JP2009203185A - Silicon compound and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon compound imparting high hydrophilicity. <P>SOLUTION: The silicon compound is represented by formula (1): (MOSO<SB>2</SB>-R<SP>1</SP>-)<SB>m</SB>Z-R<SP>3</SP>-Si(CH<SB>3</SB>)<SB>n</SB>(-Y)<SB>3-n</SB>äwherein M is a hydrogen atom, a 1-4C alkyl group, an alkali metal atom or ammonium (NH<SB>4</SB>); R<SP>1</SP>and R<SP>3</SP>are each a 1-4C alkylene group or a 6-8C arylene group; Z is a group represented by formula: -O(CO)-R<SP>2</SP>-S-, -O(CO)-R<SP>2</SP>-O-, -O(CO)-R<SP>2</SP>-NH-, (-O(CO)-R<SP>2</SP>-)<SB>2</SB>N-, -S-, -O-, -NH-, >N-, -S-R<SP>2</SP>-CO<SB>2</SB>- or -NHCONH- (wherein R<SP>2</SP>is ethylene or 1-ethylmethylene); Y is a 1-3C alkoxy group; C is a carbon atom; O is an oxygen atom; N is a nitrogen atom; S is a sulfur atom; H is a hydrogen atom; Si is a silicon atom; m is 1 or 2; and n is 0 or 1}. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a silicon compound and a method for producing the same. More particularly, the present invention relates to a silicon compound suitable for a modifier and a method for producing the same.

Conventionally, a silicon compound having a polyoxyalkylene chain as a hydrophilic group is known (Patent Document 1).
JP 2007-238820 A

  However, conventional silicon compounds have a problem that hydrophilicity cannot be imparted insufficiently. An object of the present invention is to provide a silicon compound capable of imparting high hydrophilicity.

The feature of the silicon compound of the present invention is summarized in the point represented by the formula (1).

^{_{(MOSO 2 -R 1 -) m}} Z-R 3 -Si (CH 3) n (-Y) 3-n (1)

However, M is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom or ammonium _(NH 4), ^{R 1} and ^{R 3} is an alkylene group or an arylene group having a carbon number of 6-8 having from 1 to 4 carbon atoms, Z represents —O (CO) —R ² —S—, —O (CO) —R ² —O—, —O (CO) —R ² —NH—, (—O (CO) —R ² —) _2. A group represented by N—, —S—, —O—, —NH—,> N—, —S—R ² —CO ₂ — or —NHCONH— (R ² is ethylene or 1-methylethylene), Y Is an alkoxy group having 1 to 3 carbon atoms, C is a carbon atom, O is an oxygen atom, N is a nitrogen atom, S is a sulfur atom, H is a hydrogen atom, Si is a silicon atom, m is 1 or 2, and n is 0 or 1 is represented.

  The feature of the silicon compound of the present invention is summarized in the point represented by any one of formulas (2) to (6).

However, M is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom or ammonium _(NH 4), ^{R 1} and ^{R 3} is an alkylene group or an arylene group having a carbon number of 6-8 having from 1 to 4 carbon atoms, R ² is ethylene or 1-methylethylene, R ⁴ is ethylene or a phenyleneethylene group (—C ₆ H ₄ —CH ₂ CH ₂ —), X is —S—, —O—, —NH— or> N—. A group represented by the formula, Y is an alkoxy group having 1 to 4 carbon atoms, C is a carbon atom, O is an oxygen atom, N is a nitrogen atom, S is a sulfur atom, H is a hydrogen atom, Si is a silicon atom, and m is 1 or 2, n represents 0 or 1;

  The characteristic of the modifier of the present invention is that it contains the above silicon compound.

A feature of the production method of the present invention is a method for producing the above silicon compound,
A reaction step (1) of reacting (meth) acryloyloxyalkanesulfonic acid (ester or salt) with alkoxysilylalkanethiol, alkoxysilylalkylamine, alkoxysilylarenethiol or alkoxysilylarylamine;

Reaction step (2) for reacting vinylbenzenesulfonic acid (ester or salt) or vinylsulfonic acid (ester or salt) with alkoxysilylalkanethiol, alkoxysilylalkylamine, alkoxysilylarenethiol or alkoxysilylarylamine;

A reaction step (3) of reacting hydroxyalkanesulfonic acid (ester or salt) with alkoxysilylalkyl isocyanate or alkoxysilylaryl isocyanate;

Reaction step (4) of reacting mercaptoalkanesulfonic acid (ester or salt) with alkoxysilylalkyl (meth) acrylate, or

Reaction step (5) of reacting aminoalkanesulfonic acid (ester or salt) or aminoarenesulfonic acid (ester or salt) with alkoxysilylalkyl isocyanate or alkoxysilylaryl isocyanate
The point including

  The silicon compound of the present invention can impart high hydrophilicity. Since the modifier of this invention contains said silicon compound, it can provide high hydrophilicity easily. Moreover, according to the manufacturing method of the silicon compound of this invention, the silicon compound which can provide high hydrophilicity can be manufactured easily.

<Silicon compound represented by formula (1)>
Among hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, alkali metal atoms or ammonium (NH ₄ ) (M), examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, isopropyl, n-butyl and t- Butyl is included.
Moreover, as an alkali metal atom, a lithium atom, a potassium atom, and a sodium atom are contained.

