JP2013079306A - Two-pack type anti-fogging agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-pack type anti-fogging agent that forms on a surface of a substrate a film being difficult to be released from the substrate and having excellent anti-fogging properties even when the film comes in contact with water and to provide an anti-fog substrate that has a film being difficult to be released from the substrate and having excellent anti-fogging properties even when the film comes in contact with water.SOLUTION: The two-pack type anti-fogging agent includes liquid I containing a (meth)acrylic polymer produced by polymerizing a monomer component containing a silicon atom-containing monomer and a nitrogen atom-containing monomer and liquid II containing a (meth)acrylic polymer having an alkoxysilyl group. The anti-fog substrate has a film composed of the two-pack type anti-fogging agent formed on a surface of a substrate and is characterized in that a film composed of liquid I is formed on the substrate and a film composed of liquid II is formed on the film composed of liquid I.

Description

  The present invention relates to a two-component antifogging agent. More specifically, the present invention relates to a two-component antifogging agent that can impart antifogging properties to a substrate surface by forming a film on the substrate surface. The two-component antifogging agent of the present invention imparts antifogging properties to the surface of a substrate such as a glass plate, metal material, ceramic material, medical material, biocompatible material, optical material, resin film, resin sheet, etc. Useful to do.

  Anti-fogging property is known as a surface property required for a substrate. As a polymer capable of imparting antifogging properties to a substrate, for example, a graft copolymer in which an acrylamide polymer is used in the graft side chain of a copolymer of (meth) acrylate and acrylamide is known (for example, Patent Document 1). However, since this graft copolymer is anionic because a carboxylate is used as a raw material, it has a drawback that the antifogging property of the graft copolymer varies greatly depending on the pH of water in contact therewith.

  Moreover, a hydrophilic layer can be used as a layer having antifogging properties. A hydrophilic layer obtained by applying a mixture of hydrophilic silica and titanium oxide to a film substrate and drying it is proposed as a hydrophilic layer that can be easily fixed to the surface of a hydrophobic resin substrate. Has been. This hydrophilic layer is used on the surface of a plastic molding by transferring it onto the surface of the plastic molding (see, for example, Patent Document 2). However, when the resin base material used for the plastic molding has flexibility, the hydrophilic layer may be cracked or peeled off when subjected to external stress.

  Further, in order to impart antifogging properties and hydrophilicity to the surface of the base material, it has been widely practiced to apply a surfactant to the surface of the base material (see, for example, Patent Document 3 and Patent Document 4). When moisture adheres to the substrate surface, the surfactant may dissolve in the moisture and be detached from the substrate surface.

JP 2002-308950 A JP 2006-231890 A Japanese Patent Laid-Open No. 02-16185 JP 2003-238207 A

  The present invention has been made in view of the above prior art, and even when it comes into contact with water, it is difficult to separate from the substrate, and a coating having excellent antifogging properties can be formed on the surface of the substrate. An object of the present invention is to provide an antifogging agent and an antifogging substrate which has a coating film having excellent antifogging properties which is difficult to be detached from the substrate even when it comes into contact with water.

The present invention
(1) Formula (I):

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. -4 alkoxy groups, wherein at least one of R ³ , R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms, and X represents an oxygen atom or a —NH— group)
And a silicon atom-containing monomer represented by formula (II):

(Wherein R ¹ , R ² and X are the same as above, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, and R ⁸ is an alkylene group having 1 to 4 carbon atoms)
A liquid I containing a (meth) acrylic polymer obtained by polymerizing a monomer component containing a nitrogen atom-containing monomer represented by formula (III):

(Wherein R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrophilic group)
Having at least one terminal of formula (IV):

(Wherein R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R ¹³ , R ¹⁴ and R ¹⁵ are And at least one group of R 4 represents an alkylene group having 1 to 4 carbon atoms, and R ¹⁶ represents an alkylene group having 1 to 12 carbon atoms.)
A two-component antifogging agent comprising a II solution containing a (meth) acrylic polymer having an alkoxysilyl group represented by:
(2) The weight ratio of the silicon atom-containing monomer represented by the formula (I) and the nitrogen atom-containing monomer represented by the formula (II) (silicon atom-containing monomer / nitrogen atom-containing monomer) is 3/97 to 95/5. The two-component antifogging agent according to (1),
(3) The monomer component further contains a monomer copolymerizable with a silicon atom-containing monomer represented by the formula (I) and a nitrogen atom-containing monomer represented by the formula (II). Two-component antifogging agent,
(4) The group in which the silicon atom-containing monomer represented by the formula (I) and the monomer copolymerizable with the nitrogen atom-containing monomer represented by the formula (II) are a styrene monomer, a carboxylic acid ester monomer, and an amide monomer. The two-component antifogging agent according to (3), which is at least one selected from
(5) The amount of the monomer that can be copolymerized with the silicon atom-containing monomer represented by the formula (I) and the nitrogen atom-containing monomer represented by the formula (II) is different from the silicon atom-containing monomer represented by the formula (I) and the formula (I The two-component antifogging agent according to (3) or (4), which is 100 parts by weight or less per 100 parts by weight of the total amount of the nitrogen atom-containing monomer represented by II)
(6) In the formula (III), R ¹² may have a hydrogen atom, a hydroxyl group or a fluorine atom, an alkyl group having 2 to 20 carbon atoms, a hydroxyl group or a fluorine atom which may have a fluorine atom. 20 aryl groups, ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydrogen atom or alkyl having 1 to 4 carbon atoms at one end A polyethylene oxide group having 2 to 20 added moles of an ethylene oxide group optionally having a hydroxyl group or a fluorine atom, a hydroxyl group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end Or a propylene oxide group which may have a fluorine atom, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and a hydroxyl group or a fluorine atom which may have a fluorine atom Polypropylene oxide group addition mole number 2 to 20 of the alkylene oxide group of the formula (V):

(Wherein R ¹⁷ and R ¹⁸ are each independently an alkylene group having 1 to 4 carbon atoms, and R ¹⁹ and R ²⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
Or a group represented by formula (VI):

Wherein R ²¹ is an alkylene group having 1 to 4 carbon atoms, R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ²⁴ is an organic group, and Y ⁻ is an anion. Show)
The two-component antifogging agent according to any one of (1) to (5), which is a group represented by:
(7) The two-component antifogging agent according to any one of (1) to (6), wherein the number of repeating units represented by formula (III) is 1-1000, and (8) (1) to (7) An antifogging base material formed by forming a coating film made of the two-component antifogging agent according to any one of the above on the surface of the base material, and forming a coating film made of I liquid on the base material, The present invention relates to an antifogging substrate characterized in that a film made of a liquid II is formed on a film made of the liquid I.

  According to the present invention, a two-component antifogging agent that does not easily come off from the substrate even when contacted with water and can form a film having excellent antifogging properties on the surface of the substrate, and water An anti-fogging substrate having excellent anti-fogging properties that does not easily come off from the substrate even when contacted is provided.

It is a schematic explanatory drawing of the anti-fogging base material of this invention.

  As described above, the two-component antifogging agent of the present invention has one major feature in that it has the liquid I and the liquid II.

