Dihydrodisiloxane compound and its manufacturing method

Abstract

To provide: a silicon-based compound which exhibits high vaporization properties and is useful as a precursor for making a silica thin film with a good deposition rate by a CVD method; and a production method thereof.SOLUTION: A dihydrodisiloxane compound is represented by general formula (1) in the figure, where R1 represents a C1-6 alkyl group and R2 represents a C1-3 alkyl group, provided that the sum of the numbers of carbon atoms in one R1 group and one R2 group is from 4 to 9 inclusive.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dihydrodisiloxane compound that is useful for producing a silicon-containing thin film, and a method for producing the same. [Background technology]

[0002] Silicon dioxide (silica) is a typical metal oxide material that has high chemical and thermal stability and good physical properties (transparency, insulation, mechanical strength), and is used industrially in various forms from bulk to nano-sized materials. The main methods for producing thin silica films are wet and dry methods, but the dry method of chemical vapor deposition (CVD) is mainly used because it requires fewer steps and is easy to obtain high-density, high-performance films. In particular, in order to impart high oxygen and water barrier properties to polymer film materials, a transparent silica film is deposited on the film by the CVD method to achieve this purpose. In film formation by the CVD method, the precursor is required to be vaporizable. Many methods have been reported so far in which various organosilicon compounds are used as precursors and silicon-containing thin films with desired compositions and properties are deposited by the CVD method.

[0003] In the molecular design of a silica thin film precursor by the CVD method, it is important that the precursor has a high vapor pressure, can deposit a silica thin film at a good film-forming rate, and can exhibit the desired functions and physical properties. Generally, monosilane compounds with one silicon atom, especially tetramethoxysilane and tetraethoxysilane, are used because of their easy availability and high vapor pressure, but there is still much room for improvement in their film-forming rate. In addition, hydrogen-substituted silanes (hydrosilanes) in which hydrogen atoms are substituted on silicon atoms have smaller molecular weights and weaker intermolecular interactions than the corresponding alkoxy and alkyl compounds, and therefore can achieve high vapor pressures, but they are often unstable against oxygen in the air, which can cause safety problems. It is expected that increasing the number of silicon atoms in the precursor (polynucleation) is effective in improving the film-forming rate, and at the same time, it is considered effective to introduce hydrogen atoms onto the silicon atoms of the precursor in order to avoid low vapor pressure due to an increase in molecular weight.

[0004] Non-Patent Document 1 reports on a silica barrier film deposited on a polymer film using hexamethyldisiloxane as a precursor by the CVD method. However, thin films using hexamethyldisiloxane as a precursor tend to have residual carbon and are easily discolored. In Patent Document 1, a SiCHO film is deposited by the CVD method using 1,3-dimethyl-1,3-diethoxydisiloxane, but the resulting thin film is a low dielectric constant film and there is no mention of the water vapor barrier properties of the film. Patent Document 2 discloses the production of a polyethylene naphthalate (PEN) film with a silica gas barrier layer formed by plasma-assisted chemical vapor deposition (PECVD) using tetraethoxysilane and oxygen as raw materials. The water vapor barrier properties (WVTR) of this thin film is 1.7×10 -3 g / m 2 Although the film formation rate was as low as 67 nm / min, there was room for improvement in the film formation rate. Patent Document 3 discloses a method for forming a gas barrier film at a film formation rate of 257 nm / min by the PECVD method using an alkylhydrodisiloxane compound, and in a single layer film with a thickness of 2570 nm, the WVTR was 4.0 × 10 -3 g / m 2 A gas barrier film that exhibits a low value of 0.4 MPa (day) has been described. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 144960 [Patent Document 2] JP 2016-176091 A [Patent Document 3] Patent No. 6007662 [Non-patent literature]

[0006] [Non-Patent Document 1] Lin Han et al., Journal of The Electrochemical Society, Vol. 156, pp. H106-H114, 2009 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a silicon-based compound which exhibits high vaporization properties and is useful as a precursor for producing a silica thin film at a good film formation rate in a CVD method, and a method for producing the same. [Means for solving the problem]

[0008] As a result of intensive research conducted by the inventors in order to solve the above problems, they discovered that a dihydrodisiloxane compound having, on a silicon atom, one hydrogen atom, one alkyl group having a specific number of carbon atoms, and one alkoxy group exhibits high vaporization characteristics and is useful as a precursor for producing a thin silica film at a good film formation rate by a CVD method, and thus completed the present invention.

[0009] That is, the present invention comprises the following: [1] General formula (1)

[0010] [ka]

[0011] (1) (In the formula, R 1 represents an alkyl group having 1 to 6 carbon atoms, R 2 R represents an alkyl group having 1 to 3 carbon atoms. 1 and R 2 The sum of the carbon numbers of the alkyl groups represented by the formula (I) is 4 or more and 9 or less. [2] In general formula (1), R 1 is a methyl group, an ethyl group, or an isopropyl group. [3] In general formula (1), R 1 isopropyl group, R 2 is a methyl group. [4] General formula (2)

[0012] [ka]

[0013] (2) (In the formula, X 1 R represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. 1 represents an alkyl group having 1 to 6 carbon atoms, R 2 represents an alkyl group having 1 to 3 carbon atoms, R 1 and R 2 The sum of the carbon numbers of the alkyl groups represented by the general formula (1) is 4 or more and 9 or less.

[0014] [ka]

[0015] (1) (In the formula, R 1 , R 2 has the same meaning as defined above. [5] General formula (3)

[0016] [ka]

[0017] (3) (In the formula, X 2 R represents a halogen atom. 1 represents an alkyl group having 1 to 6 carbon atoms.) is reacted with a dihalodihydrodisiloxane compound represented by the general formula (4): (R2 O) n M (4) (R 2 represents an alkyl group having 1 to 3 carbon atoms; M represents a hydrogen atom, an alkali metal or an alkaline earth metal; n is 1 or 2, and represents 1 when M is a hydrogen atom or an alkali metal, and represents 2 when M is an alkaline earth metal, respectively.

[0018] [ka]

[0019] (1) (In the formula, R 1 and R 2 is as defined above, and R 1 and R 2 wherein the sum of the carbon atoms in the alkyl groups represented by the formula (I) is 4 or more and 9 or less. Effect of the Invention

[0020] The dihydrodisiloxane compound (1) of the present invention exhibits high vaporization properties and is useful as a precursor for producing a thin silica film at a good film formation rate by a CVD method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The present invention will be described in detail below.