  Among these, from the viewpoint of hydrophilicity, an alkali metal atom is preferable, and a lithium atom, a potassium atom, and a sodium atom are more preferable.

Among alkylene groups having 1 to 4 carbon atoms or arylene groups having 6 to 8 carbon atoms (R ¹ , R ³ ), the alkylene groups include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene and 2-methyl. Trimethylene and the like. Examples of the arylene group include phenyl, methylenephenylene (—CH ₂ —C ₆ H ₄ —), ethylene phenylene (—CH ₂ CH ₂ —C ₆ H ₄ —), and phenylene ethylene (—C ₆ H ₄ —CH _2). CH ₂ —) and the like.

  Examples of the alkoxy group having 1 to 4 carbon atoms (Y) include methyl, ethyl, n-propyl, iso-propyl, n-butyl and tert-butyl.

<Silicon compound represented by formulas (2) to (5)>
Of the silicon compounds represented by the formula (1), the silicon compounds represented by any one of the formulas (2) to (5) are preferable.

Examples of the silicon compound represented by the formula (2) include a compound represented by the following chemical formula.

LiOSO ₂ CH ₂ CH ₂ CH ₂ OCOCH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

NaOSO ₂ CH ₂ CH ₂ CH ₂ OCOCH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

KOSO ₂ CH ₂ CH ₂ OCOCH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

KOSO ₂ CH ₂ CH ₂ CH ₂ OCOCH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

KOSO ₂ CH ₂ CH ₂ CH ₂ OCOCH (CH ₃ ) CH ₂ —S—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

KOSO ₂ CH ₂ CH ₂ CH ₂ OCOCH ₂ CH ₂ —NH—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) <sub>3

(KOSO 2 CH 2 CH 2 CH</sub> 2 OCOCH 2 CH 2) 2 N-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{KOSO 2 CH 2 CH 2 CH 2} OCOCH 2 CH 2 -S-CH 2 CH 2 CH 2 SiCH 3 (OCH 3) 2

KOSO ₂ CH ₂ CH ₂ CH ₂ OCOCH ₂ CH ₂ —S—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) <sub>3

CH 3 OSO 2 CH 2 CH 2</sub> CH 2 OCOCH 2 CH 2 -S-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{CH 3 OSO 2 CH 2 CH 2} CH 2 OCOCH 2 CH 2 -S-CH 2 CH 2 CH 2 Si (OCH 3) 3

Examples of the silicon compound represented by the formula (3) include compounds represented by the following chemical formulas.

_{LiOSO 2 -p-C 6 H 4} CH 2 CH 2 -S-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{LiOSO 2 -p-C 6 H 4} CH 2 CH 2 -NH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{(LiOSO 2 -p-C 6 H} 4 CH 2 CH 2) 2 N-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{LiOSO 2 -p-C 6 H 4} CH 2 CH 2 -S-CH 2 CH 2 CH 2 SiCH 3 (OCH 3) 2

_{LiOSO 2 -p-C 6 H 4} CH 2 CH 2 -S-CH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3

_{LiOSO 2 -p-C 6 H 4} CH 2 CH 2 -S-CH 2 CH 2 CH 2 SiCH 3 (OCH 3) 2

_{CH 3 CH 2 OSO 2 -p-} C 6 H 4 CH 2 CH 2 -S-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{CH 3 CH 2 OSO 2 -p-} C 6 H 4 CH 2 CH 2 -NH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{CH 3 OSO 2 -p-C 6} H 4 CH 2 CH 2 -NH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{NaOSO 2 -p-C 6 H 4} CH 2 CH 2 -S-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{KOSO 2 -p-C 6 H 4} CH 2 CH 2 -S-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{NaOSO 2 -CH 2 CH 2 -S-} CH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3

Examples of the silicon compound represented by the formula (4) include a compound represented by the following chemical formula.

LiOSO ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

NaOSO ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

NaOSO ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) <sub>3

CH 3 OSO 2 CH 2 CH 2</sub> -OCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{CH 3 CH 2 OSO 2 CH 2} CH 2 -OCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

KOSO ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

LiOSO ₂ CH ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

NaOSO ₂ CH ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

NaOSO ₂ CH ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) <sub>3

CH 3 OSO 2 CH 2 CH 2</sub> CH 2 -OCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{CH 3 CH 2 OSO 2 CH 2} CH 2 CH 2 -OCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{CH 3 OSO 2 CH 2 CH 2} CH 2 -OCONH-CH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3

NaOSO ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

Examples of the silicon compound represented by the formula (5) include compounds represented by the following chemical formula.

NaOSO ₂ CH ₂ CH ₂ —S—CH ₂ CH ₂ COO—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

NaOSO ₂ CH ₂ CH ₂ CH ₂ —S—CH ₂ CH ₂ COO—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

LiOSO ₂ CH ₂ CH ₂ —S—CH ₂ CH ₂ COO—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

LiOSO ₂ CH ₂ CH ₂ —S—CH ₂ CH ₂ COO—CH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃

CH ₃ OSO ₂ CH ₂ CH ₂ —S—CH ₂ CH ₂ COO—CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Examples of the silicon compound represented by the formula (6) include a compound represented by the following chemical formula.

