3 ) ₂ , _{C4 H9Si} ( _CH3 )(OCH3) _{2 , ( C4H9 ) 2Si} ( _OCH3 ) _{2 , C5H11Si ( CH3} )( _OCH3 ) ₂ , _C6H13Si (CH3)( _OCH3 ) ₂ , _{C7H 15} Si( _CH3 )( _{OCH3 ) 2} , _{C8H17 Si} ( _{CH3 )} ( _OCH3 ) _{2 , C9H19Si ( CH3} )( _OCH3 ) ₂ , C10H21Si( _CH3 )( _OCH3 ) _{2, C11H23Si(CH3)(OCH3 ) 2 , C 12H25Si} ( _CH3 )( _OCH3 ) _{2 ,} C13H27Si _{( CH3} )( _OCH3 ) ₂ , _{C14H29Si ( CH3} )( _{OCH3 ) 2} , _{C15H31Si ( CH3} )( _OCH3 ) ₂ , C ₁₆ H ₃₃ Si(CH ₃ )(OCH ₃ ) ₂ , C _{17 H35Si} ( _{CH3 )} ( _OCH3 ) _{2 , C18H37Si (CH3)(OCH3)2 , ( CH3 ) 3SiOCH3 , C2H5Si} ( _CH3 )2OCH3 _{, ( C2H5} ) ₂ Si( _CH3 ) _OCH3 , _{( C2H5} ) _{3SiOCH3 , C3H7Si ( CH3 )} 2OCH3 _{, ( C3H7} ) _2Si ( _CH3 ) _OCH3 , ( _{C3H7 ) 3SiOCH3 ,} C _{4H9Si ( CH3 ) 2OCH3 ,} ( _C4H9 ) _{3 SiOCH3 , C5H11Si ( CH3} ) _{2OCH3 , C6H13Si ( CH3 ) 2OCH3} , _{C7H15Si ( CH3} ) _{2OCH3 , C8H17Si} ( _CH3 ) _{2 OCH3 , C9H19Si (} CH3) _{2OCH3 , C10H21Si ( CH3} ) _{2OCH3 , C11H23Si ( CH3 ) 2OCH3 , C12H25Si} ( _CH3 ) _{2 OCH3} , _{C13H27Si ( CH3 ) 2OCH3 , C14H29 Si} ( _{CH3 ) 2OCH3 , C15H31Si (} CH3) _{2OCH3 , C16H33Si ( CH3} ) _{2OCH3 , C17H35Si ( CH3 ) 2OCH3 , C18H37} Si( _{CH3 )2OCH3, (CH3)2Si(H)OCH3 , CH3Si ( H ) 2OCH3 , ( C2H5 ) 2Si ( H} ) _OCH3 , _C2H5Si (H) _2OCH3 , _C2H5 Si( _CH3 )( _H ) _OCH3 , ( _C3H7 ) _2Si (H)OCH _{Alkylmethoxysilane} such as ₃ , or _{CF3CH2CH2Si ( OCH3} ) _{3 , C2F5CH2CH2Si ( OCH3 ) 3 , C3F7CH2CH2Si ( OCH3 ) 3 , C4F9CH 2 CH2Si ( OCH3} ) _{3 , C5F11CH2CH2Si ( OCH3 ) 3 , C6F13CH2CH2Si ( OCH3 ) 3 , C7F15CH2CH2Si ( OCH3} ) _{3 , C8F17CH2CH2Si ( OCH3 ) 3 , CF3CH2CH 2} Si( _{CH3 )} ( _OCH3 ) _{2, C2F5CH2CH2Si ( CH3 )} ( _OCH3 ) _{2 , C3F7CH2CH2Si ( CH3 )} ( _{OCH3 ) 2 , C4F9CH2CH 2} Si( _{CH3 )} ( _OCH3 ) _{2 , C5F11CH2CH2Si ( CH3} )( _OCH3 ) _{2 , C6F13CH2CH2Si} ( _{CH3 ) ( OCH3 ) 2 , C7F15CH2 CH2Si} ( _{CH3 ) ( OCH3 ) 2} , _{C8F17CH2CH2 Si} ( _CH3 )( _{OCH3 ) 2 , CF3CH2CH2Si ( CH3} ) _{2OCH3 , C2F5CH2CH2Si ( CH3 ) 2OCH3 , C3F7CH2CH2Si ( CH 3 ) 2OCH3 , C4F9CH2CH2Si ( CH3 ) 2OCH3 , C5F11CH2CH2Si ( CH3 ) 2OCH3 , C6F13CH2CH2Si ( CH3 ) ​ ​ 2} OCH ₃ , C ₇ F ₁₅ CH ₂ CH ₂ Si(CH ₃ ) ₂ OCH ₃ , C ₈ F
Fluoroalkylmethoxysilanes such as _17CH2CH2Si ( _CH3 ) _{2OCH3 and CF3CH2CH2Si} ( _{CH3 )} (H) _OCH3 , or compounds in which the methyl group portion of the methoxy group of the above methoxysilanes is replaced with a monovalent hydrocarbon group having 2 to ₁₈ carbon atoms _in which _some or all of the hydrogen atoms may be replaced with fluorine atoms. ), -O-S(=O) ₂ -R ^a17 (wherein R ^a17 is an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group, a phenyl group, a tolyl group, or an -O-Si(CH ₃ ) ₃ group. For example, trimethylsilyl sulfonate, trimethylsilyl benzene sulfonate, trimethylsilyl toluene sulfonate, trimethylsilyl trifluoromethane sulfonate, trimethylsilyl perfluorobutane sulfonate, bistrimethylsilyl sulfate, etc.), or one replaced with -O-P(-O-Si(CH ₃ ) ₃ ) ₂ (for example, tristrimethylsilyl phosphite, etc.).

Furthermore, specific examples of the silylating agent in which X in the above general formula [1] is a monovalent group in which the atom bonded to the Si atom is oxygen, other than those mentioned above, include hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1, 3-bis(trifluoropropyl)tetramethyldisiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, hexaethyldisiloxane, hexavinyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, vinylpentamethyldisiloxane, 1,3-bis (3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane, 1,1,1-triethyl-3,3,3-trimethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane, 1,1,3,3-tetraphenyldimethyldisiloxane, pentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, 1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane, n-butyl-1,1 ,3,3-tetramethyldisiloxane, 1,3-di-t-butyldisiloxane, vinyl-1,1,3,3,-tetramethyldisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 3,3-diphenyltetramethyltrisiloxane, 3-phenylheptamethyltrisiloxane, hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane, 3-ethylheptamethyltrisiloxane, 3-(3,3,3-trifluoropropane Pyr) heptamethyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane, hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane, 1,3,5-trivinyl-1,1,3,5,5-pentamethyl trisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 3-octylheptamethyltrisiloxane, 1,3,5-triphenyltrimethylcyclotrisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane, furfuryloxytrisiloxane, tetrakis(dimethylsiloxy)silane Ran, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, diphenylsiloxane-dimethylsiloxane copolymer, 1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylcyclohexasiloxane Also included are siloxane compounds such as poly(3,3,3-trifluoropropylmethylsiloxane), polydimethylsiloxane terminated with trimethylsiloxy, and 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane.

Examples of silylating agents in which X in the above general formula [1] is a monovalent group in which the atom bonded to the Si ^atom is carbon include those in which the amino group ( _-NH2 group) of the above aminosilane is replaced with -C(S(=O) _2R7 ) ₃ (wherein ^R7 is each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced with fluorine atoms, and fluorine atoms; for example, (trimethylsilyl)tris(trifluoromethanesulfonyl)methide, etc.).

In addition, examples of the silylating agent in which X in the above general formula [1] is a monovalent group in which the atom bonded to the Si atom is a halogen include those in which the amino group (—NH ₂ group) of the above aminosilane is replaced with a chloro group, a bromo group, or an iodo group (e.g., chlorotrimethylsilane, bromotrimethylsilane, etc.).

The above general formula [1] is preferably a silicon compound having a trialkylsilyl group. ^R1 is preferably a methyl group. b is preferably 0. X is more preferably a monovalent group in which the atom bonded to the Si atom is nitrogen or oxygen, and more preferably the atom bonded to the Si atom is nitrogen.

As a silylating agent in which the atom bonded to the Si atom of X in the above general formula [1] is nitrogen, it is more preferable to use a silazane compound. Examples of silazane compounds include non-cyclic disilazane compounds such as hexamethyldisilazane, heptamethyldisilazane, tetramethyldisilazane, diethyltetramethyldisilazane, dipropyltetramethyldisilazane, dibutyltetramethyldisilazane, dihexyltetramethyldisilazane, dioctyltetramethyldisilazane, and didecyltetramethyldisilazane; cyclic disilazane compounds such as 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disila-1-azacyclohexane; cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; and cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane.

Moreover, specific examples of suitable silylating agents include one or more selected from the group consisting of hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylimidazole, trimethylsilyltriazole, bistrimethylsilyl sulfate, 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, and 2,2,4,4,6,6-hexamethylcyclotrisilazane.

The content of the silylating agent in 100% by mass of the film-forming composition is not particularly limited as long as the desired water repellency can be imparted to the substrate.
The lower limit of the content of the silylation agent may be, for example, 0.1 mass % or more, preferably 0.2 mass % or more, more preferably 0.3 mass % or more, and further preferably 0.5 mass % or more. This makes it easier to improve the water repellency of the substrate.
On the other hand, the upper limit of the content of the silylation agent may be, for example, 35% by mass or less, preferably 33% by mass or less, and more preferably 30% by mass or less. By setting it within the above range, water repellency can be imparted more efficiently with respect to the content of the silylation agent.

When two or more kinds of the silylating agents are used, the total content of the silylating agents should be within the above range. When a silylamide compound or an aminosilane compound described later is used in combination, it is preferable that the total content of the silylating agent, the silylamide compound, and the aminosilane compound is within the above range.
In addition, when two or more kinds are used, it is preferable to use the highest content of any one of hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylimidazole, trimethylsilyltriazole, bistrimethylsilyl sulfate, 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, and 2,2,4,4,6,6-hexamethylcyclotrisilazane among the silylating agents contained in the film-forming composition, since this tends to improve water repellency.

((II) Silyl ester compounds)
The silyl ester compound is a chlorine-containing accelerator that acts as an accelerator in the chemical solution of the film-forming composition. The silyl ester compound includes one or more compounds represented by the following general formula [2]:
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms;
i is an integer of 1 to 3; h is an integer of 1 to 3; and i+h is an integer of 2 to 4.