[0022] First, R in general formulas (1), (2), (3), and (4) 1 and R 2 This article explains:

[0023] R 1is an alkyl group having 1 to 6 carbon atoms, which may be linear, branched, or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, cyclopentyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, 2-methyl-2-butyl, 3-methyl-2-butyl, hexyl, 1-methylpentyl, 1-ethylbutyl, 2,3-dimethyl-2-butyl, and cyclohexyl. Among these, from the viewpoints of the production cost, stability against oxygen, and vapor pressure of the dihydrodisiloxane compound (1) of the present invention, methyl, ethyl, propyl, or isopropyl is preferred, methyl, ethyl, or isopropyl is more preferred, methyl or isopropyl is particularly preferred, and isopropyl is particularly preferred.

[0024] R 2 is an alkyl group having 1 to 3 carbon atoms, which may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. Among these, from the viewpoints of the production cost, the stability against oxygen, and the vapor pressure of the dihydrodisiloxane compound (1) of the present invention, a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferred, a methyl group, an ethyl group, or an isopropyl group is more preferred, a methyl group or an isopropyl group is particularly preferred, and a methyl group is particularly preferred.

[0025] Next, the dihydrodisiloxane compound (1) of the present invention will be described. The dihydrodisiloxane compound (1) of the present invention is represented by the following general formula (1):

[0026] [ka]

[0027] (1) (In the formula, R 1 R represents an alkyl group having 1 to 6 carbon atoms. 2R represents an alkyl group having 1 to 3 carbon atoms. 1 and R 2 The sum of the carbon numbers of the alkyl groups represented by is 4 or more and 9 or less.

[0028] In the dihydrodisiloxane compound (1), R 1 and R 2 If the sum of the carbon numbers of the alkyl groups represented by R exceeds 9, the vapor pressure decreases due to the increase in molecular weight, making it difficult to vaporize and evaporate, making it unsuitable for use as a CVD material. 1 and R 2 When the sum of the carbon numbers of the alkyl groups represented by the formula (I) is 3 or less, the hydrogen atoms on the silicon atoms are easily oxidized by oxygen in the air, and high molecular weight silicon oxides produced by oxidation during storage or film formation may deteriorate the quality of the thin film or interfere with film formation.

[0029] The dihydrodisiloxane compound (1) represented by the general formula (1) includes three isomers, the (1R,3R) form, the (1R,3S) form, and the (1S,3S) form, depending on the stereochemistry of the silicon atoms at the 1- and 3-positions. The (1R,3R) form and the (1S,3S) form are enantiomers of each other. The dihydrodisiloxane compound (1) of the present invention may be a mixture of these isomers, or may contain one of the isomers predominantly. In this specification, there is no distinction between these isomers.

[0030] Specific examples of the dihydrodisiloxane compound (1) of the present invention represented by general formula (1) include the following compounds: In this specification, Me, Et, Pr, i-Pr, Bu, i-Bu, sec-Bu, tert-Bu, Pen, and Hex represent methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl, respectively.

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] Among these, in terms of the high vapor pressure of the dihydrodisiloxane compound (1) of the present invention, the stability against oxygen, the high water vapor barrier properties of the silica film after film formation, and excellent economy, (1-1-2), (1-2-1), (1-2-3), (1-4-1), (1-4-2), (1-7-1) or (1-8-1) are preferred, (1-1-2), (1-2-3), (1-4-1), (1-7-1) or (1-8-1) are more preferred, and (1-1-2) or (1-4-1) are especially preferred.

[0035] Next, a method for producing the dihydrodisiloxane compound (1) of the present invention will be described.

[0036] First, X in general formulas (2), (3) and (4) 1 , X 2 and M will be explained.

[0037] X 1 is a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, from the viewpoints of the production cost and stability of the dihydrodisiloxane compound (1) of the present invention, a fluorine atom, a chlorine atom, or a bromine atom is preferred, a chlorine atom or a bromine atom is more preferred, and a chlorine atom is particularly preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group. Among these, from the viewpoints of the production cost, production yield, and ease of purification of the dihydrodisiloxane compound (1) of the present invention, a methoxy group, an ethoxy group, or an isopropyloxy group is preferred, and a methoxy group or an ethoxy group is more preferred.

[0038] X1 In the dialkylamino group having 2 to 12 carbon atoms, the two alkyl groups on the nitrogen may be the same or different. The amino group may be substituted with a linear alkyl group or a branched alkyl group, and the two alkyl groups may be linked to each other to form a ring containing nitrogen. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a diisopropylamino group, a dibutylamino group, a piperidino group (N-piperidin-1-yl group), a pyrrolidino group (pyrrolidin-1-yl group), and a dihexylamino group. Among these, from the viewpoints of economy and safety in handling, a dimethylamino group, a diethylamino group, or a diisopropylamino group is preferred, and a dimethylamino group or a diethylamino group is more preferred.

[0039] X 2 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, from the viewpoints of yield and economy, a fluorine atom, a chlorine atom, or a bromine atom is preferred, a chlorine atom or a bromine atom is more preferred, and a chlorine atom is particularly preferred.

[0040] M is a hydrogen atom, an alkali metal or an alkaline earth metal, and examples of the alkali metal or alkaline earth metal include lithium, sodium, potassium, cesium, magnesium, calcium, strontium and barium. Among these, from the viewpoints of yield and raw material cost, lithium, sodium, potassium, magnesium and calcium are preferred, and sodium, potassium and magnesium are more preferred.

[0041] The dihydrodisiloxane compound (1) of the present invention can be produced by either Production Method 1 (hereinafter referred to as Production Method 1 of the present invention) or Production Method 2 (hereinafter referred to as Production Method 2 of the present invention) described below.

[0042] The following describes Production Method 1 of the present invention. Production Method 1 of the present invention is a method for producing the dihydrodisiloxane compound (1) of the present invention by reacting a hydroalkoxysilane compound (2) represented by general formula (2) with water or a metal oxide.

[0043] [ka]

[0044] (In the formula, R 1 and R 2 are the same as those in the general formula (1). 1 represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms).

[0045] Examples of the hydroalkoxysilane compound (2) that can be used as a raw material in Production Method 1 of the present invention include the following compounds.

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] Among these, from the viewpoints of raw material cost, yield, and stability, compounds (2-1-2), (2-1-8), (2-2-1), (2-2-10), (2-4-1), (2-4-13), (2-7-13) and (2-8-13) are preferred, and compounds (2-1-8), (2-2-10), (2-4-13) and (2-8-13) are more preferred.