_{NaOSO 2 -p-C 6 H 4} -NHCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{NaOSO 2 -p-C 6 H 4} -NHCONH-CH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3

_{LiOSO 2 -p-C 6 H 4} -NHCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{KOSO 2 -p-C 6 H 4} -NHCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{CH 3 OSO 2 -p-C 6} H 4 -NHCONH-CH 2 CH 2 CH 2 Si (OCH 3) 3

_{NaOSO 2 -CH 2 CH 2 CH 2} -NHCONH-CH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3

The silicon compound of the present invention can be easily obtained by a known production method.
The method for producing the silicon compound represented by the general formula (2) includes (meth) acryloyloxyalkanesulfonic acid (ester or salt), alkoxysilylalkanethiol, alkoxysilylalkylamine, alkoxysilylarenethiol or alkoxysilylaryl. It is preferable to include a reaction step (1) for reacting with an amine.

  In the reaction step (1), a reaction solvent may be used. The reaction solvent is not limited as long as it does not react with (meth) acryloyloxyalkanesulfonic acid (ester or salt), alkoxysilylalkanethiol, and the like. For example, ether {diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane And dioxane, etc.}, ketones {acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.}, aprotic solvents {N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide (DMSO), etc.} and carbonization Examples include hydrogen {hexane, octane, benzene, toluene, xylene, etc.}.

  When using alkoxysilylalkanethiol or alkoxysilylarenethiol in the reaction step (1), use a known radical initiator {for example, 2,2′-azobisisobutyronitrile} or irradiate with ultraviolet rays. Is preferred. On the other hand, when using alkoxysilylalkylamine or alkoxysilylarylamine, it is not necessary to use a radical initiator or to irradiate ultraviolet rays.

  The reaction temperature in the reaction step (1) is not limited as long as the addition reaction proceeds. For example, -10 to 200 ° C (preferably 0 to 150 ° C, more preferably 10 to 150 ° C, particularly preferably 20 to 130 ° C). Degree.

  The method for producing the silicon compound represented by the general formula (3) includes vinylbenzenesulfonic acid (ester or salt) or vinylsulfonic acid (ester or salt), alkoxysilylalkanethiol, alkoxysilylalkylamine, alkoxysilylarene. It is preferable to include a reaction step (2) of reacting with thiol or alkoxysilylarylamine.

  In the reaction step (2), it is preferable to use a known radical initiator {for example, 2,2'-azobisisobutyronitrile} or irradiate with ultraviolet rays.

  In the reaction step (2), a reaction solvent may be used. The reaction solvent is not limited as long as it does not react with vinyl benzene sulfonic acid (ester or salt) or vinyl sulfonic acid (ester or salt) and alkoxysilylalkanethiol. For example, in the case of reaction step (1) The same solvent and alcohol (ethyl alcohol etc.) etc. are mentioned.

  The reaction temperature in the reaction step (2) is not limited as long as the reaction proceeds, and is, for example, about −10 to 150 ° C. (preferably 0 to 150 ° C., more preferably 10 to 150 ° C., particularly preferably 20 to 130 ° C.). It is.

  The method for producing a silicon compound represented by the general formula (4) includes a reaction step (3) in which a hydroxyalkanesulfonic acid (ester or salt) is reacted with an alkoxysilylalkyl isocyanate or an alkoxysilylaryl isocyanate. It is preferable.

  In the reaction step (3), a reaction solvent may be used. The reaction solvent is not limited as long as it does not react with hydroxyalkanesulfonic acid (ester or salt), alkoxysilylalkyl isocyanate, and the like, and examples thereof include the same solvents as in the reaction step (1).

  In the reaction step (3), a known urethanization catalyst {for example, di-n-butyltin dilaurate} may be used.

  The reaction temperature in the reaction step (3) is not limited as long as the reaction proceeds, and is, for example, about −10 to 150 ° C. (preferably 0 to 150 ° C., more preferably 10 to 150 ° C., particularly preferably 20 to 130 ° C.). It is.

  The method for producing a silicon compound represented by the general formula (5) preferably includes a reaction step (4) in which mercaptoalkanesulfonic acid (ester or salt) is reacted with alkoxysilylalkyl (meth) acrylate. .

  In the reaction step (4), a reaction solvent may be used. The reaction solvent is not limited as long as it does not react with mercaptoalkanesulfonic acid (ester or salt), alkoxysilylalkyl (meth) acrylate, etc. For example, the same solvent as in the reaction step (1), etc. Can be mentioned.

  In the reaction step (4), it is preferable to use a known radical initiator {for example, 2,2'-azobisisobutyronitrile} or irradiate with ultraviolet rays.

  The reaction temperature in the reaction step (4) is not limited as long as the addition reaction proceeds. For example, -10 to 150 ° C (preferably 0 to 150 ° C, more preferably 10 to 150 ° C, particularly preferably 20 to 130 ° C). Degree.

  The production method of the silicon compound represented by the general formula (6) includes aminoalkanesulfonic acid (ester or salt) or aminoarenesulfonic acid (ester or salt), alkoxysilylalkyl isocyanate or alkoxysilylaryl isocyanate. The reaction step (5) is preferably included.

  In the reaction step (5), a reaction solvent may be used. The reaction solvent is not limited as long as it does not react with aminoalkanesulfonic acid (ester or salt), aminoarenesulfonic acid, alkoxysilylalkyl isocyanate, etc. For example, the same solvent as in reaction step (1) Etc.

