JP2019048966A - Method for producing antifogging coating composition liquid - Google Patents

Abstract

To provide a production method for obtaining an antifogging coating composition liquid conveniently, without requiring dehydration of solvent at all, and without the need for controlling humidity in a reaction and an atmosphere of post-processing at all.SOLUTION: The present invention provides a method for producing an antifogging coating composition liquid that contains, in a solvent, a hydrolysate and/or hydrolytic condensate of a betaine silicon compound of the following formula (3), obtained by the reaction between a hydrolysate and/or hydrolytic condensate of a compound of the following formula (1) and a betaine agent. (X)(CH)Si-R-(Y-R)-N(R)(R)(1), (X)(CH)Si-R-(Y-R)-N(R)(R)-Z(3). {In formulae (1), (3), X is an alkoxy group or a hydroxy group, Y is -NHCOO-, -NHCONH-, -S- or -SO-}. {In formula (3), Z is (CH)COor (CH)SO}.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a method for producing an antifogging coating composition liquid comprising a hydrolysis condensate and / or a hydrolysis mixture of a coatable betaine-based silicon compound capable of producing an antifogging effect and low cost.

The present inventors have found an antifogging coating composition comprising a betaine-based silicon compound as an antifogging coating agent that can be applied to inorganic and organic substrates, and have filed a patent application (Patent Document 1).
However, in order to obtain the present antifogging coating composition, the solvent used (for example, ethyl alcohol etc.) to prevent hydrolysis of the alkoxy group of the target betaine silicon compound when producing the betaine silicon compound first It is necessary to dehydrate the reaction atmosphere and to make the reaction atmosphere free of water. In addition, when it is necessary to filter out the formed salt, in order to prevent hydrolysis of the alkoxy group of the product betaine silicon compound, the filtration atmosphere also needs to be in a state free of water, and the above operation is complicated. It is.
As a result, there is a problem that the preparation of the antifogging coating composition becomes complicated, and as a result, the cost increases.

WO 2016-167097

  The present invention has been made in view of the above-mentioned prior art, and it is not necessary to dehydrate the solvent at all, and it is not necessary to control the humidity of the atmosphere during the reaction and post-treatment at all. The purpose is to provide a manufacturing method for obtaining

  As a result of intensive studies conducted by the inventor paying attention to the problems of the prior art as described above, it has been found that betaine-based hydrolyzate and / or hydrolytic condensate of dialkylaminosilicon compound, which is a raw material of silicon compound, is It has been found that the above problems can be solved by acting an agent, and the present invention has been made.

｛式中、Ｒ^７は炭素数２から７のアルキレン基であり、Ｚ^１は−ＣＯ−Ｏ−又は−ＳＯ_２−Ｏ−である。｝
（Ｘ）_３−ｋ（ＣＨ_３）_ｋＳｉ−Ｒ^１−（Ｙ−Ｒ^２）_ｍ−Ｎ^＋（Ｒ^３）（Ｒ^４）−Ｚ
（３）
｛式中Ｘ、ｋ、Ｒ^１、Ｙ、ｍ、Ｒ^２、Ｒ^３及びＲ^４は式（１）と同一であり、Ｚは−（ＣＨ_２）_ｎＣＯ_２ ⁻（ｎは１〜５の整数）又は−（ＣＨ_２）_ｎＳＯ_３ ⁻（ｎは１〜５の整数）である。｝
〔２〕 水の存在下、
前記式（１）化合物等と、
下記式（４）で表される化合物と下記式（４）で表される化合物の活性水素と反応可能な官能基を有するシランカップリング剤から誘導される化合物（以下「界面活性シランカップリング剤」という。）、界面活性シランカップリング剤を加水分解した加水分解物及び加水分解縮合物（以上を総称して「界面活性シランカップリング剤等」という。）、シランカップリング剤である下記式（５）で表される化合物、下記式（５）で表される化合物を加水分解した加水分解物及び加水分解縮合物（以上を総称して「シランカップリング剤等」という。）並びに加水分解可能な炭素−ケイ素結合を有しないケイ素化合物、加水分解可能な炭素−ケイ素結合を有しないケイ素化合物を加水分解した加水分解物及び加水分解縮合物、加水分解可能なチタン化合物、加水分解可能なチタン化合物を加水分解した加水分解物及び加水分解縮合物、加水分解可能なジルコニウム化合物、加水分解可能なジルコニウム化合物を加水分解した加水分解物及び加水分解縮合物、加水分解可能なアルミニウム化合物及び加水分解可能なアルミニウム化合物を加水分解した加水分解物及び加水分解縮合物（以上を総称して「加水分解可能金属化合物等」という。）からなる群から選ばれる少なくとも１種類以上と、
前記ベタイン化剤と、
を加えて反応並びに加水分解及び／又は加水分解縮合させることを特徴とする前記〔１〕に記載の防曇性コーティング組成液の製造方法。
Ｒ^５−Ｘ^１−（ＣＨ_２ＣＨ_２Ｏ）_ｐ−Ｙ^１ （４）
｛式中Ｒ^５は水素原子、炭素数１〜２０のアルキル基（該アルキル基はフッ素原子、ケイ素原子、ベンゼン環及び二重結合を含んでいてもよい。）又は水素原子、Ｘ^１は−Ｏ−、−ＣＯＯ−あるいは−ＣＯＮＨ−であり、ｐは１〜３０の整数であり、Ｙ^１は水素原子、−ＣＨ_２ＣＯＯＨを表す。｝
（Ｘ）_３−ｋ（ＣＨ_３）_ｋＳｉ−（Ｒ^６）_ｍ Ｘ^２ （５）
｛式中、Ｘは同一又は異なっても良い炭素数１〜５のアルコキシ基、水酸基及びハロゲン原子のいずれかを表し、ｋは０又は１を表し、ｍは、０又は１を表し、Ｘ^２は、アルキル基（該アルキル基は、ヘテロ原子、不飽和結合を含んでもよく、また環状構造であってもよい）、ビニル基、チオール基、アミノ基、塩素原子、アクリル基、メタクリル基、スチリル基、フェニル基、トリル基、グリシドキシ基、３，４−エポキシシクロヘキシル基及びブロック化イソシアネート基からなる群から選ばれる官能基であり、Ｒ^６は炭素数１〜５のアルキレン基を表す。｝
〔３〕 水の存在下、前記式（１）化合物等と、前記〔２〕に記載の界面活性シランカップリング剤等、前記〔２〕に記載のシランカップリング剤等及び前記〔２〕に記載の加水分解可能金属化合物等からなる群から選ばれる1種以上とを加水分解及び／又は加水分解縮合させた後、前記ベタイン化剤を加えて反応並びに加水分解及び／又は加水分解縮合させることを特徴とする前記〔１〕に記載の防曇性コーティング組成液の製造方法。
〔４〕 水の存在下、前記式（１）化合物等と前記ベタイン化剤を反応並びに加水分解及び／又は加水分解縮合させた後、前記〔２〕に記載の界面活性シランカップリング剤等、前記〔２〕に記載のシランカップリング剤等及び前記〔２〕に記載の加水分解可能金属化合物等からなる群から選ばれる１種類以上を加えて加水分解及び／又は加水分解縮合させることを特徴とする前記〔１〕に記載の防曇性コーティング組成液の製造方法。 That is, the present invention is characterized by having the following constitution, and solves the above-mentioned problems.
[1] A method for producing a coating composition liquid, which is a compound represented by the following formula (1) or a hydrolyzate obtained by hydrolyzing a compound represented by the following formula (1) in the presence of water A decomposition condensate (generally referred to as “formula (1) compound etc.”) and a betaining agent represented by the following formula (2) and / or the following formula (2 ′) (collectively “betaine” ) Is reacted and subjected to hydrolysis and / or hydrolytic condensation to prevent hydrolysis including hydrolysis and / or hydrolysis condensate of a betaine silicon compound represented by the following formula (3) in a solvent: Method of producing a cloudy coating composition liquid.
^{_{(X) 3-k (CH}} 3) k Si-R 1 - (Y-R 2) m -N (R 3) (R 4) (1)
{Wherein X represents any of the same or different 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 Y represents -NHCOO-, -NHCONH-, -S- or -SO _2- , m represents 0 or 1, and R ² contains an ether bond having 1 to 10 carbon atoms, an ester bond or an amide bond But alkylene group or _{^{-CH 2 CH 2 n + (CH}} 3) (Z) CH 2 CH 2 OCH 2 CH 2 - (Z is ^{_{(CH 2) n CO 2 -}} (n is an integer of from 1 to 5) or ( ^{_{CH 2) n SO 3 - (}} n represents an integer)) of 1 to 5, ^{R 3} and ^{R 4} represent the same or different and alkyl group having 1 to 3 carbon atoms. }
X ³ -R ⁶ -Z-Y ³ (2)
{Wherein ^{X 3} is a chlorine atom, a bromine atom and an iodine atom, ^{R 6} is an alkylene group having 1 to 7 carbon atoms, Z is CO ₂ ^- or SO ₃ ^- represents, ^{Y 3} is ^Li +, Na ^{+ And} K ⁺ . }