[Liquid I]
The liquid I is used for surface coating of a substrate, and as described above, the formula (I):

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. -4 alkoxy groups, wherein at least one of R ³ , R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms, and X represents an oxygen atom or a —NH— group)
And a silicon atom-containing monomer represented by formula (II):

(Wherein R ¹ , R ² and X are the same as above, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, and R ⁸ is an alkylene group having 1 to 4 carbon atoms)
A (meth) acrylic polymer obtained by polymerizing a monomer component containing a nitrogen atom-containing monomer represented by the formula:

  Since the liquid I is used for the two-component antifogging agent of the present invention, even if moisture adheres to the coating formed by the two-component antifogging agent of the present invention, the coating made of the liquid I does not absorb moisture. Since it has the property to absorb, the outstanding effect that anti-fogging property is maintained is show | played.

  The liquid I is usually applied to the surface of the base material, but at that time, it may be applied directly to the surface of the base material, or within the range where the object of the present invention is not impaired, An underlayer may be formed on the surface.

In the silicon atom-containing monomer represented by the formula (I), R ¹ is a hydrogen atom or a methyl group. R ² is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of R ² include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, and the like, but the present invention is limited to such examples. Is not to be done.

R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and at least one of R ³ , R ⁴ and R ⁵ The group is an alkoxy group having 1 to 4 carbon atoms. The reason why at least one of R ³ , R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms is to firmly fix the two-component antifogging agent of the present invention to the substrate. Thus, R ^3, at least one of the radicals R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms, R ^3, R ⁴ and at least two groups 1 to carbon atoms of R ⁵ 4 is preferred alkoxy group, more preferably any of R ^3, R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms. Among the alkyl groups having 1 to 4 carbon atoms, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. Among the alkoxy groups having 1 to 4 carbon atoms, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable. X is an oxygen atom or a —NH— group.

  Examples of the silicon atom-containing monomer represented by the formula (I) include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and γ- (meth) acryloyloxypropyltriisosilane. Propoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropylmethyldipropoxysilane, and the like can be mentioned. It is not limited only to such illustration. These silicon atom-containing monomers may be used alone or in combination of two or more.

  In the present specification, “(meth) acryl” means “acryl” or “methacryl”.

In the nitrogen atom-containing monomer represented by the formula (II), R ¹ , R ² and X may be the same as described above. More specifically, R ¹ is a hydrogen atom or a methyl group. R ² is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms. Specific examples of R ² include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group and the like. X is an oxygen atom or a —NH— group.

R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. It is not limited to illustration only.

R ⁸ is an alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and a tert-butylene group. It is not limited only to such illustration.

  Examples of the nitrogen atom-containing monomer represented by the formula (II) include N- (meth) acryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloylaminoethyl-N. , N-dimethylammonium-α-N-methylcarboxybetaine and the like, but the present invention is not limited to such examples. These nitrogen atom-containing monomers may be used alone or in combination of two or more. The nitrogen atom-containing monomer represented by the formula (II) may be a hydrate. N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine is, for example, disclosed in JP-A-9-95474, JP-A-9-95586, and JP-A-11-222470. Can be easily prepared with high purity.

  The weight ratio of the silicon atom-containing monomer represented by the formula (I) and the nitrogen atom-containing monomer represented by the formula (II) (silicon atom-containing monomer / nitrogen atom-containing monomer) is from the viewpoint of improving the adhesion to the substrate. , Preferably 3/97 or more, more preferably 5/95 or more, and preferably 95/5 or less, more preferably 85/15 or less, from the viewpoint of improving the antifogging property of the coating film composed of the two-component antifogging agent. More preferably, it is 75/25 or less.

  The monomer composition used in the present invention contains a silicon atom-containing monomer represented by the formula (I) and a nitrogen atom-containing monomer represented by the formula (II). And a monomer copolymerizable with the silicon atom-containing monomer represented by formula (II) and the nitrogen atom-containing monomer represented by formula (II). Representative examples of the copolymerizable monomer include monomers having a carbon-carbon unsaturated double bond.

  Examples of the monomer copolymerizable with the silicon atom-containing monomer represented by the formula (I) and the nitrogen atom-containing monomer represented by the formula (II) include carbon such as styrene monomer, carboxylic acid ester monomer, and amide monomer. -Although the monomer etc. which have a carbon unsaturated double bond are mentioned, this invention is not limited only to this illustration. These monomers capable of copolymerization may be used alone or in combination of two or more.

  When the monomer component contains a styrene monomer, there is an advantage that the heat resistance of the two-component antifogging agent of the present invention can be improved. Examples of the styrenic monomer include styrene, α-methylstyrene, α-hydroxystyrene, p-hydroxystyrene, and the like, but the present invention is not limited to such examples. These styrenic monomers may be used alone or in combination of two or more.

  When the carboxylic acid ester monomer is contained in the monomer component, there is an advantage that the lipophilicity of the two-component antifogging agent of the present invention can be improved. Examples of carboxylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) Tert-butyl acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, (meth) ) Ethyl carbitol acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, (meth) (Meth) acrylic acid alkyl esters such as benzyl acrylate, hydroxy (meth) acrylic acid But also includes methyl itaconate, ethyl itaconate, vinyl acetate, vinyl propionate, and the like. It is not limited. These carboxylic acid ester monomers may be used alone or in combination of two or more.

  When the monomer component contains an amide monomer, there is an advantage that the hydrolysis resistance of the two-component antifogging agent of the present invention can be improved. Examples of amide monomers include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N Acrylamide monomers such as tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, diacetone (meth) acrylamide, (Meth) acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned, but the present invention is not limited to such examples. These amide monomers may be used alone or in combination of two or more.

  The amount of the monomer that can be copolymerized with the silicon atom-containing monomer represented by the formula (I) and the nitrogen atom-containing monomer represented by the formula (II) is the same as that of the silicon atom-containing monomer represented by the formula (I) and the formula (II). From the viewpoint of improving the antifogging property per 100 parts by weight of the total amount of the nitrogen atom-containing monomer represented, it is preferably 100 parts by weight or less, that is, 0 to 100 parts by weight, more preferably 50 parts by weight or less, and further preferably 10 parts by weight. From the viewpoint of sufficiently expressing the properties imparted by using the copolymerizable monomer, it is preferably 0.3% by weight. Part or more, more preferably 1 part by weight or more, still more preferably 3 parts by weight or more.

  By polymerizing a monomer component containing a silicon atom-containing monomer represented by the formula (I), a nitrogen atom-containing monomer represented by the formula (II), and, if necessary, a monomer copolymerizable with these monomers, (meth) An acrylic polymer is obtained.

  When polymerizing the monomer component, it is preferable to use a polymerization initiator. Examples of the polymerization initiator include azobisisobutyronitrile, azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketones Derivatives, phenylthioether derivatives, azide derivatives, diazo derivatives, disulfide derivatives and the like can be mentioned, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator is not particularly limited, but usually it is preferably about 0.01 to 10 parts by weight per 100 parts by weight of the monomer component.

  In the present invention, a chain transfer agent may be used when the monomer component is polymerized. Chain transfer agents can usually be used by mixing with monomer components. Examples of the chain transfer agent include mercaptan group-containing compounds such as lauryl mercaptan, dodecyl mercaptan, and thioglycerol, and inorganic salts such as sodium hypophosphite and sodium hydrogen sulfite. It is not limited. These chain transfer agents may be used alone or in combination of two or more.

  The amount of the chain transfer agent is not particularly limited, but it may be usually about 0.01 to 10 parts by weight per 100 parts by weight of the monomer component.

  Examples of the method for polymerizing the monomer component include a solution polymerization method, but the present invention is not limited to such examples. When the monomer component is polymerized by the solution polymerization method, for example, the monomer component can be polymerized by dissolving the monomer component in a solvent and adding a polymerization initiator while stirring the obtained solution.

  Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene. Examples include compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl acetate and ethyl acetate. However, the present invention is limited only to such examples. is not. These solvents may be used alone or in combination of two or more.

  Usually, the amount of the solvent is preferably adjusted so that the concentration of the monomer component in the solution obtained by dissolving the monomer component in the solvent is about 10 to 80% by weight.

  The polymerization conditions such as the polymerization temperature and polymerization time for polymerizing the monomer component are preferably adjusted as appropriate according to the composition of the monomer component, the type and amount of the polymerization initiator, and the like.

  The atmosphere when the monomer component is polymerized is preferably an inert gas. Examples of the inert gas include nitrogen gas and argon gas, but the present invention is not limited to such examples.

  The completion of the polymerization reaction and the presence or absence of unreacted monomers in the reaction system can be confirmed by, for example, a general analysis method such as gas chromatography.

  By polymerizing the monomer component as described above, a (meth) acrylic polymer can be obtained.

  The viscosity average molecular weight of the (meth) acrylic polymer is preferably 100 or more, more preferably 500 or more from the viewpoint of sufficiently exhibiting antifogging properties, and the solubility of the (meth) acrylic polymer having an alkoxysilyl group. From the viewpoint of increasing the viscosity, it is preferably 100,000 or less, more preferably 50000 or less. The viscosity average molecular weight of the (meth) acrylic polymer can be measured, for example, by gel permeation chromatography.

  The liquid I contains the (meth) acrylic polymer, but other polymers, solvents, various additives, and the like may be included in the liquid I as long as the object of the present invention is not impaired. .

  The solvent may be the same as the solvent used when polymerizing the monomer component. Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol and propylene glycol, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran, and aromatic carbonization such as benzene, toluene and xylene. Examples include hydrogen compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl acetate and ethyl acetate. However, the present invention is limited to such examples. It is not a thing. These solvents may be used alone or in combination of two or more.

  The amount of the solvent is not particularly limited. Usually, the concentration of the (meth) acrylic polymer (resin solid content) in the solution obtained by dissolving the (meth) acrylic polymer in the solvent is about 5 to 80% by weight. It is preferable to adjust so that it becomes.

  Since the liquid I obtained as described above has a property that the film made of the liquid I absorbs moisture even if moisture adheres to the film formed by the two-component antifogging agent of the present invention. It has an excellent property of maintaining antifogging properties. The liquid I is usually applied to the surface of the base material, but at that time, it may be applied directly to the surface of the base material, or within the range where the object of the present invention is not impaired, An underlayer may be formed on the surface.

[Liquid II]
The liquid II is used for top coating of the substrate, and as described above, the formula (III):

(Wherein R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrophilic group)
Having at least one terminal of formula (IV):

(Wherein R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R ¹³ , R ¹⁴ and R ¹⁵ are And at least one group of R 4 represents an alkylene group having 1 to 4 carbon atoms, and R ¹⁶ represents an alkylene group having 1 to 12 carbon atoms.)
(Meth) acrylic-type polymer which has the alkoxy silyl group represented by these is contained.

  Since the two-component antifogging agent of the present invention uses the II liquid, even if moisture adheres to the film formed by the two-component antifogging agent of the present invention, excellent antifogging properties are exhibited. .

  The liquid II is usually applied on the film formed by the liquid I, but other films may be formed on the film formed by the liquid I as long as the object of the present invention is not impaired. .

In the repeating unit represented by the formula (III), R ¹¹ is a hydrogen atom or a methyl group.
R ¹² is a hydrophilic group. As R ¹² , for example, a hydrogen atom, an ethylene oxide group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and optionally having a hydroxyl group or a fluorine atom, a hydrogen atom or carbon number at one end Polyethylene oxide group having 1 to 4 alkyl groups and an ethylene oxide group which may have a hydroxyl group or a fluorine atom and having an addition mole number of 2 to 20, a hydrogen atom or an alkyl having 1 to 4 carbon atoms at one end Propylene oxide group which has a group and may have a hydroxyl group or a fluorine atom, a propylene oxide group which has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and may have a hydroxyl group or a fluorine atom A polypropylene oxide group having an added mole number of 2 to 20, formula (V):

(Wherein R ¹⁷ and R ¹⁸ are each independently an alkylene group having 1 to 4 carbon atoms, and R ¹⁹ and R ²⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
A group represented by formula (VI):

Wherein R ²¹ is an alkylene group having 1 to 4 carbon atoms, R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ²⁴ is an organic group, and Y ⁻ is an anion. Show)
Although the group etc. which are represented by these are mentioned, this invention is not limited only to this illustration. Among these groups, the group represented by the formula (V) is preferable from the viewpoint of increasing the coating film strength.

In the formula (V), R ¹⁷ and R ¹⁸ are each independently an alkylene group having 1 to 4 carbon atoms. R ¹⁷ is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group. R ⁸ is preferably a methylene group or an ethylene group.

In the formula (VI), R ²¹ is an alkylene group having 1 to 4 carbon atoms. R ²¹ is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group. R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ²⁴ is an organic group. Specific examples of the organic group include an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carboxyalkyl group having 2 to 6 carbon atoms. However, the present invention is limited only to such examples. Is not to be done. Y ⁻ is an anion. Y ^- Preferred examples of the alkyl chloride ion having 1 to 4 carbon atoms, a monovalent dialkyl sulfate ion carbon atoms in the alkyl group is 1-4, 6 to 8 carbon atoms aryl chloride ions, carbon atoms in the alkyl group Alkyl sulfate halides having 1 to 4 numbers, halogen ions, acetate ions, borate ions, citrate ions, tartaric acid ions, hydrogen sulfate ions, bisulfite ions, sulfate ions, phosphate ions, etc. may be mentioned. However, the present invention is not limited to such examples. Examples of the halogen atom in the halide include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the halogen atom in the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among Y ⁻ , alkyl chloride ions having 1 to 4 carbon atoms, monovalent dialkyl sulfate ions having 1 to 4 carbon atoms in the alkyl group, and aryl chloride ions having 6 to 8 carbon atoms are preferable.

  Specific examples of the monomer having a group represented by the formula (VI) include methyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate, dimethyl sulfate salt of N, N-dimethylaminoethyl (meth) acrylate, N , N-dimethylaminoethyl (meth) acrylate diethyl sulfate, N, N-dimethylaminoethyl (meth) acrylate benzyl chloride, N, N-dimethylaminopropyl (meth) acrylate methyl chloride, N, N -Dimethylsulfate of dimethylaminopropyl (meth) acrylate, diethylsulfate of N, N-dimethylaminopropyl (meth) acrylate, benzyl chloride salt of N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylamino Ethyl (meth) acrylate methyl Chloride salt, N, N-diethylaminoethyl (meth) acrylate dimethyl sulfate, N, N-diethylaminoethyl (meth) acrylate diethyl sulfate, N, N-diethylaminoethyl (meth) acrylate benzyl chloride salt, N, N N-diethylaminopropyl (meth) acrylate methyl chloride salt, N, N-diethylaminopropyl (meth) acrylate dimethyl sulfate, N, N-diethylaminopropyl (meth) acrylate diethyl sulfate, N, N-diethylaminopropyl ( Examples include benzyl chloride salts of (meth) acrylates, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more. Among these monomers, N, N-dimethylaminoethyl (meth) acrylate methyl chloride salt, N, N-dimethylaminoethyl (meth) acrylate diethyl sulfate salt and the like because they are inexpensive and easily available Is preferred.