  In the reaction step (5), a known urea catalyst {for example, di-n-butyltin dilaurate} may be used.

  The reaction temperature in the reaction step (5) is not limited as long as the reaction proceeds, and is, for example, about −10 to 150 ° C. (preferably 0 to 150 ° C., more preferably 10 to 150 ° C., particularly preferably 20 to 130 ° C.). It is.

  The silicon compound of the present invention can be applied to a modifier or the like, and is suitable as, for example, a silane coupling agent or a coating agent {by sol-gel method}.

  Although the modifier of this invention should just contain said silicon compound, it is preferable that alkoxysilane, an alkoxysilane oligomer, a metal oxide fine particle, and / or a silica sol other than said silicon compound are included.

  Examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

  Examples of the alkoxysilane oligomer include methyl silicate 51 and ethyl silicate 48 (Colcoat Co., Ltd.).

  Examples of the metal oxide fine particles include Aerosil 300 and Aerosil R974 (Nippon Aerosil Co., Ltd., “Aerosil” is a registered trademark of Degussa Aktiengesellschaft).

  As the silica sol, alcoholic silica sol of Colcoat Co., Ltd. {Colcoat P, Colcoat N-103X, Colcoat HSA-6, etc .; “Colcoat” is a registered trademark of Lion Corporation and Colcoat Corporation. }.

  When alkoxysilane is included, the content (% by weight) of alkoxysilane is preferably 10 to 90, more preferably 15 to 75, and particularly preferably 20 to 60, based on the weight of the silicon compound.

  When the alkoxysilane oligomer is included, the content of the alkoxysilane oligomer is preferably 10 to 90, more preferably 15 to 75, and particularly preferably 20 to 20% by weight based on the weight of the silicon compound as the weight percent of silicon dioxide. 60.

  When the metal oxide fine particles are included, the content of the metal oxide fine particles is preferably 10 to 90, more preferably 15 to 75, and particularly preferably 20 to 60 based on the weight of the silicon compound.

  When the silica sol is included, the content of the silica sol is preferably 10 to 90, more preferably 15 to 75, and particularly preferably 20 to 60 based on the weight of the silicon compound as the weight% of silicon dioxide.

  Furthermore, the modifying agent of the present invention may contain a diluting solvent in order to improve workability (handleability, paintability, etc.). The diluting solvent is not limited as long as it does not react with the silicon compound, alkoxysilane, alkoxysilane oligomer, metal oxide fine particles and silica sol of the present invention and dissolves them. Alcohol {methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol etc.}, ketone {acetone, methyl ethyl ketone and methyl isobutyl ketone etc.} and aprotic solvent {N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and the like} and the like.

  In the case of containing a diluting solvent, the workability of the modifier of the present invention is improved, so that the content of the diluting solvent is not limited, and the content of the diluting solvent is, for example, the silicon compound, alkoxysilane, alkoxysilane of the present invention The content of the oligomer, metal oxide fine particles and silica sol is 0.05 to 10% by weight based on the total weight of the silicon compound, alkoxysilane, alkoxysilane oligomer, metal oxide fine particles, silica sol and diluting solvent of the present invention ( The amount is preferably 0.1 to 5% by weight, particularly preferably 0.2 to 2% by weight.

The modifier of the present invention may contain the silicon compound of the present invention as it is, but it is preferable to hydrolyze the silicon compound from the viewpoint of film-forming properties.
When hydrolyzing, it is preferable to add a catalyst in order to promote hydrolysis.
Catalysts include acids {inorganic acids (such as hydrochloric acid, sulfuric acid and nitric acid) and organic acids (such as formic acid, acetic acid and butyric acid)} and bases {inorganic bases (such as ammonia, sodium hydroxide and potassium hydroxide) and organic bases ( Triethylamine, diethylamine, monoethylamine, 3-aminopropyltrimethoxysilane and the like)} and the like.

  When hydrolyzing, the amount of water added (molar ratio) is preferably 1 to 1000, more preferably 5 to 500, and particularly preferably 10 to 300, based on the number of moles of the silicon compound of the present invention.

When the modifier of the present invention contains, in addition to the silicon compound of the present invention, alkoxysilane, alkoxysilane oligomer, metal oxide fine particles, silica sol and / or diluent solvent, the modifier of the present invention contains the above silicon compound. And alkoxysilane, alkoxysilane oligomer, metal oxide fine particles, silica sol and / or solvent.
When the above silicon compound is hydrolyzed, it may be hydrolyzed before being uniformly mixed with alkoxysilane, alkoxysilane oligomer, metal oxide fine particles, silica sol and / or solvent, or hydrolyzed after uniform mixing. Also good.

Unless otherwise specified, parts mean parts by weight.
<Example 1>
3- (Triethoxysilyl) propyl isocyanate (Chisso Corporation) 6.86 parts (27.8 moles), sodium 3-hydroxypropanesulfonate (Aldrich, technical grade) 4.5 parts (27.8 moles) Part) and 0.2 part of di-n-butyltin dilaurate were dissolved in 100 parts of N, N-dimethylformamide (hereinafter abbreviated as DMF) and then reacted at 80 ° C. for 17 hours under an argon atmosphere. Silicon compound of the present invention (1) {3- (N- (3- (triethoxysilyl) propyl) carbamoyloxy) propane sulfonate sodium; NaOSO ₂ —CH ₂ CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ A DMF solution containing —Si (OCH ₂ CH ₃ ) ₃ } was obtained.