In the formula, R ⁷ is an alkylene group having 2 to 7 carbon atoms, and Z ¹ is —CO—O— or —SO ₂ —O—. }
(X) _3-k (CH ₃ ) _k Si-R ^1- (Y-R ² ) _m- N ⁺ (R ³ ) (R ⁴ ) -Z
(3)
Wherein X, k, R ¹ , Y, m, R ² , R ³ and R ⁴ are the same as in formula (1), and Z is — (CH ₂ ) _n CO ₂ ^— (n is 1 to 5 integer) or - (n is an integer of from 1 to ^{_{5) - (CH 2) n SO}} 3. }
[2] In the presence of water,
The compound of the formula (1) and the like,
Compound derived from a compound represented by the following formula (4) and a silane coupling agent having a functional group capable of reacting with active hydrogen of a compound represented by the following formula (4) (hereinafter referred to as “surface active silane coupling agent ), Hydrolysates obtained by hydrolyzing surface-active silane coupling agents and hydrolytic condensates (collectively referred to as "surface-active silane coupling agents etc."), and the following formulas which are silane coupling agents: The compound represented by (5), the hydrolyzate and the hydrolysis condensate obtained by hydrolyzing the compound represented by the following formula (5) (these are generically referred to as "silane coupling agent etc.") and the hydrolysis Silicon compounds having no possible carbon-silicon bond, hydrolysates and hydrolysis condensates of silicon compounds having no hydrolysable carbon-silicon bond, and hydrolysable hydrolysates Compounds, hydrolysates and hydrolytic condensates of hydrolysable titanium compounds, hydrolyzable zirconium compounds, hydrolysates and hydrolytic condensates of hydrolysable zirconium compounds, and hydrolysates And at least one selected from the group consisting of a possible aluminum compound and a hydrolyzate obtained by hydrolyzing a hydrolysable aluminum compound and a hydrolytic condensate (the above are collectively referred to as "hydrolyzable metal compounds etc.") When,
Said betaine agent,
In the reaction and hydrolysis and / or hydrolysis condensation as described in [1] above.
R ^5- X ^1- (CH ₂ CH ₂ O) _p- Y ¹ (4)
{Wherein R ⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (the alkyl group may contain a fluorine atom, a silicon atom, a benzene ring and a double bond) or a hydrogen atom, X ¹ is — O-, -COO-, or -CONH-, p is an integer of 1 to 30, and Y ¹ represents a hydrogen atom, -CH ₂ COOH. }
(X) _3-k (CH ₃ ) _k Si-(R ⁶ ) _m X ² (5)
{Wherein X represents any one of an alkoxy group having 1 to 5 carbon atoms which may be the same or different, a hydroxyl group, and a halogen atom, k represents 0 or 1, m represents 0 or 1, and X ² Is an alkyl group (the alkyl group may contain a hetero atom, an unsaturated bond, or may be a cyclic structure), a vinyl group, a thiol group, an amino group, a chlorine atom, an acrylic group, a methacrylic group, a styryl group It is a functional group selected from the group consisting of a group, a phenyl group, a tolyl group, a glycidoxy group, a 3,4-epoxycyclohexyl group and a blocked isocyanate group, and R ⁶ represents an alkylene group having 1 to 5 carbon atoms. }
[3] The compound of the formula (1) or the like in the presence of water, the surface active silane coupling agent or the like according to the above [2], the silane coupling agent or the like according to the above [2], and the above [2] Hydrolysis and / or hydrolytic condensation with one or more selected from the group consisting of the hydrolyzable metal compounds described above, and then adding the above-mentioned betainizing agent to cause reaction and hydrolytic and / or hydrolytic condensation The manufacturing method of the antifogging coating composition liquid as described in said [1] characterized by the above-mentioned.
[4] The surface active silane coupling agent as described in the above [2] or the like after reacting the compound of the formula (1) or the like with the betainizing agent in the presence of water and subjecting the same to hydrolysis and / or hydrolysis condensation. It is characterized in that one or more selected from the group consisting of the silane coupling agent etc. described in the above [2] and the hydrolysable metal compound etc. described in the above [2] are added to cause hydrolysis and / or hydrolysis condensation. The manufacturing method of the anti-fogging coating composition liquid as described in said [1] made into said.

The hydrolyzate means that the compound is hydrolyzed as it is, and the hydrolytic condensate means that the compound is condensed and / or two or more kinds of the compound are randomly or in block. Means condensed.
In the presence of water, when the compound of the formula (1) is reacted with the formula (2) and / or the following formula (2 ′), it means both in the case of first existing and in the middle of the reaction. Do.

The method for producing the antifogging coating composition according to the present invention does not require any dehydration of the solvent, does not require any complicated process such as control of the reaction solvent or the water content of the reaction atmosphere, and is a simple process as a result. Antifogging coating compositions can be prepared.
And the antifogging coating composition liquid manufactured with the manufacturing method of this invention can provide hydrophilic property and antifogging property by coating to glass, a plastics, a metal, etc.

  The method for producing the antifogging coating composition liquid of the present invention comprises hydrolysing product and / or hydrolysis of the betaine silicon compound represented by the formula (3) contained in the antifogging coating composition liquid in the presence of water. In the preparation of a condensate, a hydrolyzate and / or a hydrolysis condensate of a dialkylaminosilicon compound (a compound of the above formula (1)) which is a raw material of a betaine silicon compound is added to a betainizing agent (the above formula (2) and / or Alternatively, it is characterized in that the compound of the following formula (2 ′) is reacted and subjected to hydrolysis and / or hydrolysis and condensation.

  The hydrolyzate and / or hydrolytic condensate of the dialkylaminosilicon compound (the compound of the above formula (1)) is prepared by dissolving the compound of the above (1) in a water-soluble solvent and adding water thereto. It is obtained by hydrolysis and / or hydrolytic condensation.

The reaction temperature is from room temperature to 150 ° C., preferably the reflux temperature of the solvent used.
The reaction time is 0.5 hour to 48 hours, preferably 2 hours to 24 hours, particularly preferably 4 hours to 24 hours.
The above reaction may be carried out under normal pressure or under pressure.

Examples of the water-soluble solvent in which the compound (1) is dissolved include 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-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide etc. Can be mentioned.
Among these, alcohol solvents (ethyl alcohol, iso-propyl alcohol) are preferred.

  The following can be mentioned as a preferable compound of the dialkylamino silicon compound of said Formula (1).

  In said Formula (1), a C1-C5 alkoxy group, a hydroxyl group, and a halogen atom are mentioned as X. Among these, preferred are a methoxy group, an ethoxy group and an isopropyloxy group, and particularly preferred are a methoxy group and an ethoxy group.

In the formula (1), 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, trimethylene group is preferable in consideration of the availability of the raw material.

  In the formula (1), k is 0 or 1, preferably 0.

Wherein in formula (1), Y -NHCOO -, - NHCONH -, - S- or -SO ₂ -, preferably -NHCOO- and -NHCONH-.
In the above formula (1), as R ² , an ether bond, an ester bond or an amide bond may be contained as an alkylene group having 1 to 10 carbon atoms or —CH ₂ CH ₂ N ⁺ (CH ₃ ) (Z) CH ₂ CH ₂ OCH ₂ CH ₂ - is. Preferred among these ethylene group, trimethylene group and ethylene oxyethylene groups and ^{_{-CH 2 CH 2 N + (CH}} 3) (Z) CH 2 CH 2 OCH 2 CH 2 - is.

In the formula (1), the alkyl group having 1 to 3 carbon atoms in ^{R 3} and ^{R 4,} a methyl group, an ethyl group, and a n- propyl group. Of these, preferred is a methyl group.

  The compound represented by said Formula (1) can use a commercially available thing, or can be obtained by the manufacturing method of WO2016 / 167097.

The following are mentioned as a specific compound represented by said Formula (1).
(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 )
(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 ) (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 NH CONHCH 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)
(C ₂ H ₅ O) ₂ Si (CH ₃ ) CH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ (1-11)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ COOCH ₂ CH ₂ N (CH ₃ ) ₂ (1-12)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH (CH ₃ ) COOCH ₂ CH ₂ N (CH ₃ ) ₂ (1-13)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CONHCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ (1-14)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ SCH ₂ CH (CH ₃ ) CONHCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ (1-15)
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ CH ₂ SCH ₂ CH (CH ₃ ) CONHCH ₂ CH ₂ CH ₂ N (CH ₃ ) ₂ (1-16)
(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 (1-17)

  The hydrolyzate and / or hydrolytic condensate of the betaine-based silicon compound represented by the above formula (3) contained in the antifogging coating composition liquid comprises a hydrolyzate of a dialkylaminosilicon compound (a compound of the above-mentioned formula (1)) It can be obtained by reacting a decomposition product and / or a hydrolysis condensation product with a betainizing agent (a compound of the above formula (2) and / or a formula (2 ′) below). It is.

  That is, the hydrolyzate and / or hydrolysis condensate of the betaine-based silicon compound represented by the formula (3) is obtained by hydrolysis and / or hydrolysis condensation of the dialkylaminosilicon compound represented by the formula (1) After that, it can be obtained by adding the above-mentioned betainizing agent to the reaction solution and reacting (betaining).

  Alternatively, the dialkylaminosilicon compound represented by the above-mentioned formula (1) can be obtained by being hydrolyzed and / or hydrolyzed and condensed simultaneously in the presence of a betainizing agent in the presence of water and betinized simultaneously.