Suitable R ¹² includes, for example, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms having at least one hydroxyl group, and a polyethylene having 1 to 20 carbon atoms having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end. Examples thereof include a glycol group, a polypropylene glycol group having 1 to 10 carbon atoms having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, and a group represented by the formula (III). Among these groups, the group represented by the formula (III) is more preferable from the viewpoint of increasing the coating film strength. The lower limit of the number of repeating units represented by the formula (III) is preferably 1 or more, more preferably 10 or more, from the viewpoint of imparting hydrophilicity to the substrate surface, and the repeating unit represented by the formula (III) The upper limit of the number is preferably 1000 or less, more preferably 500 or less, from the viewpoint of imparting hydrophilicity to the substrate surface.

In the alkoxysilyl group represented by the formula (IV), R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ¹³ , R ¹⁴ and R ¹⁵ are each an alkoxy group having 1 to 4 carbon atoms. The reason why at least one of R ¹³ , R ^14, and R ¹⁵ is an alkoxy group having 1 to 4 carbon atoms is to firmly adhere the film made of the II liquid to the film made of the I liquid. Thus, R ^13, R ¹⁴ and it is preferable that at least one of the radicals R ¹⁵ is an alkoxy group having 1 to 4 carbon atoms, R ^13, R ¹⁴ and at least two groups having a carbon number of R ¹⁵ It is more preferable that it is a 1-4 alkoxy group, and it is still more preferable that all of R < ¹³ >, R <^14> and R < ¹⁵ > are a C1-C4 alkoxy group. Among the alkyl groups having 1 to 4 carbon atoms, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. Among the alkoxy groups having 1 to 4 carbon atoms, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

In the alkoxysilyl group represented by the formula (IV), R ¹⁶ is an alkylene group having 1 to 12 carbon atoms. Among R ¹⁶ , an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable.

  The alkoxysilyl group represented by the formula (IV) is present at least at one end of the (meth) acrylic polymer, but the (meth) acrylic polymer is used from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer. It is preferable that it exists only in the one terminal. When the alkoxysilyl group represented by the formula (IV) is present only at one end of the (meth) acrylic polymer, from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer at the other end, For example, it is preferable that a group such as a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a residue of a polymerization initiator is present.

  A (meth) acrylic polymer having a repeating unit represented by the formula (III) and having an alkoxysilyl group represented by the formula (IV) at least at one end is, for example, the formula (VII):

(Wherein R ¹¹ and R ¹² are the same as above)
A (meth) acrylic monomer represented by formula (VIII):

(Wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are the same as above)
It can prepare by polymerizing in presence of the alkoxysilyl group containing compound represented by these.

  Examples of the (meth) acrylic monomer represented by the formula (VII) include N- (meth) acryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloylaminoethyl. -N, N-dimethylammonium-α-N-methylcarboxybetaine, methoxytriethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl methacrylate, and the like can be mentioned, but the present invention is limited only to such examples. Is not to be done. These (meth) acrylic monomers may be used alone or in combination of two or more. N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine is, for example, disclosed in JP-A-9-95474, JP-A-9-95586, and JP-A-11-222470. Can be easily prepared with high purity.

  Examples of the alkoxysilyl group-containing compound represented by the formula (VIII) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriisopropoxysilane, 3-mercaptopropylmethyldimethoxysilane, Although 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldipropoxysilane, etc. are mentioned, this invention is not limited only to this illustration. These alkoxysilyl group-containing compounds may be used alone or in combination of two or more.

  The amount of the alkoxysilyl group-containing compound represented by the formula (VIII) is not particularly limited, but it is usually preferably about 0.01 to 10 parts by weight per 100 parts by weight of the total amount of monomers to be subjected to polymerization.

  Note that the (meth) acrylic monomer represented by the formula (VII) may be used in combination with other polymerizable monomers as long as the object of the present invention is not inhibited.

  Examples of other polymerizable monomers include styrene, α-hydroxystyrene, p-hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. Isobutyl, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, cetyl (meth) acrylate, ethyl carbitol (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methoxyethyl (meth) acrylate , Methoxybutyl (meth) acrylate, N-methyl (meth) acrylamide, N-ethyl (meth) acrylate Luamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone (meth) acrylamide, styrene, methyl itaconate, ethyl itaconate, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, N -Vinylcaprolactam etc. are mentioned, However, this invention is not limited only to this illustration. These other polymerizable monomers may be used alone or in combination of two or more.

  When the (meth) acrylic monomer represented by the formula (VII) is polymerized in the presence of the alkoxysilyl group-containing compound represented by the formula (VIII), it is preferable to use a polymerization initiator.

  Examples of the polymerization initiator include azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketone derivatives, phenylthioether derivatives, azides Derivatives, diazo derivatives, disulfide derivatives and the like can be mentioned, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator is not particularly limited, but is usually about 0.01 to 5 parts by weight per 100 parts by weight of the total amount of the monomer including the (meth) acrylic monomer represented by the formula (VII). It is preferable.

  Examples of the method for polymerizing the (meth) acrylic monomer represented by the formula (VII) include a solution polymerization method, but the present invention is not limited to such examples. When the (meth) acrylic monomer represented by the formula (VII) is polymerized by a solution polymerization method, for example, the (meth) acrylic monomer represented by the formula (VII) is dissolved in a solvent, and the resulting solution is Polymerization can be performed by adding a polymerization initiator while stirring.

  Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene. Examples include compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl acetate and ethyl acetate. However, the present invention is limited only to such examples. is not. These solvents may be used alone or in combination of two or more.

  The amount of the solvent is such that the concentration of the monomer in the solution obtained by dissolving the monomer to be subjected to polymerization containing the (meth) acrylic monomer represented by the formula (VII) in the solvent is about 10 to 80% by weight. It is preferable to adjust so that it becomes.

  The polymerization conditions such as polymerization temperature and polymerization time when polymerizing the (meth) acrylic monomer represented by the formula (VII) depend on the type of monomer and the amount used, the type of polymerization initiator and the amount used. It is preferable to adjust appropriately.

  The atmosphere when the (meth) acrylic monomer represented by the formula (VII) is polymerized is preferably an inert gas. Examples of the inert gas include nitrogen gas and argon gas, but the present invention is not limited to such examples.

  The completion of the polymerization reaction and the presence or absence of unreacted monomers in the reaction system can be confirmed by, for example, a general analysis method such as gas chromatography.

  A (meth) acrylic polymer having an alkoxysilyl group can be obtained by polymerizing the (meth) acrylic monomer represented by the formula (VII) and other monomers used as necessary as described above. The viscosity average molecular weight of the (meth) acrylic polymer having an alkoxysilyl group can be measured by, for example, gel permeation chromatography.

  The viscosity average molecular weight of the (meth) acrylic polymer having an alkoxysilyl group is preferably 100 or more, more preferably 500 or more from the viewpoint of sufficiently exhibiting antifogging properties, and the (meth) acrylic having an alkoxysilyl group. From the viewpoint of increasing the solubility of the polymer, it is preferably 100,000 or less, more preferably 50,000 or less.

  The II liquid contains the (meth) acrylic polymer having the alkoxysilyl group, may be composed only of the (meth) acrylic polymer having the alkoxysilyl group, and contains a solvent. Also good.

  Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene. Examples include compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl acetate and ethyl acetate. However, the present invention is limited only to such examples. is not. These solvents may be used alone or in combination of two or more.