A part of this DMF solution was concentrated and the chemical structure was confirmed by ¹ H-NMR analysis {JEOL (JEOL), JNM-GSX270 FT-NMR SYSTEM, CDCl ₃ , and so on. ; 4.10 (m, 2H, -C H 2 OCONH -), 3.82 (q, 6H, -OC H 2 CH 3), 3.0-3.2 (m, 4H, NaOSO 2 C H 2 _{-, - OCONHC H 2 -)} , 2.02 (m, 2H, NaOSO 2 CH 2 C H 2 -), 1.55 (m, 2H, -C H 2 CH 2 Si≡), 1.22 (t _{, 9H, -CH 2 C H 3} ), 0.63 (m, 2H, -C H 2 Si≡)}.

<Example 2>
10.0 parts (40.5 mol parts) of 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation), sodium 2-hydroxyethanesulfonate (Tokyo Chemical Industry Co., Ltd., Tokyo Chemical Industry Grade 1) 6.0 parts (40.5 mol parts) and 0.2 parts of dilauric acid di-n-butyltin were dissolved in 114 parts of dry dimethyl sulfoxide (hereinafter abbreviated as DMSO), followed by reaction at 80 ° C. for 17 hours in an argon atmosphere. The silicon compound of the present invention (2) {2- (N- (3- (triethoxysilyl) propyl) carbamoyloxy) ethane sulfonate sodium; NaOSO ₂ —CH ₂ CH ₂ —OCONH—CH ₂ CH ₂ CH A DMF solution containing _2- Si (OCH ₂ CH ₃ ) ₃ } was obtained.

Incidentally, concentrated part of the DMF ^solution, 1 H-NMR confirmed the chemical structure by analysis {4.41 (m, 2H, -C H 2 OCONH -), 3.82 (q, 6H, - _{OC H 2 CH 3), 3.0-3.2} (m, 4H, NaOSO 2 C H 2 -, - OCONHC H 2 -), 1.58 (m, 2H, -C H 2 CH 2 Si≡) , 1.22 (t, 9H, -CH 2 C H 3), 0.63 (m, 2H, -C H 2 Si≡)}.

<Example 3>
3- (acryloyloxy) propane sulfonate potassium (Aldrich) 10 parts (43.1 mole parts), 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) 4.73 parts (24.1 moles) Part) and 2,2′-azobisisobutyronitrile 353 × 10 ⁻³ parts (2.15 mole parts) were dissolved in 166.5 parts DMSO and reacted at about 25 ° C. for 17 hours under an argon atmosphere. The silicon compound of the present invention (3) {3- (3- (3- (3- (trimethoxysilyl) propylthio) propionyloxy) propanesulfonate potassium; KOSO ₂ —CH ₂ CH ₂ CH ₂ —OCO—CH ₂ CH ₂ A DMSO solution containing —S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ } was obtained.

A part of this DMSO solution was concentrated under reduced pressure, and the chemical structure was confirmed by ¹ H-NMR analysis {4.22 (m, 2H, -C H ₂ OCO-), 3.57 (s, 9H, _{-OC H 3), 2.88 (m} , 2H, KOSO 2 C H 2 -), 2.5-2.8 (m, 6H, -OCOC H 2 C H 2 -S-C H 2 -), _{2.06 (m, 2H, KOSO 2} CH 2 C H 2 -), 1.70 (m, 2H, -C H 2 CH 2 Si≡), 0.75 (m, 2H, -C H 2 Si≡ )}.

<Example 4>
Sodium 4-styrenesulfonate (Tokyo Chemical Industry Co., Ltd.) 10 parts (48.5 mol parts) and 3- (trimethoxysilyl) propane-1-thiol (Chisso Corporation) 9.5 parts (48.5 mol parts) ) Was dissolved in 175.5 parts of DMF, and 2,2′-azobisisobutyronitrile 398 × 10 ⁻³ parts (2.42 mol parts) was added under an argon atmosphere, and the mixture was stirred at 80 to 90 ° C. for 17 hours. The silicon compound of the present invention (4) {4- (2- (3- (trimethoxysilyl) propylthio) ethyl) benzenesulfonate sodium; NaOSO ₂ -p-C ₆ H ₄ CH ₂ CH ₂ -S A DMF solution containing —CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ } was obtained.

Incidentally, a part of the DMF solution was concentrated under reduced ^pressure, 1 H-NMR confirmed the chemical structure by analysis _{{7.53 (m, 2H, NaOSO} 2 -o-C 6 H 4 -), 7.16 ( _{m, 2H, NaOSO 2 -m-} C 6 H 4 -), 3.48 (s, 9H, -OC H 3), 2.78 (m, 2H, -C 6 H 4 C H 2 -), 2 _{.70 (m, 2H, -C 6} H 4 CH 2 C H 2 -S -), 2.50 (m, 2H, -S-C H 2 CH 2 -), 1.57 (m, 2H, - C H ₂ CH ₂ Si≡), 0.70 (m, 2H, —C H ₂ Si≡)}.

