JP2018062500A - Sulfobetaine-based silicon-based compound and manufacturing method therefor - Google Patents

Abstract

A coating composition that forms an excellent antifogging and hydrophilic film even on the surface of the substrate, which does not easily separate from inorganic, carbon, metal and polymer substrates even when contacted with water. Of a method for easily producing a sulfobetaine-based silicon compound which is a component of SOLUTION: A dialkylamino group-containing silicon compound and a cyclic sulfonic acid ester having 3 to 10 carbon atoms are used as a water-soluble secondary or tertiary alcohol solvent, a water-soluble ether solvent having no primary alcoholic hydroxyl group, A method for producing a compound represented by the following formula, which is reacted in a water-soluble ester solvent, a water-soluble ketone solvent and an aprotic solvent. (R1O) 3-k (R2) kSi-R3- (X-R4) m-N + (R5) (R6)-(CH2) n-SO3- {R1, R2, R5 and R6 are alkyl groups; R3 and R4 Represents an alkylene group; X represents —NHCOO—, —NHCONH—, —S— or —SO 2 —. } [Selection figure] None

Description

  The present invention relates to a method for producing a sulfobetaine-based silicon compound for hydrophilizing the surface and a sulfobetaine-based silicon compound for hydrophilizing the surface. More specifically, the present invention relates to a hydrophilic coating composition capable of imparting hydrophilicity to the substrate surface by forming a film on the substrate surface and a structure obtained by curing the coating composition after coating.

Known surface properties required for substrates include hydrophilicity, antifogging properties, antistatic properties, antifouling properties, biocompatibility, and the like.
These surface properties are generally imparted by imparting hydrophilicity to the substrate.

As a sulfobetaine-based silicon compound capable of imparting antifogging properties to a substrate, a reaction product of N, N-dimethyl-3- (trimethoxysilyl) propylamine and 1,3-propane sultone is known. (For example, refer to Patent Document 1). However, the surface treatment agent derived only from this compound can be coated on an inorganic oxide substrate such as glass, and the surface treatment agent's silanol group and the hydroxyl group on the surface of the inorganic oxide are chemically bonded to provide durability. However, when it is applied to a plastic substrate, it has the disadvantage that there is almost no interaction with the plastic substrate and the durability is poor.
As a coating agent that can be applied to an organic substrate, the present inventors have disclosed a metal oxide sol modified with a silicon-based compound having a sulfonic acid group and a hydrophilic coating composition comprising the metal oxide sol (for example, Patent Documents). No. 2) has already been filed, but this coating agent is required to have a higher antifogging substance.

  In addition, since N, N-dimethylaminopropyltrimethoxysilane is not available as an industrial raw material, sulfobetaine-based silane coupling agents derived from this raw material are difficult to produce in large quantities and are expensive. Has the disadvantage of becoming.

In order to overcome the above problems, the present inventors comprise a metal oxide sol modified with a sulfobetaine-based silicon compound as an antifogging coating agent that can be applied to inorganic and organic substrates, and the metal oxide sol. The antifogging coating composition has been found and a patent application has been filed (for example, see Japanese Patent Application No. 2006-123562), but the sulfobetaine silicon compound as a raw material is produced using a water-insoluble organic solvent.
That is, a water-insoluble organic solvent (hydrocarbon solvents such as benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, N, N-dialkylaminoalkyltrialkoxysilanes {for example, N, N-dimethyl- in halogenated hydrocarbon solvents such as 1,1,2,2-tetrachloroethane, trichlorotrifluoroethane and tetrachlorodifluoroethane) 3- (trimethoxysilyl) propylamine, etc.} and a cyclic sulfonic acid ester having 3 to 10 carbon atoms (for example, 1,3-propane sultone), and the resulting precipitation product (sulfobetaine silicon compound) Isolation by filtration, followed by metal oxide solution in a mixed solution of water and water-soluble solvent And by reacting, to obtain the anti-fogging coating composition comprising consisting modified metal oxide sol and the metal oxide sol sulfobetaine silicon compound.

However, since the organic solvent used in the step of producing the sulfobetaine-based silicon compound is insoluble in water, the step of removing the organic solvent insoluble in water during the production of the antifogging coating composition comprising the sulfobetaine-based silicon compound is necessary.
Further, since the produced sulfobetaine-based silicon compound is deliquescent, it easily absorbs water and easily hydrolyzes, so that handling is complicated such as preventing moisture.
Therefore, the manufacturing process becomes complicated, and as a result, there is a problem that the manufacturing cost of the sulfobetaine-based silicon compound and the antifogging coating composition derived from the compound is increased.

A production method using a water-soluble solvent is also known (for example, see Patent Document 3). However, since acetonitrile used in the examples is a deleterious substance and is highly toxic, it is difficult to use as a component of an antifogging coating composition, and it is necessary to isolate a sulfobetaine-based silicon compound in order to remove acetonitrile. There is a problem that the production process becomes complicated and the production cost of the antifogging coating composition derived from the sulfobetaine silicon compound and the compound increases.
In addition, although methanol and ethanol are described as water-soluble solvents that can be used in the specification of this document, N, N-dimethyl-3- (trimethoxysilyl) propylamine and 1,3-propanesal in ethanol are described. As a result, it was confirmed that a compound insoluble in ethanol or water was produced and could not be used as an antifogging coating composition liquid.

Japanese Patent Laid-Open No. 5-222064 Japanese Patent No. 5750436 Japanese Patent Laid-Open No. 7-101965

The present invention has been made in view of the prior art, and aims to provide a raw material sulfobetaine-based silicon compound by a simpler process in order to provide an anti-fogging coating composition liquid at a lower cost. And
The second object of the present invention is that it is difficult to separate from an inorganic base material even when it comes into contact with water, and it is easy to form a uniform antifogging film on the surface of the inorganic base material. An object of the present invention is to provide a silane coupling agent and a surface hydrophilizing agent comprising the compound in large quantities at a low cost using raw materials available as industrial raw materials.

As a result of intensive investigations while paying attention to the problems of the prior art as described above, the present inventors have found that water-soluble secondary alcohol solvents, water-soluble solvents are used as organic solvents used in the process of producing sulfobetaine-based silicon compounds. The present invention has been found out that the above-mentioned problems can be solved by using an ether solvent, a water-soluble ketone solvent and an aprotic solvent that do not have a primary alcoholic hydroxyl group.
Also, an isocyanate group-containing silane coupling agent and N, N-dialkylaminoalkyl alcohol or N, N-dialkylaminoalkyl which can be obtained as an industrial raw material in place of N, N-dimethylaminopropyltrimethoxysilane which is expensive and cannot be obtained as an industrial raw material The present inventors have found that the above-mentioned problems can be solved by using an amine reaction product, or a thiol group-containing silane coupling agent and N, N-dialkylaminoallylamine as raw materials, and have reached the present invention.