[0054] Regarding obtaining the hydroalkoxysilane compound (2), if a commercially available product is available, it may be obtained and used as is or after appropriate purification. As a method for producing the hydroalkoxysilane compound (2), various known synthesis methods can be adopted, and those skilled in the art can easily synthesize and utilize them. As long as it does not interfere with the production method 1 of the present invention, the production process of these hydroalkoxysilane compounds (2) may be included as a pre-step of the production method 1 of the present invention.

[0055] In the production method 1 of the present invention, X of the hydroalkoxysilane compound (2) 1 When is a halogen atom, the compound (2) is reacted with water or a metal oxide to produce the compound (2) (hereinafter referred to as Production Method 1-1).

[0056] X 1 The halogen represented by the formula (I) may be any one of a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. From the viewpoints of economy and good yield of the precursor, a chlorine atom or a bromine atom is preferred, and a chlorine atom is more preferred.

[0057] When water is used in the production method 1-1 of the present invention (hereinafter referred to as production method 1-1-1), the dihydrodisiloxane compound (1) of the present invention can be produced in good yield by reacting 0.3 to 10 molar equivalents of water with 1 mole of the raw material hydroalkoxysilane compound (2). From the viewpoints of economy, production efficiency, and reaction yield, the equivalent of water is preferably an equivalent appropriately selected from the range of 0.4 to 0.7 molar equivalents. In addition, in order to accelerate the production reaction, a base such as an organic amine may be added. Examples of the organic amine include primary amines such as butylamine and hexylamine, secondary amines such as dimethylamine and diethylamine, tertiary amines such as triethylamine and diisopropylethylamine, aromatic amines such as aniline, and heterocyclic amines such as pyridine, quinoline, and piperidine. From the viewpoints of economy and yield, triethylamine, diisopropylethylamine, or pyridine is preferred, and triethylamine or pyridine is more preferred.

[0058] In the production method 1-1-1, the production may be carried out in an organic solvent. Examples of the organic solvent that can be used include hydrocarbon solvents such as hexane, heptane, toluene, xylene, and benzene, ether solvents such as diethyl ether, dioxane, tetrahydrofuran, diisopropyl ether, methyl-tert-butyl ether, and cyclopentyl methyl ether, and halogenated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride. From the viewpoints of yield and economy, diethyl ether, tetrahydrofuran, dioxane, or cyclopentyl methyl ether is preferred, and diethyl ether or tetrahydrofuran is more preferred. These organic solvents may be used alone or in combination of two or more solvents at an appropriate ratio.

[0059] There are no particular limitations on the order of mixing the hydroalkoxysilane compound (2) and water when carrying out Production Method 1-1-1. For example, a method in which the hydroalkoxysilane compound (2) is mixed in an organic solvent and then water (or a metal oxide) is added thereto is preferred from the standpoints of yield and safety.

[0060] When carrying out the production method 1-1-1, it is preferable to carry out the method under an inert gas atmosphere in terms of good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, etc. Nitrogen or argon is preferable in terms of low cost.

[0061] In the production method 1-1-1, there are no limitations on the reaction temperature and reaction time, and general conditions used by those skilled in the art when carrying out a hydrolysis reaction of a functional silane can be used. As a specific example, the dihydrodisiloxane compound (1) can be produced in a good yield by appropriately selecting a reaction temperature within the range of -80°C to 300°C and an appropriate reaction time within the range of 1 minute to 120 hours.

[0062] When a metal oxide is used in Production Method 1-1 (hereinafter referred to as Production Method 1-1-2), examples of the metal oxide include zinc oxide, iron oxide, cobalt oxide, copper (I) oxide, copper (II) oxide, rhenium oxide, silver oxide, etc. Zinc oxide is preferably used from the viewpoint of high yield.

[0063] In the production method 1-1-2, the molar equivalent of the metal oxide is not particularly limited, and the compound can be produced in good yield at a molar ratio of, for example, the metal in the metal oxide within a range appropriately selected from between 0.5 and 20 molar equivalents per 1 molar equivalent of halogen atoms in the hydroalkoxysilane compound (2).

[0064] In the production method 1-1-2, the production may be carried out in an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, tert-butyl methyl ether, 1,4-dioxane, 1,2-dimethoxyethane, tetrahydrofuran, cyclopentyl methyl ether, and diglyme, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and carboxylate solvents such as ethyl acetate and methyl acetate. Among these, tetrahydrofuran, ethyl acetate, and methyl acetate are preferred from the viewpoints of economy, safety, and yield.

[0065] In the production method 1-1-2, it is preferable to carry out the method under an inert gas atmosphere in terms of a good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, etc. Nitrogen or argon is preferable in terms of low cost.

[0066] In the production method 1-1-2, there are no limitations on the reaction temperature and reaction time, and general conditions used by those skilled in the art when producing functional disiloxanes can be used. As a specific example, the dihydrodisiloxane compound (1) can be produced in good yield by appropriately selecting a reaction temperature within the range of -10°C to 300°C and an appropriate reaction time within the range of 1 minute to 120 hours.

[0067] In the production method 1 of the present invention, X of the hydroalkoxysilane compound (2) 1 When X is an alkoxy group (hereinafter referred to as Production Method 1-2), water is reacted with a hydroalkoxysilane compound (2) to produce a dihydrodisiloxane compound (1) of the present invention. 1 Examples of the alkoxy group represented by X include a methoxy group, an ethoxy group, a propyloxy group, and an isopropyloxy group. From the viewpoints of economy and good yield of the precursor, a methoxy group, an ethoxy group, and an isopropyloxy group are preferred, and a methoxy group or an ethoxy group is more preferred. 1 When X is an alkoxy group, 1 OR 2 From the viewpoint of yield, it is preferable that the alkoxy group is the same as the alkoxy group represented by the following formula:

[0068] In the production method 1-2, a dihydrodisiloxane compound can be produced in good yield by reacting 0.3 to 10 molar equivalents of water with 1 molar equivalent of the raw material hydroalkoxysilane compound (2). From the viewpoints of economy, production efficiency, and reaction yield, it is preferable that the equivalent of water is appropriately selected from the range of 0.4 to 0.7 molar equivalents. In addition, an acidic or basic catalyst may be used to accelerate the reaction.