The reaction temperature for betaination is from room temperature to 150 ° C., preferably the reflux temperature of the solvent used.
The reaction time for betaination is 0.5 hours to 48 hours, preferably 2 hours to 24 hours, particularly preferably 4 hours to 24 hours.
The above reaction may be carried out under normal pressure or under pressure.

  The betainizing agent can be added as it is, but may be added after being dissolved in a solvent (such as water) in which the betaining agent is dissolved.

  The following can be mentioned as a preferable compound of the betainizing agent (the said Formula (2) or (2 ')) used for reaction.

In the above formula (2), Z CO ₂ ^- and SO ₃ ^- is.
In the above formula (2), X ³ is a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom and a bromine atom from the viewpoint of availability.
In the formula (2), R ⁶ is an alkylene group having 1 to 7 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.
In the above formula (2), Y ³ is Li ⁺ , Na ⁺ and K ⁺ , preferably Na ⁺ from the viewpoint of availability.

The following are mentioned as a specific compound represented by said Formula (2).
ClCH ₂ COONa
ClCH ₂ CH2 COONa
ClCH ₂ CH2CH2COONa
ClCH ₂ COOK
BrCH ₂ COONa
BrCH ₂ SO ₃ Na
BrCH ₂ CH ₂ SO ₃ Na
BrCH ₂ CH ₂ CH ₂ SO ₃ Na
BrCH ₂ CH ₂ CH ₂ SO ₃ K
ClCH ₂ CH ₂ CH ₂ SO ₃ Na

In the formula (2 '), R ⁷ is an alkylene group having from 7 to 2 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms.
In the formula (2 '), ^{Z 1} is -CO-O- or _-SO 2 -O-.
The compounds represented by the above formula (2 ') are lactones or sultones, and preferred specific compounds are lactones such as β-propiolactone, γ-butyrolactone, δ-valerolactone, etc. 1,3-propane sultone, 1,4-butane sultone, 1,6-hexane sultone and the like.

  The hydrolyzate and / or hydrolytic condensate formed by the above-mentioned betaination is a hydrolyzate and / or hydrolytic condensate of the compound represented by the above formula (3), and is represented by the above formula (3) The following compounds may be mentioned as specific compounds.

(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ SO ₃ ⁻
(3-1)
_{(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 - (3-2)
_{(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 - (3-3)
_{(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 - (3-4)
_{(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 - (3-5)
_{(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 - (3-6)
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOCH ₂ CH ₂ N ⁺ (CH ₂ CH ₂ CH ₂ SO ₃ ⁻ ) (CH ₃ ) CH ₂ CH ₂ OCH ₂ CH ₂ N (CH ₃ ) ₂ CH ^{_{2 CH 2 CH 2 SO 3 -}} (3-7)
_{(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 - (3-8)
_{(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 - (3-9)
_{(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 - (3-10)
_{(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 - (3-11)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-12)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH (CH 3) COOCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-13)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH 2 CONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-14)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH (CH 3) CONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-15)
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3) CONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-16)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 3) (CH 2 CH 2 CH 2 SO 3 -) CH 2 CH 2 OCH 2 CH 2 N + (CH 3) 2 _{CH 2 CH 2 CH 2 SO 3} - (3-17)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ SO ₃ ⁻
(3-18)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SO 2 CH 2 CH 2 COOCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-19)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SO 2 CH 2 CH (CH 3) COOCH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-20)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-21)
(CH ₃ O) ₂ Si (CH ₃ ) CH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CO ₂ ⁻
(3-22)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-23)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-24)
_{(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 CO 2 - (3-25)
_{(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 CO 2 - (3-26)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 2 CO 2 -) (CH 3) CH 2 CH 2 OCH 2 CH 2 N (CH 3) 2 CH 2 CO 2 - (3-27)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-28)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-29)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-30)
_{(C 2 H 5 O) 2} Si (CH 3) CH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 -
(3-31)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-32)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH (CH 3) COOCH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-33)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH 2 CONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-34)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SCH 2 CH (CH 3) CONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-35)
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3) CONHCH 2 CH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-36)
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOOCH 2 CH 2 N + (CH 3) (CH 2 CO 2 -) CH 2 CH 2 OCH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 ^- (3-37)
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ CO ₂ ⁻
(3-38)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SO 2 CH 2 CH 2 COOCH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-39)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 SO 2 CH 2 CH (CH 3) COOCH 2 CH 2 N + (CH 3) 2 CH 2 CO 2 - (3-40)
_{(CH 3 O) 3 SiCH 2} CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 CO 2 -
(3-41)

  The antifogging coating composition liquid obtained by the production method of the present invention is prepared by adding usually 0 hydrolyzate and / or hydrolytic condensate of the betainized dialkylaminosilicon compound (compound of the above formula (3)) in the composition liquid. The content is preferably from 0.1 to 30% by weight, more preferably from 0.05 to 20% by weight, particularly preferably from 0.1% to 15% by weight.

  In the method for producing the antifogging coating composition liquid of the present invention, as the second method, the compound of the formula (1) or the like, the surface active silane coupling agent or the like, the silane coupling agent or the like, or the like can be hydrolyzed Addition of at least one or more selected from the group consisting of metal compounds and the like (generally referred to as "additive compounds etc.") and the above-mentioned betainizing agent to cause reaction and hydrolysis and / or hydrolysis and condensation. Thus, it is possible to obtain an antifogging coating composition containing a hydrolyzate and / or a hydrolysis condensate of the betaine-based silicon compound represented by the formula (3) in a solvent.

  The surface active silane coupling agent is a compound represented by the formula (4) and a silane coupling agent having a functional group capable of reacting with the active hydrogen of the compound represented by the formula (4). It can obtain with the manufacturing method of statement.

The formula (4) of the compound represented by the formula (4), the alkyl group having 1 to 20 carbon atoms R ^5, a methyl group, an ethyl group, an octyl group, a decyl group, dodecyl group, tetradecyl group, Pentadecyl group, hexadecyl group, palmitol group, heptadecyl group, octadecyl group, oleyl group, C ₄ F ₉ CH ₂ CH ₂ group, C ₆ F ₁₃ CH ₂ CH ₂ group, C ₄ F ₉ CH ₂ group, C ₆ F ₁₃ CH ₂ group, polydimethylsiloxane group and the like can be mentioned. Among them, in consideration of availability of raw materials, preferably, methyl group, dodecyl group, heptadecyl group, C ₄ F ₉ CH ₂ CH ₂ group, C ₆ F ₁₃ CH ₂ CH ₂ group, C ₄ F ₉ CH ₂ group C ₆ F ₁₃ CH ₂ group, perfluoroalkyl group-containing poly (meth) acrylic group and polydimethylsiloxane group. p is a natural number of 1 to 30, and preferably 1 to 15 from the viewpoint of obtaining raw materials.

The compound represented by the above formula (4) is a surfactant, and a commercially available surfactant can be used.
The commercially available surfactant comprising the compound represented by the above formula (4) is usually not a fixed number of additions of ethylene oxide, and as a result is not a single thing, but the number of additions of ethylene oxide It exists as a different mixture.

The following compounds may be mentioned as specific compounds represented by the formula (4).
HO (CH ₂ CH ₂ O) ₂ H
HO (CH ₂ CH ₂ O) ₃ H
HO (CH ₂ CH ₂ O) ₄ H
HO (CH ₂ CH ₂ O) ₅ H
HO (CH ₂ CH ₂ O) ₆ H
CH ₃ O (CH ₂ CH ₂ O) ₂ H
CH ₃ O (CH ₂ CH ₂ O) ₃ H
CH ₃ O (CH ₂ CH ₂ O) ₄ H
CH ₃ O (CH ₂ CH ₂ O) ₅ H
CH ₃ O (CH ₂ CH ₂ O) ₆ H
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₃ CH ₂ COOH
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₄ CH ₂ COOH
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₅ CH ₂ COOH
C ₁₃ H ₂₇ O (CH ₂ CH ₂ O) ₃ CH ₂ COOH
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₇ H
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₈ H
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₉ H
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H
C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₁ H
C ₁₇ H ₃₅ COO (CH ₂ CH ₂ O) ₉ H
C ₁₇ H ₃₃ COO (CH ₂ CH ₂ O) ₅ H
C ₁₇ H ₃₃ COO (CH ₂ CH ₂ O) ₉ H
C ₁₇ H ₃₃ COO (CH ₂ CH ₂ O) ₁₄ H
C ₁₇ H ₃₅ CONHCH ₂ CH ₂ OH
C ₄ F ₉ CH ₂ O (CH ₂ CH ₂ O) _q H
C ₄ F ₉ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _q H
C ₆ F ₁₃ CH ₂ O (CH ₂ CH ₂ O) _q H
C ₆ F ₁₃ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _q H
However, q represents the integer of 1-30.
-{CH ₂ C (CH ₃ ) (COOCH ₂ CH ₂ C ₆ F ₁₃ )} _r- {CH ₂ C (CH ₃ ) (COOCH ₂ CH ₂ O (CH ₂ CH ₂ O) _t H)} _s-
-{CH ₂ CH (COOCH ₂ CH ₂ C ₆ F ₁₃ )} _r- {CH ₂ CH (COOCH ₂ CH ₂ O (CH ₂ CH ₂ O) _s H)} _t-
However, r, s and t represent the integer of 1-30.
_{(CH 3)} 3 SiO - _{[(CH 3) Si {(CH} 2) u (CH 2 CH 2 O) v H} ] _w -O- [Si _{(CH 3) 2} O] _z -Si _(CH 3) ₃
However, u, v, w and z represent the integer of 1-30.