In the monovalent hydrocarbon group of ^R2 in the general formula [2], the carbon number is 1 to 5, preferably 1 to 3, and more preferably 1 to 2. This enhances water repellency. ^R2 also includes the case where all hydrogen atoms are replaced by chlorine atoms, and the case where all hydrogen atoms are replaced by atoms other than hydrogen atoms is also described as a hydrocarbon group.
In the monovalent hydrocarbon group of ^R2 in the general formula [2], it is preferable that at least one hydrogen atom bonded to the carbon atom closest to the "C(=O)O" skeleton is substituted with a chlorine atom, thereby improving the catalytic performance of the silyl ester compound.
In addition, in the general formula [2], when R ² is a hydrocarbon group having two or more carbon atoms, it is more preferable that at least one hydrogen atom of each hydrocarbon group is substituted with a chlorine atom.

R ² in the general formula [2] may be a group represented by -C _q Y _(2q+1-r) Cl _r (wherein each Y is independently a hydrogen atom or a fluorine atom bonded to carbon, Cl is a chlorine atom, q is an integer of 1 to 5, and r is 1 to 2q).
In addition, it is preferable that the total number of chlorine atoms and fluorine atoms bonded to the carbon atoms contained in ^R2 is greater than the total number of hydrogen atoms, since this makes it easier to improve the water repellency of the film forming composition.
More preferably, the atoms bonded to the carbon contained in ^R2 may be only fluorine atoms and chlorine atoms (however, ^R2 does not include _-CF3 and _-CF2- ), or the atoms bonded to the carbon contained in ^R2 may be only hydrogen atoms and chlorine atoms (however, the total number of chlorine atoms is greater than the total number of hydrogen atoms).

From the viewpoint of obtaining good water repellency, the above-mentioned R ² may be, -CHClF, -CClF ₂ , -CHCl ₂ , -CCl ₂ F, -CHClCH ₃ , -CCl ₂ CH ₃ , -CH ₂ CHCl ₂ , -CHClCH ₂ Cl, -CHClCCl ₃ , -CCl ₂ CHCl ₂ , -CCl ₂ CCl ₃ , -CClFCF ₃ , -CF ₂ CClF ₂ , CCl ₂ CF ₃ , -CClFCCl ₂ F, -CF ₂ CCl ₃ , -CClFCCl ₃ , -CCl ₂ CCl ₂ F, -CClFCH ₃ , -CCl ₂ CH ₂ F, -CHFCHCl ₂ , -CClFCH ₂ Cl, -CClCHClF, -CCl ₂ It is preferable to use CHClF, -CF ₂ CH ₂ Cl, -CHClCF ₃ , -CClFCHF ₂ , -CF ₂ CHClF, -CHFCClF _2, etc., and -CHClF, -CClF ₂ , -CHCl ₂ , -CCl ₂ F, -CHClCH ₃ , _-CCl2CH3 , _{-CH2CHCl2 , -CHClCH2Cl , -CHClCCl3 , -CCl2CHCl2 , -CCl2CCl3} , _-CClFCCl2F , _-CClFCCl3 , _{-CCl2CCl 2} F, -CClFCH ₃ , -CCl ₂ CH ₂ F, -CHFCHCl ₂ , -CClFCH ₂ Cl, -CHClCHClF, -CCl ₂ It is more preferable to use CHClF, --CClFCHF ₂ , --CHFCClF _{2 ,} etc.

^R3 in the general formula [2] may contain not only hydrogen, carbon, nitrogen, oxygen, a fluorine atom, or a chlorine atom, but also silicon, sulfur, a halogen atom (other than fluorine), etc. Furthermore, ^R3 in the general formula [2] may contain an unsaturated bond, an aromatic ring, or a cyclic structure.

R ³ in the above general formula [2] is independently at least one group selected from C _ee H _2ee+1 (ee=1 to 18) and C _ff F _2ff+1 CH ₂ CH ₂ (ff=1 to 8).

Specific examples of silyl ester compounds include trimethylsilyl chloroacetate, trimethylsilyl dichloroacetate, trimethylsilyl chlorodifluoroacetate, trimethylsilyl dichlorofluoroacetate, trimethylsilyl chlorofluoroacetate, dimethylsilyl chloroacetate, dimethylsilyl dichloroacetate, dimethylsilyl chlorodifluoroacetate, butyldimethylsilyl chloroacetate, trimethylsilyl-2-chloropropionate, trimethylsilyl-3-chloropropionate, trimethylsilyl-2,2-dichloropropionate, trimethylsilyl-2,3-dichloropropionate, triethylsilyl-2-chloropropionate, trimethylsilyl trichloroacetate, etc. These may be used alone or in combination of two or more. Of the above, trimethylsilyl dichloroacetate, trimethylsilyl chlorodifluoroacetate, trimethylsilyl dichlorofluoroacetate, trimethylsilyl-2,2-dichloropropionate, and trimethylsilyl-2,3-dichloropropionate are more preferred.

The content of the silyl ester compound in 100% by mass of the film-forming composition is not particularly limited as long as it can impart the desired water repellency to the substrate.
The lower limit of the content of the silyl ester compound is, for example, 0.01 mass % or more, preferably 0.05 mass % or more, and more preferably 0.2 mass % or more.
On the other hand, the upper limit of the content of the silyl ester compound is, for example, 10 mass % or less, preferably 5 mass % or less, and more preferably 3 mass % or less.
By setting the content within the above range, the water repellency of the substrate can be easily improved, which is preferable.

In addition, when the content of the silylating agent in 100 mass% of the film-forming composition is _CSi and the content of the silyl ester compound Ces is _Ces , the lower limit of _CSi / _Ces is, for example, 1.0 or more, preferably 5.0 or more, and more preferably 10 or more. This makes it possible to impart water repellency with a shorter treatment time.
On the other hand, the upper limit of C _Si /C _es is not particularly limited as long as the desired water repellency is obtained, but it may be, for example, 40 or less, and is preferably 30 or less.

When two or more kinds of silyl ester compounds are used, the total amount of the silyl ester compounds contained in the film-forming composition is the amount of the silyl ester compounds. When two or more kinds of silyl ester compounds are used, it is preferable that the silyl ester compound with the highest amount is trimethylsilyl chloroacetate, trimethylsilyl dichloroacetate, trimethylsilyl chlorodifluoroacetate, trimethylsilyl dichlorofluoroacetate, trimethylsilyl chlorofluoroacetate, dimethylsilyl chloroacetate, dimethylsilyl dichloroacetate, dimethylsilyl chlorodifluoroacetate, butyldimethylsilyl chloroacetate, trimethylsilyl-2-chloropropionate, trimethylsilyl-3-chloropropionate, trimethylsilyl-2,3-dichloropropionate, triethylsilyl-2-chloropropionate, or trimethylsilyl trichloroacetate. Among the above, trimethylsilyl dichloroacetate, trimethylsilyl chlorodifluoroacetate, trimethylsilyl dichlorofluoroacetate, trimethylsilyl-2,2-dichloropropionate, and trimethylsilyl-2,3-dichloropropionate are more preferred.

(III) Aprotic Solvents
The aprotic solvent refers to a solvent that does not contain a group in which a hydrogen atom is bonded to an oxygen atom or a nitrogen atom, such as a hydroxyl group or an amino group, but the aprotic solvent is not particularly limited as long as it dissolves the silylating agent and the silyl ester compound.

An example of the aprotic solvent may include one or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen atom-containing solvents, sulfoxide-based solvents, carbonate-based solvents, polyhydric alcohol derivatives having no OH group, nitrogen atom-containing solvents having no N—H group, and silicone solvents.
Among these, among hydrocarbons, esters, ethers, halogen atom-containing solvents, sulfoxide solvents, and polyhydric alcohol derivatives, those having no OH group are preferred.

Examples of the above-mentioned hydrocarbons include linear, branched, or cyclic hydrocarbon solvents, aromatic hydrocarbon solvents, terpene solvents, etc., such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-icosane, and branched hydrocarbons corresponding to the carbon numbers thereof (e.g., isododecane, isocetane, etc.), cyclohexane, These include methylcyclohexane, decalin, benzene, toluene, xylene, (ortho-, meta-, or para-)diethylbenzene, 1,3,5-trimethylbenzene, butylbenzene, naphthalene, p-menthane, o-menthane, m-menthane, diphenylmenthane, limonene, α-terpinene, β-terpinene, γ-terpinene, bornane, norbornane, pinane, α-pinene, β-pinene, carane, longifolene, and abietane.

Examples of the above esters include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl ethoxyacetate.

Furthermore, cyclic esters such as lactone compounds may be used as the esters. Examples of lactone compounds include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, and ε-hexanolactone.

Examples of the above ethers include di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-amyl ether, di-n-amyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, as well as ethers with branched hydrocarbon groups such as diisopropyl ether and diisoamyl ether that correspond to the carbon numbers of these ethers, dimethyl ether, diethyl ether, methyl ethyl ether, methyl cyclopentyl ether, diphenyl ether, tetrahydrofuran, and dioxane.

Examples of the above ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

Examples of the above halogen atom-containing solvents include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, hydrofluorocarbons such as 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, and Zeorola H (manufactured by Zeon Corporation), methyl perfluoropropyl ether, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, methyl perfluorohexyl ether, ethyl perfluorohexyl ether, and Asahiklin AE-3. These include hydrofluoroethers such as 000 (manufactured by AGC Corporation), Novec HFE-7100, Novec HFE-7200, Novec 7300, and Novec 7600 (all manufactured by 3M Japan Ltd.), chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, hydrochlorofluorocarbons such as 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, and 1,2-dichloro-3,3,3-trifluoropropene, perfluoroethers, and perfluoropolyethers.

An example of the above sulfoxide solvent is dimethyl sulfoxide.

Examples of the above carbonate solvents include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

Examples of derivatives of the above polyhydric alcohols that do not have an OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene ethylene 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, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol diacetate acetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methylpropyl 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 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, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerin triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.

Examples of non-cyclic nitrogen atom-containing solvents that do not have the above N-H group include N,N-dimethylacetamide and triethylamine.

Examples of the above silicone solvents include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

From the standpoint of cost and solubility, polyhydric alcohol derivatives (which do not have an OH group in the molecule) are preferred, such as diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, ethylene glycol dimethyl ether, 3-methoxy-3-methyl-1-butyl acetate, propylene glycol At least one selected from the group consisting of propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol 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, and dipropylene glycol diacetate is preferred. Also preferred are propylene carbonate, linear or branched hydrocarbon solvents having 6 to 12 carbon atoms, p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, pinane, and the like.