  The amount of the solvent is not particularly limited. Usually, a (meth) acrylic polymer having an alkoxysilyl group in a solution obtained by dissolving a (meth) acrylic polymer having an alkoxysilyl group in the solvent (resin solid content). It is preferable to adjust so that the density | concentration of may become about 5 to 80 weight%.

  Since the liquid II obtained as described above has the property that the film made of the liquid II absorbs moisture even when water adheres to the film formed by the two-component antifogging agent of the present invention, It has an excellent property of maintaining antifogging properties. The liquid II is usually applied on the film formed by the liquid I, but other films may be formed on the film formed by the liquid I as long as the object of the present invention is not impaired. .

[Anti-fogging substrate]
The antifogging base material of the present invention is a film in which a film made of a two-component antifogging agent is formed on the surface of the base material. A film made of I liquid is formed on the base material, and the I liquid A film made of II liquid is formed on the film made of

  The antifogging substrate of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic explanatory view of the antifogging substrate of the present invention. In the antifogging substrate of the present invention, as shown in FIG. 1, a film 2 made of I liquid is formed on the surface of the substrate 1, and a film 3 made of II liquid is formed on the film 2. Is formed.

  The antifogging substrate of the present invention can be produced, for example, by applying the I solution on the surface of the substrate 1, applying the II solution on the formed coating 2, and forming the coating 3. .

  As the base material 1, from the viewpoint of fixing the liquid I to the base material 1, a base material having a hydroxyl group on its surface can be suitably used.

  Examples of the material of the substrate 1 include, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide typified by nylon, polyimide, polyurethane, urea resin, polylactic acid, polyvinyl alcohol, polyvinyl acetate, acrylic resin, polysulfone, and polycarbonate. , ABS resin, AS resin, silicone resin, glass, ceramic, metal and the like, but the present invention is not limited to such examples.

  Since the liquid I is more firmly fixed to the base material 1 having a hydroxyl group on the surface, when using the base material 1 having no hydroxyl group on the surface, It is preferable to modify the surface so that hydroxyl groups are present. In addition, for example, when the surface of the substrate 1 made of glass, metal, or the like has sufficient hydroxyl groups, the surface need not be modified so that the hydroxyl groups are present on the surface. Needless to say, it is good.

  Moreover, the surface of the base material 1 may be imparted with hydrophilicity by performing, for example, oxygen plasma treatment, corona discharge treatment, ozone treatment, or surface treatment that provides fine irregularities. .

  The shape of the substrate 1 is not particularly limited, and examples thereof include a film, a sheet, a plate, a rod, and a molded body formed into a predetermined shape. However, the present invention is not limited only to such illustration. .

  Examples of the method for applying the liquid I to the substrate 1 include a flow coating method, a spray coating method, a dipping method, a brush coating method, and a roll coating method, but the present invention is limited to such examples. It is not a thing.

  The atmosphere at the time of applying the liquid I to the substrate 1 may be air. Moreover, the temperature at the time of application | coating may be normal temperature normally, and may be heating. The coating amount of the liquid I when the liquid I is applied to the base material 1 varies depending on the use of the base material 1 and cannot be determined unconditionally. Therefore, it is preferable to appropriately adjust according to the use etc. Usually, the thickness of the coating after drying is adjusted to be about 10 nm to 10 μm.

  After applying the liquid I to the base material 1, it is preferable to dry the base material 1 by heating or the like from the viewpoint of increasing production efficiency. The temperature at which the substrate 1 is heated varies depending on the heat-resistant temperature of the substrate 1 and the like and cannot be determined unconditionally. However, the temperature suitable for the substrate 1 is usually within a range of 50 to 150 ° C. It is preferable to select.

  In addition, the base material 1 on which the coating film 2 made of the liquid I is formed is applied with a monomer component used when preparing the liquid I on the surface of the base material 1 and irradiated with light or heated. Thus, the monomer component can be polymerized to form the coating film 2.

  As described above, the coating 2 made of the liquid I is formed on the surface of the substrate 1. Next, a film 3 made of the II liquid is formed on the formed film 2.

  The coating 3 made of the II liquid can be formed by applying the II liquid to the coating 2 formed on the substrate 1. Examples of the method for applying the II liquid to the substrate 1 include a flow coating method, a spray coating method, a dipping method, a brush coating method, and a roll coating method, but the present invention is limited to such examples. It is not a thing.

  The atmosphere when the II liquid is applied to the substrate 1 may be air. Moreover, the temperature at the time of application | coating may be normal temperature normally, and may be heating. Since the amount of the II liquid applied when the II liquid is applied to the base material 1 varies depending on the use of the base material 1 and cannot be determined unconditionally, it is preferably adjusted as appropriate according to the use. Usually, the thickness of the coating after drying is adjusted to be about 10 nm to 10 μm.

  After applying the II liquid to the base material 1, it is preferable to dry the base material 1 by heating or the like from the viewpoint of increasing production efficiency. The temperature at which the substrate 1 is heated varies depending on the heat-resistant temperature of the substrate 1 and the like and cannot be determined unconditionally. However, the temperature suitable for the substrate 1 is usually within a range of 50 to 150 ° C. It is preferable to select.

  As described above, the II liquid is applied to the coating film 2 formed on the base material 1, and the coating film 3 made of the II liquid is formed on the surface of the base material 1 through the coating film 2. An antifogging substrate is obtained.

  Since the coating film 1 and the coating film 2 are fixed on the surface of the antifogging substrate of the present invention, the antifogging property can be imparted to the substrate 1, and a conventional surfactant is used. It is possible to prevent the water from being lost when moisture adheres as in the formed film. Furthermore, since the coating film 3 having excellent anti-fogging properties is formed together with the coating film 2 having excellent hygroscopicity on the anti-fogging substrate of the present invention, excellent anti-fogging properties are maintained.

  Accordingly, the antifogging substrate of the present invention is excellent in antifogging properties because it is difficult to be detached from the substrate even when it comes into contact with water.

  Next, the present invention will be described in more detail based on production examples. However, the present invention is not limited to such production examples.

[Preparation of solution I]
Preparation Example 1
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 30.6 g and ethyl alcohol 500.3 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 2.8 g of azobisisobutyronitrile was added into the Kolben, and after aging for 8 hours while maintaining the temperature of the Kolben content at 70 ° C., it was cooled to 30 ° C. in a water bath, A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 39000. This (meth) acrylic polymer solution was used as Liquid I.

Preparation Example 2
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 11.4 g and ethyl alcohol 327.7 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 1.8 g of azobisisobutyronitrile was added into the Kolben, and after aging for 8 hours while maintaining the temperature of the Kolben content at 70 ° C., it was cooled to 30 ° C. in a water bath, A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. When determined, the viscosity average molecular weight was 10,000. This (meth) acrylic polymer solution was used as I liquid B.

Preparation Example 3
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 30.0 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 3.6 g and ethyl alcohol 302.0 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 1.7 g of azobisisobutyronitrile was added into the Kolben, and after aging for 8 hours while maintaining the temperature of the Kolben content at 70 ° C., it was cooled to 30 ° C. in a water bath, A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. When determined, the viscosity average molecular weight was 10,000. This (meth) acrylic polymer solution was used as I liquid C.

Preparation Example 4
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 4.4 g, butyl methacrylate 7.6 g and ethyl alcohol 333.5 g. Added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 1.9 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 24,000. This (meth) acrylic polymer solution was used as I liquid D.