  The silane coupling agent having a functional group capable of reacting with active hydrogen in the compound represented by the formula (4) is a silane having a functional group of any of an epoxy group, an isocyanate group, an acid anhydride group or an amino group. It is a coupling agent.

  And as a silane coupling agent which can be reacted with active hydrogen in preferable said Formula (4), 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane, 3-glycidoxy propyl methyl Dimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3- Aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane and the like can be mentioned.

  Specific compounds of the compound derived from the compound represented by the formula (4) and the silane coupling agent having a functional group capable of reacting with active hydrogen in the formula (4) include the following compounds: .

_{CH 3 -O- (CH 2 CH 2} O) 2 CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{CH 3 -O- (CH 2 CH 2} O) 2 CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2
_{CH 3 -O- (CH 2 CH 2} O) 3 CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{CH 3 -O- (CH 2 CH 2} O) 3 CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2
_{C 12 H 25 -O- (CH 2} CH 2 O) 6 CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 6 CH 2 COOCH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 7 CH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 7 CH 2 COOCH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 8 CH 2 COOCH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 9 CH 2 COOCH 2 CH (OH) CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3
_{HO- (CH 2 CH 2 O)} 2 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{HO- (CH 2 CH 2 O)} 3 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{HO- (CH 2 CH 2 O)} 4 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{HO- (CH 2 CH 2 O)} 5 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOO (CH 2 CH 2 O) 2 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOO (CH 2 CH 2 O) 3 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOO (CH ₂ CH ₂ O) ₄ CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
(C 2 H 5 O) 3} SiCH 2 CH 2 CH 2 NHCOO (CH 2 CH 2 O) 5 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{CH 3 -O- (CH 2 CH 2} O) 2 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{CH 3 -O- (CH 2 CH 2} O) 3 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{CH 3 -O- (CH 2 CH 2} O) 4 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 10 H 21 -O- (CH 2} CH 2 O) 6 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₇ CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ OCONHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) _{3
C 10 H 21 -O- (CH 2} CH 2 O) 9 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 6 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 7 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 8 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 9 CH 2 CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 8 CH 2 CONHCH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 9 CH 2 CONHCH 2 CH 2 CH 2 Si (OCH 3) 3
_{CH 3 -O- (CH 2 CH 2} O) 3 COCH 2 CH (COOH) CH 2 CH 2 CH 2 Si (OCH 3) 3
_{CH 3 -O- (CH 2 CH 2} O) 3 COCH (CH 2 COOH) CH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 7 COCH 2 CH (COOH) CH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 12 H 25 -O- (CH 2} CH 2 O) 8 COCH (CH 2 COOH) CH 2 CH 2 CH 2 Si (OCH 3) 3
C ₁₇ H ₃₅ -COO- (CH ₂ CH ₂ O) ₉ COCH ₂ CH (COOH) CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3
C 17 H 33 -COO- (CH 2} CH 2 O) 5 COCH (CH 2 COOH) CH 2 CH 2 CH 2 Si (OCH 3) 3
_{C 17 H 35 -CONH-CH 2} CH 2 OCONHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
C ₄ F ₉ CH ₂ O (CH ₂ CH ₂ O) _q CONHNHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₄ F ₉ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _q CONHNHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₆ F ₁₃ CH ₂ O (CH ₂ CH ₂ O) _q CONHNHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
C ₆ F ₁₃ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _q CONHNHCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
However, in the above formula, q represents an integer of 1 to 30.
-{CH ₂ C (CH ₃ ) (COOCH ₂ CH ₂ C ₆ F ₁₃ )} _r- {CH ₂ C (CH ₃ ) (COOCH ₂ CH ₂ O (CH ₂ CH ₂ O) _t CONHNHCH ₂ CH ₂ CH ₂ Si (OC ₂₎ H ₅ ) ₃ )} _s −
_{- {CH 2 CH (COOCH 2} CH 2 C 6 F 13)} r - {CH 2 CH (COOCH 2 CH 2 O (CH2CH2O) s CONHNHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3)} t -
However, in said formula, r, s, and t represent the integer of 1-30.
_{(CH 3)} 3 SiO - _{[(CH 3) Si {(CH} 2) u (CH 2 CH 2 O) v CONHNHCH 2 CH 2 CH 2 Si (OC 2 H 5) 3} ] _w -O- [Si ( CH ₃ ) ₂ O] _z -Si (CH ₃ ) ₃
However, in said formula, u, v, w and z represent the integer of 1-30.

Next, the compound represented by the said Formula (5) which is a silane coupling agent is what is called an alkoxy silicon type compound.
In said Formula (5), a C1-C5 alkoxy group, a hydroxyl group, and a halogen atom are mentioned as X. Among these, preferred are a methoxy group, an ethoxy group and an isopropyloxy group, and particularly preferred are a methoxy group and an ethoxy group.

In the formula (5), R ⁶ is an alkylene group having 1 to 5 carbon atoms, preferably a trimethylene group.

In the above formula (5), X ² is an alkyl group (the alkyl group may contain a hetero atom, an unsaturated bond, or may be a cyclic structure), a vinyl group, a thiol group, an amino group, chlorine It is a functional group selected from the group consisting of an atom, an acryl group, a methacryl group, a styryl group, a tolyl group, a phenyl group, a glycidoxy group, a 3,4-epoxycyclohexyl group and a blocked isocyanate group. Among these, preferred are a vinyl group, an amino group, a chlorine atom, an acryl group, a methacryl group, a styryl group, a tolyl group, a phenyl group and a blocked isocyanate group.

  As an example of the silicon type compound represented by said Formula (5), the silicon compound of Unexamined-Japanese-Patent No. 2015-218139, and the following are mentioned.

CH ₃ Si (OCH ₃ ) ₃
CH ₃ Si (OC ₂ H ₅ ) ₃
C ₈ H ₁₇ Si (OCH ₃ ) ₃
C ₈ H ₁₇ Si (OC ₂ H ₅ ) ₃
C ₁₈ H ₃₇ Si (OCH ₃ ) ₃
C ₁₈ H ₃₇ Si (O ₂ H ₅ ) ₃
CH ₂ = CHSi (OCH ₃ ) ₃
CH ₂ = CHSi (OC ₂ H ₅ ) ₃
H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
H ₂ NCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃
ClCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
SHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
SHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CH ₂ = CHCOOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CH ₂ CC (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
C ₆ H ₅ Si (OCH ₃ ) ₃
C ₆ H ₅ Si (OC ₂ H ₅ ) ₃
(CH ₃ ) ₃ COCOCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CH ₃ ) ₃ COCOCH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ (CH ₃ ) Si (OCH ₃ ) _{2
p-CH 3 C 6 H 4} CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
o-CH ₃ C ₆ H ₄ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) _{3
p-ClCH 2 C 6 H 4} CH 2 CH 2 SCH 2 CH 2 CH 2 Si (OCH 3) 3
o-ClCH ₂ C ₆ H ₄ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
C ₆ H ₄ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

  Among the compounds represented by the formula (5), a blocked isocyanate compound can be obtained, for example, by the production method described in JP-A-2017-071725.

  Subsequently, hydrolyzable carbon-silicon bond-free silicon compounds, hydrolyzable titanium compounds, hydrolyzable zirconium compounds, hydrolyzable aluminum which can be included in the antifogging coating composition liquid of the present invention The compounds (the above are collectively referred to as "hydrolyzable metal compounds") will be described.

  Examples of silicon compounds having no hydrolyzable carbon-silicon bond include tetraethoxysilane and oligomers thereof, such as Corcoat series (Methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS 485, manufactured by Corcoat Co., Ltd. , SS 101, HAS-5, HAS-1, HAS-10, Colcoat P, Colcoat 103-X, etc.) and the like.

  Examples of hydrolyzable titanium compounds, hydrolyzable zirconium compounds and hydrolyzable aluminum compounds include the following products manufactured by Matsumoto Fine Chemical Co., Ltd.