Among the above aprotic solvents, those having polarity (hereinafter, sometimes referred to as aprotic polar solvents) may be used. Examples of the aprotic polar solvent include non-cyclic nitrogen atom-containing solvents such as N,N-dimethylacetamide, lactone compounds such as γ-butyrolactone, and sulfoxide solvents such as dimethyl sulfoxide.

The solvent contained in the film-forming composition is preferably substantially only an aprotic solvent. In addition, multiple aprotic solvents may be used. Specifically, when the total solvent contained in the film-forming composition is taken as 100 mass%, it is preferable that 90 mass% or more is an aprotic solvent, more preferably 95 mass% or more, even more preferably 98 mass% or more, and even more preferably 99.5 mass% or more. Note that the above "aprotic solvent" also includes aprotic polar solvents, and when there are two or more types of solvents, the total amount of the solvents is the aprotic solvent content.

It is desirable that the film-forming composition is substantially free of water. Moreover, a film-forming composition that is substantially free of water is more preferable, which is obtained by not adding water during preparation of the film-forming composition, or by using raw materials for each component that contain no water or have a low water content. For example, the water content in the film-forming composition may be 0.3 mass % or less, preferably 0.1 mass % or less. It may also be less than the measurement limit of the Karl Fischer titration method, for example, less than 10 mass ppm. By preparing such a film-forming composition, it is possible to suppress the deactivation of the silylation agent.

The film-forming composition may further contain one or more selected from the group consisting of a silylamide compound represented by the following general formula [5] and an aminosilane compound represented by the following general formula [6]. By using it in combination with the above-mentioned (I) silylating agent, it becomes easier to suppress the composition fluctuation of the composition, and also to impart water repellency with good reproducibility. The following general formula [5] and the following general formula [6] are included in the above-mentioned general formula [1] of the (I) silylating agent, and both can be used as the (I) silylating agent when used alone. The compound of the following general formula [6] may be generated by the contact of the film-forming composition of the present disclosure with a protic substance such as water. For example, it may be generated by moisture in the air when the film-forming composition is prepared under the air.
The following describes the case where it is used in combination with the silylating agent (I). Specifically, the general formula [5] having a content less than the content of the compound used as the silylating agent (I) contained in the film-forming composition is the "silylamide compound used in combination", and the general formula [6] having a content less than the content of the compound used as the silylating agent (I) contained in the film-forming composition is the "aminosilane compound used in combination". In addition, the film-forming composition corresponding to the general formula [6] having a content less than the content of the compound used as the silylating agent (I) contained in the film-forming composition as the "aminosilane compound used in combination" is preferable because it is easy to impart excellent water repellency to the substrate surface.

(R ^b2 -C(=O)N(H)) _j -Si(H) _4-j-t (R ^b3 ) _t [5]

In the above general formula [5],
R ^b2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms,
R ^b3 each independently represents an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
j is an integer of 1 to 3; t is an integer of 1 to 3; and j+t is an integer of 2 to 4.

(R ^b4 ) _u Si(H) _v (NH ₂ ) _4-uv [6]

In the above general formula [6],
R ^b4 each independently represents an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
u is an integer of 1 to 3; v is an integer of 0 to 2; the sum of u and v is 1 to 3.

R ^b2 in the above general formula [5] is the same as R ² in the above general formula [2], and details are the same as those for R ² , so a detailed explanation will be omitted below. R ^b3 in the general formula [5] is the same as R ³ in the above general formula [2], and details are the same as those for R ³ , so a detailed explanation will be omitted below.
R ^b4 in the above general formula [6] is the same as R ¹ in the above general formula [1], and details are similar to those of R ¹ , so that the following description will be omitted.

　Examples of the silylamide compounds represented by the general formula [5] include N-(trimethylsilyl)chloroacetamide, N-(trimethylsilyl)dichloroacetamide, N-(trimethylsilyl)-2-chloropropionamide, N-(trimethylsilyl)-3-chloropropionamide, N-(trimethylsilyl)-2,3-dichloropropionamide, N-(trimethylsilyl)-2,2-dichloropropionamide, and N-(trimethylsilyl)-2,2,3-trichloropropionamide. , N-(trimethylsilyl)-2,3,3,3-tetrachloropropionamide, N-(trimethylsilyl)-2,2,3,3,3-pentachloropropionamide, N-(trimethylsilyl)chlorodifluoroacetamide, N-(trimethylsilyl)dichlorofluoroacetamide, N-(trimethylsilyl)chlorofluoroacetamide, N-(trimethylsilyl)-3-chloro-2,2-difluoropropionamide, N-(trimethylsilyl)-3-chloro-2,2,3,3-tetrachloropropionamide, Fluoropropionamide, N-(trimethylsilyl)-2-chloro-2,3,3,3-tetrafluoropropionamide, N-(trimethylsilyl)-2,3-dichloro-2,3-difluoropropionamide, N-(trimethylsilyl)-3,3-dichloro-2,2-difluoropropionamide, N-(trimethylsilyl)-2,2-dichloro-3,3,3-trifluoropropionamide, N-(trimethylsilyl)-2,3-dichloro-2,3,3-trifluoropropionamide, Examples include N-(trimethylsilyl)-2,2,3-trichloro-3,3-difluoropropionamide, N-(trimethylsilyl)-2,3,3-trichloro-2,3-difluoropropionamide, N-(trimethylsilyl)-3,3,3-trichloro-2,2-difluoropropionamide, N-(trimethylsilyl)-2,3,3,3-tetrachloro-2-fluoropropionamide, and N-(trimethylsilyl)-2,2,3,3-tetrachloro-3-fluoropropionamide.

Specific examples of the aminosilane compound represented by the general formula [6] include _CH3Si ( _NH2 ) ₃ , _C2H5Si ( _NH2 ) ₃ , _C3H7Si (NH2) ₃ , C4H9Si( _NH2 ) ₃ , C5H11Si ₍ NH2) ₃ , _C6H13Si ( _NH2 ) _{3 ,} C7H15Si(NH2) _{3 , C8H17Si ( NH2 ) 3 , C9H19Si} ( _NH2 ) _{3 , C10H21Si ( NH2 ) 3 , C11H23Si ( NH2 ) 3} , _{and C12H15Si} ( _NH2 ) _{3 . H25Si} ( _NH2 ) ₃ , C13H27Si ₍ NH2) _{3 , C14H29Si} ( _NH2 ) _{3 , C15H31Si ( NH2 ) 3 , C16H33Si} ( _NH2 ) ₃ , _{C17H 35} Si( _NH2 ) _{3 , C18H37Si} (NH2) ₃ , ( _CH3 ) _2Si ( _NH2 ) _{2 , C2H5Si ( CH3} )( _{NH2 ) 2} , ( _C2H5 ) _2Si ( _NH2 ) ₂ , C _3H7Si ( _{CH3 )} ( _NH2 ) ₂ , ( _C3H7 ) _2Si ( _NH2 ) ₂ , _{C4H9Si ( CH3} )( _NH2 ) ₂ , ( _{C4H9 ) 2Si} ( _NH2 ) _{2 , C5H11Si ( CH3} )( _NH2 ) ₂ , _{C6H 13} Si( _CH3 )( _NH2 ) _{2 , C7H15Si (} CH3)( _NH2 ) ₂ , _C8H17Si ( _CH3 )( _{NH2 ) 2 , C9H19Si} ( _CH3 )( _NH2 ) ₂ , _{C10H 21} Si( _CH3 )( _NH2 ) ₂ , _{C11 H23Si} ( _CH3 )( _NH2 ) ₂ , _{C12H25Si ( CH3} )(NH2) _{2 , C13H27Si ( CH3} )( _{NH2 ) 2} , _C14H29Si ( _CH3 )( _NH2 ) ₂ , C _{15 H31} Si( _CH3 )( _NH2 ) ₂ , _{C16H33Si ( CH3} ) _(NH2 ) _{2 , C17H35Si ( CH3} )( _NH2 ) _{2 ,} C18H37Si( _CH3 )( _NH2 ) ₂ , _{( CH3} ) _{3SiNH2 , C2H5} Si( _CH3 ) _2NH2 , _{( C2H5 ) 2Si} ( _CH3 ) _{NH2 , ( C2H5} ) _{3SiNH2 , C3H7Si ( CH3} ) _{2NH2, (C3H7 ) 2Si ( CH3} ) _NH2 , ( _C3H7 ) _{3SiNH2 , C4H9Si ( CH3 ) 2NH2} , _{( C4H9 ) 3SiNH2 , C5H11Si ( CH3} ) _{2NH2 , C6H13Si (} CH ₃ ) _{2NH2 , C7H15Si ( CH3} ) _{2 NH2} , _{C8H17Si (} CH3) _{2NH2 , C9H19Si ( CH3 ) 2NH2 , C10H21Si ( CH3 ) 2NH2 , C11H23Si ( CH3} ) _2NH2 , _{C12H25Si (} CH3) _{2NH2 , C13H27Si ( CH3} ) _{2NH2 , C14H29Si ( CH3 ) 2NH2 , C15H31Si ( CH3 ) 2NH2 , C16 H33Si} ( _CH3 ) _{2NH2 , C17H 35} Si( _CH3 ) _{2NH2 , C18H37Si} ( _CH3 ) _2NH2 , _{(CH3)2Si ( H ) NH2} , _CH3Si (H) _{2NH2 ,} ( _C2H5 ) _2Si ( _H ) _NH2 , _{C2 H5Si} (H) _{2NH2 , C2H5Si(CH3} )( _{H ) NH2} , ( _C3H7 ) _2Si ( _H ) _{NH2 , C3H7Si ( H ) 2NH2 , CF3CH2CH2Si} ( _NH2 ) _{3 , C2F5CH2CH2Si ( NH2 ) 3 , C3F7CH2CH2Si ( NH2 ) 3 , C4F9CH2CH2Si ( NH2 ) 3 , C5F11CH2CH2Si ( NH2 ) 3 , C6F13CH2CH2 ​ ​ Si} ( _NH2 ) ₃ , _{C7F15CH2CH2Si ( NH2} ) _{3 , C8F17CH2CH2Si ( NH2} ) _{3 , CF3CH2CH2Si ( CH3 )} ( _{NH2 ) 2} , _{C2F 5 CH2CH2Si ( CH3 )} ( _NH2 ) ₂ , _{C3F7 CH2CH2Si} ( _CH3 )( _{NH2 ) 2 , C4F9CH2CH2Si ( CH3 )} ( _{NH2 ) 2 , C5F11CH2CH2Si ( CH3 )} ( _NH2 ) ₂ , _{C6F13 CH2CH2Si ( CH3} )( _NH2 ) _{2 , C7F15CH2CH2Si ( CH3 )} ( _{NH2 ) 2 , C8F17CH2CH2Si ( CH3 )} ( _NH2 ) ₂ , _{CF3CH2 CH2Si ( CH3 ) 2NH2 , C2F5CH2CH2 ​ Si ( CH3 ) 2NH2 , C3F7CH2CH2Si ( CH3 ) 2NH2 , C4F9CH2CH2Si ( CH3 ) 2NH2 , C5F11CH2CH2Si ( CH3 ​ ) 2NH2 , C6F13CH2CH2Si ( CH3 ) 2NH2 , C7F15CH2CH2Si ( CH3 ) 2NH2 , C8F17CH2CH2Si ( CH3 ) 2NH ​ ​ 2} , _CF3CH2CH2Si ( _{CH3 )} (H) _{NH2, and} the like.