Preparation Example 5
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 4.4 g, styrene 5.6 g and ethyl alcohol 315.2 g were added. did. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 1.8 g of azobisisobutyronitrile was added into the Kolben, and after aging for 8 hours while maintaining the temperature of the Kolben content at 70 ° C., it was cooled to 30 ° C. in a water bath, A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 26000. This (meth) acrylic polymer solution was used as I solution E.

Preparation Example 6
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 4.4 g, tert-butyl methacrylamide 7.6 g and ethyl alcohol 333 0.0 g was added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 1.9 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 22,000. This (meth) acrylic polymer solution was used as I solution F.

Preparation Example 7
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, γ-methacryloyloxypropylmethyldimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-502] 30.6 g and ethyl alcohol 500.3 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 2.8 g of azobisisobutyronitrile was added into the Kolben, and after aging for 8 hours while maintaining the temperature of the Kolben content at 70 ° C., it was cooled to 30 ° C. in a water bath, A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. When determined, the viscosity average molecular weight was 34,000. This (meth) acrylic polymer solution was used as I liquid G.

Preparation Example 8
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 25.0 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 30.6 g and ethyl alcohol 500.3 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 2.8 g of azobisisobutyronitrile was added into the Kolben, and after aging for 8 hours while maintaining the temperature of the Kolben content at 70 ° C., it was cooled to 30 ° C. in a water bath, A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. When determined, the viscosity average molecular weight was 35,000. This (meth) acrylic polymer solution was used as I liquid H.

Preparation Example 9
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 40 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 10 g and ethyl alcohol 500 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 3 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. ) An acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 18,000. This (meth) acrylic polymer solution was used as Liquid I.

Preparation Example 10
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 30 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 5 g, cyclohexyl methacrylate 15 g and ethyl alcohol 500 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 3 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. ) An acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. When determined, the viscosity average molecular weight was 16000. This (meth) acrylic polymer solution was used as I liquid J.

Preparation Example 11
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT] 30 g, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 5 g, isobornyl methacrylate 15 g and ethyl alcohol 500 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 3 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. ) An acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. When determined, the viscosity average molecular weight was 21,000. This (meth) acrylic polymer solution was used as I liquid K.

Comparative Preparation Example 1
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine monohydrate [Osaka Organic Chemical Co., Ltd.] was added to a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer. , Trade name: GLBT], 21.5 g, butyl methacrylate 28.5 g and ethyl alcohol 450.0 g were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 2.5 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. When determined, the viscosity average molecular weight was 32,000. This (meth) acrylic polymer solution was used as a comparative I liquid A.

Comparative Preparation Example 2
To a 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer, 21.5 g of methyl chloride salt of N, N-dimethylammonium methacrylate, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., Trade name: KBM-503] 28.5 g and 450.0 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 2.5 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 29000. This (meth) acrylic polymer solution was used as Comparative Liquid I.

Comparative Preparation Example 3
A 1 L Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer was mixed with 21.5 g of methacrylic acid, γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503). 5 g and 450.0 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 2.5 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 22,000. This (meth) acrylic polymer solution was used as a comparative I liquid C.

Comparative Preparation Example 4
1L-volume Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer, 21.5 g of butyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 5 g and 450.0 g of ethyl alcohol were added. After deaeration by depressurizing the inside of the Kolben, nitrogen gas was introduced into the Kolben and returned to normal pressure.

  Next, 2.5 g of azobisisobutyronitrile was added into Kolben, and the contents of Kolben were aged for 8 hours while maintaining the temperature of Kolben at 70 ° C., and then cooled to 30 ° C. in a water bath. A (meth) acrylic polymer solution (resin solid content: 10% by mass) was obtained. By measuring the viscosity of the obtained (meth) acrylic polymer solution at 25 ° C. using an Ubbelohde viscometer [manufactured by Reciprocal Chemical Glass Co., Ltd., product number: U-0327-26], the viscosity average molecular weight is determined. As a result, the viscosity average molecular weight was 36000. This (meth) acrylic polymer solution was used as a comparative I liquid D.

Experimental example 1
Flow-coat the liquid I or liquid I for comparison prepared in each preparation example or each comparative preparation example on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and wash the excess liquid with ethyl alcohol. After removing by this, this glass plate was put in a warm air dryer, and warm air drying was performed at a temperature of 120 ° C. for 30 minutes to obtain an antifogging substrate.

  Next, as physical properties of the antifogging base material obtained above, the contact angle to water, friction resistance, water resistance, solvent resistance, and film thickness were evaluated based on the following methods. The results are shown in Table 1.

[Contact angle with water]
A water droplet is dropped on an antifogging substrate, and the contact angle with water is measured at 25 ° C. using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number: DM-501Hi). Based on the following evaluation criteria And evaluated.
(Evaluation criteria)
○: Contact angle with water is less than 10 degrees ×: Contact angle with water is 10 degrees or more

(Abrasion resistance)
A wiping cloth (manufactured by Nippon Paper Crecia Co., Ltd., trade name: Kimwipe S-200) was rubbed 3000 times with a load of 100 g on an anti-fogging base material, and then water droplets were dropped on the surface, and the contact angle with water was 25 ° C. And was evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: Contact angle with water is less than 10 degrees ×: Contact angle with water is 10 degrees or more

〔water resistant〕
After immersing the antifogging base material in hot water heated to 80 ° C. for 5 hours, the antifogging base material is taken out from the hot water, and the liquid I on the antifogging base material is used for comparison. Whether or not the (meth) acrylic polymer contained in the liquid I was dissolved in hot water was examined by measuring the contact angle with water, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: Contact angle with water after water resistance test is less than 10 degrees ×: Contact angle with water after water resistance test is 10 degrees or more

[Solvent resistance]
After the solvent resistance test was performed by immersing the antifogging base material in acetone heated at 40 ° C. for 1 hour, the antifogging base material was taken out from the acetone, and the antifogging group was removed. Investigate whether (meth) acrylic polymer contained in I liquid on the material or comparative I liquid is eluted in acetone by measuring the contact angle with water, and evaluate based on the following evaluation criteria did.
(Evaluation criteria)
○: Contact angle with water after solvent resistance test is less than 10 degrees ×: Contact angle with water after solvent resistance test is 10 degrees or more

[Thickness of coating]
The thickness of the film formed of the liquid I or the liquid I for comparison formed on the antifogging substrate was measured using a stylus type step gauge [manufactured by KLA-Tencor Co., Ltd., product number: P-10]. .

  From the results shown in Table 1, it can be seen that the antifogging property can be imparted to the base material according to the liquid I obtained in each of the preparation examples. In addition, the liquid I obtained in each of the preparation examples, as apparent from comparison with the liquid I for comparison obtained in Comparative Preparation Examples 1 to 4, has excellent anti-friction properties, water resistance and solvent resistance. It can be seen that an anti-fogging film that is difficult to be detached from the base material can be formed even when it comes into contact with water since it can be applied to the base material.

(Production of II solution)
Production Example 1
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine [manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name] in a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer : GLBT] 32.31 g, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 1.55 g and ethanol 146.20 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.

  Next, after heating the contents of Kolben to 65 ° C. with an oil bath provided in Kolben, 1.83 g of azobisisobutyronitrile is added, and the temperature of the contents of Kolben is maintained at 70 ° C. The mixture was aged for 4 hours. Thereafter, 0.37 g of azobisisobutyronitrile was further added to the Kolben, and a polymer solution was obtained by aging for 4 hours while maintaining the reaction temperature at 70 ° C.