<Example 5>
Lithium 4-styrenesulfonate (Tosoh Corp.) 12.12 parts (63.8 mol parts) and 3- (trimethoxysilyl) propane-1-thiol (Chisso Corp.) 12.5 parts (63. 8 mol parts) was dissolved in 175 parts of dry ethanol, and 2,2′-azobisisobutyronitrile 520 × 10 ⁻³ parts (3.17 mol parts) was added under an argon atmosphere, and the mixture was refluxed. by time reaction, a silicon compound of the present invention (5) {4- (2- (3- (trimethoxysilyl) propylthio) ethyl) lithium benzenesulfonic _{acid; LiOSO 2 -p-C 6 H} 4 CH 2 CH 2 - An ethanol solution containing S—CH ₂ CH ₂ CH ₂ —Si (OCH ₃ ) ₃ } was obtained.

A part of this ethanol solution was concentrated under reduced ^pressure, 1 H-NMR confirmed the chemical structure by analysis _{{7.76 (m, 2H, LiOSO} 2 -o-C 6 H 4 -), 7.30 ( _{m, 2H, LiOSO 2 -m-} C 6 H 4 -), 3.53 (s, 9H, -OC H 3), 2.89 (m, 2H, -C 6 H 4 C H 2 -), 2 _{.75 (m, 2H, -C 6} H 4 CH 2 C H 2 -S -), 2.52 (m, 2H, -S-C H 2 CH 2 -), 1.68 (m, 2H, - CH ₂ CH ₂ Si≡), 0.75 (m, 2H, —CH ₂ Si≡)}.

<Example 6>
2 parts (30.5 mol parts) of 2-mercaptoethanesulfonic acid atrium (Tokyo Chemical Industry Co., Ltd.) and 5.8 parts (30.5 mol parts) of vinyltriethoxysilane (Chisso Corporation) dried under reduced pressure were dried. After being dissolved in 100 parts of DMSO, 2,2′-azobisisobutyronitrile 250 × 10 ⁻³ parts (1.52 mol parts) was added under an argon atmosphere and reacted for 17 hours while refluxing. DMSO containing silicon compound (6) {2- (3- (triethoxysilyl) ethylthio) ethanesulfonic acid sodium; NaOSO ₂ —CH ₂ CH ₂ —S—CH ₂ CH ₂ —Si (OCH ₂ CH ₃ ) ₃ } A solution was obtained.

A part of this DMSO solution was concentrated under reduced pressure, and the chemical structure was confirmed by ¹ H-NMR analysis.

<Example 7>
9.2 parts (37.2 mol parts) of 3- (triethoxysilyl) propyl isocyanate (Chisso Corporation), 5 parts (37.2 mol parts) of sodium 2-hydroxymethanesulfonate (Kanto Chemical Co., Ltd.) and After dissolving 0.2 part of dilauric acid di-n-butyltin in 128 parts of dry DMF, the reaction was carried out at 80 ° C. for 17 hours under an argon atmosphere to obtain the silicon compound (7) {N- (3- (tri A DMF solution containing sodium ethoxysilyl) propyl) carbamoyloxymethanesulfonate; NaOSO ₂ —CH ₂ —OCONH—CH ₂ CH ₂ CH ₂ —Si (OCH ₂ CH ₃ ) ₃ } was obtained.

A part of this DMF solution was concentrated and the chemical structure was confirmed by ¹ H-NMR analysis.

<Example 8>
3- (Triethoxysilyl) propyl isocyanate (Chisso Corporation) 8.02 parts (32.5 mole parts), sodium 4-aminobenzenesulfonate (Tokyo Chemical Co., Ltd.) 7.5 parts (32.5 mole parts) ) And 0.2 parts of di-n-butyltin dilaurate are dissolved in 140 parts of dry DMF, and then reacted at 80 ° C. for 17 hours under an argon atmosphere to obtain the silicon compound (8) {4- (N— D3-solution containing (3- (triethoxysilyl) propyl) carbamoylamino) benzene sulfonate; NaOSO ₂ —C ₆ H ₄ —NHCONH—CH ₂ CH ₂ CH ₂ —Si (OCH ₂ CH ₃ ) ₃ } It was.

A part of this DMF solution was concentrated and the chemical structure was confirmed by ¹ H-NMR analysis.

<Example 9>
Dehydrated sodium 2-mercaptoethylenesulfonate (Aldrich) 5.5 parts (33.5 moles), 3- (trimethoxysilyl) propyl acrylate (Shin-Etsu Chemical Co., Ltd.) 7.85 parts (33.5) Mol part) and 2,2′-azobisisobutyronitrile 353 × 10 ⁻³ part (2.15 mol part) were dissolved in 120 parts of DMF and then reacted at about 25 ° C. for 17 hours under an argon atmosphere. , Silicon compound of the present invention (9) {2- (2- (3- (trimethoxysilyl) propyloxycarbonyl) ethylthio) ethanesulfonic acid sodium; NaOSO ₂ —CH ₂ CH ₂ —S—CH ₂ CH ₂ —CO _{2 -CH 2 CH 2 CH 2 -Si} (OCH 3) to give a DMF solution containing _3}.

A part of this DMF solution was concentrated under reduced pressure, and the chemical structure was confirmed by ¹ H-NMR analysis.