The content of the above-mentioned silylamide compound and aminosilane compound used in combination with the silylating agent (I) is not particularly limited as long as it is within a range that does not impair the performance of the film-forming composition. For example, the content of the silylamide compound and aminosilane compound used in combination with the silylating agent (I) may be 10 mass% or less, respectively, in 100 mass% of the film-forming composition. The lower limit is not particularly limited, but may be, for example, 0.01 mass% or more.

According to experiments conducted by the present inventors, it has been confirmed that the film-forming composition may become cloudy.
Further investigation revealed that one of the causes of the cloudiness is the presence of some amide compounds (especially amide compounds having a hydrocarbon group with a _Cl3C moiety, a _Cl2HC moiety, or a _Cl2FC moiety) in an insoluble state in the film-forming composition.

When the film-forming composition contains the above-mentioned silylamide compound, some of the above-mentioned amide compounds (especially amide compounds having a hydrocarbon group with a _Cl3C moiety, a _Cl2HC moiety, or a _Cl2FC moiety) which are presumed to be decomposition products from the above-mentioned silylamide compound may also be contained in the composition.

Here, some of the above amide compounds (particularly, amide compounds having a hydrocarbon group with a Cl ₃ C moiety, a Cl ₂ HC moiety, or a Cl ₂ FC moiety) are defined by an amide compound represented by the following general formula [4].
R ^b1 -C(=O)N(H)Z [4]
In the above general formula [4],
R ^b1 is a hydrocarbon group having a Cl ₃ C moiety, a Cl ₂ HC moiety, or a Cl ₂ FC moiety;
Z is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms bonded to a nitrogen atom.

The film-forming composition may contain one or more of the amide compounds represented by the general formula [4]. From the viewpoint of suppressing the clouding of the film-forming composition, however, it is preferable that the content of the amide compound represented by the general formula [4] in the film-forming composition is as small as possible.
Examples of the amide compound represented by the general formula [4] include 2,2-dichloroacetamide, 2,2,2-trichloroacetamide, 2,3,3,3-tetrachloropropionamide, 2,2,3,3,3-pentachloropropionamide, 2,2-dichloro-2-fluoroacetamide, 3,3-dichloro-2,2-difluoropropionamide, 2,3,3-trichloro-2,3-difluoropropionamide, 3,3,3-trichloro-2,2-difluoropropionamide, 2,3,3,3-tetrachloro-2-fluoropropionamide, and 2,2,3,3-tetrachloro-3-fluoropropionamide.

　As a result of thorough investigation based on these findings, it was found that the clouding of the film-forming composition can be suppressed by the following methods (i) to (iv). Each method may be used alone, or any two or more of them may be used in combination.

(i) The film-forming composition does not contain the amide compound represented by the above general formula [4].
An example of a process for producing a film-forming composition described below includes a reaction step (I) of reacting a silylating agent with a chlorocarboxylic acid compound to obtain a silyl ester compound (II).
(ia) In the above reaction step, it is preferable to use a chlorocarboxylic acid as the chlorocarboxylic acid compound, without using a chlorocarboxylic anhydride. By not using a chlorocarboxylic anhydride, a silylamide compound is not generated, and the amide compound represented by the above general formula [4], which is presumed to be a decomposition product of the silylamide compound, is not generated, so that the composition can be prevented from becoming cloudy.
(ib) Furthermore, in the case where a silazane compound is not used as a silylating agent (I), even if a chlorocarboxylic anhydride is used, a silylamide compound is not generated, and the amide compound represented by the above general formula [4], which is presumed to be a decomposition product of the silylamide compound, is not generated, so that the composition can be inhibited from becoming cloudy.
(ic) It is preferable to carry out the above reaction step under an inert atmosphere such as a nitrogen atmosphere. This can suppress the generation of the amide compound represented by the above general formula [4] even when the composition contains a silylamide compound. Therefore, it is possible to suppress the composition from becoming cloudy.
In this specification, not containing a component includes the component being below the detection limit.

(ii) The film-forming composition contains an aprotic solvent having a relatively high solubility for the amide compound represented by the general formula [4].
The (III) aprotic solvent in the film-forming composition preferably contains the above aprotic polar solvent.
In addition, all of the aprotic solvents contained in the film-forming composition may be the above-mentioned aprotic polar solvents, but the aprotic polar solvent may coexist with other solvents. In this case, when the solvent contained in the film-forming composition is taken as 100% by mass, the aprotic polar solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. In addition, the solvent to be coexisted with the aprotic polar solvent is not particularly limited as long as it is an aprotic solvent that is compatible with the aprotic polar solvent. For example, it is preferable to use a derivative of a polyhydric alcohol (but one that does not have an OH group in the molecule) as described above, because it is inexpensive.

(iii) The film-forming composition contains an amide compound having a structure with high solvent solubility in place of at least a part or all of the amide compound represented by the general formula [4].
In the above general formula [4], it is preferable that the film-forming composition contains an amide compound having a structure in which the R ^b1 is a hydrocarbon group having no Cl ₃ C moiety, Cl ₂ HC moiety, or Cl ₂ FC moiety, instead of the amide compound represented by the above general formula [4]. As described above, by making the R ^b1 in the above general formula [4] a structure in which the R b1 is a hydrocarbon group having no Cl ₃ C moiety, Cl ₂ HC moiety, or Cl ₂ FC moiety, it is possible to increase the solubility in aprotic solvents (III) more than the amide compound represented by the above general formula [4]. This makes it possible to suppress the composition from becoming cloudy.
In this case, the content of the amide compound having the above-mentioned structure with high solvent solubility is, for example, preferably 3.0 mass% or less, more preferably 1.2 mass% or less, and even more preferably 1.0 mass% or less, based on 100 mass% of the film-forming composition.

(iv) The content of the amide compound represented by the above general formula [4] in the film-forming composition is kept low.
The film-forming composition may not contain the amide compound represented by the above general formula [4], or if it does contain the amide compound, the content of the amide compound may be 0.1 mass% or less relative to 100 mass% of the film-forming composition, thereby making it possible to suppress clouding of the composition.

In this specification, turbidity measured using a turbidimeter can be used as an index of the degree of white turbidity.
The turbidity of the film forming composition without white turbidity is preferably 10 or less, more preferably 6 or less, and even more preferably 1.0 or less.

The film-forming composition may contain other components in addition to the components described above, provided that the purpose of the present disclosure is not hindered. Examples of such other components include oxidizing agents such as hydrogen peroxide and ozone, surfactants, and antioxidants such as BHT.

(Method for producing film-forming composition)
A method for producing the film-forming composition of the present embodiment will be described.

One example of a method for producing a film-forming composition includes a step of mixing (I) a silylating agent, (II) a silyl ester compound, and (III) an aprotic solvent.

In one example of the manufacturing method, the film-forming composition is obtained by mixing the above-mentioned components. There are no particular limitations on the order in which different components are added, or on the number of times the same component is added. Each component may be added to a solvent, or a solvent may be added to a mixture of components, or other components may be added to a mixture containing one or more components and a solvent. The temperature and atmosphere during mixing may be appropriately selected so as not to impair the performance of the film-forming composition.

Another example of a method for producing a film-forming composition includes a reaction step in which (I) a silylating agent is reacted with (II') a chlorocarboxylic acid compound containing at least one of a chlorocarboxylic acid and a chlorocarboxylic acid anhydride to obtain (II) a silyl ester compound. This makes it possible to obtain a reaction liquid containing at least (I) the silylating agent and (II) the silyl ester compound.

In another example of the manufacturing method, the reaction step may be carried out in (III) an aprotic solvent. If necessary, the reaction liquid after the reaction step may include a step of adding (I) a silylation agent and/or (III) an aprotic solvent. It is preferable that the water content of (III) an aprotic solvent is adjusted to a predetermined amount or less before mixing with (I) a silylation agent, (II') a chlorocarboxylic acid compound, or (II) a silyl ester compound. The water content is not particularly limited as long as it does not impair the water repellency of the film-forming composition, but may be, for example, 0.3% by mass or less when (III) an aprotic solvent is taken as 100% by mass.

The chlorocarboxylic acid may include one or more compounds represented by the following general formula [7]. In addition, even when the chlorocarboxylic acid or chlorocarboxylic anhydride contains an atom other than a chlorine atom (for example, a fluorine atom), the chlorocarboxylic acid or chlorocarboxylic anhydride is referred to as a chlorocarboxylic acid or chlorocarboxylic anhydride in this specification.
R ^C2 -C(=O)OH [7]
In the above general formula [7],
R ^C2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by chlorine atoms and the other unreplaced hydrogen atoms may be partially or entirely replaced by fluorine atoms.

The chlorocarboxylic anhydride may contain one or more compounds represented by the following general formula [8]:
R ^C2 -C(=O)OC (=O)-R ^C2 [8]
In the above general formula [8],
R ^C2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by chlorine atoms and the other unreplaced hydrogen atoms may be partially or entirely replaced by fluorine atoms.

R ^C2 in the above general formula [7] and general formula [8] is the same as R ² in the above general formula [2], and details are similar to those of R ² , so that a detailed explanation will be omitted below.