  The obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 182.76 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group (resin solid content: 10% by mass). Obtained. This (meth) acrylic polymer solution was used as II solution A.

  By measuring the viscosity of the resulting (meth) acrylic polymer solution having an alkoxysilyl group at 25 ° C. using an Ubbelohde viscometer [manufactured by Mutual Science Glass Co., Ltd., product number: U-0327-26]. When the viscosity average molecular weight was determined, the viscosity average molecular weight was 15,000.

Production Example 2
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine [manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name] in a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer : GLBT] 35.00 g, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 3.27 g and ethanol 153.10 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.

  Next, after the contents of Kolben are heated to 65 ° C. using an oil bath provided in Kolben, 0.38 g of azobisisobutyronitrile is added to keep the temperature of the Kolben contents at 70 ° C. The mixture was aged for 4 hours. Thereafter, 0.38 g of azobisisobutyronitrile was further added to the Kolben, and a polymer solution was obtained by aging for 4 hours while maintaining the reaction temperature at 70 ° C.

  The obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 191.37 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group (resin solid content: 10% by mass). Obtained.

  By measuring the viscosity of the resulting (meth) acrylic polymer solution having an alkoxysilyl group at 25 ° C. using an Ubbelohde viscometer [manufactured by Mutual Science Glass Co., Ltd., product number: U-0327-26]. When the viscosity average molecular weight was determined, the viscosity average molecular weight was 3000. This (meth) acrylic polymer solution was used as the II liquid B.

Production Example 3
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine [manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name] in a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer : GLBT] 35.00 g, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 0.75 g and ethanol 143.02 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.

  Next, after the contents of Kolben are heated to 65 ° C. using an oil bath provided in Kolben, 0.89 g of azobisisobutyronitrile is added, and the temperature of the contents of Kolben is maintained at 70 ° C. The mixture was aged for 4 hours. Thereafter, 0.36 g of azobisisobutyronitrile was further added to the Kolben, and a polymer solution was obtained by aging for 4 hours while maintaining the reaction temperature at 70 ° C.

  The obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 178.78 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group (resin solid content: 10% by mass). Obtained.

  By measuring the viscosity of the resulting (meth) acrylic polymer solution having an alkoxysilyl group at 25 ° C. using an Ubbelohde viscometer [manufactured by Mutual Science Glass Co., Ltd., product number: U-0327-26]. When the viscosity average molecular weight was determined, the viscosity average molecular weight was 5000. This (meth) acrylic polymer solution was used as II liquid C.

Production Example 4
In a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer, 30.00 g of methoxytriethylene glycol acrylate [manufactured by Osaka Organic Chemical Industry Co., Ltd., product number: V-MTG], 3-mercaptopropyltrimethoxysilane [Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 1.44 g and ethanol 125.68 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.

  Next, after the contents of Kolben were heated to 65 ° C. using an oil bath provided in Kolben, 1.57 g of azobisisobutyronitrile was added, and the temperature of the contents of Kolben was maintained at 70 ° C. The mixture was aged for 4 hours. Thereafter, 0.31 g of azobisisobutyronitrile was further added to the Kolben, and a polymer solution was obtained by aging for 4 hours while maintaining the reaction temperature at 70 ° C.

  The obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 157.10 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group (resin solid content: 10% by mass). Obtained.

  By measuring the viscosity of the resulting (meth) acrylic polymer solution having an alkoxysilyl group at 25 ° C. using an Ubbelohde viscometer [manufactured by Mutual Science Glass Co., Ltd., product number: U-0327-26]. When the viscosity average molecular weight was determined, the viscosity average molecular weight was 5000. This (meth) acrylic polymer solution was used as II solution D.

Production Example 5
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine [manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name] in a 500 mL Kolben equipped with a nitrogen gas inlet tube, a condenser and a stirrer : GLBT] 32.31 g, 3-mercaptopropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-803] 1.55 g and ethanol 146.20 g were added. After degassing by reducing the pressure inside the Kolben, nitrogen gas was introduced into the Kolben to return to normal pressure, and oxygen gas in the Kolben was eliminated as much as possible.

  Next, after heating the contents of Kolben to 65 ° C. with an oil bath provided in Kolben, 1.83 g of azobisisobutyronitrile is added, and the temperature of the contents of Kolben is maintained at 70 ° C. The polymer solution was obtained by aging for 4 hours. The obtained polymer solution was cooled to 30 ° C. in a water bath and diluted with 182.76 g of ethanol to obtain a (meth) acrylic polymer solution having an alkoxysilyl group (resin solid content: 10% by mass). Obtained.

  By measuring the viscosity of the resulting (meth) acrylic polymer solution having an alkoxysilyl group at 25 ° C. using an Ubbelohde viscometer [manufactured by Mutual Science Glass Co., Ltd., product number: U-0327-26]. When the viscosity average molecular weight was determined, the viscosity average molecular weight was 15,000. This (meth) acrylic polymer solution was used as II solution E.

Comparative production example 1
A 1% sodium laurate aqueous solution, which is a conventional surfactant solution, was used as Comparative Solution II A.

Comparative production example 2
A 1% sodium myristate aqueous solution, which is a conventional surfactant solution, was used as Comparative Solution II B.

Comparative production example 3
A 1% sodium palmitate aqueous solution, which is a conventional surfactant solution, was used as Comparative Solution II C.

Experimental example 2
The liquid II obtained in each production example or the liquid II for comparison obtained in each comparative production example was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess liquid was ethanol. Then, the glass plate was placed in a warm air dryer and dried with warm air at 120 ° C. for 30 minutes to obtain a test substrate.

  Next, as the physical properties of the test substrate obtained above, the hot water resistance, the contact angle with water, and the thickness of the coating were evaluated based on the following methods. The results are shown in Table 2.

[Heat resistant water]
A water droplet was dropped on the test substrate, and the contact angle with water was measured in an atmosphere at 25 ° C. using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number: DM-501Hi). Thereafter, this test base material was immersed in hot water heated to 80 ° C. for 5 hours to conduct a heat resistant water test. Next, remove the test substrate from this hot water, wash it with water, dry the water adhering to the test substrate with an air gun, and then drop water droplets onto the test substrate for automatic contact. A contact angle with water was measured using an angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number: DM-501Hi) in the atmosphere at 25 ° C., and hot water resistance was evaluated based on the following evaluation criteria.

(Evaluation criteria)
○: The absolute value of the difference in contact angle with water before and after the hot water test is less than 10 degrees X: The absolute value of the difference in contact angle with water before and after the hot water test is 10 degrees or more

[Contact angle with water]
A water droplet was dropped on the test substrate, and the contact angle with water was measured in an atmosphere at 25 ° C. using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number: DM-501Hi).

[Thickness of coating]
The thickness of the coating film made of the II liquid formed on the test substrate was measured using a stylus type step gauge [manufactured by KLA-Tencor Corporation, product number: P-10].

  Further, the liquid II obtained in each production example or the liquid II for comparison obtained in each comparative production example is flow-coated on a glass plate, dried with hot air at 120 ° C. for 30 minutes, and then steam at 90 ° C. The solution was exposed to a glass plate coated with the solution II or the solution II for comparison for 5 minutes. By visually observing the antifogging property of this glass plate, it evaluated based on the following evaluation criteria.