[0069] In the production method 1 of the present invention, X of the hydroalkoxysilane compound (2) 1 When X is a dialkylamino group (hereinafter referred to as Production Method 1-3), water is reacted with a hydroalkoxysilane compound (2) to produce the dihydrodisiloxane compound (1) of the present invention. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a diisopropylamino group, a dibutylamino group, a piperidino group (N-piperidin-1-yl group), a pyrrolidino group (pyrrolidin-1-yl group), and a dihexylamino group. Of these, from the standpoint of economy and safety in handling, a dimethylamino group, a diethylamino group, or a diisopropylamino group is preferred, and a diethylamino group or a diisopropylamino group is more preferred. 1 When is a dialkylamino group, the dihydrodisiloxane compound (1) of the present invention can be produced in good yield by reacting 0.3 to 10 molar equivalents of water with 1 molar equivalent of the raw material hydroalkoxysilane compound (2). From the standpoints of economy, production efficiency, and reaction yield, it is preferable that the equivalent of water is appropriately selected from the range of 0.4 to 0.7 molar equivalents.

[0070] In the production method 1-3, the order of mixing the hydroalkoxysilane compound (2) and water is not particularly limited. For example, a method in which the hydroalkoxysilane compound (2) is mixed in an organic solvent and then water (or a metal oxide) is added thereto is preferred from the standpoints of yield and safety.

[0071] In Production Methods 1-2 and 1-3, similarly to Production Methods 1-1-1 and 1-1-2, production can be carried out using an organic solvent under an inert gas atmosphere, and the temperature and time conditions can also be similar.

[0072] The dihydrodisiloxane compound (1) produced by the production method 1 of the present invention can be purified by a person skilled in the art by appropriately selecting and using a general purification method used when purifying alkoxylated silanes. Specific purification methods include filtration, concentration, extraction, washing, drying, centrifugation, distillation, and chromatographic separation. Since purity is important for CVD materials, it is preferable to include a purification step using distillation.

[0073] Next, the production method 2 of the present invention will be described. The production method 2 of the present invention comprises reacting a dihalodisiloxane compound represented by the general formula (3) with a compound represented by the general formula (4) (R 2 O) n M (4) (R 2 is as defined above. M represents a hydrogen atom, an alkali metal, or an alkaline earth metal. n is 1 or 2, and is 1 when M is a hydrogen atom or an alkali metal, and is 2 when M is an alkaline earth metal. The method is characterized in that the dihydrodisiloxane compound (1) of the present invention is produced by reacting an alcohol or metal alkoxide represented by the formula (I) with an alcohol or metal alkoxide represented by the formula (I)

[0074] [ka]

[0075] (In the formula, R 1 represents an alkyl group having 1 to 6 carbon atoms. 2 R represents a halogen atom. 2 represents an alkyl group having 1 to 3 carbon atoms. The alcohol that can be used in the production method 2 is an aliphatic alcohol having 1 to 3 carbon atoms. Examples of the alcohol include methanol, ethanol, propyl alcohol, isopropyl alcohol, etc. Among these, from the viewpoints of yield and raw material cost, methanol, ethanol, or isopropyl alcohol is preferred, and methanol or ethanol is more preferred. The alcohol can be used as a commercially available product or after appropriate purification.

[0076] The metal alkoxide that can be used in the production method 2 is an alkali metal salt or an alkaline earth metal salt of an aliphatic alcohol having 1 to 3 carbon atoms, and examples of the metal alkoxide include lithium methoxide, lithium ethoxide, lithium isopropyl oxide, sodium methoxide, sodium ethoxide, sodium isopropyl oxide, potassium methoxide, potassium ethoxide, potassium isopropyl oxide, cesium methoxide, cesium ethoxide, cesium isopropyl oxide, magnesium methoxide, magnesium ethoxide, magnesium isopropyl oxide, etc. Among these, from the viewpoints of yield and raw material cost, sodium methoxide, sodium ethoxide, sodium propyl oxide, potassium methoxide, potassium ethoxide, magnesium methoxide, magnesium ethoxide, magnesium isopropyl oxide are preferred, and sodium methoxide, sodium ethoxide, and sodium propyl oxide are more preferred.

[0077] The metal alkoxide may be used as it is in the form of a commercially available powder, or may be used as a purchased alcohol solution of the metal alkoxide, or may be prepared by, for example, reacting an alkali metal with an alcohol, and these can be easily utilized by those skilled in the art.

[0078] The amount of alcohol used in Production Method 2 of the present invention is preferably an amount appropriately selected from 1.6 to 200 molar equivalents relative to the molar equivalent of dihalodisiloxane compound (3), more preferably an amount appropriately selected from 2 to 20 molar equivalents, and even more preferably an amount appropriately selected from 2 to 4 molar equivalents.

[0079] The amount of metal alkoxide used in Production Method 2 of the present invention is preferably an amount appropriately selected from 1.6 to 200 molar equivalents relative to the molar equivalent of dihalodisiloxane compound (3), more preferably an amount appropriately selected from 2 to 20 molar equivalents, and even more preferably an amount appropriately selected from 2 to 4 molar equivalents.

[0080] Examples of the dihalodisiloxane compound (3) that can be used as a raw material in Production Method 2 of the present invention include the following compounds.

[0081] [ka]

[0082] Among these, from the viewpoints of yield and economy, (3-1-1), (3-2-1) or (3-4-1) is preferred, with (3-1-1) being more preferred.

[0083] The production method 2 of the present invention is preferably carried out in an organic solvent. Examples of the organic solvent include ether solvents such as diethyl ether, tert-butyl methyl ether, 1,4-dioxane, 1,2-dimethoxyethane, tetrahydrofuran, cyclopentyl methyl ether, and diglyme, and hydrocarbon solvents such as pentane, hexane, heptane, octane, benzene, and toluene. Among these, diethyl ether, tetrahydrofuran, and cyclopentyl methyl ether are preferred from the viewpoints of economy, safety, and yield. The alcohol used as a raw material may be used in an equivalent amount or more to serve as both an organic solvent and an organic solvent.

[0084] When the production method 2 of the present invention is carried out using an alcohol, an organic amine compound may be used in combination. The organic amine compound reacts with hydrogen halide produced as a by-product in the reaction, and has the effect of increasing the reaction yield and promoting the reaction. Examples of the organic amine compound include trimethylamine, triethylamine, ethyldiisopropylamine, pyridine, and quinoline, and triethylamine or pyridine is preferred. The amount of the organic amine compound used is preferably a molar equivalent appropriately selected from 0.8 to 10 molar equivalents relative to 1 molar equivalent of the number of halogen atoms on silicon atoms of the dihalodisiloxane compound (3), more preferably a molar equivalent appropriately selected from 1.0 to 2.0 molar equivalents, and even more preferably a molar equivalent appropriately selected from 1.0 to 1.2 molar equivalents.