Examples of chlorocarboxylic acids include monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, 2,3-dichloropropionic acid, 2,2-dichloropropionic acid, 2,2,3-trichloropropionic acid, 2,3,3,3-tetrachloropropionic acid, 2,2,3,3,3-pentachloropropionic acid, chlorodifluoroacetic acid, dichlorofluoroacetic acid, chlorofluoroacetic acid, 3-chloro-2,2-difluoropropionic acid, 3-chloro-2,2,3,3-tetrafluoropropionic acid, and 2-chloro-2,3,3,3-tetrafluoropropionic acid. pionic acid, 2,3-dichloro-2,3-difluoropropionic acid, 3,3-dichloro-2,2-difluoropropionic acid, 2,2-dichloro-3,3,3-trifluoropropionic acid, 2,3-dichloro-2,3,3-trifluoropropionic acid, 2,2,3-trichloro-3,3-difluoropropionic acid, 2,3,3-trichloro-2,3-difluoropropionic acid, 3,3,3-trichloro-2,2-difluoropropionic acid, 2,3,3,3-tetrachloro-2-fluoropropionic acid, 2,2,3,3-tetrachloro-3-fluoropropionic acid, and the like.
Preferably, dichloroacetic acid, trichloroacetic acid, 2,3-dichloropropionic acid, 2,2-dichloropropionic acid, 2,2,3-trichloropropionic acid, 2,3,3,3-tetrachloropropionic acid, chlorodifluoroacetic acid, dichlorofluoroacetic acid, 3-chloro-2,2-difluoropropionic acid, 2,3-dichloro-2,3-difluoropropionic acid, 3,3-dichloro-2,2-difluoropropionic acid, 2,2-dic 2,3-dichloro-2,3,3-trifluoropropionic acid, 2,2,3-trichloro-3,3-difluoropropionic acid, 2,3,3-trichloro-2,3-difluoropropionic acid, 3,3,3-trichloro-2,2-difluoropropionic acid, 2,3,3,3-tetrachloro-2-fluoropropionic acid, 2,2,3,3-tetrachloro-3-fluoropropionic acid. More preferably, dichloroacetic acid, 2,3-dichloropropionic acid, 2,2-dichloropropionic acid, 2,2,3-trichloropropionic acid, 2,3,3,3-tetrachloropropionic acid, chlorodifluoroacetic acid, dichlorofluoroacetic acid, 3-chloro-2,2-difluoropropionic acid, 2,3-dichloro-2,3-difluoropropionic acid, 3,3-dichloro-2,2-difluoropropionic acid, 2,2-dichloro-3, 3,3-trifluoropropionic acid, 2,3-dichloro-2,3,3-trifluoropropionic acid, 2,2,3-trichloro-3,3-difluoropropionic acid, 2,3,3-trichloro-2,3-difluoropropionic acid, 3,3,3-trichloro-2,2-difluoropropionic acid, 2,3,3,3-tetrachloro-2-fluoropropionic acid, 2,2,3,3-tetrachloro-3-fluoropropionic acid may be used. More preferably, dichloroacetic acid, 2,3-dichloropropionic acid, 2,2-dichloropropionic acid, chlorodifluoroacetic acid, and dichlorofluoroacetic acid may be used. In addition, examples of the chlorocarboxylic acid anhydride include the anhydrides of the chlorocarboxylic acids listed above.

The chlorocarboxylic acid compound may include at least one of a chlorocarboxylic acid having a pKa of −0.2 or more and 4.5 or less and an anhydride thereof.
The lower limit of the pKa of the chlorocarboxylic acid may be, for example, −0.2 or more, −0.1 or more, 0 or more, or 0.2 or more. The upper limit may be, for example, 4.5 or less, 3.0 or less, 2.0 or less, or 1.5 or less. By setting the pKa to the upper limit or less, the reactivity of the obtained silyl ester compound (II) with the silylating agent (I) is easily improved.

In addition, each step of producing the film-forming composition may be carried out in air or, if necessary, in an inert atmosphere such as a nitrogen atmosphere. For example, when the chlorocarboxylic acid or chlorocarboxylic anhydride is highly reactive with moisture in the air, it is preferable to carry out each step in a humidity-controlled environment or in an inert atmosphere, since this prevents cloudiness during production.

In addition to the above, the above-mentioned silylamide compound or aminosilane compound may be mixed in. In addition, in the production process of the film-forming composition, a silylamide compound or an aminosilane compound may be generated as a by-product after mixing the respective raw materials, and these may be used as a component to be used in combination with the (I) silylating agent.
For example, when a silazane compound is used as a raw material for the silylating agent (I) and a chlorocarboxylic anhydride is used as a raw material for the chlorocarboxylic acid compound (II'), a silylamide compound may be obtained as a by-product of a silyl ester compound (II).
Furthermore, for example, when a silazane compound is used as a raw material for the silylating agent (I) and a chlorocarboxylic acid is used as a raw material for the chlorocarboxylic acid compound (II'), an aminosilane compound may be obtained as a by-product of a silyl ester compound (II), or may be produced by a reaction between the silylating agent (I) and a component having an OH group (e.g., water, alcohol, various carboxylic acids, etc.) contained in the raw materials or composition.

The mixture obtained in the above example and/or the reaction liquid obtained in the other examples may be purified using an adsorbent, filter, etc., as necessary. Also, each component may be purified in advance by distillation, and may be purified using an adsorbent, filter, etc.

(Substrate manufacturing method)
A method for producing a substrate using the film-forming composition of this embodiment will be described.
Figures 1 to 3 show an example of a method for manufacturing a substrate. Figure 1 is a top view of a substrate 10 as viewed from a direction perpendicular to a main surface 12 of the substrate. Figure 2 is a schematic diagram of a cross-section of the substrate 10 in a predetermined direction. Figures 3(a) to 3(c) are schematic diagrams of cross-sections of steps in the manufacturing process of the substrate 10.

One example of a method for manufacturing a substrate includes a substrate preparation step of preparing a substrate 10 (semiconductor substrate), and a surface treatment step of supplying a film-forming composition 60 to the substrate 10 and forming a water-repellent film 70 on at least a portion of the surface (principal surface 12) of the substrate 10.

In the above-mentioned substrate 10 preparation process, as shown in Figures 1 and 2, a substrate 10 is prepared with a pattern (relief structure 20) formed on the main surface 12.

Here, as an example of forming the uneven structure 20 on the surface of the substrate 10, the following method may be used.
First, a resist is applied to the wafer surface, and then the resist is exposed through a resist mask, and the exposed or unexposed resist is removed to produce a resist having a desired uneven pattern. A resist having an uneven pattern can also be obtained by pressing a mold having a pattern against the resist. Next, the wafer is etched. At this time, the substrate surface corresponding to the concave portions of the resist pattern is selectively etched. Finally, the resist is peeled off to obtain a wafer (substrate 10) having an uneven structure 20 on its surface.

The wafer on which the uneven structure 20 is formed and the material of the uneven structure 20 are not particularly limited.
The wafer may be made of various materials, such as a silicon wafer, a silicon carbide wafer, a wafer made of a plurality of components including silicon element, a sapphire wafer, or a wafer made of various compound semiconductors.

The material of the uneven structure 20 may include one or more selected from the group consisting of Si, Ti, Ge, W, and Ru, and oxides, nitrides, nitrogen oxides, carbonitrides, and carbon oxides containing at least one of these. For example, the material of the uneven structure 20 may include silicon-based materials such as silicon oxide, silicon nitride, polycrystalline silicon, single crystal silicon, and silicon germanium, metal-based materials such as titanium nitride, tungsten, ruthenium, tantalum nitride, and tin, and combinations of these materials, resist (photoresist) materials, and the like.
Among these, silicon-based materials such as silicon oxide, silicon nitride, polycrystalline silicon, single crystal silicon, and silicon germanium are more preferable.

The substrate 10 in FIG. 1 may have, on the main surface 12, a pattern-formed region 30 in which a pattern (relief structure 20) is formed, and a pattern-unformed region 32 in which no pattern is formed.
1 may have a notch 14 formed in a portion of the periphery thereof. The notch 14 may be a straight notch that indicates the direction of the crystal axis and is called an orientation flat, or a V-shaped notch that is called a notch, for the purpose of positioning in an exposure device or the like.

The pattern formation region 30 is a region in which one or more uneven structures 20 are formed when viewed from a direction perpendicular to the main surface 12, i.e., when viewed from above. The pattern formation region 30 may include an element formation region in which one or more semiconductor elements are formed.

The uneven structure 20 may be configured, for example, as a three-dimensional structure having one or more structures arranged along the vertical direction of the main surface 12, and/or one or more structures arranged along a horizontal direction perpendicular to the vertical direction. Examples of such three-dimensional structures may constitute at least a part of a logic device or memory device, such as a FinFET, a nanowire FET, a nanosheet FET, or other multi-gate type FET, a three-dimensional memory cell, etc.

The pattern non-formation region 32 is a region that is formed in at least a part of the periphery or the entire periphery of the pattern formation region 30 when viewed from above. The pattern non-formation region 32 may be formed continuously with each other or may be formed in a plurality of partitions.
The pattern non-forming region 32 has at least a part of a smooth surface region where the concave-convex structure 20 is not formed.

One or more cut regions for dicing may be formed in the pattern forming region 30 and/or between the pattern forming region 30 and the non-pattern forming region 32.

The pattern dimension of the unevenness structure 20 can be defined as at least one width dimension in the in-plane direction of the main surface 12 and/or at least one height dimension in a direction perpendicular to the main surface 12, as shown in FIG.
In the cross-sectional structure (in the thickness direction of the substrate) in the pattern of the unevenness structure 20, at least one of the pattern dimensions of the width and height, or in the three-dimensional structure (three-dimensional coordinates of XYZ) in the pattern of the unevenness structure 20, at least one of the pattern dimensions of the width (length in the X-axis direction), the height (length in the Y-axis direction), and the depth (length in the Z-axis direction) may be, for example, 30 nm or less, 20 nm or less, or 10 nm or less. This may be the interval between the patterns. Even when a substrate 10 having such a fine unevenness structure 20 is used, the film-forming composition of this embodiment can be applied.

Such a film-forming composition is suitable for use in surface treatment of a substrate 10 having a relief structure 20 with a pattern dimension of 30 nm or less, preferably 20 nm or less.

The aspect ratio of the protrusions 22 may be, for example, not less than 3, not less than 5, or not less than 10. Even in the concave-convex structure 20 having the protrusions 22 with a fragile structure, pattern collapse can be suppressed.
On the other hand, the aspect ratio of the protrusion 22 is not particularly limited, but may be 100 or less.
The aspect ratio of the protrusion 22 is expressed by the value obtained by dividing the height of the protrusion 22 by the width of the protrusion 22 .