That is, the present invention is characterized by having the following configuration and solves the above problems.
[1] A compound represented by the following formula (1) and a cyclic sulfonic acid ester having 3 to 10 carbon atoms, a water-soluble secondary or tertiary alcohol solvent, an ether system having no water-soluble primary alcoholic hydroxyl group A process for producing a compound represented by the following formula (2), wherein the reaction is carried out in a solvent, a water-soluble ester solvent, a water-soluble ketone solvent and an aprotic solvent.
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 - (X-R 2) m -N (R 3) (R 4) (1)
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 - (X-R 2) m -N + (R 3) (R 4) - (CH 2) n -SO 3 - (2)
{In the formula, X ¹ may be the same or different and represents any of an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group and a halogen atom; k represents 0 or 1; and R ¹ represents an alkylene group having 1 to 5 carbon atoms. X represents —NHCOO—, —NHCONH—, —S— or —SO ₂ —, m represents 0 or 1, and R ² represents an ether bond, ester bond or amide bond having 1 to 10 carbon atoms. Represents an alkylene group which may be included or —CH ₂ CH ₂ N ⁺ (CH ₃ ) {(CH ₂ ) _n SO ₃ ⁻ )} CH ₂ CH ₂ OCH ₂ CH ₂ —, and R ³ and R ⁴ may be the same or different. Represents an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 3 to 10. }
[2] The process according to [1], wherein the cyclic sulfonic acid ester having 3 to 10 carbon atoms is 1,3-propane sultone.
[3] The method according to [1] or [2], wherein the water-soluble solvent is isopropyl alcohol.
[4] A betaine-based silicon compound represented by the following formula (3).
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 -NHCONH-R 2 -N + (R 3) (R 4) - (CH 2) n -SO 3 - (3)
{In the formula, X ¹ may be the same or different and represents any of an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group and a halogen atom; k represents 0 or 1; and R ¹ represents an alkylene group having 1 to 5 carbon atoms. R ² represents an alkylene group which may contain an ether bond, an ester bond or an amide bond having 1 to 10 carbon atoms, —CH ₂ CH ₂ N ⁺ (CH ₃ ) (R ⁵ —SO ₃ ^— ) CH ₂ CH ₂ Represents OCH ₂ CH ₂ —, R ³ and R ⁴ represent the same or different alkyl group having 1 to 3 carbon atoms, and n represents an integer of 3 to 10}.
[5] A hydrophilic coating composition solution containing the hydrolysis product of the betaine-based silicon compound according to [4] in a solution.
[6] A structure obtained by curing the hydrophilic coating composition according to [5] after coating.

  According to the production method of the present invention, the sulfobetaine-based silicon compound can be produced at a low cost, and an operation of filtration and isolation is unnecessary, and as a result, there is little possibility of hydrolysis. A coatable sulfobetaine-based silicon compound having a large antifogging effect, hydrophilic effect and antistatic effect on organic substrates and high durability can be provided at low cost.

  That is, when producing an antifogging coating composition from a sulfobetaine-based silicon compound, a process for removing the organic solvent insoluble in water is required, compared to the conventional production method using an organic solvent insoluble in water. Therefore, the manufacturing process can be simplified. As a result, handling of the sulfobetaine-based silicon compound that is deliquescent, easily absorbs water and easily hydrolyzes, has troublesome handling such as preventing moisture, but also has an effect of easy handling.

  Further, the sulfobetaine-based silicon compound and the hydrophilic coating composition of the present invention are hydrophilic on the surface of a substrate such as a glass plate, a medical material, a biocompatible material, a cosmetic material, an optical material, a resin film, and a resin sheet. It is useful for imparting uniform properties and antifogging properties.

The production method of the present invention comprises a dialkylamino group-containing silicon compound represented by the following formula (1) and a cyclic sulfonic acid ester having 3 to 10 carbon atoms, a water-soluble secondary or tertiary alcohol solvent, a water-soluble 1 Production of a compound represented by the following formula (2), which is reacted in an ether solvent having no secondary alcoholic hydroxyl group, a water-soluble ester solvent, a water-soluble ketone solvent and an aprotic solvent Is the method.
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 - (X-R 2) m -N (R 3) (R 4) (1)
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 - (X-R 2) m -N + (R 3) (R 4) - (CH 2) n -SO 3 - (2)
{In the formula, X ¹ may be the same or different and represents any of an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group and a halogen atom; k represents 0 or 1; and R ¹ represents an alkylene group having 1 to 5 carbon atoms. X represents —NHCOO—, —NHCONH—, —S— or —SO ₂ —, m represents 0 or 1, and R ² represents an ether bond, ester bond or amide bond having 1 to 10 carbon atoms. Represents an alkylene group which may be included or —CH ₂ CH ₂ N ⁺ (CH ₃ ) {(CH ₂ ) _n SO ₃ ⁻ )} CH ₂ CH ₂ OCH ₂ CH ₂ —, and R ³ and R ⁴ may be the same or different. Represents an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 3 to 10. }

The compound of the present invention is a betaine silicon compound represented by the following formula (3).
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 -NHCONH-R 2 -N + (R 3) (R 4) - (CH 2) n -SO 3 - (3)
{In the formula, X ¹ may be the same or different and represents any of an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group and a halogen atom; k represents 0 or 1; and R ¹ represents an alkylene group having 1 to 5 carbon atoms. R ² represents an alkylene group which may contain an ether bond, an ester bond or an amide bond having 1 to 10 carbon atoms, —CH ₂ CH ₂ N ⁺ (CH ₃ ) (R ⁵ —SO ₃ ^— ) CH ₂ CH ₂ Represents OCH ₂ CH ₂ —, R ³ and R ⁴ represent the same or different alkyl group having 1 to 3 carbon atoms, and n represents an integer of 3 to 10}.

Formula (1) and (2) and (3), as the ^{X 1,} an alkoxy group having 1 to 5 carbon atoms and a hydroxyl group and a halogen atom. Of these, a methoxy group, an ethoxy group, and an isopropyloxy group are preferable, and a methoxy group and an ethoxy group are particularly preferable.

Formula (1) and (2) and (3), the alkylene group having 1 to 5 carbon atoms for ^{R 1,} a methylene group, an ethylene group, trimethylene group, tetramethylene group, pentamethylene group. Among these, a trimethylene group is preferable in view of easy availability of raw materials.