[0085] When carrying out the production method 2, it is preferable to carry out the process under an inert gas atmosphere in terms of good yield. Specific examples of the inert gas include nitrogen, helium, neon, argon, etc. Nitrogen or argon is preferable in terms of low cost. The reaction is preferably carried out under a pressure appropriately selected from the range of 0.1 to 1000 atm, more preferably from the range of 0.1 to 10 atm, and particularly preferably at 1 atm.

[0086] There are no particular limitations on the reaction temperature in Production Method 2 of the present invention, and from the standpoints of yield, safety, and operability, the reaction is preferably carried out at a temperature appropriately selected from the range of -80 to 200°C, more preferably from the range of -20 to 50°C, and especially preferably at room temperature. The reaction time is appropriately determined by checking the progress of the reaction by instrumental analysis, and dihydrodisiloxane compound (1) can be produced in good yield by carrying out the reaction for a reaction time appropriately selected from the range of 1 minute to 200 hours.

[0087] The dihydrodisiloxane compound (1) of the present invention produced by Production Method 2 can be purified by a purification method generally used by those skilled in the art when purifying alkoxysilanes, which is appropriately selected and carried out. Specific purification methods include filtration, concentration, extraction, washing, drying, centrifugation, distillation, etc. In particular, since purity is important for CVD materials, it is preferable to include a purification step using distillation.

[0088] When the dihydrodisiloxane compound (1) of the present invention is used as a precursor for a CVD process, specific means for the CVD process can include general means that are commonly used by those skilled in the art to prepare a silica thin film by a CVD method. When producing a silica thin film by a CVD method, the dihydrodisiloxane compound (1) of the present invention is vaporized and supplied as a gas to a reaction chamber. Examples of methods for vaporizing the dihydrodisiloxane compound (1) of the present invention include a bubbling method and a liquid injection method. The bubbling method is a method in which the dihydrodisiloxane compound (1) of the present invention is placed in a material container kept at a constant temperature by a thermostatic bath, and a carrier gas such as helium, neon, argon, krypton, xenon, or nitrogen is blown in to vaporize the dihydrodisiloxane compound (1) of the present invention. The liquid injection method is a method in which the dihydrodisiloxane compound (1) of the present invention is sent in a liquid state to a vaporizer and vaporized by heating in the vaporizer, etc. In the liquid injection method, the dihydrodisiloxane compound (1) of the present invention can also be used as a solution by dissolving it in a solvent.

[0089] A thin silica film can be produced on a substrate by decomposing the dihydrodisiloxane compound (1) of the present invention, which is supplied as a gas to a reaction chamber. Examples of methods for decomposing the dihydrodisiloxane compound (1) of the present invention include a method using heat, a method using plasma or light, and a method in which a reactive gas is fed into a reaction chamber to cause a chemical reaction. By using these methods alone or in combination, the dihydrodisiloxane compound (1) of the present invention can be decomposed to produce a thin silica film. [Industrial Applicability]

[0090] The dihydrodisiloxane compound (1) of the present invention contains, on the silicon atom, two different reactive functional groups, a hydrogen atom and an alkoxy group, and therefore can be used as a raw material for silicon-containing materials, such as various functional siloxane materials and organic silsesquioxane materials, or as a reducing agent or protecting group in organic synthesis reactions. EXAMPLES

[0091] The present invention will be described in more detail below with reference to examples and comparative examples. However, the scope of the present invention should not be construed as being limited to the specific examples shown below.

[0092] All preparations described in the examples were carried out under an argon atmosphere. 1 H-NMR (proton nuclear magnetic resonance spectrum), 13 C-NMR (Carbon-13 Nuclear Magnetic Resonance Spectrum) and 29 Si-NMR (silicon-29 nuclear magnetic resonance spectrum) measurements were performed using a Bruker Avance series Ascend 400 nuclear magnetic resonance spectrometer. Deuterated chloroform was used as the nuclear magnetic resonance spectrum measurement solvent, and chemical shifts were determined using tetramethylsilane as an internal standard. Infrared spectra were measured using a Horiba FT-720 spectrophotometer and a SensIRtechnologies DuraSamplIRII (reflection type) measurement cell. Mass spectrum and gas chromatography measurements were performed using a Shimadzu GCMS-QP2010 gas chromatography mass spectrometer and an Agilent Technologies DB-5MS capillary column.

[0093] The 1,3-dichloro-1,3-dimethyldisiloxane used in the production was synthesized according to the method described in the literature (U.S. Pat. No. 2,519,881). Tert-butyldichlorosilane (reagent manufactured by Sigma-Aldrich Japan Co., Ltd.), trichlorosilane (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 2-chloropropane (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), 2-chlorobutane (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), magnesium (reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), dehydrated diethyl ether (reagent manufactured by Kanto Chemical Co., Ltd.), dehydrated tetrahydrofuran (hereinafter, abbreviated as dehydrated THF) (reagent manufactured by Kanto Chemical Co., Ltd.), dehydrated hexane (reagent manufactured by Kanto Chemical Co., Ltd.), dehydrated methanol (reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), isopropyl alcohol (reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), pyridine (reagent manufactured by Kanto Chemical Co., Ltd.), triethylamine (reagent manufactured by Kanto Chemical Co., Ltd.), and diethylamine (reagent manufactured by Kanto Chemical Co., Ltd.) were purchased commercially and used as they were.