As shown in FIG. 2, the substrate 10 may have a bevel region 50 formed on at least a portion of the edge of the substrate 10. The substrate 10 in the bevel region 50 may have an inclined surface (bevel) formed on the main surface 12, and may have, for example, a top edge 51, an upper bevel 52, a front shoulder 53, an end surface 54, and a lower bevel 55.

If desired, the major surface 12 of the substrate 10 may be cleaned, such as by contacting it with an aqueous cleaning solution (cleaning step).
Examples of the aqueous cleaning solution include water, alcohol, an aqueous ammonium hydroxide solution, an aqueous tetramethylammonium solution, an aqueous hydrochloric acid solution, an aqueous hydrogen peroxide solution, an aqueous sulfuric acid solution, and an organic solvent, etc. These may be used alone or in combination of two or more kinds.

The above cleaning step may be carried out once or twice or more before the surface treatment step or the first rinsing step.
Between multiple cleaning steps, and between a cleaning step and a surface treatment step, other steps may be included.

If necessary, the main surface 12 of the substrate 10 may be brought into contact with a first rinse solution (first rinse step). The first rinse solution may be a cleaning solution different from the aqueous cleaning solution, and may be, for example, water, an organic solvent, a mixture thereof, or a mixture of at least one of an acid, an alkali, a surfactant, and an oxidizing agent.
Examples of the organic solvent used in the first rinse solution include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, etc. Among these, it is preferable to use at least one type of organic solvent selected from alcohols having 3 or less carbon atoms, such as methanol, 1-propanol, and 2-propanol (isopropanol).

More than one type of first rinse solution may be used. For example, rinsing may be performed in the order of an acid or alkaline aqueous solution, followed by an organic solvent. Alternatively, an additional aqueous cleaning solution may be added, followed by a solution containing an acid or alkaline aqueous solution, followed by an aqueous cleaning solution, followed by an organic solvent.

The above-mentioned first rinsing step may be carried out once or twice or more times after the cleaning step or before the surface treatment step. Other steps may be included between multiple first rinsing steps or between the first rinsing step and the surface treatment step.

Next, in the above surface treatment step, as shown in FIG. 3(a), the film-forming composition 60 of this embodiment is supplied to the surface (main surface 12) of the substrate 10.

The film forming composition 60, which is a liquid, is preferably supplied to the unevenness structure 20 formed on the surface of the substrate 10. At this time, the film forming composition 60 may be supplied so as to fill a part or all of the recesses 24 of the unevenness structure 20.
The film-forming composition 60 may be supplied in a state where the first rinsing solution or the aqueous cleaning solution is held on the main surface 12. That is, by replacing the first rinsing solution or the aqueous cleaning solution with the film-forming composition 60, it becomes possible to carry out a surface treatment step before the surface of the concave-convex structure 20 on the main surface 12 of the substrate 10 becomes dry.

The film-forming composition 60 can be supplied by any known means, and may be supplied in liquid form or gas form. For example, a sheet-type method, such as a spin method (spin coating method), in which a liquid composition is supplied near the center of rotation while holding each wafer almost horizontally and rotating it, replacing cleaning fluids and the like held in the uneven pattern of the wafer, and filling the wafer with the composition, or a batch method in which multiple wafers are immersed in a composition tank, replacing cleaning fluids and the like held in the uneven pattern of the wafer, and filling the wafer with the composition, may be used. When the composition is supplied as a gas, a method in which vapor of the film-forming composition 60 is supplied to the uneven pattern of the wafer and condensed on the wafer may be used.

Subsequently, as shown in FIG. 3( b ), the film-forming composition 60 is brought into contact with the main surface 12 of the substrate 10 , thereby forming a water-repellent film 70 on at least a portion of the main surface 12 .
If necessary, the film-forming composition 60 on the main surface 12 may be subjected to known means such as heating, reducing pressure, or drying to promote the formation of the water-repellent film 70 .

The water-repellent film 70 is formed on at least the pattern-forming region 30 and the pattern-non-forming region 32 on the main surface 12 of the substrate 10. The water-repellent film 70 may be formed on the bevel region 50 on the main surface 12, or may be formed on the entire main surface 12.

If necessary, the main surface 12 on which the water-repellent film 70 is formed may be brought into contact with a second rinsing liquid (second rinsing step).
As the second rinsing solution, the same as those exemplified as the first rinsing solution can be used.
For example, rinsing can be performed in the order of water → organic solvent such as isopropanol, or in the order of an organic solvent such as isopropanol → water.

The second rinsing step may be carried out once or twice or more times after the surface treatment step. Other steps may be included between multiple second rinsing steps or between the second rinsing step and the surface treatment step.

If necessary, a drying step may be carried out to dry the main surface 12 of the substrate 10 .
The drying process can remove any liquid present on the major surface 12 of the substrate 10 .
As the drying means, for example, known means such as spin drying, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, hot air drying, vacuum drying, etc. may be used.

The above drying step may be performed once or twice or more, for example, after the surface treatment step or after the second rinsing step. The drying step and the second rinsing step may be repeated alternately.

If necessary, after the surface treatment step, the water-repellent film 70 on the main surface 12 of the substrate 10 may be removed as shown in FIG. 3(c) (removal step).
The removal means may include heating, UV irradiation, ozone exposure, plasma irradiation, corona discharge, etc. Treatment with a concentrated fluid such as a supercritical fluid (which may contain an acid, a base, or an oxidizing agent) or steam treatment may also be performed. These may be used alone or in combination of two or more. These treatments may be performed under atmospheric pressure or reduced pressure.

In this manner, a semiconductor substrate (substrate 10) that has been surface-treated with the film-forming composition of the present embodiment is obtained.
This makes it possible to suppress pattern collapse on the semiconductor substrate.

Although the above-mentioned supplying step is performed after the cleaning step in the manufacturing method, the present invention is not limited to this, and the supplying step may be performed after various treatments performed on the concave-convex structure 20 .
In addition to the above-mentioned steps, the method for manufacturing the substrate may include one or a combination of two or more known treatments. For example, a surface treatment such as a plasma treatment may be performed after the above-mentioned removing step.

3 is intended for a wafer pattern, but the present disclosure is not limited thereto. The substrate manufacturing method of the present embodiment is intended for a resist pattern, and the film-forming composition of the present disclosure can be used in the cleaning and drying process to prevent the resist pattern from collapsing.
The film-forming composition of the present embodiment can be used to suppress pattern collapse on a substrate surface, but the application is not limited thereto.
As another application, the film-forming composition of the present embodiment can be used as a selective film. For example, by using the film-forming composition on two or more surfaces of different materials on a substrate surface, a water-repellent film can be formed to selectively impart water repellency to at least a part of the surface.

Although the embodiments of the present disclosure have been described above, these are merely examples of the present disclosure, and various configurations other than those described above may be adopted. Furthermore, the present disclosure is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope of achieving the object of the present disclosure are included in the present disclosure.
Below, examples of reference forms are given.
1. A film-forming composition used to form a water-repellent film,
(I) a silylating agent;
(II) a silyl ester compound represented by the following general formula [2],
(III) an aprotic solvent,
A film-forming composition.
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
(In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms;
i is an integer from 1 to 3, h is an integer from 1 to 3, and i+h is an integer from 2 to 4.
2. The film-forming composition according to 1.,
The film-forming composition, wherein the silylating agent contains a silicon compound represented by the following general formula [1]:
R ¹ _a Si(H) _b X _4-ab [1]
(In the above general formula [1],
R ¹ is each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
Each X is independently a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, carbon, or halogen;
a is an integer from 1 to 3, b is an integer from 0 to 2, and the sum of a and b is 1 to 3.
3. The film-forming composition according to 1. or 2,
The film-forming composition contains the silyl ester ^compound represented by -C _q Y _(2q+1-r) Cl _r (wherein each Y is independently a hydrogen atom or a fluorine atom bonded to carbon, Cl is a chlorine atom, q is an integer of 1 to 5, and r is 1 to 2q+1).
4. The film-forming composition according to any one of 1. to 3.,
The aprotic solvent comprises one or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen atom-containing solvents, sulfoxide-based solvents, carbonate-based solvents, derivatives of polyhydric alcohols having no OH group, nitrogen atom-containing solvents having no N-H group, and silicone solvents.
5. The film-forming composition according to any one of 1 to 4,
The film-forming composition, wherein the content of the silylating agent is 0.1% by mass or more and 35% by mass or less, based on 100% by mass of the film-forming composition.
6. The film-forming composition according to any one of 1. to 5.,
The film-forming composition, wherein the content of the silyl ester compound is 0.01% by mass or more and 10% by mass or less based on 100% by mass of the film-forming composition.
7. The film-forming composition according to any one of 1. to 6.,
The film-forming composition has a water contact angle of 70° or more when formed from the film-forming composition in accordance with JIS R 3257:1999.
8. The film-forming composition according to any one of 1. to 7.,
A film-forming composition which does not contain an amide compound represented by the following general formula [4], or the content of the amide compound is 1.0 mass% or less based on 100 mass% of the film-forming composition:
R ^b1 -C(=O)N(H)Z [4]
(In the above general formula [4],
R ^b1 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms,
Z is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms bonded to a nitrogen atom.
9. The film-forming composition according to any one of 1. to 8.,
A film-forming composition comprising one or more compounds selected from the group consisting of a silylamide compound represented by the following general formula [5] and an aminosilane compound represented by the following general formula [6]:
(R ^b2 -C(=O)N(H)) _j -Si(H) _4-j-t (R ^b3 ) _t [5]
(In the above general formula [5],
R ^b2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms,
R ^b3 each independently represents an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
j is an integer from 1 to 3, t is an integer from 1 to 3, and j+t is an integer from 2 to 4.
(R ^b4 ) _u Si(H) _v (NH ₂ ) _4-uv [6]
(In the above general formula [5],
R ^b4 each independently represents an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
u is an integer from 1 to 3, v is an integer from 0 to 2, and the sum of u and v is 1 to 3.
10. Preparing a substrate;
supplying a film-forming composition to the substrate to form a water-repellent film on at least a portion of a surface of the substrate,
The film forming composition,
(I) a silylating agent;
(II) a silyl ester compound represented by the following general formula [2],
(III) an aprotic solvent.
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
(In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms;
i is an integer from 1 to 3, h is an integer from 1 to 3, and i+h is an integer from 2 to 4.
11. A method for manufacturing a substrate according to 10., comprising the steps of:
A method for producing a substrate, comprising the step of cleaning the substrate before supplying the film-forming composition.
12. A method for producing a film-forming composition, comprising the step of mixing (I) a silylating agent, (II) a silyl ester compound, and (III) an aprotic solvent.
13. A method for producing a film-forming composition, comprising a reaction step of reacting (I) a silylating agent with a chlorocarboxylic acid compound containing at least one of a chlorocarboxylic acid and a chlorocarboxylic acid anhydride to obtain (II) a silyl ester compound.
14. A method for producing the film-forming composition according to 13.,
The chlorocarboxylic acid includes one or more compounds represented by the following general formula [7]:
The method for producing a film-forming composition, wherein the chlorocarboxylic anhydride contains one or more compounds represented by the following general formula [8]:
R ^C2 -C(=O)OH [7]
R ^C2 -C(=O)OC (=O)-R ^C2 [8]
(In the above general formulas [7] and [8],
R ^C2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced with chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced with fluorine atoms.
15. A method for producing the film-forming composition according to 13. or 14.,
The method for producing a film-forming composition includes the chlorocarboxylic acid compound, which contains at least one of the chlorocarboxylic acid having a pKa of -0.2 or more and 4.5 or less, and an anhydride thereof.
16. A method for producing the film-forming composition according to any one of 13. to 15.,
The method for producing a film-forming composition, wherein the reaction step is carried out in an aprotic solvent (III).