  In the above formulas (1), (2) and (3), k is 0 or 1.

In the formulas (1) and (2), X is —NHCOO—, —NHCONH—, —S— or —SO ₂ —.

Formula (Formula (1), (2) and (3), an ether bond as ^{R 2,} an alkylene group of good C1-10 contain an ester bond or an amide bond or _-CH 2 _CH 2 ^{N +} _{(CH 3) {(CH 2} ) n SO 3 -)} CH 2 CH 2 OCH 2 CH 2 - is. Among these, an ethylene group, a trimethylene group and an ethyleneoxyethylene group and —CH ₂ CH ₂ N ⁺ (CH ₃ ) {(CH ₂ ) _n SO ₃ ⁻ )} CH ₂ CH ₂ OCH ₂ CH ₂ — are preferable. .

  In the formulas (1) and (2), m is 0 or 1.

In the above formulas (in the above formulas (1), (2) and (3), examples of the alkyl group having 1 to 3 carbon atoms of R ³ and R ⁴ include a methyl group, an ethyl group, and an n-propyl group. Of these, a methyl group is preferred.

Specific examples of the compound represented by the formula (1) include silicon compounds having the following dimethylamino group at the terminal.
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ (1-1)
_{(CH 3 O) 2 Si (} CH 3) CH 2 CH 2 CH 2 N (CH 3) 2 (1-2)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N (CH 3) 2
(1-3)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 N (CH 3) 2
(1-4)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 CH 2 N (CH 3) 2 (1-5)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 OCH 2 CH 2 N (CH 3) 2 (1-6)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N (CH 3) CH 2 CH 2 OCH 2 CH 2 N (CH 3) 2 (1-7)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 N (CH 3) 2
(1-8)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 N (CH 3) 2 (1-9)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂
(1-10)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ COOCH ₂ CH ₂ N (CH ₃ ) ₂ (1-11)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH (CH 3) COOCH 2 CH 2 N (CH 3) 2 (1-12)
_{(CH 3 O) 2 Si (} CH 3) CH 2 CH 2 CH 2 SCH 2 CH 2 CH 2 N (CH 3) 2
(1-13)
_{(C 2 H 5 O) 2} Si (CH 3) CH 2 CH 2 CH 2 N (CH 3) 2 (1-14)

Specific examples of the cyclic sulfonic acid ester having 3 to 10 carbon atoms include 1,3-propane sultone, 1,3-butane sultone, 1,4-butane sultone, 2,4-butane sultone, 1,5-pentane sultone, Examples include 2,4-pentane sultone, 1,4-hexane sultone, 4,6-heptane sultone, and the like.
Among these, 1,3-propane sultone, 1,4-butane sultone, and 2,4-butane sultone are preferable, 1,3-propane sultone and 1,4-butane sultone are more preferable, and 1,3-butane sultone is more preferable. Propane sultone.

  The charged molar ratio of the cyclic sulfonic acid ester having 3 to 10 carbon atoms to the compound represented by the formula (1) is 0.1 to 1.5 with respect to the compound represented by the formula (1), preferably Is 0.25 to 1.0, particularly preferably 0.5 to 1.0.

In the present invention, the water-soluble organic solvent means a solvent that dissolves 1% by weight or more in water.
Preferred are those that dissolve 10% by weight or more, and more preferably those that dissolve 25% by weight or more.

  Examples of the water-soluble solvent used in the above reaction include secondary or tertiary alcohol solvents (iso-propanol, sec-butyl alcohol, tert-butyl alcohol, propylene glycol monomethyl ether, etc.), ether solvents (tetrahydrofuran, 1, 4-dioxane, 1,3-dioxolane, triethylene glycol butyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetraethylene glycol Dimethyl ether, triethylene glycol dimethyl Ether, tripropylene glycol dimethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, etc.), ester solvents (methyl acetate, ethyl acetate, ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether acetate, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, γ-butyrolactone, etc., ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisopropyl ketone, Clohexanone, etc.) and aprotic solvents (dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, etc.).

  Among these, a secondary alcohol solvent, an ether solvent, an ester solvent, and a ketone solvent are preferable, and a secondary alcohol solvent is particularly preferable.

The reaction temperature is usually 0 ° C. to 200 ° C., preferably the boiling point or higher of the solvent used, and the reaction may be carried out under pressure to bring the temperature to the boiling point or higher.
The reaction time is usually 1 hour to 36 hours, preferably 4 hours to 36 hours, particularly preferably 4 hours to 24 hours.

  When the dialkylamino group-containing silicon compound represented by the formula (1) and the cyclic sulfonic acid ester compound having 3 to 10 carbon atoms are reacted in the above-mentioned solvent which is the production method of the present invention, the sulfobetaine-based silicon compound is a solvent. Dissolved in or obtained as a precipitate.

  In the next step, hydrolysis is performed using a water-soluble solvent and water. In the production method of the present invention, since the organic solvent used for producing the sulfobetaine-based silicon compound is soluble in water, the next step {hydrolysis of the sulfobetaine silicon compound or metal oxide sol by the sulfobetaine silicon compound] It becomes possible to use the organic solvent used in the production of the surface antifogging (hydrophilic) agent by modification of a functional group (for example, silica sol) (for example, silica sol) without separation, and complicated filtration and the like. This is effective in simplifying the manufacturing process, that is, reducing the manufacturing cost.

  As the dialkylamino group-containing silicon compound represented by the formula (1) as a raw material, a commercially available product can be used as it is. Examples of commercially available dialkylamino group-containing silicon compounds include N, N′-dimethylaminopropyltrimethoxysilane.

  Alternatively, commercially available dimethylamino group-containing alcohols (eg: 2-dimethylaminoethanol, 3-dimethylaminopropanol, 4-dimethylaminobutanol, 2-dimethylaminoethoxyethanol and N, N, N′-trimethyl-N ′-( 2-hydroxyethyl) -bis (2-aminoethyl ether or the like) is reacted with a silane coupling agent having an isocyanate group (for example, 3-isocyanatopropyltriethoxysilane or the like) to form a compound having an —NHCOO— group, A commercially available dimethylamino group-containing amine (for example, N, N-dimethylethylenediamine, N, N-dimethyl-1,3-propanediamine, etc.) and a silane coupling agent having an isocyanate group (for example, 3-isocyanatopropyltrimethyl). Ethoxysilane etc.) Compounds having an -NHCONH- group Te the obtained can be used.