Comparative Example 1 Synthesis Example 1 of Patent Document 1
Uniform mixing of 100 parts of methoxy polyethylene glycol allyl ether (SDD-01203, Nippon Emulsifier Co., Ltd., number average molecular weight 400) and platinum catalyst {PT-VTSC-3.0X, Umicore Precious Metals} at 100 ° C Then, 181 parts of triethoxysilane {SIT8185, Azmax Co., Ltd.} was added dropwise at 100 ° C. over 2 hours, and then reacted at 100 ° C. for 7 hours. Subsequently, excess triethoxysilane was removed under reduced pressure to obtain a comparative silicon compound {methoxypolyethyleneglycol-modified triethoxysilane}.

Note that the silicon compound ^was confirmed the chemical structure by 1 H-NMR analysis {3.82 (q, 6H, -OC H 2 CH 3), 3.24 (s, 3H, C H 3 OCH 2 CH 2 O -), 3.5 (m, -OC H 2 C H 2 O -), 3.27 (q, 2H, -CH 2 OC H 2 CH 2 CH 2 -), 1.5 (m, 2H, _{-C H 2 CH 2 Si≡),} 1.22 (t, 9H, -OCH 2 C H 3), 0.61 (m, 2H, -C H 2 Si≡)}.

Using the silicon compounds obtained in Examples and Comparative Examples, the surface of the slide glass was modified as follows, and the contact angle was measured.
Sample for evaluation (15 parts of a solution containing the silicon compound of the present invention; or a mixture of 1.5 parts of a comparative silicon compound and 13.5 parts of MEK), 30 parts of ethanol, 3 parts of water and 0.3 part of acetic acid are uniformly mixed. Then, the mixture was stirred at about 25 ° C. for 2 days to prepare a treatment liquid (modifier).
Slide glass {76 mm, 26 mm, 1.2 mm; immersed in 2-propanol saturated solution of sodium hydroxide for 17 hours, then washed with water and dried (60 ° C., 2 hours)} as treatment liquid (modifier) After dipping and taking out the slide glass, the liquid was drained and heat-treated at 130 ° C. for 10 minutes to obtain a surface-modified slide glass.

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. These results are shown in Table 1.
In addition, about the surface of the glass slide which is not surface-modified, the contact angle (degree) was measured similarly, and these average values were shown in Table 1 as a blank.

  The silicon compound of the present invention was able to impart higher hydrophilicity than the silicon compound of the comparative example.

<Example 10>
After uniformly mixing 15 parts of a DMF solution containing the silicon compound (1) obtained in Example 1, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, 2 parts at about 25 ° C. The modifier (1) of the present invention was prepared by stirring for a day.

<Example 11>
After uniformly mixing 15 parts of a DMF solution containing the silicon compound (2) obtained in Example 2, 30 parts of ethanol, 0.5 parts of tetraethoxysilane, 3 parts of water and 0.3 parts of acetic acid, 2 parts at about 25 ° C. The modifier (2) of the present invention was prepared by stirring for a day.

<Example 12>
After uniformly mixing 10 parts of the modifier (2) obtained in Example 11 and 30 parts of ethanol, the mixture was stirred at about 25 ° C. for 2 days to prepare the modifier (3) of the present invention.

<Example 13>
After 10 parts of the DMF solution containing the silicon compound (2) obtained in Example 2 and 20 parts of silica sol (Colcoat N-103X; Colcoat Co., Ltd.) were uniformly mixed, the mixture was stirred at about 25 ° C. for 2 days. A modifier (4) was prepared.

<Example 14>
After uniformly mixing 6 parts of the DMF solution containing the silicon compound (2) obtained in Example 2 and 30 parts of silica sol (Colcoat HSA-6; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days, A modifier (5) was prepared.

<Example 15>
After 10 parts of the DMF solution containing the silicon compound (2) obtained in Example 2 and 20 parts of silica sol (Colcoat HSA-6; Colcoat Co., Ltd.) were uniformly mixed, the mixture was stirred at about 25 ° C. for 2 days. A modifier (6) was prepared.

<Example 16>
After 15 parts of the DMF solution containing the silicon compound (3) obtained in Example 3 and 15 parts of silica sol (Colcoat HSA-6; Colcoat Co., Ltd.) were uniformly mixed, the mixture was stirred at about 25 ° C. for 2 days, A modifier (7) was prepared.

<Example 17>
After uniformly mixing 15 parts of a DMSO solution containing the silicon compound (3) obtained in Example 3, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, 2 parts at about 25 ° C. The modifier (8) of the present invention was prepared by stirring for a day.

<Example 18>
After uniformly mixing 15 parts of a DMF solution containing the silicon compound (4) obtained in Example 4, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, 2 parts at about 25 ° C. Stirring for a day, the modifier (9) of the present invention was prepared.

<Example 19>
After uniformly mixing 6 parts of a DMSO solution containing the silicon compound (4) obtained in Example 4 and 30 parts of silica sol (Colcoat HSA-6; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A modifier (10) was prepared.

<Example 20>
After uniformly mixing 15 parts of an ethanol solution containing the silicon compound (5) obtained in Example 5, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, 2 parts at about 25 ° C. The modifier (11) of the present invention was prepared by stirring for a day.