(Evaluation criteria for anti-fogging properties)
○: No fogging on the glass plate ×: Clouding on the glass plate

  In addition, the manufacture example number and comparative manufacture example number described in the column of “type of glass plate” in Table 2 are the flow of the II solution or the comparison II solution obtained by the manufacture example number or the comparison manufacture example number. This means that the physical properties were examined using the prepared glass plate.

  From the results shown in Table 2, the II solution obtained in each production example is a base material having excellent hot water resistance, as apparent from the comparison with the II solution for comparison obtained in Comparative Production Examples 1 to 3. From this, it can be seen that a film that is difficult to be detached from the substrate can be formed even in contact with water.

Examples 1-11 and Comparative Examples 1-2
After the I liquid shown in Table 3 or the comparative I liquid was flow-coated on a glass plate (length: 100 mm, width: 100 mm, thickness: 1 mm), and the excess liquid was removed by washing with ethanol, this glass was removed. The plate was placed in a hot air dryer and dried with hot air at a temperature of 100 ° C. for 10 minutes to obtain a substrate on which a film made of the liquid I or the liquid I for comparison was formed.

  Next, the surface of the base material on which the film made of the liquid I or the liquid for comparison I is formed is flow-coated with the liquid II or liquid for comparison II shown in Table 3, and the excess liquid is washed with ethyl alcohol. Then, the substrate was placed in a warm air dryer and dried with warm air at a temperature of 100 ° C. for 20 minutes to obtain an antifogging substrate.

  Next, as the physical properties of the substrate on which the coating film obtained above was formed, the contact angle with water and the antifogging property were evaluated based on the following methods. The results are shown in Table 3.

[Contact angle]
A water droplet was dropped on the substrate on which the film was formed, and the contact angle with water was measured at 25 ° C. using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product number: DM-501Hi).

[Anti-fogging property]
(1) Initial stage After exposing the antifogging substrate to an atmosphere of humidified air (temperature: 30 ° C., relative humidity: 90%) for 30 seconds, the film formed on the antifogging substrate is visually observed. The evaluation is based on the following evaluation criteria.

(2) Late stage After exposing the antifogging substrate to an atmosphere of humidified air (temperature: 30 ° C., relative humidity: 90%) for 120 seconds, the film formed on the antifogging substrate is visually observed. The evaluation is based on the following evaluation criteria.

(Evaluation criteria)
◯: The substrate can be clearly visually recognized through the film.
(Triangle | delta): A base material can be visually recognized a little through a film.
X: A base material cannot be visually recognized clearly through a film.

  From the results shown in Table 3, each of the antifogging substrates obtained in each Example showed excellent antifogging properties from the initial stage of contact with moisture and after absorbing moisture. It can be seen that excellent antifogging properties are maintained. Therefore, by using the two-pack type antifogging agent obtained in each example, it is difficult to separate from the base material even when it comes into contact with water, and a coating having excellent antifogging properties is formed on the base material surface. It can be seen that it can be formed.

  The two-pack type antifogging agent of the present invention can impart antifogging properties to the surface of the base material by applying it to the base material made of various materials such as glass, metal, and organic matter. It is expected to be applied to a technology for hydrophilizing the surface of a silicone resin used for artificial organs and the like, and a technology for preventing adhesion of proteins, cells and the like. Furthermore, when the two-component antifogging agent of the present invention is applied to a food packaging material, bacteria and bacteria are less likely to adhere to the surface of the two-component antifogging agent.

  In addition, the two-component antifogging agent of the present invention can easily hydrophilize the surfaces of automobile glass, mirrors, etc., so that it is antifogging on mirrors, glass surfaces of solar battery panels, residential window glass, etc. It is also useful for providing a self-cleaning function or preventing dust or dust from adhering to the liquid crystal display from being charged.

1 Substrate 2 Coating made of liquid I 3 Coating made of liquid II

Claims (8)

Formula (I):
Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 6 carbon atoms, R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms or 1 carbon atom. -4 alkoxy groups, wherein at least one of R ³ , R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms, and X represents an oxygen atom or a —NH— group)
And a silicon atom-containing monomer represented by formula (II):
(Wherein R ¹ , R ² and X are the same as above, R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, and R ⁸ is an alkylene group having 1 to 4 carbon atoms)
A liquid I containing a (meth) acrylic polymer obtained by polymerizing a monomer component containing a nitrogen atom-containing monomer represented by formula (III):
(Wherein R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrophilic group)
Having at least one terminal of formula (IV):
(Wherein R ¹³ , R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, wherein R ¹³ , R ¹⁴ and R ¹⁵ are And at least one group of R 4 represents an alkylene group having 1 to 4 carbon atoms, and R ¹⁶ represents an alkylene group having 1 to 12 carbon atoms.)
And a liquid II containing a (meth) acrylic polymer having an alkoxysilyl group represented by the formula:   The weight ratio of the silicon atom-containing monomer represented by the formula (I) to the nitrogen atom-containing monomer represented by the formula (II) (silicon atom-containing monomer / nitrogen atom-containing monomer) is 3/97 to 95/5. Item 2. The two-component antifogging agent according to Item 1.   The two-component antifogging according to claim 1 or 2, wherein the monomer component further contains a monomer copolymerizable with a silicon atom-containing monomer represented by the formula (I) and a nitrogen atom-containing monomer represented by the formula (II). Agent.   The silicon atom-containing monomer represented by the formula (I) and the monomer copolymerizable with the nitrogen atom-containing monomer represented by the formula (II) are selected from the group consisting of styrene monomers, carboxylic acid ester monomers, and amide monomers. The two-component antifogging agent according to claim 3, which is at least one kind.   The amount of the monomer that can be copolymerized with the silicon atom-containing monomer represented by the formula (I) and the nitrogen atom-containing monomer represented by the formula (II) is the same as that of the silicon atom-containing monomer represented by the formula (I) and the formula (II). The two-component antifogging agent according to claim 3 or 4, which is 100 parts by weight or less per 100 parts by weight of the total amount of the nitrogen atom-containing monomer represented. In the formula (III), R ¹² is an alkyl group having 2 to 20 carbon atoms which may have a hydrogen atom, a hydroxyl group or a fluorine atom, or an aryl having 6 to 20 carbon atoms which may have a hydroxyl group or a fluorine atom. Group, an ethylene oxide group which has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and may have a hydroxyl group or a fluorine atom, and has a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end A polyethylene oxide group in which the number of added moles of an ethylene oxide group optionally having a hydroxyl group or a fluorine atom is 2 to 20, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and a hydroxyl group or a fluorine atom A propylene oxide group optionally having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end and a hydroxyl group or a fluorine atom Polypropylene oxide group addition mole number 2 to 20 of Kisaido group, the formula (V):
(Wherein R ¹⁷ and R ¹⁸ are each independently an alkylene group having 1 to 4 carbon atoms, and R ¹⁹ and R ²⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
Or a group represented by formula (VI):
Wherein R ²¹ is an alkylene group having 1 to 4 carbon atoms, R ²² and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ²⁴ is an organic group, and Y ⁻ is an anion. Show)
The two-component antifogging agent according to any one of claims 1 to 5, wherein   The two-component antifogging agent according to any one of claims 1 to 6, wherein the number of repeating units represented by formula (III) is 1-1000. A film formed of the two-component antifogging agent according to any one of claims 1 to 7 is formed on the surface of the substrate, and an antifogging substrate formed of the liquid I is formed on the substrate. An antifogging base material, wherein a film made of a liquid II is formed on a film made of the liquid I.