As hydrolysable titanium compounds, organics TA-8 {titanium tetraisopropoxide: Ti (Oi-C ₃ H ₇ ) ₄ }, organics TA-21 {titanium tetra-normal butoxide: Ti (O— n-C ₄ H ₉ ) ₄ }, organics TA-23 {titanium butoxide dimer: (n-C ₄ H ₉ O) ₃ Ti-O-Ti (O-n-C ₄ H ₉ ) ₃ }, organtics TA-30 {titanium tetra-2-ethylhexoxide: Ti (OC ₈ H ₁₇ ) ₄ }, organtics WX-700, organtics TC-100 {titanium diisopropoxy (acetyl acenate): Ti (O- _{i-C 3 H 7) 2} (C 5 H 7 O 2) 2}, Orgatix TC-120 {titanium diisopropoxy (acetyl A cetearyl sulfonate) _{Ti (O-i-C 3} H 7) 2 (C 5 H 7 O 2) 2}, Orgatix TC-230,245 {titanium octylene glycolate} Orgatix TC-315 {titanium lactate: Ti (OH ) ₂ [OCH (CH ₃ ) COOH] ₂ }, organtics TC-335 {titanium lactate ammonium salt: Ti (OH) ₂ [OCH (CH ₃ ) COO ⁻ ] ₂ (NH ₄ ⁺ ) ₂ }, organtics TC _{-401 {Ti (C 5 H 7} O 2) 4}, Orgatix TC-500 {titanium diethanol aminate} Orgatix TC-510 {titanium aminoethylamino ethanolate _{rate: Ti (O-i-C} 3 H 7) (OC ₂ H ₄ NHC ₂ H ₄ NH ₂ ) ₃ }, organics TC-710 {titanium diisopropoxy bis ( _{Ethylacetoacetate): Ti (O-i-} C 3 H 7) 2 (C 6 H 9 O 3) 2}, Orgatix TC-800 {Titanium _{isostearate: Ti (O-i-C} 3 H 7) _{(OCO-i-C 18 H} 37) 3}, Orgatix TC-1040 {titanium phosphate compound}, Orgatix TC-201 {titanium 2-ethylhexoxide bis (2-ethyl-3-hydroxy-hexoxide : Ti (O-n-C ₈ H ₁₇ ) ₂ (C ₈ H ₁₇ O ₂ ) ₂ }, Orgatics TC-750 {titanium diisopropoxy bis (diacetyl acetate): Ti (O-i-C ₃ H _{7) ) 2 (C 6 H 9 O} 3) 2}, Orgatix TC-300 {titanium lactate ammonium salt: Ti _{(OH) 2 [OCH} (CH 3) COO ^-] ₂ NH4 ⁺⁾ _2}, Orgatics TC-310 {titanium lactate: Ti _{(OH) 2 [OCH} (CH 3) COOH] _2}, ORGATICS TC-400 {titanium diisopropoxy bis (triethanolaminate): Ti _{(O-i-C 3 H} 7) 2 (C 6 H 14 O 3 N) 2} and their oligomers (Orgatix PC-200, ORGATIX PC-250, ORGATIX PC-601, ORGATIX PC-620 Etc.).

As hydrolyzable zirconium compounds, organics ZC-150 {zirconium tetraacetylacetonate: Zr (C ₅ H ₇ O ₂ ) ₄ }, organics ZA-35 {zirconium tetranormpropoxide: Zr (O-n) —C ₃ H ₇ ) ₄ }, organtics ZA-65 {zirconium tetranormal butoxide: Zr (O—n—C ₃ H ₇ ) ₄ }, organtics ZC-162 {zirconium tetraacetylacetonate: Zr (C ₅₎ H ₇ O ₂ ) ₄ }, organics ZC-540 {zirconium tributoxy monoacetylacetonate: Ti (On-C ₄ H ₉ ) ₃ (C ₅ H ₇ O ₂ )}, organics ZC-700 { zirconium tetra _{acetylacetonate: Zr (C 5 H 7 O} 2) 4 , Orgatics ZC-580 {zirconium dibutoxy bis (ethyl acetoacetate Teo _{preparative): Ti (O-n-} C 4 H 9) 2 (C 6 H 9 O 3) 2}, Orgatics ZC-200 {zirconium octylate Organoges ZC-320 (zirconium stearate: Ti (O-n-C ₄ H ₉ ) ₃ (OCO-n-C ₁₇ H ₃₅ )), orgatics ZC- 126 {zirconium chloride}, Orgatics ZC- 300 {zirconium lactate ammonium salt: Zr (OH) _[OCH (CH 3) COO ^-] ₃ ^(NH4 _{+) 3}} and the like.

As a hydrolysable aluminum compound, organics AL3001 {aluminum trisecondary butoxide: Al (O-sec-C ₄ H ₉ ) ₃ }, organics AL ₃ 100 {aluminum tris (acetylacetonate): Al (C ₅ H ₇₎ O ₂ ) ₃ }, organics AL 3200 {aluminum bisethylacetoacetate monoacetylacetonate: Al (C ₅ H ₇ O ₂ ) (C ₆ H ₉ O ₃ ) ₂ }, organics AL 3215 {aluminum tris (ethyl acetoacetate) ): Al (C ₆ H ₉ O ₃ ) ₃ } and the like.

  The surface active silane coupling agent, the compound represented by the formula (5), and the hydrolyzate and / or hydrolytic condensate of the hydrolyzable metal compound can be prepared from the compound of the above (1) to the compound of the above (1) It can be obtained by the same method as obtaining a hydrolyzate and / or a hydrolysis condensate of a compound.

  In addition, the method of adding the compound of the formula (1) or the like, the additive compound or the like, and the betaining agent in the presence of water to cause a reaction and hydrolysis and / or hydrolysis and condensation is the method of the formula (1) It can carry out by the method similar to the method of making a compound etc. and the said betaine agent add, and making it react.

  Next, in the method for producing the anti-fogging coating composition liquid of the third invention, the compound of the formula (1) or the like and the additive compound or the like are hydrolyzed and / or hydrolyzed and condensed in the presence of water. By adding the above-mentioned betainizing agent, reaction and hydrolysis and / or hydrolysis condensation and containing the hydrolyzate and / or hydrolysis condensation product of the betaine silicon compound represented by the above formula (3) in the solvent A cloudy coating composition can be obtained.

  The compound of formula (1) or the like and the additive compound or the like are hydrolyzed and / or hydrolyzed and condensed in the presence of the third water, and then the betainizing agent is added to cause reaction and hydrolysis // Alternatively, the method of hydrolytic condensation can be carried out by the same method as the method of adding the compound of the formula (1) etc. and the above-mentioned betaining agent and reacting them.

  In the fourth method for producing an antifogging coating composition liquid of the present invention, the compound of the formula (1) or the like and the betainizing agent are reacted and hydrolyzed and / or hydrolyzed and / or condensed in the presence of water An antifogging agent containing a hydrolyzate and / or a hydrolytic condensate of the betaine silicon compound represented by the formula (3) in a solvent by adding the above-mentioned additive compound and the like to cause hydrolysis and / or hydrolytic condensation Coating composition can be obtained.

  The conditions such as the solvent used for the reaction to which the betaine agent of the former stage was added in the fourth method, hydrolysis and / or hydrolysis condensation, and the reaction of the latter stage hydrolysis and / or hydrolysis condensation, reaction temperature and reaction time, etc. It is the same as obtaining the hydrolyzate and / or hydrolysis condensate of the dialkylamino silicon compound (the compound of the formula (1)) and the betaine compound.

  A hydrolyzate and / or a hydrolysis condensate of a betaine silicon compound represented by the above formula (3) obtained by the production method of the present invention and / or a hydrolysis condensate and / or a hydrolysis condensate such as additive compounds In the cloudy coating composition liquid, a mixture as it is hydrolyzed, or one obtained by condensation of these in a random or block shape, or both of them exist.

With respect to the compound represented by said Formula (3), the addition amount of an additive compound etc. is 0 to 500 weight% with respect to the compound represented by said Formula (3), respectively, Preferably 0 to 300 weight %, Particularly preferably 10 to 200% by weight.
The characteristics (for example, hydrophilicity, antifogging property, etc.) of the film | membrane produced | generated by the anti-fogging coating composition liquid as it is the said range can exhibit more.

  The concentration of the total solids {the compound represented by the formula (3) and the additive compound, etc.} relative to the combined solvent is usually 0.01 to 30 wt%, preferably 0.05 to 20 wt%, particularly preferably 0. 1% to 15% by weight.

  The antifogging coating composition liquid obtained by the production method of the present invention can be obtained an antifogging coating composition by diluting with a dilution solvent in order to improve workability (handling property and coating property etc.) .

  The dilution solvent does not react with the above-mentioned formula (3) obtained by the production method of the present invention, and is not limited as long as it dissolves and / or disperses these. 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, dimethylsulfoxide and the like), water and the like.

  When the dilution solvent is contained, the content of the dilution solvent is, for example, 0.001% by weight of the compound represented by the formula (3) or the compound represented by the formula (3) and the additive compound with respect to the whole solvent. The amount is 15 wt%, preferably 0.01 to 10 wt%, particularly preferably 0.05 to 7.5 wt%.

  The antifogging coating composition obtained by the production method of the present invention may be 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, polybutadiene, polyisoprene, SBR, nitrile rubber, EPM, EPDM, epichlorohydrin rubber, neoprene rubber, porsulfide and butyl rubber, etc., metal (iron, aluminum, Stainless steel, titanium, copper, brass and their alloys), cellulose, cellulose derivatives, cellulose analogues (chitin, chitosan and Substrate such Rufiran etc.) or natural fibers (silk and cotton, etc.), sheets, can be applied to the film and surface hydrophilizing such fibers.

  Further, if necessary, in order to improve the adhesion to a substrate or the like, a surface activation treatment such as a primer or corona discharge treatment (a method of increasing the surface energy of the substrate surface) may be used.

  As a method of applying a coating liquid comprising the antifogging coating composition obtained by the production method of the present invention, dip coating, spin coating, flow coating, spray coating and the like can be mentioned.

  When the coating solution is cured 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., and the heat treatment time is usually 0.05 to 48 hours, preferably 0.1 to 48 hours, particularly preferably 0.5 to 36 hours.