[0094] (Example 1) Synthesis of 1,3-dimethyl-1,3-di(isopropyloxy)disiloxane (exemplified compound number (1-1-2))

[0095] [ka]

[0096] A 200mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a Dimroth condenser and a three-way cock was replaced with argon, and 60mL of dehydrated diethyl ether, 14.3g (181mmol) of dehydrated pyridine and 15.0g (85.6mmol) of 1,3-dichloro-1,3-dimethyldisiloxane (exemplified compound number (3-1-1)) were placed in it. The container was cooled to 0°C, and a solution of 10.3g (171mmol) of 2-propanol in 40mL of dehydrated diethyl ether was dropped from the dropping funnel over 2 hours, stirred at room temperature for 16 hours, and heated to reflux for another 2 hours. Under an argon atmosphere, the precipitate was filtered off using a sintered glass filter. The filtrate was concentrated to remove low boiling point components, and the resulting crude product was distilled under reduced pressure (boiling point 76°C / 6.5 kPa) to obtain 14.5 g (yield 76%) of 1,3-dimethyl-1,3-di(isopropyloxy)disiloxane (exemplified compound number (1-1-2)) as a colorless liquid. Mass spectrum (electron impact ionization, 70 eV), m / z (%): 221 ([MH] + ,7),179([M-Pr] + ,23),137(100); 1 H-NMR (400MHz, CDCl 3 )δ(ppm):0.20(d,6H,J=1.6Hz),1.22(dd,12H,J=2.5,6.1Hz),4.16(m,2H),4.69(d,2H,J=1.3Hz); 13 C-NMR (101MHz, CDCl 3 )δ(ppm):-0.61,-0.59,25.38,25.51,66.09; 29 Si-NMR (79MHz, CDCl 3 ) δ(ppm):-28.19,-28.16; Infrared spectrum (neat, cm -1 ):2972,2933,2877,2139,1456,1383,1369,1257,1174,1124,1070,1030,903,874,860,762,667.

[0097] (Example 2) Production of 1,3-diisopropyl-1,3-dimethoxydisiloxane (exemplified compound number (1-4-1))

[0098] [ka]

[0099] 9.40g (387mmol) of magnesium metal cuttings was placed in a 500mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a Dimroth condenser, and a three-way cock, and the inside of the apparatus was replaced with argon. 10mL of dehydrated THF was placed in the three-neck flask, and 0.1mL of 1,2-dibromoethane was added to activate the magnesium. Next, 29.9g (381mmol) of 2-chloropropane in 190mL of dehydrated THF was dropped from the dropping funnel over 1.5 hours, and after the dropwise addition, the mixture was stirred at room temperature for another 1.5 hours to prepare an isopropyl magnesium chloride solution.

[0100] Separately, a 1000mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a Dimroth condenser, and a three-way cock was purged with argon, and 50.9g (376mmol) of trichlorosilane and 300mL of dehydrated THF were placed in the reaction vessel. The reaction vessel was cooled to -10℃, and the previously prepared isopropyl magnesium chloride solution was added dropwise from the dropping funnel over 4.5 hours. After the dropwise addition was completed, the reaction vessel was returned to room temperature and stirred for 72 hours to prepare an isopropyldichlorosilane solution.

[0101] The above isopropyldichlorosilane solution was cooled to 0°C, and a mixture of 77.5g (0.765mol) of triethylamine and 27.1g (0.376mol) of diethylamine was added dropwise from the dropping funnel over 1 hour, followed by stirring for another 2 hours. Next, a solution of 12.1g (0.376mol) of methanol in 40mL of dehydrated THF was added dropwise from the dropping funnel at 0°C over 2 hours. After the dropwise addition was completed, the mixture was stirred at room temperature for 16 hours to prepare a solution of (diethylamino)isopropylmethoxysilane (exemplified compound number (2-4-13)).

[0102] Next, 3.99 g (0.188 mol) of distilled water was slowly added to the three-neck flask with stirring from a syringe, and the mixture was then heated to reflux for 2 hours. The solution was concentrated to about half its original volume under reduced pressure, 300 mL of dehydrated hexane was added, and the solids were filtered off using a sintered glass filter under an argon atmosphere. This was concentrated again, diluted with dehydrated hexane, and the solids were filtered off again using a sintered glass filter. The crude product obtained after concentration was distilled under reduced pressure (boiling point 86°C / 4.8 kPa) to obtain 22.6 g (54% yield from trichlorosilane) of 1,3-diisopropyl-1,3-dimethoxydisiloxane (exemplified compound number (1-4-1)) as a colorless liquid. This compound is a mixture of molecules with stereochemistry of (1R,3R) and (1S,3S) based on the stereoisomerism on silicon, and (1R,3S), and a nuclear magnetic resonance spectrum based on the presence of two diastereomeric isomers was observed. Mass spectrum (electron impact ionization, 70 eV), m / z (%): 179 ([M-Pr] + ,100),151(72),121(65); 1 H-NMR (400MHz, CDCl 3 )δ(ppm):0.842~0.932(m,2H),1.01(dd,12H,J=7.1,1.3Hz),3.57(s,6H),4.44(d,2H,J=0.68Hz); 13 C-NMR (101MHz, CDCl 3 ) δ(ppm):13.49,15.67,51.28; 29 Si-NMR (79MHz, CDCl 3 ) δ(ppm):-21.90,-21.87; Infrared spectrum (neat, cm -1 ):2945,2897,2868,2837,2131,1464,1385,1246,1190,1165,1088,1057,1001,922,881,825,766,683,661,648.

[0103] (Synthesis Example 1) Preparation of sec-butyldichlorosilane

[0104] [ka]

[0105] 13.4g (552mmol) of magnesium metal cuttings was placed in a 500mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a Dimroth condenser, and a three-way cock, and the inside of the apparatus was replaced with argon. 20mL of dehydrated diethyl ether was placed in the three-neck flask, and 0.1mL of 1,2-dibromoethane was added to activate the magnesium. Next, 50.2g (0.543mol) of 2-chlorobutane in 700mL of dehydrated diethyl ether was dropped from the dropping funnel over a period of 2 hours while maintaining reflux, and after the dropwise addition was completed, the mixture was stirred at room temperature for 1.5 hours to prepare a sec-butylmagnesium chloride solution.

[0106] Separately, a 1000mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a Dimroth condenser, and a three-way cock was replaced with argon, and 66.6g (492mmol) of trichlorosilane and 400mL of dehydrated diethyl ether were placed in the reaction vessel. The solution was cooled to -10℃, and the previously prepared sec-butyl magnesium chloride solution was added dropwise from the dropping funnel over 3.5 hours. After the dropwise addition was completed, the reaction vessel was returned to room temperature and stirred for 18 hours. 150mL of dehydrated diethyl ether and 300mL of hexane were added to the reaction mixture, and the solid precipitate was filtered out using a sintered glass filter under an argon atmosphere. The solution was concentrated and then distilled (boiling point 123℃) at normal pressure to obtain 45.2g (yield 58.5%) of sec-butyldichlorosilane as a colorless liquid. 1 H-NMR (400MHz, CDCl 3 )δ(ppm):1.03(t,3H,J=7.4Hz),1.11-1.21(m,4H),1.36-1.47(m,1H); 13 C-NMR (101MHz, CDCl 3 )δ(ppm):12.06,12.72,23.31,25.72; 29 Si-NMR (79MHz, CDCl 3 ) δ(ppm):13.00.