  Further, dimethylallylamine, 2- (dimethylamino) ethyl acrylate, 2- (dimethylamino) ethyl methacrylate, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide and the like A thioether group-containing silicon compound (for example, 3-mercaptopropyltrimethoxy, 3-mercaptopropylmethyldimethoxysilane, etc.) can be reacted with a thioether group-containing silicon compound to be used.

All the reactions described in paragraphs [0034] and [0035] may or may not use a solvent.
When a solvent is used in the above reaction, the solvent to be used is a dehydrating solvent (ester solvent: methyl acetate, ethyl acetate, butyl acetate, etc., alcohol solvent: methanol, ethanol, isopropanol, n-butanol, tert-butanol, pentanol, etc. , Ethylene glycol, propylene glycol, propylene glycol monomethyl ether, 1,4-butanediol, etc., ether solvents: diethyl ether, tetrahydrofuran, dioxane, etc., ketone solvents: acetone, methyl ethyl ketone, etc., aprotic solvent: dimethyl sulfoxide Side, N, N-dimethylformamide and the like, aromatic hydrocarbon solvents: toluene, xylene and the like) and mixed solvents thereof.
Of these, no solvent, ester solvents (for example, ethyl acetate and butyl acetate) or ether solvents (for example, tetrahydrofuran, 1,2-dimethoxyethane, etc.) are preferable.

  In addition, a tin-based catalyst (for example, dibutyldilauryltin) may be used for the reaction of the dimethylamino group-containing alcohol and the isocyanate group-containing silicon compound, and dimethylallylamine, 2- (dimethylamino) ethyl acrylate, 2- ( In the reaction of dimethylamino) ethyl methacrylate, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide and the like with a thiol group-containing silicon compound, an azo catalyst (for example, azo Bisisobutyronitrile and the like) may be used.

  In addition, the reaction temperature of all the reactions described in paragraphs [0031], [0032], [0034] and [0035] can be performed at 0 ° C. to 200 ° C., preferably room temperature to 150 ° C., particularly room temperature. To 120 ° C is preferred.

Specific examples of the sulfobetaine-based silicon compound represented by the formula (2) obtained by the production method of the present invention include the following.
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻
(2-1)
(CH ₃ O) ₂ Si (CH ₃ ) CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻ (2-2)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (2-3)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (2-4)
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOCH ₂ CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻ (2-5)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 OCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (2-6)
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOCH ₂ CH ₂ N (CH ₃ ) CH ₂ CH ₂ OCH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻ (2- 7)
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCONHCH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻ (2-8)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (2-9)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻ (2-10)
(C ₂ H ₅ O) ₂ Si (CH ₃ ) CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻ (2-11)

The betaine silicon compound of the present invention is a novel compound represented by the formula (3).
Specific examples of the sulfobetaine-based silicon compound represented by the formula (3) include the following.
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-1)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-2)

The sulfobetaine-based silicon compound obtained by the production method of the present invention and the sulfobetaine-based silicon compound of the present invention are themselves hydrolyzed or metal oxide sol (for example, organosilica sol: organ silica sol IPA-ST manufactured by Nissan Chemical Co., Ltd.) A surface hydrophilizing (antifogging) agent can be obtained by reacting with the above silanol. As a solvent in the case of reaction, alcohol solvents: methanol, ethanol, isopropanol, n-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, 1,4-butanediol and the like, ether solvents: diethyl ether, Examples include tetrahydrofuran and dioxane, ketone solvents: acetone and methyl ethyl ketone, aprotic solvents: dimethyl sulfoxide, N, N-dimethylformamide, water, and mixed solvents thereof.
Among these, alcohol solvents and water are preferable, and these solvents can be used alone or in combination of two or more.

  The sulfobetaine-based silicon compound obtained by the production method of the present invention and the sulfobetaine-based silicon compound of the present invention are themselves hydrolyzed or metal oxide sol (for example, organosilica sol: organ silica sol IPA-ST manufactured by Nissan Chemical Co., Ltd.) By reacting with the above silanol, it can be used as a hydrophilic coating composition.

  The hydrophilic coating composition of the present invention may further contain a diluting solvent in order to improve workability (handling property, coating property, etc.). The diluent solvent is not limited as long as it does not react with the hydrolyzate of the sulfobetaine-based silicon compound of the present invention and can dissolve and / or disperse them. For example, ether solvents (tetrahydrofuran, dioxane, etc.) ), Alcohol solvents (methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) and aprotic solvents (N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like) and water.

  When the dilution solvent is contained, the content of the dilution solvent is, for example, 0.01 to 15% by weight (preferably 0.05 to 10% by weight) of the modified metal oxide sol of the present invention based on the total solvent. , Particularly preferably 0.05 to 5.0% by weight).

  The hydrophilic coating composition of the present invention may further contain 1 ppm to 1% of a surfactant in order to further improve workability (eg wettability with a substrate). Examples of the surfactant include ordinary hydrocarbon surfactants and fluorine surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants). Of these, fluorine-based surfactants that exhibit an effect when added in a small amount are preferred.

Specific examples of the fluorosurfactant include Neogene Corporation's footage (trade name) shown below.
Aftergent 100, Aftergent 100C, Aftergent 110, Aftergent 150, Aftergent 150CH, Aftergent AK, Aftergent 501, Aftergent 250, Aftergent 251, Aftergent 222F, Aftergent 208G, Aftergent 300, Examples of the solvent include a solvent 310 and a solvent 400SW.

  The coating composition of the present invention comprises glass, plastic {polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ABS, polycarbonate, polystyrene, epoxy, unsaturated polyester, melamine, diallyl phthalate, polyimide, urethane, nylon, Polyethylene, polypropylene, polyvinyl chloride, fluorine resin (polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyvinylidene fluoride resin, polyvinyl fluoride resin, perfluoroalkoxy fluorine resin, ethylene tetrafluoride / hexafluoropropylene copolymer) Combined resin, ethylene / tetrafluoroethylene copolymer resin, ethylene / chlorotrifluoroethylene copolymer resin, etc.), polybutadiene, poly Prene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, porsulfide, butyl rubber, etc.}, metal (iron, aluminum, stainless steel, titanium, copper, brass and alloys thereof), cellulose, cellulose derivatives, It can be applied to surface hydrophilization of substrates, sheets, films and fibers of cellulose analogs (chitin, chitosan, porphyran, etc.) or natural fibers (silk, cotton, etc.).

  In addition, surface activation treatment such as primer, ultraviolet irradiation, ozone, vacuum plasma, atmospheric pressure plasma, flame and corona discharge treatment (in order to increase the surface energy of the substrate surface, in order to improve the adhesion to the substrate etc. if necessary Method).

  Examples of the method for applying the coating liquid comprising the coating composition of the present invention include dip coating, spin coating, flow coating and spray coating.