The present invention will be specifically described below by way of Examples. The examples illustrate the invention and do not limit it. Unless otherwise specified, parts mean parts by weight.
Preparation of Surface Active Silane Coupling Agent [Synthesis Example 1]
Sanyo Kasei Kogyo Co., Ltd. Surfactant (Burelite LCA-H, polyoxyethylene lauryl ether acetic acid, acid value: 107) 7.57 g and 3.4 g of 3-glycidoxypropyltrimethoxysilane under an argon atmosphere, 100 By reacting for 2 days at .degree. C., 10.3 g of a surface active silane coupling agent (A) in which Boulelite LCA-H and 3-glycidoxypropyltrimethoxysilane were linked via an ester bond was obtained. ^{From the 1} H-NMR measurement, it was confirmed that the absorption of protons (2.62, 2.80, 3.16 ppm) on the epoxy ring of 3-glycidoxypropyltrimethoxysilane as a raw material disappeared.

Synthesis Example 2
Under an argon atmosphere, polyoxyethylene lauryl ether (manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: Emulmin L 90-S, about 9 molecules of ethylene oxide added to lauryl alcohol, having a hydroxyl value of 98.3) to 10.0 g By adding 4.33 g (17.5 mmol) of 3- (triethoxysilyl) propyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.) and reacting at 90 ° C. for 48 hours, the surface active silane coupling agent (B) 14 is obtained. I got .3g.
^{From 1} H-NMR, it was confirmed that the chemical shift of the methylene group at the α-position of the isocyanate group of 3- (triethoxysilyl) propyl isocyanate was shifted from 3.29 ppm to 3.16 ppm.

Synthesis Example 3
20.2 g of surfactant (Emulmin L-90-S, ethylene oxide adduct of dodecyl alcohol, hydroxyl value: 98.3) manufactured by Sanyo Chemical Industries, Ltd. and 8.4 g of 3-glycidoxypropyl trimethoxysilane, An interface in which emalmin L-90-S and glycidoxypropyltrimethoxysilane are bonded via an ether bond by reacting 0.1 g of p-toluenesulfonic acid as a catalyst under argon atmosphere for 2 days at 100 ° C. 28.1 g of active silane coupling agents (C) were obtained. ^{From the 1} H-NMR measurement, it was confirmed that the absorption of protons (2.62, 2.80, 3.16 ppm) on the epoxy ring of 3-glycidoxypropyltrimethoxysilane as a raw material disappeared.

(Synthesis of blocked isocyanate compound)
Synthesis Example 4
4.81 g (50.0 mmol) of 3,5-dimethylpyrazole and 12.35 g (50.0 mmol) of 3-isocyanatopropyltriethoxysilane were dissolved in 100 ml of dehydrated ethyl acetate and stirred at room temperature for 3 days. After completion of the reaction, ethyl acetate was removed to obtain 16.8 g of a blocked isocyanate compound (D) in which the isocyanate group of 3-isocyanatopropyltriethoxysilane was blocked with 3,5-dimethylpyrazole.

(Preparation of dimethylamino-based silane coupling agent)
Synthesis Example 5
Under argon atmosphere, 20.0 g (80.8 mmol) of 3- (triethoxysilyl) propyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 7.2 g (80.8 mmol) of dimethylaminoethanol (manufactured by Nacalai Tesque, Inc.) The reaction is carried out at 90 ° C. for 24 hours to obtain 26.4 g of a dimethylamino-based silane coupling agent (1-3) in which a dimethylaminoethyl group is bonded to a 3- (triethoxysilyl) propyl group via a carbamate bond. The
The absorption of proton (3.30 ppm) of carbon bonded to isocyanate group of 3- (triethoxysilyl) propyl isocyanate as raw material disappears from ¹ H-NMR measurement, and carbon newly bonded to carbamate group of object Absorption of proton (3.17 ppm) of

Synthesis Example 6
Under argon atmosphere, 3- (triethoxysilyl) propyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.) in 3.4 g (40.4 mmol) of 3- (dimethylamino) -1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 8. Add 3 g (40.4 mmol), and react at 90 ° C. for 48 hours to obtain a compound (1-4) in which a dimethylaminopropyl group is linked to a 3- (triethoxysilyl) propyl group via a carbamate bond 10. I got 1 g.
The absorption of proton (3.30 ppm) of carbon bonded to isocyanate group of 3- (triethoxysilyl) propyl isocyanate as raw material disappears from ¹ H-NMR measurement, and carbon newly bonded to carbamate group of object Absorption of proton (3.17 ppm) of

Synthesis Example 7
Under argon atmosphere, 4.4 g (50.0 mmol) of N, N-dimethyl-1,2-ethylene diamine (manufactured by Nacalai Tesque, Inc.) to 3- (triethoxysilyl) propyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.) 12 By adding .35 g (50.0 mmol) and reacting at room temperature for 48 hours, the N, N-dimethyl-1,2-ethylenediamino group is bonded to the 3- (triethoxysilyl) propyl group via a urea bond. 16.1 g of obtained compound (1-8) was obtained.
The absorption of the proton (3.30 ppm) of carbon bonded to the isocyanate group of 3- (triethoxysilyl) propyl isocyanate which is a raw material is disappeared from ¹ H-NMR measurement, and carbon newly bonded to the target urea group Absorption of proton (3.14 ppm) of

Synthesis Example 8
3- (triethoxysilyl) propyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd.) to 5.1 g (50.0 mmol) of N, N-dimethyl-1,3-propanediamine (manufactured by Nacalai Tesque, Inc.) under an argon atmosphere 12.35 g (50.0 mmol) is added and reacted at room temperature for 48 hours, whereby the N, N-dimethyl-1,3-propanediamino group is reacted with the 3- (triethoxysilyl) propyl group via a urea bond. 16.7 g of bound compound (1-9) was obtained.
The absorption of the proton (3.30 ppm) of carbon bonded to the isocyanate group of 3- (triethoxysilyl) propyl isocyanate which is a raw material is disappeared from ¹ H-NMR measurement, and carbon newly bonded to the target urea group Absorption of proton (3.14 ppm) of

Synthesis Example 9
Under argon atmosphere, 10.0 g (100 mmol) of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 19.6 g (100 mmol) of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and azobisisobutyro After dissolving 821 mg (5 mmol) of nitrile (manufactured by Nacalai Tesque) in 150 ml of dehydrated ethanol, the solution was heated under reflux for 24 hours. After completion of the reaction, ethanol was removed to obtain 28.1 g of a compound (E) in which a thiol group was added to the methacryl group of methyl methacrylate.
The structure of Compound ¹ was confirmed from the _{H-NMR [3.70 (s,} 3H, C H 3 OCO -), 3.58 {s, 9H, -Si (OC H 3) 3}, 2.86~2 _{.64 (m, 2H, -SC H} 2 CHCH 3 -), 2.55 (t, 2H, -SiCH 2 CH 2 C H 2 SCH 2 -), 1.79~1,62 (m, 2H, - _{SiCH 2 C H 2 CH 2 SCH} 2 -), 1.25 {d, 3H, -SCH 2 CH (C H 3) -}, 0.79~0.72 (m, 2H, -SiC H 2 CH 2 CH ₂ SCH _2- )].

Example 1
1.04 g (5.0 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.4 g of a surface active silane coupling agent (A) obtained in Synthesis Example 1 It was dissolved in 10 ml of alcohol and 3 ml of water and heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-21) according to the production method of the present invention.

Example 2
1.68 g of the dimethylamino-based silane coupling agent (1-3) obtained in Synthesis Example 5 and 0.4 g of the surface active silane coupling agent (B) obtained in Synthesis Example 2 are dissolved in 10 ml of ethyl alcohol and 3 ml of water. , Heated to reflux overnight. In the resulting solution, 1.06 g (4.75 mmol) of sodium 3-bromopropane sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 ml of water were added, and the mixture was heated and refluxed overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-3) according to the production method of the present invention.

[Example 3]
1.75 g of the dimethylamino-based silane coupling agent (1-4) obtained in Synthesis Example 6 and 0.4 g of the surface active silane coupling agent (C) obtained in Synthesis Example 3 are dissolved in 10 ml of ethyl alcohol and 3 ml of water. , Heated to reflux overnight. In the resulting solution, 1.06 g of sodium 3-bromopropane sulfonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (4.75 mmol) and 5 ml of water were added, and the mixture was heated and refluxed overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-4) according to the production method of the present invention.

Example 4
1.04 g (5.0 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.4 g of a surface active silane coupling agent (C) obtained in Synthesis Example 3 It was dissolved in 10 ml of alcohol and 3 ml of water and heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-21) according to the production method of the present invention.

[Example 5]
1.68 g of the dimethylamino-based silane coupling agent (1-8) obtained in Synthesis Example 7, 0.4 g of the surface-active silane coupling agent (A) obtained in Synthesis Example 1 and a titanium compound (TC-400, Matsumoto Fine Chemical Co., Ltd. 1.0 g of ethyl alcohol was dissolved in 10 ml of ethyl alcohol and 2 ml of water, and the mixture was heated to reflux overnight. Sodium chloroacetate (made by Nacalai Tesque, Inc.) 1.06g (4.75 mmol) and 5 ml of water were added to the obtained solution, and it heated and refluxed overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-28) according to the production method of the present invention.

[Example 6]
1.75 g of the dimethylamino-based silane coupling agent (1-9) obtained in Synthesis Example 8, 0.4 g of the surface-active silane coupling agent (B) obtained in Synthesis Example 2 and a titanium compound (TC-400, Matsumoto Fine Chemical Co., Ltd.) 1.0 g of ethyl alcohol was dissolved in 10 ml of ethyl alcohol and 2 ml of water, and the mixture was heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-29) according to the production method of the present invention.