[0107] (Example 3) Synthesis of 1,3-di-sec-butyl-1,3-dimethoxydisiloxane (exemplified compound number (1-7-1))

[0108] [ka]

[0109] A 300 mL three-neck flask equipped with a dropping funnel, a Dimroth condenser, a magnetic stirrer, and a three-way cock was replaced with argon. 120 mL of dehydrated THF and 9.98 g (63.5 mmol) of sec-butyldichlorosilane obtained in Synthesis Example 1 were placed in the three-neck flask. The reaction vessel was cooled to -10 degrees, and a mixture of 10.0 g (0.127 mol) of pyridine and 4.66 g (63.7 mmol) of diethylamine was added dropwise from the dropping funnel over 1.5 hours, and then the mixture was returned to room temperature and stirred for 2 hours to prepare a solution of sec-butylchloro(diethylamino)silane.

[0110] The reaction vessel was cooled again to -10°C, and a solution of 2.08g (64.8mmol) of methanol in 10mL of dehydrated THF was added dropwise from the dropping funnel over 1 hour. After the dropping was completed, the mixture was stirred at room temperature for 30 minutes and further heated under reflux for 2 hours to prepare a solution of sec-butyl(diethylamino)methoxysilane (exemplified compound number (2-7-13)).

[0111] The mixture was returned to room temperature, 0.575 g (31.9 mmol) of distilled water was added via syringe, and the mixture was stirred at room temperature for 16 hours, and then heated to reflux for 1 hour. The solution was concentrated under reduced pressure until the volume was reduced to about half, and filtered under an argon atmosphere using a Schlenk tube equipped with a glass filter and lined with Celite. The filtrate was concentrated again under reduced pressure, and the obtained crude product was distilled under reduced pressure (boiling point 110°C / 3.6 kPa), to obtain 34.3 g (yield from sec-butyldichlorosilane: 47.1%) of 1,3-di-sec-butyl-1,3-dimethoxydisiloxane (exemplified compound number (1-7-1)) as a colorless liquid. This compound is a mixture of molecules having stereochemistry of (1R,3R) and (1S,3S) based on stereoisomerism on silicon, and (1R,3S), and a nuclear magnetic resonance spectrum based on the presence of two diastereoisomers was observed.

[0112] Mass spectrum (electron impact ionization, 70 eV), m / z (%): 193 ([M-Bu] + ,53),151(25),137(100); 1 H-NMR (400MHz, CDCl 3 )δ(ppm):0.675~0.766(m,2H),0.95~1.00(m,12H),1.23~1.34(m,2H),1.54~1.65(m,2H),3.57(s,6H),4.49(s,2H); 13 C-NMR (101MHz, CDCl 3 )δ(ppm):12.43,12.53,13.07,13.10,21.31,21.35,23.69,23.77,51.32,51.33; 29 Si-NMR (79MHz, CDCl 3 ) δ(ppm):-22.26,-22.20,-22.15; Infrared spectrum (neat, cm -1 ):2960,2933,2871,2856,2837,2127,1458,1379,1338,1296,1261,1211,1190,1161,1088,1066,1032,1001,968,953,931,829,764,706,667.

[0113] Example 4: Synthesis of 1,3-di(tert-butyl)-1,3-dimethoxydisiloxane (exemplified compound number (1-8-1))

[0114] [ka]

[0115] A 200mL three-neck flask equipped with a magnetic stirrer, a dropping funnel, a Dimroth condenser and a three-way cock was replaced with argon, and 5.22g (33.2mmol) of tert-butyldichlorosilane, 5.30g (67.1mmol) of dehydrated pyridine and 40mL of dehydrated THF were placed in the flask. The flask was cooled to -10°C, and a solution of 2.43g (33.2mol) of diethylamine in 30mL of THF was added dropwise from the dropping funnel over 30 minutes, and then the mixture was stirred at room temperature for 16 hours. The reaction mixture was then heated to reflux for 30 minutes. The reaction vessel was cooled again to -10°C, and a solution of 1.06g (33.3mmol) of methanol in 20mL of THF was added dropwise from the dropping funnel over 30 minutes. After the dropwise addition was completed, the reaction mixture was heated to reflux for 1 hour. After cooling the reaction vessel to -10°C again, a solution of 0.301g (16.7mmol) of distilled water in 20mL of THF was added dropwise from the dropping funnel over 30 minutes. After the dropwise addition was completed, the reaction mixture was heated to reflux for 1 hour. The solution was concentrated under reduced pressure until the liquid volume was reduced to about half, and the solid matter was filtered out using a sintered glass filter under an argon atmosphere. The filtrate was concentrated, and the obtained crude product was distilled under reduced pressure (distillation temperature 95°C / 6.0kPa) using a Kugelrohr distillation apparatus, to obtain 1.67g (yield from tert-butyldichlorosilane) of 1,3-di(tert-butyl)-1,3-dimethoxydisiloxane (exemplified compound number (1-8-1)) as a colorless liquid (40.0% yield from tert-butyldichlorosilane). This compound is a mixture of molecules with stereochemistry at silicon, (1R,3R) and (1S,3S), as well as (1R,3S), and the nuclear magnetic resonance spectrum was observed based on the existence of two diastereoisomers. Mass spectrum (electron impact ionization, 70 eV), m / z (%): 249 ([MH] + ,0.3),219([M-OMe] +,0.2),193([M-Bu] + ,100); 1 H-NMR (400MHz, CDCl 3 ) δ(ppm): 0.941(s,18H), 3.59(s,6H), 4.39(s,Si-H of one geometric isomer), 4.49(s,Si-H of the other geometric isomer); 13 C-NMR (101MHz, CDCl 3 )δ(ppm):17.83,17.84,24.71,51.61,51.64; 29 Si-NMR (79MHz, CDCl 3 ) δ(ppm):-22.31,-22.26,-22.15; Infrared spectrum (neat, cm -1 ):2954,2931,2900,2860,2837,2125,1473,1464,1390,1363,1227,1190,1074,1005,941,883,827,762,702.