  The structure of the present invention is characterized in that the hydrophilic coating composition is coated and then cured.

After the coating liquid is applied and dried by the above application method, etc., the coating film is processed by treatment with a substance (catalyst, for example, basic substance: ammonia gas, etc.) that promotes dehydration condensation to cure the formed coating film. The mechanical properties and chemical properties may be improved.
Alternatively, the mechanical properties and chemical properties of the coating film may be improved by proceeding with dehydration condensation by heat treatment and curing.
Alternatively, the above two methods may be performed.

Examples of the dehydration condensation catalyst include a base and an acid.
Bases include inorganic bases (lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium acetate, lithium acetate, potassium acetate, calcium hydroxide, barium hydroxide, calcium nitrate, barium nitrate, ammonia, etc.), organic bases {tri Ethanolamine, triethylamine, triethylenediamine, N, N-dimethylpiperazine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol} and the like.
Examples of the acid include inorganic acids (hydrochloric acid, sulfuric acid, etc.), organic acids (acetic acid, trifluoroacetic acid, etc.) and the like.
A compound that generates a base or an acid by light or heat can also be used.

  These catalysts may be coated after being added to the coating solution, or after film formation, a solution in which the catalyst is dissolved may be sprayed or exposed to a catalyst atmosphere.

  In the case of curing only by heat treatment, the heat treatment temperature is usually room temperature to 250 ° C, preferably room temperature to 200 ° C, particularly preferably room temperature to 150 ° C.

  The time for the heat treatment is usually 0.05 to 48 hours, preferably 0.1 to 48 hours, and particularly preferably 0.5 to 36 hours.

  When a dehydration condensation catalyst is used, the heat treatment temperature is from room temperature to the above temperature, and the heat treatment time is also the same as the above time.

  Hereinafter, the present invention will be specifically described with reference to examples. The examples are illustrative of the invention and are not limiting. In addition, an Example is an Example of the manufacturing method of the compound of this invention, and Example 5 and 10 also serves as the Example of the betaine-type silicon compound of this invention among them.

[Example 1]
N, N-dimethyl-3-aminopropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) 5.71 g (27.5 mmol) and 1,3-propane sultone (Nacalai Tesque) 3.36 g (27.5) Mmol) was dissolved in 40 ml of dehydrated isopropyl alcohol and heated under reflux overnight to obtain the target N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine (1- A colorless transparent solution in which 1) was dissolved was obtained. About 30 ml of dehydrated ethanol was added to the reaction solution, and 53.3 g of a transparent isopropyl alcohol / ethanol mixed solution in which N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine was dissolved was added. Obtained. By infrared absorption spectrum analysis, 1344 cm ^−1, which is a feature of the starting 1,3-propane sultone compound, was destroyed, and absorption at 1641 cm ⁻¹ , which is a feature of the product, was newly confirmed.

[Example 2]
N, N-dimethyl-3-aminopropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) 5.71 g (27.5 mmol) and 1,3-propane sultone (Nacalai Tesque) 3.36 g (27.5) Millimoles) is dissolved in 40 ml of dehydrated propylene glycol monomethyl ether acetate and heated to reflux overnight to obtain the target N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine. A white precipitate of (1-1) was formed. By adding about 50 ml of dehydrated ethanol to the reaction solution, a clear propylene glycol monomethyl ether acetate / ethanol mixed solution in which N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine is dissolved 86.7 g was obtained. By infrared absorption spectrum analysis, 1344 cm ⁻¹ absorption characteristic of the raw material 1,3-propane sultone compound disappeared and 1641 cm ⁻¹ absorption characteristic of the product was newly confirmed.

Example 3
N, N-dimethyl-3-aminopropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) 5.71 g (27.5 mmol) and 1,3-propane sultone (Nacalai Tesque) 3.36 g (27.5) Mmol) is dissolved in 40 ml of dehydrated propylene glycol dimethyl ether and heated under reflux overnight to obtain the target N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine (1 A white precipitate of -1) was formed. By adding about 30 ml of dehydrated ethanol to the reaction solution, a transparent propylene glycol dimethyl ether / ethanol mixed solution in which N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine was dissolved 64. 6 g was obtained. By infrared absorption spectrum analysis, 1344 cm ⁻¹ absorption characteristic of the raw material 1,3-propane sultone compound disappeared and 1641 cm ⁻¹ absorption characteristic of the product was newly confirmed.

Example 4
N, N-dimethyl-3-aminopropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) 5.71 g (27.5 mmol) and 1,3-propane sultone (Nacalai Tesque) 3.36 g (27.5) Mmol) was dissolved in 40 ml of dehydrated isopropanol and stirred at room temperature for 2 days to obtain N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine (1-1) ) Formed a white precipitate. About 30 ml of dehydrated ethanol was added to the reaction solution to obtain 60.4 g of a transparent isopropyl alcohol / ethanol mixed solution in which N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine was dissolved. Got. By infrared absorption spectrum analysis, 1344 cm ⁻¹ absorption characteristic of the raw material 1,3-propane sultone compound disappeared and 1641 cm ⁻¹ absorption characteristic of the product was newly confirmed.

Example 5
(1) N, N-dimethyl-1,2-ethylenediamine (manufactured by Nacalai Tesque Co., Ltd.) 4.4 g (50.0 mmol) to 3- (triethoxysilyl) propyl isocyanate (Shin-Etsu Chemical Co., Ltd.) under an argon atmosphere 12.35 g (50.0 mmol) was added and reacted at room temperature for 48 hours, whereby the N, N-dimethyl-1,2-ethylenediamino group was converted to 3- (triethoxysilyl) propyl via a urea bond. 16.1g of compounds (1-8) couple | bonded with group were obtained.
^{From the 1} H-NMR measurement, the absorption of the proton (3.30 ppm) of the carbon to which the isocyanate group of 3- (triethoxysilyl) propyl isocyanate, which is the raw material, has disappeared, and the target urea group has been newly bonded. Absorption of protons (3.14 ppm) was confirmed.
(2) 7.44 g (22.2 mmol) of the compound obtained in (1) and 2.69 g (22.0 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque) were dissolved in 40 ml of dehydrated isopropyl alcohol. By heating and refluxing overnight, a colorless transparent solution in which betaine (2-8) as the target product was dissolved was obtained. About 30 ml of dehydrated ethanol was added to the reaction solution to obtain 51.6 g of a transparent isopropyl alcohol / ethanol mixed solution in which the betaine compound was dissolved. By infrared absorption spectrum analysis, 1344 cm ⁻¹ absorption characteristic of the raw material 1,3-propane sultone compound disappeared, and 1653 cm ⁻¹ absorption characteristic of the product was newly confirmed.