[Example 7]
1.68 g of the dimethylamino based silane coupling agent (1-3) obtained in Synthesis Example 5, 0.4 g of the surface active silane coupling agent (A) obtained in Synthesis Example 1 and a titanium compound (TC-400, Matsumoto Fine Chemical Co., Ltd. 1.0 g of ethyl alcohol was dissolved in 10 ml of ethyl alcohol and 2 ml of water, and the mixture was heated to reflux overnight. In the resulting solution, 1.06 g (4.75 mmol) of sodium 3-bromopropane sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 ml of water were added, and the mixture was heated and refluxed overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-3) according to the production method of the present invention.

Example 8
1.68 g of the dimethylamino-based silane coupling agent (1-3) obtained in Synthesis Example 5, 0.4 g of the surface active silane coupling agent (B) obtained in Synthesis Example 2 and the blocked isocyanate obtained in Synthesis Example 4 0.4 g of the inert compound (D) was dissolved in 10 ml of ethyl alcohol and 3 ml of water, and the mixture was heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-23) according to the production method of the present invention.

[Example 9]
1.68 g of the dimethylamino based silane coupling agent (1-4) obtained in Synthesis Example 6, 0.4 g of the surface active silane coupling agent (B) obtained in Synthesis Example 2 and 3-methacryloxypropyltrimethoxysilane ( 0.4 g of Shin-Etsu Chemical Co., Ltd.) was dissolved in 10 ml of ethyl alcohol and 3 ml of water, and the mixture was heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-24) according to the production method of the present invention.

[Example 10]
1.68 g of the dimethylamino-based silane coupling agent (1-4) obtained in Synthesis Example 6, 0.4 g of the surface active silane coupling agent (B) obtained in Synthesis Example 2 and the silicon-based compound obtained in Synthesis Example 9 (E) 0.8 g was dissolved in 10 ml of ethyl alcohol and 3 ml of water and heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-24) according to the production method of the present invention.

[Example 11]
1.68 g of the dimethylamino-based silane coupling agent (1-4) obtained in Synthesis Example 6, 0.4 g of the surface active silane coupling agent (B) obtained in Synthesis Example 2 and the silicon-based compound obtained in Synthesis Example 9 (E) 0.4 g and 1.0 g of a titanium compound (TC-400, manufactured by Matsumoto Fine Chemical Co., Ltd.) were dissolved in 10 ml of ethyl alcohol and 2 ml of water and heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-24) according to the production method of the present invention.

[Example 12]
1.04 g (5.0 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 g of the surface active silane coupling agent (A) obtained in Synthesis Example 1 and zirconium 0.64 g of a compound (ZC-580, manufactured by Matsumoto Fine Chemical Co., Ltd.) was dissolved in 10 ml of ethyl alcohol and 2 ml of water, and the mixture was heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-21) according to the production method of the present invention.

[Example 13]
1.68 g of the dimethylamino-based silane coupling agent (1-4) obtained in Synthesis Example 6, 0.4 g of the surface active silane coupling agent (A) obtained in Synthesis Example 1, and the silicon-based compound obtained in Synthesis Example 9 (E) 0.4 g of a titanium compound (TC-400, manufactured by Matsumoto Fine Chemical Co., Ltd.) and 1.04 of a zirconium compound (ZC-580, manufactured by Matsumoto Fine Chemical Co., Ltd.) were dissolved in 10 ml of ethyl alcohol and 2 ml of water , Heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-24) according to the production method of the present invention.

Example 14
1.04 g (5.0 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 10 ml of ethyl alcohol and 2 ml of water, and the mixture was heated to reflux overnight. In the resulting solution, 1.06 g (4.75 mmol) of sodium 3-bromopropane sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 ml of water were added, and the mixture was heated and refluxed overnight. The water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of antifogging properties derived from the betaine compound (3-1) according to the production method of the present invention.

[Example 15]
In 10 ml of ethyl alcohol and 3 ml of water were dissolved 1.68 g of the dimethylamino-based silane coupling agent (1-4) obtained in Synthesis Example 6 and 0.4 g of the blocked isocyanate compound (D) obtained in Synthesis Example 4. Heated to reflux overnight. In the resulting solution, 1.06 g (4.75 mmol) of sodium 3-bromopropane sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 ml of water were added, and the mixture was heated and refluxed overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of antifogging properties derived from the betaine compound (3-4) according to the production method of the present invention.

[Example 16]
1.68 g of the dimethylamino-based silane coupling agent (1-4) obtained in Synthesis Example 6, 0.4 g of the silicon-based compound (E) obtained in Synthesis Example 9 and a titanium compound (TC-400, manufactured by Matsumoto Fine Chemical Co., Ltd. 1.0 g was dissolved in 10 ml of ethyl alcohol and 2 ml of water and heated to reflux overnight. In the resulting solution, 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of antifogging properties derived from the betaine compound (3-24) according to the production method of the present invention.

[Example 17]
1.04 g (5.0 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.64 g of a zirconium compound (ZC-580, manufactured by Matsumoto Fine Chemical Co., Ltd.) in 10 ml of ethyl alcohol And dissolved in 2 ml of water and heated to reflux overnight. In the resulting solution, 1.06 g (4.75 mmol) of sodium 3-bromopropane sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 ml of water were added, and the mixture was heated and refluxed overnight. The water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of antifogging properties derived from the betaine compound (3-1) according to the production method of the present invention.

[Example 18]
2.60 g (12.5 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.45 g (12.5 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) It was dissolved in 5 ml of alcohol and 2 ml of water and heated to reflux overnight. Water was added and diluted to obtain 50.0 g of antifogging properties derived from the betaine compound (3-21) according to the production method of the present invention.

[Example 19]
2.60 g (12.5 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of a surface active silane coupling agent obtained in Synthesis Example 1 and sodium chloroacetate ( 1.45 g (12.5 mmol) of Nacalai Tesque, Inc. was dissolved in 5 ml of ethyl alcohol and 2 ml of water, and the mixture was heated to reflux overnight. Water was added and diluted to obtain 50.0 g of the antifogging agent according to the production method of the present invention derived from the betaine compound (3-21).

Example 20
1.68 g of the dimethylamino silane coupling agent (1-4) obtained in Synthesis Example 6, 0.4 g of the surface active silane coupling agent (A) obtained in Synthesis Example 1, titanium compound (TC-400, Matsumoto Fine Chemical Co., Ltd.) Ltd. 1.0 g of a zirconium compound (ZC-580, manufactured by Matsumoto Fine Chemical Co., Ltd.) and 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) in 10 ml of ethyl alcohol and 8 ml of water And heated to reflux overnight. A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-24) according to the production method of the present invention.

[Example 21]
1.04 g (5.0 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.55 g (4.75 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) It was dissolved in 10 ml of alcohol and 5 ml of water and heated to reflux overnight. In the resulting solution, 0.4 g of the surface active silane coupling agent (A) obtained in Synthesis Example 1 and 0.64 g of a zirconium compound (ZC-580, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added and heated to reflux overnight. . A water / ethyl alcohol mixed solution (1/1, weight ratio) was added and diluted to obtain 50.0 g of an antifogging agent derived from the betaine compound (3-21) according to the production method of the present invention.

[Example 22]
2.60 g (12.5 mmol) of N, N-dimethyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 5 ml of isopropyl alcohol and 2 ml of water, and the mixture was heated to reflux overnight. Into the obtained solution, 1.45 g (11.9 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque, Inc.) was added, and the mixture was further heated to reflux overnight. Water was added and diluted to obtain 50.0 g of the antifogging agent according to the production method of the present invention derived from the betaine compound (3-21).

[Example 23]
5.20 g (12.5 mmol) of N, N-dimethyl-3-aminopropyl trimethoxysilane (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1.0 g of the surfactant silane coupling agent (A) obtained in Synthesis Example 1 It was dissolved in 10 ml of alcohol and 2 ml of water and heated to reflux overnight. Into the obtained solution, 3.05 g (25.0 mmol) of 1,3-propane sultone (manufactured by Nacalai Tesque, Inc.) was added, and the mixture was further heated under reflux for 1 hour. 10 ml of water was added, the mixture was heated under reflux overnight, and diluted with water to obtain 50.0 g of an antifogging agent according to the production method of the present invention derived from a betaine compound (3-21).

Comparative Example 1
(1) 5.2 g (25.0 mmol) of N, N-dimethyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.9 g (23 manufactured by Nacalai Tesque) of 1,3-propane sultone .7 mmol) was dissolved in 50 ml of dehydrated acetonitrile and heated to reflux overnight. Betaine compound by the resulting precipitate is filtered under an argon atmosphere of _{(CH 3 O) 3 SiCH 2} CH 2 CH 2 N + (CH 3) 2 CH 2 CH 2 CH 2 SO 3 - (3-1) 6. I got 5g. The resulting betaine silicon compound was analyzed by infrared absorption spectroscopy.
1344 cm ^-1 which is the feature of the 1,3-propane sultone compound of the raw material is destroyed and absorption of 1641 cm ^-1 which is the feature of the product is newly confirmed.
(2) 1.7 g (5.0 mmol) of the compound obtained in (1) and 0.4 g of the surface active silane coupling agent (B) obtained in Synthesis Example (2), 42.9 g of ethyl alcohol, 5.0 g of water And heated overnight under reflux to obtain 50.0 g of an aqueous solution in which the antifogging agent is dissolved.