The present disclosure will be described in detail below with reference to examples, but the present disclosure is in no way limited to the description of these examples.

(Preparation of film-forming composition)
<Examples 1 to 31, 36 to 41>
The raw materials shown in Table 1, (I) silylating agent, (II') chlorocarboxylic acid compound, and (III) aprotic solvent, were mixed in a predetermined mass ratio at a liquid temperature of 25°C under air and stirred for 1 minute to obtain a film-forming composition containing (I) silylating agent, (II) silyl ester compound, and (III) aprotic solvent in the mass ratio shown in Table 1. Some compositions in the examples contain an amide compound represented by the general formula [4], an aminosilane compound represented by the general formula [6], and/or a silylamide compound. When contained, the type and the content relative to the total amount of the film-forming composition are shown in Table 1, and when not contained, they are shown as "-" in Table 1. The aprotic solvents used before mixing all had a water content of 0.01 mass% or less. In Example 31, white turbidity was observed visually immediately after all the raw materials were mixed, so when various measurements and evaluations were performed, the white turbidity (solid matter) was filtered and removed from the measurement target. In Table 1, the content of each component other than (III) relative to the total amount of the film-forming composition was determined by the following gas chromatography measurement.

<Examples 32 to 34>
A film-forming composition was obtained in the same manner as in Examples 1 to 31 using the raw materials in Table 1, except that the water content of the aprotic solvent (III) was 0.1 mass %. The aminosilane compound represented by general formula [6], presumably produced by the reaction of the raw material (I) silylating agent with water, was measured in the same manner as above, and the results are shown in Table 1. The silylamide compound contained in the film-forming composition was measured in the same manner as above, and the confirmed compounds are shown in Table 1. The amide compound represented by general formula [4] was also measured in the same manner as above, and the results are shown in Table 1.

<Examples 35, 42 to 44>
Using the raw materials in Table 1, (I) a silylating agent, (II') a chlorocarboxylic acid compound, and (III) an aprotic solvent were mixed in a glove box under a nitrogen atmosphere at a liquid temperature of 25°C in a predetermined mass ratio, and stirred for 1 minute to obtain a film-forming composition containing (I) a silylating agent, (II) a silyl ester compound, and (III) an aprotic solvent in the mass ratio shown in Table 1. In Example 35, by mixing under an inert atmosphere, the amide compound of the general formula [4] was not formed, and a film-forming composition that did not become cloudy like Example 31 was obtained.

The content (mass%) of each component in the film-forming composition in Table 1 is determined by quantitative determination according to the absolute calibration curve method from the GC area of the obtained gas chromatography chart using gas chromatography under the following analytical conditions. The concentration of the aminosilane compound represented by the general formula [6] is shown in GC area% when the total area of each component is 100 GC area%. The detected GC area% is rounded off to the nearest digit. For example, 0.00% indicates less than 0.005 GC area%.
(Gas Chromatography Analysis Conditions)
Measurement sample: 1.0 μL
Equipment: GC-2010plus (Shimadzu Corporation)
Detector: Flame ionization detector (FID)
Column used: TC-1, length 30 m x inner diameter 0.32 mm (GL SCIENCES)
Analysis conditions: injection temperature 270°C, detection temperature 300°C
Carrier gas: Helium

<Comparative Example 1>
The (I) silylation agent and (III) aprotic solvent shown in the raw materials in Table 1 were mixed in a mass ratio of 5 mass%:95 mass% at a liquid temperature of 25°C under air and stirred for 1 minute to obtain a film-forming composition. The aprotic solvent used before mixing had a water content of 0.01 mass% or less.

<Comparative Examples 2 to 4>
The raw materials shown in Table 1, (I) a silylating agent, (II') an acid compound, and (III) an aprotic solvent, were mixed in a predetermined mass ratio at a liquid temperature of 25°C under atmospheric pressure and stirred for 1 minute to obtain a film-forming composition containing (I) a silylating agent, (II) a silyl ester compound not corresponding to the general formula [2] of the present disclosure, and (III) an aprotic solvent in the mass ratio shown in Table 1.

<Reference Examples 1 to 5>
(I) a silylating agent, a chlorine-free acid compound corresponding to (II') in the Examples, and (III) an aprotic solvent shown in the raw materials of Table 1 were mixed in a predetermined mass ratio at a liquid temperature of 25°C under air and stirred for 1 minute to obtain a film-forming composition containing the components shown in Table 1 in the mass ratio shown in Table 1. In Reference Examples 1 to 5, none of the components corresponding to (II) in the Examples or the amide compound represented by general formula [4] contain a chlorine element.

The compound names corresponding to the abbreviations in Table 1 are shown below.
(I) Silylating agent HMDS: 1,1,1,3,3,3-hexamethyldisilazane TMSDMA: N-(trimethylsilyl)dimethylamine Silylamide compounds, silylamide compounds according to reference examples TMSDCAAm: N-trimethylsilyldichloroacetamide TMSCDFAAm: N-trimethylsilylchlorodifluoroacetamide TMSDCFAAm: N-trimethylsilyldichlorofluoroacetamide TMSTFAAm: N-trimethylsilyltrifluoroacetamide TMSTFMSAAm: N-trimethylsilyltrifluoromethanesulfonamide

(II') Chlorocarboxylic acid compounds used in the examples and acid compounds used in the comparative examples MCA: monochloroacetic acid DCA: dichloroacetic acid DCAA: dichloroacetic anhydride CDFA: chlorodifluoroacetic acid CDFAA: chlorodifluoroacetic anhydride DCFA: dichlorofluoroacetic acid CFA: chlorofluoroacetic acid 2CP: 2-chloropropionic acid 23DCP: 2,3-dichloropropionic acid 22333PCP: 2,2,3,3,3-pentachloropropionic acid 223TCP: 2,2,3 -Trichloropropionic acid 3C2233TFP: 3-chloro-2,2,3,3-tetrafluoropropionic acid 2C2333TFP: 2-chloro-2,3,3,3-tetrafluoropropionic acid 23DC23DFP: 2,3-dichloro-2,3-difluoropropionic acid DCFAA: dichlorofluoroacetic anhydride TFAA: trifluoroacetic anhydride TFMSA: trifluoromethanesulfonic acid TFMSAA: trifluoromethanesulfonic anhydride MSA: methanesulfonic acid

(II) Silyl ester compounds according to the examples and comparative examples, and silyl compounds according to the comparative examples TMSMCA: trimethylsilyl chloroacetate TMSDCA: trimethylsilyl dichloroacetate TMSCDFA: trimethylsilyl chlorodifluoroacetate TMSDCFA: trimethylsilyl dichlorofluoroacetate TMSCFA: trimethylsilyl chlorofluoroacetate TMS2CP: trimethylsilyl-2-chloropropionate TMS23DCP: trimethylsilyl-2,3-dichloropropionate TMS22333PCP: trimethylsilyl-2,2,3,3,3-pentachloropropionate TMS223TCP: trimethylsilyl chloropropionate TMS3C2233TFP: Trimethylsilyl-3-chloro-2,2,3,3-tetrafluoropropionate TMS2C2333TFP: Trimethylsilyl-2-chloro-2,3,3,3-tetrafluoropropionate TMS23DC23DFP: Trimethylsilyl-2,3-dichloro-2,3-difluoropropionate TMSMSA: Trimethylsilyl methanesulfonate TMSCA: Trimethylsilyl acetate TMSSA: Trimethylsilyl sulfonate TMSTFA: Trimethylsilyl trifluoroacetate TMSTFMSA: Trimethylsilyl trifluoromethanesulfonate

(III) Aprotic Solvent PGMEA: Propylene glycol monomethyl ether acetate

(IV) Amide Compounds DCAm: 2,2-dichloroacetamide CDFAm: 2-chloro-2,2-difluoroacetamide DCFAm: 2,2-dichloro-2-fluoroacetamide TFAm: trifluoroacetamide

(VI) Aminosilane compound TMSA: aminotrimethylsilane

<pKa of chlorocarboxylic acids used in the examples and acid compounds used in the comparative examples>
In Table 1, the pKa was calculated based on a chemical substance search ^using CAS SciFinder. Here, the pKa value calculated using Advanced Chemistry Development (ACD/Labs) Software V11.02 (Copyright 1994-2023 ACD/Labs) was used.
In addition, the pKa values marked with * in Table 1 indicate those of the acids corresponding to the acid anhydrides.

The obtained film-forming composition was evaluated for the following items:

In Table 1, the turbidity was measured using a portable turbidity meter, 2100Q (manufactured by HACH), at room temperature after stirring the film-forming composition for 10 seconds. The smaller the turbidity value, the higher the transparency, and a value of 10 or less was determined to indicate no cloudiness.