[Usage example 1]
9.9 g of an isopropyl alcohol / ethanol mixed solution of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in Example 1 and organosilica sol (manufactured by Nissan Chemical Co., IPA) -ST) 6.0 g of ethanol was dissolved in 30 g of ethanol and 50 g of water, and then 200 mg of lithium hydroxide monohydrate (manufactured by Nacalai Tesque) was dissolved in water in a small amount and heated to reflux overnight. After cooling, water is added to the obtained reaction solution to adjust to 100.0 g, whereby (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group 100.0 g of a transparent mixed solution of isopropyl alcohol, ethanol and water containing the modified oxide sol modified with (1) was obtained.

[Usage example 2]
After dissolving 9.9 g of the isopropyl alcohol / ethanol mixed solution of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in Example 1 in 30.0 g of water. Lithium hydroxide monohydrate (Nacalai Tesque 300 mg dissolved in 10.0 g of water was added and heated to reflux overnight. After cooling, water was added to the resulting reaction solution to 50.0 g. Isopropyl alcohol, ethanol and water containing modified oxide sol modified with (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group by adjusting A mixed clear solution 50.0 g was obtained.

[Usage example 3]
After dissolving 9.9 g of the isopropyl alcohol / ethanol mixed solution of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in Example 1 in 40.0 g of water. Then, 1 ml of acetic acid was added and heated to reflux overnight. After cooling, by adding water to the obtained reaction solution to adjust to 50.0 g, (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group 50.0 g of a transparent mixed solution of isopropyl alcohol, ethanol and water containing the modified oxide sol modified with 1.

[Usage example 4]
After dissolving 9.9 g of the isopropyl alcohol / ethanol mixed solution of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in Example 1 in 41.0 g of water. , Heated to reflux overnight. After cooling, by adding water to the obtained reaction solution to adjust to 50.0 g, (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group 50.0 g of a transparent mixed solution of isopropyl alcohol, ethanol and water containing the modified oxide sol modified with 1.

[Usage Example 5]
16.0 g of a propylene glycol monomethyl ether acetate / ethanol mixed solution of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in Example 2 was dissolved in 34.0 g of water. And then heated to reflux overnight. After cooling, by adding water to the obtained reaction solution to adjust to 50.0 g, (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group 50.0 g of a mixed transparent solution of propylene glycol monomethyl ether acetate, ethanol and water containing the modified oxide sol modified with (1) was obtained.

[Usage Example 6]
12.0 g of a propylene glycol dimethyl ether / ethanol mixed solution of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in Example 3 was dissolved in 38.0 g of water. Thereafter, the mixture was heated to reflux overnight. After cooling, by adding water to the obtained reaction solution to adjust to 50.0 g, (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group 50.0 g of a transparent mixed solution of propylene glycol dimethyl ether, ethanol and water containing the modified oxide sol modified with (1) was obtained.

[Usage Example 7]
After dissolving 11.2 g of the isopropyl alcohol / ethanol mixed solution of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in Example 4 in 38.8 g of water. , Heated to reflux overnight. After cooling, by adding water to the obtained reaction solution to adjust to 50.0 g, (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group 50.0 g of a transparent mixed solution of isopropyl alcohol, ethanol and water containing the modified oxide sol modified with 1.

[Usage Example 8]
After 11.7 g of the isopropyl alcohol / ethanol mixed solution of the betaine compound obtained in Example 5 was dissolved in 38.3 g of water, the mixture was heated to reflux overnight. After cooling, water is added to the resulting reaction solution to adjust to 50.0 g by adjusting (—O—) ₃ SiCH ₂ CH ₂ CH ₂ HNCONHCH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^- isopropyl alcohol containing modified oxide sol modified with groups to give a mixture a clear solution 50.0g of ethanol and water.
[Comparative Example 1]
(1) Dissolve 5.59 g of N, N-dimethyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.36 g of 1,3-propane sultone (manufactured by Nacalai Tesque) in 30 ml of dehydrated methylene chloride. And allowed to stir at room temperature for 24 hours. The produced white precipitate was filtered under an argon atmosphere to obtain 6.5 g of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine. The structure of the compound was confirmed by ¹ H-NMR (CD ₃ OD). _{0.65 {m, 2H, -CH 2} C H 2 Si (OCH 3) 3}, 1.83 {m, 2H, -C H 2 CH 2 Si (OCH 3) 3}, 2.15 {m, _{-CH 2 C H 2 CH 2 N} + (CH 3) 2 CH 2 CH 2 CH 2 Si -}, 2.82 {t, 2H, -C H 2 CH 2 CH 2 Si (OCH 3) 3}, 3 _{.06 {m, 8H, -CH 2} CH 2 C H 2 N + (C H 3) 2 CH 2 CH 2 CH 2 Si -}, 3.26 {m, 2H, -C H 2 CH 2 CH 2 N ^{_{+ (CH 3) 2 CH 2}} CH 2 CH 2 Si -}, 3.46 {s, 9H, -CH 2 CH 2 Si (OC H 3) 3}
(2) 1.65 g of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine obtained in (1) above and organosilica sol (manufactured by Nissan Chemical Co., IPA-ST) 6.0 g was dissolved in 30 g ethanol and 50 g water and heated to reflux overnight. After cooling, 200 mg of lithium hydroxide monohydrate (manufactured by Nacalai Tesque) was dissolved in a small amount of water and added to the reaction solution. The resulting reaction solution was modified with (—O—) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ^— group by adding water to 100.0 g. 100.0 g of a mixed transparent solution of ethanol and water containing the modified oxide sol was obtained.

[Comparative Example 2]
N, N-dimethyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.59 g and 1,3-propane sultone (manufactured by Nacalai Tesque) 3.36 g were dissolved in 40 ml of dehydrated ethanol at room temperature. For 48 hours. A white precipitate formed. An attempt was made to add about 50 ml of dehydrated ethanol to make a homogeneous solution, but the white solid did not dissolve. By infrared absorption spectrum analysis, absorption of 1641 cm ⁻¹ , which is a characteristic of N-propyltrimethoxysilane-N, N-dimethyl-N- (3-sulfopropyl) ammonium betaine, which is the target, Absorption at 1344 cm ⁻¹ , characteristic of 3-propane sultone, was not observed.