<Example 21>
After uniformly mixing 10 parts of an ethanol solution containing the silicon compound (5) obtained in Example 5 and 20 parts of silica sol (Colcoat N-103X; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A modifier (12) was prepared.

<Example 22>
After uniformly mixing 6 parts of an ethanol solution containing the silicon compound (5) obtained in Example 5 and 30 parts of silica sol (Colcoat N-103X; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A modifier (13) was prepared.

<Example 23>
After uniformly mixing 6 parts of an ethanol solution containing the silicon compound (5) obtained in Example 5 and 30 parts of silica sol (Colcoat HSA-6; Colcoat Co., Ltd.), the mixture was stirred at about 25 ° C. for 2 days. A modifier (14) was prepared.

<Example 24>
After uniformly mixing 15 parts of a DMSO solution containing the silicon compound (6) obtained in Example 6, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, 2 parts at about 25 ° C. The modifier (15) of the present invention was prepared by stirring for a day.

<Example 25>
After uniformly mixing 15 parts of a DMF solution containing the silicon compound (7) obtained in Example 7, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, 2 parts at about 25 ° C. By stirring for a day, the modifier (16) of the present invention was prepared.

<Example 26>
After uniformly mixing 15 parts of a DMF solution containing the silicon compound (8) obtained in Example 8, 30 parts of ethanol, 0.5 part of tetraethoxysilane, 3 parts of water and 0.3 part of acetic acid, 2 parts at about 25 ° C. By stirring for a day, the modifier (17) of the present invention was prepared.

<Example 27>
After uniformly mixing 15 parts of a DMF solution containing the silicon compound (9) obtained in Example 9, 30 parts of ethanol, 0.5 parts of tetraethoxysilane, 3 parts of water and 0.3 parts of acetic acid, 2 parts at about 25 ° C. The modifier (18) of the present invention was prepared by stirring for a day.

  For the modifiers obtained in Examples 10 to 27, a surface-modified glass slide was prepared in the same manner as described above, the contact angle (degree) was measured, and the average value was calculated. These results are shown in Table 2.

  When the silicon compound of the present invention and a known surface modifier (for example, alkoxysilane or silica sol) were used, the contact angle was equivalent to that when only the silicon compound of the present invention was used.

Claims (5)

A silicon compound represented by the formula (1):

^{_{(MOSO 2 -R 1 -) m}} Z-R 3 -Si (CH 3) n (-Y) 3-n (1)

However, M is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom or ammonium _(NH 4), ^{R 1} and ^{R 3} is an alkylene group or an arylene group having a carbon number of 6-8 having from 1 to 4 carbon atoms, Z represents —O (CO) —R ² —S—, —O (CO) —R ² —O—, —O (CO) —R ² —NH—, (—O (CO) —R ² —) _2. A group represented by N—, —S—, —O—, —NH—,> N—, —S—R ² —CO ₂ — or —NHCONH— (wherein R ² represents ethylene, 1-methylethylene or 2- Methyl ethylene), Y is an alkoxy group having 1 to 3 carbon atoms, C is a carbon atom, O is an oxygen atom, N is a nitrogen atom, S is a sulfur atom, H is a hydrogen atom, Si is a silicon atom, and m is 1 or 2 , N represents 0 or 1. A silicon compound represented by any one of formulas (2) to (6).

However, M is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom or ammonium _(NH 4), ^{R 1} and ^{R 3} is an alkylene group or an arylene group having a carbon number of 6-8 having from 1 to 4 carbon atoms, R ² is ethylene or 1-methylethylene, R ⁴ is ethylene or a phenyleneethylene group (—C ₆ H ₄ —CH ₂ CH ₂ —), X is —S—, —O—, —NH— or> N—. A group represented by the formula, Y is an alkoxy group having 1 to 3 carbon atoms, C is a carbon atom, O is an oxygen atom, N is a nitrogen atom, S is a sulfur atom, H is a hydrogen atom, Si is a silicon atom, and m is 1 or 2, n represents 0 or 1; A modifying agent comprising the silicon compound according to claim 1. Furthermore, the modifier of Claim 3 containing an alkoxysilane, an alkoxysilane oligomer, a metal oxide fine particle, and / or a silica sol. A method for producing the silicon compound according to claim 1 or 2,
A reaction step (1) of reacting (meth) acryloyloxyalkanesulfonic acid (ester or salt) with alkoxysilylalkanethiol, alkoxysilylalkylamine, alkoxysilylarenethiol or alkoxysilylarylamine;
Reaction step (2) for reacting vinylbenzenesulfonic acid (ester or salt) or vinylsulfonic acid (ester or salt) with alkoxysilylalkanethiol, alkoxysilylalkylamine, alkoxysilylarenethiol or alkoxysilylarylamine;
A reaction step (3) of reacting hydroxyalkanesulfonic acid (ester or salt) with alkoxysilylalkyl isocyanate or alkoxysilylaryl isocyanate;
Reaction step (4) of reacting mercaptoalkanesulfonic acid (ester or salt) with alkoxysilylalkyl (meth) acrylate, or aminoalkanesulfonic acid (ester or salt) or aminoarenesulfonic acid (ester or salt) , Reaction step (5) for reacting with alkoxysilylalkyl isocyanate or alkoxysilylaryl isocyanate
The manufacturing method characterized by including.