<Water contact angle>
The water contact angle (°) of the obtained film-forming composition was measured according to the following coupon test procedure. The results are shown in Table 1. Note that only Example 35 was subjected to the coupon test under a nitrogen atmosphere, and the other Examples were subjected to the test under air.
(Procedure for coupon testing)
A silicon wafer having no uneven pattern on its surface and a 1 μm-thick silicon oxide film on its surface was cut to prepare coupons made of silicon substrates with dimensions of length, width and thickness of 4 cm, 1 cm and 0.75 mm.
The coupon was immersed in 1% by weight hydrofluoric acid at room temperature, then in water at room temperature, then in 2-propanol at room temperature, and then in propylene glycol monomethyl ether acetate at room temperature for cleaning. The "room temperature" was 25° C.
An evaluation solution made of a film-forming composition was prepared, and the cleaned coupon was immersed in the evaluation solution at room temperature for 20 seconds.
The coupon was removed from the evaluation solution and washed by immersing it in 2-propanol at room temperature, and then the surface of the coupon was dried with nitrogen gas.
With the dried coupon placed on a horizontal surface, 2 μl of pure water was placed on the surface of the coupon on which the silicon oxide film was formed at room temperature of 25° C., and the water contact angle (°) was measured in accordance with JIS R 3257:1999.
The coupon using Example 31 as the evaluation solution had deposits on its surface due to white turbidity, but these were removed during subsequent immersion in 2-propanol, and the coupon was then dried before measuring the water contact angle.

<Evaluation of pattern collapse rate>
First, a silicon substrate was prepared having a pattern formation area on whose surface a convex structure was formed having a plurality of approximately cylindrical convex portions having an aspect ratio of 22 in a cross-sectional view and a pattern width of 19 nm at a pitch of 90 nm (the total distance between the width of the convex portions and the distance between adjacent convex portions).
The surface of the substrate was dry-cleaned by UV/ _O3 irradiation. The surface of the substrate was oxidized to silicon oxide. The substrate was then placed on a spin coater, and while rotating the substrate at a speed of 200 rpm, 2-propanol (IPA), the film-forming composition shown in Table 1, and IPA were discharged in this order at a speed of 200 cc/min, and finally the substrate was dried while _N2 was discharged onto the substrate.
Using the substrate thus surface-treated with the film-forming composition, the pattern formation region was observed under an electron microscope (SEM, SU8010 manufactured by Hitachi High-Technologies Corporation) at a magnification such that 500 to 600 convex portions were within the field of view, and the number of convex portions where pattern collapse had occurred was counted. The ratio of convex portions where collapse had occurred to all convex portions is shown in Table 1 as the pattern collapse rate (%). Furthermore, from the calculated values, evaluation was performed according to the following criteria, and the results are shown in Table 1.
When Example 31 was used as a film-forming composition, the composition was applied to the substrate surface after removing the cloudiness.
<Evaluation criteria>
Excellent: Pattern collapse rate is less than 10%. Fair: Pattern collapse rate is 10% or more but less than 30%. Poor: Pattern collapse rate is 30% or more.

The film-forming compositions of Examples 1 to 44 showed results that they could impart excellent water repellency to the substrate surface, compared to Comparative Examples 1 to 4. In addition, the film-forming compositions of Examples 1 to 44 met the water repellency standard of a water contact angle of 70° or more, and it was confirmed that they had water repellency performance equivalent to that of Reference Examples 1 to 5, which used a perfluoroalkyl derivative as an accelerator.
Moreover, it was found that the pattern collapse rate was less than 30% in all of Examples 1 to 44, and pattern collapse could be effectively suppressed. Furthermore, when the water contact angle was 81° or more, the pattern collapse rate was less than 10%, which showed that pattern collapse could be more easily suppressed.
Furthermore, silylamide compounds were confirmed in Examples 6 to 9, 30, 31, 33, 34, 40, and 41, in which anhydrides were used as raw materials. These silylamide compounds are presumed to be by-products produced in the process of the reaction between the silylating agent of the silazane compound and the chlorocarboxylic acid anhydride.
Furthermore, in Examples 1 to 34, 40, and 41, aminosilane compounds were observed.
In addition, when comparing Example 31 prepared under air and Example 35 prepared under a nitrogen atmosphere (both using the same raw materials), it was shown that Example 31, in which an aminosilane compound is contained in the film-forming composition, can impart superior water repellency to the substrate surface.

This application claims priority based on Japanese Patent Application No. 2023-090176, filed on May 31, 2023, the entire disclosure of which is incorporated herein by reference.

10 Substrate 12 Main surface Notch 16 Back surface 20 Concave-convex structure 22 Convex portion 24 Concave 30 Pattern-forming region 32 Pattern-non-forming region 50 Bevel region 51 Top edge 52 Upper bevel 53 Front shoulder 54 End surface 55 Lower bevel 60 Film-forming composition 70 Water-repellent film

Claims (21)

A film-forming composition used to form a water-repellent film,
(I) a silylating agent;
(II) a silyl ester compound represented by the following general formula [2],
(III) an aprotic solvent,
A film-forming composition.
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
(In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms;
i is an integer from 1 to 3, h is an integer from 1 to 3, and i+h is an integer from 2 to 4. The film-forming composition according to claim 1,
The film-forming composition, wherein the silylating agent contains a silicon compound represented by the following general formula [1]:
R ¹ _a Si(H) _b X _4-ab [1]
(In the above general formula [1],
R ¹ is each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
Each X is independently a monovalent group in which the atom bonded to the Si atom is nitrogen, oxygen, carbon, or halogen;
a is an integer from 1 to 3, b is an integer from 0 to 2, and the sum of a and b is 1 to 3. The film-forming composition according to claim 1 or 2,
The film-forming composition contains the silyl ester ^compound represented by -C _q Y _(2q+1-r) Cl _r (wherein each Y is independently a hydrogen atom or a fluorine atom bonded to carbon, Cl is a chlorine atom, q is an integer of 1 to 5, and r is 1 to 2q). The film-forming composition according to claim 1 or 2,
The aprotic solvent comprises one or more selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen atom-containing solvents, sulfoxide-based solvents, carbonate-based solvents, derivatives of polyhydric alcohols having no OH group, nitrogen atom-containing solvents having no N-H group, and silicone solvents. The film-forming composition according to claim 1 or 2,
The film-forming composition, wherein the content of the silylating agent is 0.1% by mass or more and 35% by mass or less, based on 100% by mass of the film-forming composition. The film-forming composition according to claim 1 or 2,
The film-forming composition, wherein the content of the silyl ester compound is 0.01% by mass or more and 10% by mass or less based on 100% by mass of the film-forming composition. The film-forming composition according to claim 1 or 2,
The film-forming composition has a water contact angle of 70° or more when formed from the film-forming composition in accordance with JIS R 3257:1999. The film-forming composition according to claim 1 or 2,
A film-forming composition comprising the aprotic solvent (III) having polarity. The film-forming composition according to claim 1 or 2,
A film-forming composition which does not contain an amide compound represented by the following general formula [4], or the content of the amide compound is 0.1 mass % or less based on 100 mass % of the film-forming composition:
R ^b1 -C(=O)N(H)Z [4]
(In the above general formula [4],
R ^b1 is a hydrocarbon group having a Cl ₃ C moiety, a Cl ₂ HC moiety, or a Cl ₂ FC moiety;
Z is a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms bonded to a nitrogen atom. The film-forming composition according to claim 9,
A film-forming composition comprising an amide compound having a structure in which, in the general formula [4], R ^b1 is a hydrocarbon group having no Cl ₃ C moiety, Cl ₂ HC moiety, or Cl ₂ FC moiety. The film-forming composition according to claim 1 or 2,
A film-forming composition comprising one or more compounds selected from the group consisting of a silylamide compound represented by the following general formula [5] and an aminosilane compound represented by the following general formula [6]:
(R ^b2 -C(=O)N(H)) _j -Si(H) _4-j-t (R ^b3 ) _t [5]
(In the above general formula [5],
R ^b2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms,
R ^b3 each independently represents an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
j is an integer from 1 to 3, t is an integer from 1 to 3, and j+t is an integer from 2 to 4.
(R ^b4 ) _u Si(H) _v (NH ₂ ) _4-uv [6]
(In the above general formula [5],
Each R ^b4 is independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
u is an integer from 1 to 3, v is an integer from 0 to 2, and the sum of u and v is 1 to 3. providing a substrate;
supplying a film-forming composition to the substrate to form a water-repellent film on at least a portion of a surface of the substrate,
The film forming composition,
(I) a silylating agent;
(II) a silyl ester compound represented by the following general formula [2],
(III) an aprotic solvent.
(R ² -C(=O)O) _i -Si(H) _4-i-h (R ³ ) _h [2]
(In the above general formula [2],
^R2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced by chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced by fluorine atoms;
^R3 is each independently an organic group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms or chlorine atoms;
i is an integer from 1 to 3, h is an integer from 1 to 3, and i+h is an integer from 2 to 4. A method for manufacturing a substrate according to claim 12, comprising the steps of:
A method for producing a substrate, comprising the step of cleaning the substrate before supplying the film-forming composition. A method for producing a film-forming composition, comprising the step of mixing (I) a silylating agent, (II) a silyl ester compound, and (III) an aprotic solvent. A method for producing a film-forming composition, comprising a reaction step of (I) reacting a silylating agent with a chlorocarboxylic acid compound containing at least one of a chlorocarboxylic acid and a chlorocarboxylic acid anhydride to obtain (II) a silyl ester compound. A method for producing the film-forming composition according to claim 15, comprising the steps of:
The chlorocarboxylic acid includes one or more compounds represented by the following general formula [7]:
The method for producing a film-forming composition, wherein the chlorocarboxylic anhydride contains one or more compounds represented by the following general formula [8]:
R ^C2 -C(=O)OH [7]
R ^C2 -C(=O)OC (=O)-R ^C2 [8]
(In the above general formulas [7] and [8],
R ^C2 is a monovalent hydrocarbon group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms have been replaced with chlorine atoms and the remaining hydrogen atoms may be partially or entirely replaced with fluorine atoms. A method for producing the film-forming composition according to claim 15 or 16, comprising the steps of:
The method for producing a film-forming composition includes the chlorocarboxylic acid compound, which contains at least one of the chlorocarboxylic acid having a pKa of -0.2 or more and 4.5 or less, and an anhydride thereof. A method for producing the film-forming composition according to claim 15 or 16, comprising the steps of:
The method for producing a film-forming composition, wherein the reaction step is carried out in an aprotic solvent (III). A method for producing the film-forming composition according to claim 15 or 16, comprising the steps of:
The method for producing a film-forming composition, wherein in the reaction step, the chlorocarboxylic acid compound contains the chlorocarboxylic acid and does not contain the chlorocarboxylic acid anhydride. A method for producing the film-forming composition according to claim 15 or 16, comprising the steps of:
The method for producing a film-forming composition, wherein the silylating agent (I) is other than a silazane compound. A method for producing the film-forming composition according to claim 15 or 16, comprising the steps of:
The method for producing a film-forming composition, wherein the reaction step is carried out under an inert atmosphere.

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