Example 6
(1) Under argon atmosphere, dimethylaminoethanol (manufactured by Nacalai Tesque Co., Ltd.) (3.6 g, 40.4 mmol) and 3- (triethoxysilyl) propyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.) 10.0 g (40. 4 mmol) was added and reacted at 90 ° C. for 48 hours to obtain 12.7 g of a compound (1-3) in which a dimethylaminoethyl group was bonded to a 3- (triethoxysilyl) propyl group via a carbamate bond. .
Absorption of carbon protons (3.30 ppm) to which the isocyanate group of 3- (triethoxysilyl) propyl isocyanate, which is a raw material, was bonded disappeared from ¹ H-NMR measurement, and the target carbamate group was newly bonded to the carbon. Absorption of protons (3.17 ppm) was confirmed.
(2) 1.68 g (5.0 mmol) of the compound obtained in (1) and 0.61 g (5.0 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque) were dissolved in 20 ml of dehydrated isopropyl alcohol. By heating and refluxing overnight, a colorless transparent solution in which the target sulfobetaine compound (2-3) was dissolved was obtained. By infrared absorption spectrum analysis, 1344 cm ⁻¹ absorption characteristic of the raw material 1,3-propane sultone compound disappeared, and new absorption of 1716 cm ⁻¹ characteristic of the product was confirmed.
(3) Hydrophilic coating obtained by hydrolyzing the sulfobetaine compound (2-3) by adding 30 ml of water to the colorless and transparent solution obtained in (2) and heating to reflux overnight, and further adding water to make 50 g. A composition liquid was obtained.

Example 7
(1) Under argon atmosphere, 3- (trimethylsilyl) propyl isocyanate (Shin-Etsu Chemical Co., Ltd.) was added to 3.4 g (40.4 mmol) of 3- (dimethylamino) -1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.). 8.3 g (40.4 mmol) was added and reacted at 90 ° C. for 48 hours, whereby a compound in which a dimethylaminoethyl group was bonded to a 3- (triethoxysilyl) propyl group via a carbamate bond (1- 10.1 g of 4) was obtained.
Absorption of carbon protons (3.30 ppm) to which the isocyanate group of 3- (triethoxysilyl) propyl isocyanate, which is a raw material, was bonded disappeared from ¹ H-NMR measurement, and the target carbamate group was newly bonded to the carbon. Absorption of protons (3.17 ppm) was confirmed.
(2) 1.75 g (5.0 mmol) of the compound obtained in (1) and 0.61 g (5.0 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque) were dissolved in 20 ml of dehydrated isopropyl alcohol. By heating and refluxing overnight, a colorless transparent solution in which the target sulfobetaine compound (2-4) was dissolved was obtained. By infrared absorption spectrum analysis, absorption at 1344 cm ⁻¹ , which is a characteristic of the raw material 1,3-propane sultone compound, disappeared, and absorption at 1708 cm ⁻¹ which is a characteristic of the product was newly confirmed.
(3) Hydrophilic coating in which sulfobetaine compound (2-4) is hydrolyzed by adding 30 ml of water to the colorless and transparent solution obtained in (2) and heating to reflux overnight, and further adding water to make 50 g. A composition liquid was obtained.

Example 8
(1) 5.4 g (40.6 mmol) of 2- [2- (dimethylamino) ethoxy] ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3- (triethoxysilyl) propyl isocyanate (Shin-Etsu Chemical Co., Ltd.) under an argon atmosphere Co., Ltd.) 10.0 g (40.4 mmol) was added and reacted at 90 ° C. for 48 hours, whereby the 2- [2- (dimethylamino) ethoxy] ethyl group was converted to 3- (triethoxy via a carbamate bond. 14.3g of compound (1-6) couple | bonded with the (silyl) propyl group was obtained.
Absorption of carbon protons (3.30 ppm) to which the isocyanate group of 3- (triethoxysilyl) propyl isocyanate, which is a raw material, was bonded disappeared from ¹ H-NMR measurement, and the target carbamate group was newly bonded to the carbon. Absorption of protons (3.17 ppm) bound to was confirmed.
(2) 1.90 g (5.0 mmol) of the compound obtained in (1) and 0.61 g (5.0 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque) were dissolved in 20 ml of dehydrated isopropyl alcohol. By heating and refluxing overnight, a colorless transparent solution in which the target sulfobetaine compound (2-6) was dissolved was obtained. By infrared absorption spectrum analysis, absorption at 1344 cm ⁻¹ , which is a characteristic of the raw material 1,3-propane sultone compound, disappeared, and absorption at 1705 cm ⁻¹ , which is a characteristic of the product, was newly confirmed.
(3) Hydrophilic coating obtained by hydrolyzing the sulfobetaine compound (2-6) by adding 30 ml of water to the colorless and transparent solution obtained in (2) and heating to reflux overnight, and further adding water to make 50 g. A composition liquid was obtained.

Example 9
(1) 10.0 g (52.6 mmol) of N, N, N′-trimethyl-N ′-(2-hydroxyethyl) -bis (2-aminoethyl ether) (manufactured by Tokyo Chemical Industry Co., Ltd.) under an argon atmosphere ), 13.0 g (52.6 mmol) of 3- (triethoxysilyl) propyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.) is added and reacted at room temperature for 48 hours, whereby N, N, N′-trimethyl-N 22.3 g of compound (1-7) in which the hydroxyethyl group of '-(2-hydroxyethyl) -bis (2-aminoethyl ether) is bonded to the 3- (triethoxysilyl) propyl group via a carbamate bond is obtained. It was.
Absorption of carbon protons (3.30 ppm) to which the isocyanate group of 3- (triethoxysilyl) propyl isocyanate, which is a raw material, was bonded disappeared from ¹ H-NMR measurement, and the target carbamate group was newly bonded to the carbon. Absorption of protons (3.16 ppm) was confirmed.
(2) 2.19 g (5.0 mmol) of the compound obtained in (1) and 1.22 g (10.0 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque) were dissolved in 20 ml of dehydrated isopropyl alcohol. By heating and refluxing overnight, a colorless transparent solution in which the target sulfobetaine compound (2-7) was dissolved was obtained. The infrared absorption spectrum analysis confirmed the absorption of 1717 cm ^-1 which is characteristic of the newly product absorption disappeared in is characteristic 1344Cm ^-1 of 1,3-propane sultone compound ingredients.
(3) Hydrophilic coating obtained by hydrolyzing the sulfobetaine compound (2-7) by adding 30 ml of water to the colorless and transparent solution obtained in (2) and heating to reflux overnight, and further adding water to make 50 g. A composition liquid was obtained.