Comparative Example 2
(1) Dehydration of 5.04 g (15.0 mmol) of the dimethylamino-based silane coupling agent (1-3) obtained in Synthesis Example 5 and 1.80 g (15.4 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) After dissolving in 50 ml of ethanol, the mixture was heated to reflux for 24 hours. After completion of the reaction, betaine compound (C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ NHCOOCH ₂ CH ₂ N ⁺ (CH ₃ ) by removing sodium chloride and excess sodium chloroacetate formed as precipitate by suction filtration. ^{_{) 2 CH 2 CO 2 - (}} 3-23) was obtained ethanol solution 43.0g dissolved.
After collecting a small amount of the obtained ethanol solution, ethanol was removed and the betaine silicon compound was analyzed by infrared absorption spectroscopy.
Material absorption of the carbonyl group of (sodium chloroacetate) (1600 cm ^-1) disappeared, to confirm the new absorption of the carbonyl group of the desired product (1631cm ^-1).
(2) 14.6 g of the ethanol solution obtained in (1), 0.4 g of the surface active silane coupling agent (A) obtained in Synthesis Example 1 and 1.0 g of organotitanium compound TC-400 manufactured by Matsumoto Fine Chemical Co., Ltd. It was dissolved in 10 ml of ethyl alcohol and added. Further, 20 ml of water was added and the mixture was heated to reflux for 24 hours. Water was added to the obtained solution to adjust to 50.0 g, thereby obtaining 50.0 g of an aqueous solution in which the antifogging agent was dissolved.

[Preparation of antifogging coating solution]
Each of 5.0 g of the solution obtained in each of Examples 1 to 23 and Comparative Examples 1 and 2 was diluted with 45 g of water to obtain 50.0 g of an antifogging coating solution.

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

[Hydrophilicity evaluation result]
Contact angles (degrees) for any five points on the surface of the surface-modified slide glass with a contact angle measurement device (Kyowa Interface Chemical Co., Ltd., DROP MASTER 500, liquid quantity 2 μL, measurement interval 1000 ms, measurement frequency 30 times) It measured and calculated the average value. The results are shown in Table 1.

[Anti-fog evaluation result]
The substrate was placed on the upper surface of a hot water bath at 70 ° C. to evaluate the antifogging performance (presence or absence of clouding due to water vapor) of the surface-modified slide glass. The results are shown in Table 1.

As shown in the comparative example, conventionally, a hydrolyzate and / or a hydrolytic condensate is formed by synthesizing and isolating a betaine-based silicon compound and then hydrolyzing, but the production method of the present invention Since the hydrolyzate and / or hydrolytic condensate are betained, there is no need to control the reaction solvent or the moisture of the reaction atmosphere in the production process, and complex processes such as dehydration and filtration of the solvent used are required. It is a useful production method in efficiently producing a large amount of the antifogging coating liquid, since it is easy to produce in a simple and short production process.
Further, as apparent from Table 1, the betaine-based silicon compound obtained by the production method of the present invention has the same antifogging properties as the betaine-based silicon compound obtained by the conventional production method.

The anti-fogging coating composition liquid derived from the betaine-based silicon compound obtainable by the production method of the present invention is a betaine-based silicon compound obtainable by the production method of the present invention because the antifogging effect is large and can be produced in large quantities inexpensively For example, it 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, a resin sheet and the like to impart hydrophilicity and antifogging properties.

Claims (4)

A method for producing a coating composition liquid, comprising: a compound represented by the following formula (1) or a compound represented by the following formula (1) in the presence of water: a hydrolyzate and / or a hydrolytic condensate obtained by hydrolyzing a compound represented by the following formula (1) (These are generically referred to as “the compound of the formula (1) etc.”) and betaining agents represented by the following formula (2) and / or the following formula (2 ′) (the above are collectively referred to as “betaing agents” Anti-fogging coating containing a hydrolyzate and / or a hydrolytic condensate of a betaine-based silicon compound represented by the following formula (3) by reaction and hydrolysis and / or hydrolytic condensation of Method of producing composition liquid.
^{_{(X) 3-k (CH}} 3) k Si-R 1 - (Y-R 2) m -N (R 3) (R 4) (1)
{Wherein X represents any of the same or different 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 Y represents -NHCOO-, -NHCONH-, -S- or -SO _2- , m represents 0 or 1, and R ² contains an ether bond having 1 to 10 carbon atoms, an ester bond or an amide bond But alkylene group or _{^{-CH 2 CH 2 n + (CH}} 3) (Z) CH 2 CH 2 OCH 2 CH 2 - (Z is ^{_{(CH 2) n CO 2 -}} (n is an integer of from 1 to 5) or ( ^{_{CH 2) n SO 3 - (}} n represents an integer)) of 1 to 5, ^{R 3} and ^{R 4} represent the same or different and alkyl group having 1 to 3 carbon atoms. }
X ³ -R ⁶ -Z-Y ³ (2)
{Wherein ^{X 3} is a chlorine atom, a bromine atom and an iodine atom, ^{R 6} is an alkylene group having 1 to 7 carbon atoms, Z is CO ₂ ^- or SO ₃ ^- represents, ^{Y 3} is ^Li +, Na ^{+ And} K ⁺ . }

In the formula, R ⁷ is an alkylene group having 2 to 7 carbon atoms, and Z ¹ is —CO—O— or —SO ₂ —O—. }
(X) _3-k (CH ₃ ) _k Si-R ^1- (Y-R ² ) _m- N ⁺ (R ³ ) (R ⁴ ) -Z
(3)
Wherein X, k, R ¹ , Y, m, R ² , R ³ and R ⁴ are the same as in formula (1), and Z is — (CH ₂ ) _n CO ₂ ^— (n is 1 to 5 integer) or - (n is an integer of from 1 to ^{_{5) - (CH 2) n SO}} 3. } In the presence of water,
The compound of the formula (1) and the like,
Compound derived from a compound represented by the following formula (4) and a silane coupling agent having a functional group capable of reacting with active hydrogen of a compound represented by the following formula (4) (hereinafter referred to as “surface active silane coupling agent ), Hydrolysates obtained by hydrolyzing surface-active silane coupling agents and hydrolytic condensates (collectively referred to as "surface-active silane coupling agents etc."), and the following formulas which are silane coupling agents: The compound represented by (5), the hydrolyzate and the hydrolysis condensate obtained by hydrolyzing the compound represented by the following formula (5) (these are generically referred to as "silane coupling agent etc.") and the hydrolysis Silicon compounds having no possible carbon-silicon bond, hydrolysates and hydrolysis condensates of silicon compounds having no hydrolysable carbon-silicon bond, and hydrolysable hydrolysates Compounds, hydrolysates and hydrolytic condensates of hydrolysable titanium compounds, hydrolyzable zirconium compounds, hydrolysates and hydrolytic condensates of hydrolysable zirconium compounds, and hydrolysates And at least one selected from the group consisting of a possible aluminum compound and a hydrolyzate obtained by hydrolyzing a hydrolysable aluminum compound and a hydrolytic condensate (the above are collectively referred to as "hydrolyzable metal compounds etc.") When,
Said betaine agent,
The method for producing an antifogging coating composition according to claim 1, wherein the reaction and the hydrolysis and / or the hydrolytic condensation are added.
R ^5- X ^1- (CH ₂ CH ₂ O) _p- Y ¹ (4)
{Wherein R ⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (the alkyl group may contain a fluorine atom, a silicon atom, a benzene ring and a double bond) or a hydrogen atom, X ¹ is — O-, -COO-, or -CONH-, p is an integer of 1 to 30, and Y ¹ represents a hydrogen atom, -CH ₂ COOH. }
(X) _3-k (CH ₃ ) _k Si-(R ⁶ ) _m X ² (5)
{Wherein X represents any one of an alkoxy group having 1 to 5 carbon atoms which may be the same or different, a hydroxyl group, and a halogen atom, k represents 0 or 1, m represents 0 or 1, and X ² Is an alkyl group (the alkyl group may contain a hetero atom, an unsaturated bond, or may be a cyclic structure), a vinyl group, a thiol group, an amino group, a chlorine atom, an acrylic group, a methacrylic group, a styryl group It is a functional group selected from the group consisting of a group, a phenyl group, a tolyl group, a glycidoxy group, a 3,4-epoxycyclohexyl group and a blocked isocyanate group, and R ⁶ represents an alkylene group having 1 to 5 carbon atoms. }   The compound of the formula (1) or the like in the presence of water, the surface active silane coupling agent or the like according to claim 2, the silane coupling agent or the like according to claim 2, and the hydrolysable metal according to claim 2 After hydrolysis and / or hydrolytic condensation with one or more selected from the group consisting of compounds etc., the above-mentioned betainizing agent is added to cause reaction and hydrolytic and / or hydrolytic condensation. The manufacturing method of the anti-fogging coating composition liquid of 1 statement.   The surfactant silane coupling agent according to claim 2 or the like according to claim 2 after reacting the compound of the formula (1) or the like with the betainizing agent in the presence of water and subjecting the reaction to hydrolysis and / or hydrolysis and condensation. The method according to claim 1, characterized in that at least one selected from the group consisting of the silane coupling agents described above and the hydrolysable metal compound etc. according to claim 2 is added to cause hydrolysis and / or hydrolysis condensation. The manufacturing method of the anti-fogging coating composition as described.