[0116] (Evaluation Example 1) Film formation using 1,3-diisopropyl-1,3-dimethoxydisiloxane (compound (1-4-1)) Using 1,3-diisopropyl-1,3-dimethoxydisiloxane (compound (1-4-1)), together with oxygen, a silicon oxide film was formed on a PEN film by the PECVD method. The supply flow rate of 1,3-diisopropyl-1,3-dimethoxydisiloxane (compound (1-4-1)) was 13 sccm, the oxygen supply flow rate was 90 sccm, the film formation chamber pressure was 40 Pa, and the power of the high frequency power source (RF power source) with a power frequency of 13.56 MHz was 900 W, and film formation was performed for 2 minutes. In addition, the supply flow rate ratio (Y / X) of oxygen to the supply flow rate of 1,3-diisopropyl-1,3-dimethoxydisiloxane (compound (1-4-1)) was 6.9.

[0117] The thickness of the silicon oxide film obtained was 306 nm. The film formation rate was 153 nm / min. The film composition was Si=33 atom%, O=67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR was 6.4×10 -3 g / m 2 ·day.

[0118] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 86.8%.

[0119] When 1,3-diisopropyl-1,3-dimethoxydisiloxane (compound (1-4-1)) is used to form a silicon oxide film together with oxygen by the PECVD method, the WVTR is 10 -3 g / m 2 The film showed high gas barrier performance on the order of 10 days, and the film formation rate was high at over 100 nm / min, making it suitable as a gas barrier film.

[0120] (Comparative Evaluation Example 1) Film formation using tert-butyltriethoxysilane A silicon oxide film was formed on a PEN film by PECVD using tert-butyltriethoxysilane synthesized with reference to the method described in K. Lin, RJ Wiles, CB Kelly, GHMDavies, GA Molander, ACS Catalysis, 2017, Vol. 7, pp. 5129-5133. The supply flow rate of tert-butyltriethoxysilane was 80sccm, the supply flow rate of oxygen was 2100sccm, the pressure in the deposition chamber was 8Pa, and the power of the high frequency power source (RF power source) with a power frequency of 13.56MHz was 1000W. The deposition was performed for 14 minutes. The ratio of the supply flow rate of oxygen to the supply flow rate of tert-butyltriethoxysilane, Y / X, was 26.3.

[0121] The thickness of the obtained silicon oxide film was 800 nm. The composition of the film was Si=33 atom%, O=67 atom%, and the carbon concentration was less than 1.0 atm%. The WVTR value was 2.0×10 -4 g / m 2 ·day.

[0122] The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.2%.

[0123] Using tert-butyltriethoxysilane and oxygen, a silicon oxide film was formed on a PEN film by the PECVD method. The supply flow rate of tert-butyltriethoxysilane was 80sccm, the supply flow rate of oxygen was 2100sccm, the pressure in the deposition chamber was 8Pa, and the power of the high frequency power source (RF power source) with a power frequency of 13.56MHz was 1000W, and the deposition was performed for 7 minutes. The ratio of the supply flow rate of oxygen to the supply flow rate of tert-butyltriethoxysilane, Y / X, was 26.3.

[0124] The thickness of the obtained silicon oxide film was 400 nm. The film formation rate was 57 nm / min. The WVTR value was 4.3×10 -4 g / m 2 The visible light transmittance of the laminated film consisting of a silicon oxide film and a PEN film was 88.5%.

[0125] When tert-butyltriethoxysilane is used together with oxygen to form a silicon oxide film by PECVD, the WVTR is 10 -3 g / m 2 · 10 day order or less -4 g / m 2 Although the deposition rate is on the order of days, the deposition rate is low at 57 nm / min, resulting in poor productivity.

[0126] (Comparative Evaluation Example 2) Film formation using hexamethyldisiloxane Hexamethyldisiloxane was used together with oxygen to form a film on a PEN film by the PECVD method. The supply flow rate of hexamethyldisiloxane was 80sccm, the supply flow rate of oxygen was 2100sccm, the pressure in the film formation chamber was 6Pa, and the power of the high frequency power source (RF power source) with a power frequency of 13.56MHz was 1000W, and film formation was performed for 2 minutes. The ratio of the supply flow rate of oxygen to the supply flow rate of hexamethyldisiloxane, Y / X, was 26.3.

[0127] The thickness of the obtained film was 200 nm. The deposition rate was 117 nm / min. The WVTR was 2.4 × 10 -2 g / m 2 ·day, which showed a high value.

[0128] When hexamethyldisiloxane is used together with oxygen to form a silicon oxide film by the PECVD method, the film formation rate is high at 117 nm / min for a thin silicon oxide film with a thickness of 200 nm, but the WVTR is 2.4 × 10 -2 g / m 2 ·day, which showed a high value.

Claims

1. General formula (1) 【Chemistry 1】 （１） (In the formula, R １ represents a linear or branched alkyl group having 2 to 6 carbon atoms; R ２ R represents a linear or branched alkyl group having 1 to 3 carbon atoms. １ and R ２ The sum of the carbon numbers of the alkyl groups represented by the formula: is 4 or more and 9 or less. When R 1 has 2 carbon atoms, R 2 has 2 carbon atoms.

2. In general formula (1), R １ 2. The dihydrodisiloxane compound according to claim 1, wherein is an ethyl group or an isopropyl group.

3. In general formula (1), R １ is an isopropyl group, R ２ The dihydrodisiloxane compound according to claim 1 or 2, wherein is a methyl group.

4. General formula (2) 【Chemistry 2】 （２） (In the formula, X １ represents a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms. １ represents a linear or branched alkyl group having 2 to 6 carbon atoms; R ２ represents a linear or branched alkyl group having 1 to 3 carbon atoms; R １ and R ２ The sum of the carbon numbers of the alkyl groups represented by the general formula (1) is 4 or more and 9 or less. When R 1 has 2 carbon atoms, R 2 has 2 carbon atoms. 【Chemistry 3】 （１） (In the formula, R １ and R ２ has the same meaning as defined above.

5. General formula (3) 【Chemistry 4】 （３） (In the formula, X ２ represents a halogen atom. １ represents a linear or branched alkyl group having 2 to 6 carbon atoms.) is reacted with a dihalodihydrodisiloxane compound represented by the general formula (4): (R ２ O) ｎ M (4) (R ２ represents a linear or branched alkyl group having 1 to 3 carbon atoms; M represents a hydrogen atom, an alkali metal, or an alkaline earth metal; n is 1 or 2, and represents 1 when M is a hydrogen atom or an alkali metal, and represents 2 when M is an alkaline earth metal, respectively. 【Chemistry 5】 （１） (In the formula, R １ and R ２ is as defined above, R １ and R ２ The sum of the carbon numbers of the alkyl groups represented by the formula: is 4 or more and 9 or less. When R 1 has 2 carbon atoms, R 2 has 2 carbon atoms.

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