Example 10
(1) In an argon atmosphere, 5.1 g (50.0 mmol) of N, N-dimethyl-1,3-propanediamine (manufactured by Nacalai Tesque Co., Ltd.) and 3- (triethoxysilyl) propyl isocyanate (Shin-Etsu Chemical Co., Ltd.) (Company) 12.35 g (50.0 mmol) was added and reacted at room temperature for 48 hours, whereby the N, N-dimethyl-1,3-propanediamino group was converted to 3- (triethoxysilyl) via a urea bond. 16.7g of compounds (1-9) couple | bonded with the propyl group were obtained.
^{From the 1} H-NMR measurement, the absorption of the proton (3.30 ppm) of the carbon to which the isocyanate group of 3- (triethoxysilyl) propyl isocyanate, which is the raw material, has disappeared, and the target urea group has been newly bonded. The absorption of protons (3.14 ppm) was confirmed.
(2) 1.75 g (5.0 mmol) of the compound obtained in (1) and 0.61 g (5.0 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque) were dissolved in 20 ml of dehydrated isopropyl alcohol. By heating and refluxing overnight, a colorless transparent solution in which the target sulfobetaine compound (2-9) was dissolved was obtained. By infrared absorption spectrum analysis, 1344 cm ⁻¹ absorption characteristic of the raw material 1,3-propane sultone compound disappeared, and 1653 cm ⁻¹ absorption characteristic of the product was newly confirmed.
(3) Hydrophilic coating obtained by hydrolyzing the sulfobetaine compound (2-9) by adding 30 ml of water to the colorless and transparent solution obtained in (2) and heating to reflux overnight, and further adding water to make 50 g. A composition liquid was obtained.

[Adjustment of anti-fogging coating solution]
[Anti-fogging coating solution 1]
An antifogging coating solution was obtained by diluting 2.5 g of each of the solutions obtained in Use Examples 2 to 8 and Example 10 with 47.5 g of water. Moreover, the antifogging coating composition liquid was obtained by diluting 5.0 g of the solutions obtained in Use Example 1 and Comparative Example 1 with 45.0 g of water.

[Hydrophilicity evaluation results]
Slide glass {76 mm, 26 mm, 1.2 mm; immersed in 2-propanol saturated solution of sodium hydroxide for 24 hours, washed with water, dried (60 ° C., 2 hours)} immersed in antifogging coating composition solution After removing the slide glass, the liquid was drained, and a surface-modified slide glass heated at 130 ° C. for 1 hour was obtained.

  Contact angle measuring device {Kyowa Interface Chemical Co., Ltd., DROP MASTER 500, liquid suitable amount 2μL, measuring interval 1000ms, number of measurements 30 times}, contact angles (degrees) for any five points on the surface of the surface-modified glass slide. The average value was calculated. The results are shown in Tables 1 and 2.

[Anti-fogging evaluation result]
The surface-modified glass slide was placed on the upper part of a 70 ° C. warm water bath to evaluate the antifogging performance (presence of fogging due to water vapor). The results are shown in Table 1.

As is apparent from Table 1, the sulfobetaine-based silicon compound obtained by the production method of the present invention has the same characteristics as the sulfobetaine-based silicon compound obtained by the conventional production method, and the production process is short. Since it can be manufactured at a low cost, it is a production method useful in manufacturing an antifogging coating liquid at a low cost.
Further, as is apparent from Use Example 8 and Example 10 in Table 1, the sulfobetaine-based silicon compound of the present invention does not change the antifogging performance as compared with the compounds of Examples 1 to 4, but it is inexpensive and a large amount as a raw material. Since it can be produced from materials that are readily available, it is very useful in practice.

  The sulfobetaine-based silicon compound obtained by the production method of the present invention and the betaine-based silicon compound of the present invention have a large hydrophilizing effect, can be uniformly coated, and can be produced in a large amount at a low cost. The functional coating composition liquid is useful for coating a substrate surface such as a glass plate, a medical material, a biocompatible material, a cosmetic material, an optical material, a resin film, and a resin sheet to impart hydrophilicity. . That is, the coating film of the present invention has excellent hydrophilicity and antifogging property because it is difficult to be detached from the inorganic base material even when it is in contact with water.

Claims (6)

A compound represented by the following formula (1) and a cyclic sulfonic acid ester having 3 to 10 carbon atoms, a water-soluble secondary or tertiary alcohol solvent, an ether solvent having no water-soluble primary alcohol hydroxyl group, A method for producing a compound represented by the following formula (2), wherein the reaction is carried out in one or more of a solvent-based ester solvent, a water-soluble ketone solvent, and an aprotic solvent.
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 - (X-R 2) m -N (R 3) (R 4) (1)
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 - (X-R 2) m -N + (R 3) (R 4) - (CH 2) n -SO 3 - (2)
{In the formula, X ¹ may be the same or different and represents any of an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group and a halogen atom; k represents 0 or 1; and R ¹ represents an alkylene group having 1 to 5 carbon atoms. X represents —NHCOO—, —NHCONH—, —S— or —SO ₂ —, m represents 0 or 1, and R ² represents an ether bond, ester bond or amide bond having 1 to 10 carbon atoms. Represents an alkylene group which may be included or —CH ₂ CH ₂ N ⁺ (CH ₃ ) {(CH ₂ ) _n SO ₃ ⁻ )} CH ₂ CH ₂ OCH ₂ CH ₂ —, and R ³ and R ⁴ may be the same or different. Represents an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 3 to 10. }   The method according to claim 1, wherein the cyclic sulfonic acid ester having 3 to 10 carbon atoms is 1,3-propane sultone.   The production method according to claim 1, wherein the water-soluble solvent is isopropyl alcohol. Betaine silicon compound represented by the following formula (3).
^{_{(X 1) 3-k (}} CH 3) k Si-R 1 -NHCONH-R 2 -N + (R 3) (R 4) - (CH 2) n -SO 3 - (3)
{In the formula, X ¹ may be the same or different and represents any of an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group and a halogen atom; k represents 0 or 1; and R ¹ represents an alkylene group having 1 to 5 carbon atoms. R ² represents an alkylene group which may contain an ether bond, an ester bond or an amide bond having 1 to 10 carbon atoms, —CH ₂ CH ₂ N ⁺ (CH ₃ ) (R ⁵ —SO ₃ ^— ) CH ₂ CH ₂ Represents OCH ₂ CH ₂ —, R ³ and R ⁴ represent the same or different alkyl group having 1 to 3 carbon atoms, and n represents an integer of 3 to 10}.   The hydrophilic coating composition liquid which contains the hydrolysis product of the betaine-type silicon compound of Claim 4 in a solution.   A structure obtained by curing the hydrophilic coating composition according to claim 5 after coating.