JP2015107448A - Method for production of anti-fogging article, and coating liquid for forming anti-fogging film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for production of an anti-fogging article having both excellent anti-fogging property and surface hardness including the use of superheated steam for hardening, and to provide a coating liquid for anti-fogging film formation for obtaining the anti-fogging article.SOLUTION: A method for production of an anti-fogging article is characterized by having the following processes: (A) a process of preparing as a raw material, a coating liquid for anti-fogging film formation obtained by mixing at a prescribed ratio, at least (i) a copolymer having an X group imparting water absorptivity and a Y group having the crosslinking reaction with an epoxy group, (ii) an epoxy group-containing silane compound, (iii) at least one selected from the group consisting of metal oxide precursors, a hydrolysate of the precursors and a condensate of the precursors, (iv) an acid or base and (v) a solvent; (B) a process of coating the coating liquid for anti-fogging film formation on the surface of a substrate; and (C) a process of hardening a coating film after the process (B) of coating the coating liquid by exposing the coating film to a superheated steam.

Description

  The present invention provides an antifogging film having excellent antifogging properties and surface hardness on a base material in antifogging window glass, antifogging mirrors, lenses, displays and the like for vehicles and buildings. The present invention relates to a method for producing a formed antifogging article.

  Transparent substrates such as glass and plastic have a sudden temperature change with respect to the substrate when one surface falls below the dew point due to the difference in temperature and humidity between the inner and outer surfaces of the substrate. In the case (for example, when boiling water vapor comes into contact with the base material or when the low temperature portion moves to a high temperature and high humidity environment), moisture in the atmosphere adheres as water droplets, and the surface of the base material is condensed. As a result, the field of view is hindered by the so-called “cloudiness” in which light is scattered by the condensed water droplets. Such “cloudiness” significantly impairs safety and visibility in general window glass, glass for showcases, windshields of automobiles and aircraft, reflectors, glasses, sunglasses, and the like.

  As a method for imparting antifogging properties to these substrates, Patent Document 1 discloses a heat-resistant antifogging film-forming coating agent containing a binder component and polyacrylic acid, Forming a heat-resistant anti-fogging film on a substrate using a heat-resistant anti-fogging film-forming coating agent characterized in that anti-fogging properties are manifested by water absorption of components derived from polyacrylic acids when formed It is disclosed.

  Patent Document 2 discloses an antifogging property characterized by having a base material, a film containing a binder component and a polyacrylic acid copolymer, and a primer layer between the base material and the film. An anti-fogging article having excellent adhesion between a substrate and a film and heat resistance is disclosed.

Patent Document 3 discloses a composite film containing a binder component and a polyacrylic acid copolymer in an anti-fogging article having a base material and a film in close contact with the base material. The film is a film exhibiting water absorption, the water absorption of the unit volume at the time of water absorption saturation of the film is 0.05 to ³ mg / mm ³ , and the film has heat resistance against heat of 100 ° C. or less. An anti-fogging article having excellent heat resistance and anti-fogging property, characterized in that it has, is disclosed.

JP 2011-153164 A JP 2012-017220 A JP 2012-017394 A

  Antifogging articles are desired to have excellent antifogging properties that can ensure visibility even in an environment that causes fogging, and surface hardness that can withstand actual use. However, it is extremely difficult for an antifogging film with improved antifogging performance to have both sufficient antifogging properties and surface hardness. Although the antifogging films described in Patent Documents 1 to 3 have excellent antifogging properties, the surface hardness may be insufficient and there is room for improvement.

  Accordingly, the present invention relates to a method for producing an antifogging article that uses superheated steam for the curing treatment and has both excellent antifogging properties and surface hardness, and an antifogging film forming coating solution for obtaining the antifogging article. It is an issue to provide.

（式［１］で、Ｒ^１及びＲ^２は、水素基又はメチル基であり、Ｒ^３は、水素基又は炭素数が１〜５のアルキル基であり、Ｘは、−Ｃ（＝Ｏ）−ＮＲ^４（ここで、Ｒ^４は炭素数が１〜４のアルキル基）、アミノ基、スルホン酸基及び水酸基からなる群から選ばれる少なくとも１つの基、又は、アミド基、アミノ基、スルホン酸基及び水酸基からなる群から選ばれる少なくとも１つの基と脂肪族炭化水素基とから構成された１価の有機基であり、Ｙは、カルボキシル基、又は、−Ｒ^５−Ｃ（＝Ｏ）−ＯＨで表される基であり、該Ｒ^５は、２価の脂肪族炭化水素基、又は、エステル基、エーテル基、アミド基からなる群から選ばれる少なくとも１つの基と脂肪族炭化水素基とから構成された２価の有機基である。ａとｂはａ：ｂ＝０．７〜２．５：１．０である数である。なお、式［１］中の繰り返し構造単位の順序は特に限定されない。）
［Ｒ^６（ＣＨ_２Ｏ）_ｃ（ＣＨ_２）_ｄ］_ｅＳｉ（Ｒ^７）_ｆ（Ｚ^１）_{４−ｅ−ｆ} ［２］
（式［２］で、Ｒ^６はエポキシ基、グリシドキシ基、及びエポキシ基と脂肪族炭化水素基とから構成された１価の有機基から選ばれる少なくとも１つの基であり、Ｒ^７は炭素数１〜３のアルキル基であり、Ｚ^１はアルコキシ基、及びヒドロキシ基からなる群から選ばれる少なくとも１つの基である。ｃ及びｄはそれぞれ０〜３であり、ｅは１又は２であり、ｆは０又は１である。）
（Ｒ^８）_ｇＭ（Ｚ^２）_ｈ−ｇ ［３］
（式［３］中、Ｒ^８は１価の有機基、Ｚ^２はそれぞれ独立にアルコキシ基、ヒドロキシ基、ハロゲン元素、酸素元素、ハロゲン化物イオン、ＮＯ_３ ⁻及びＣＨ_３ＣＯＯ⁻からなる群から選ばれる少なくとも１つであり、ＭはＳｉ、Ｚｒ、Ａｌ及びＴｉからなる群から選ばれる少なくとも１種の元素であり、ｇは０〜３の整数であり、ｈは３又は４であり、ｈ−ｇは１〜４の整数である。）
（Ｒ^９）_ｊＭ（Ｚ^３）_ｉ−ｊ ［４］
（式［４］中、Ｒ^９はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基、Ｚ^３はアルコキシ基又はハロゲン元素であり、ＭはＳｉ、Ｚｒ、Ａｌ及びＴｉからなる群から選ばれる少なくとも１種の元素であり、ｊは０〜４の整数であり、ｉは３又は４であり、ｉ−ｊは０〜４の整数である。） The present invention
A method for producing an antifogging article having an antifogging film formed by applying a coating solution for forming an antifogging film on the surface of the base material and the base material, and curing the coated film after coating,
A method for producing an antifogging article, comprising at least the following steps.
(A) As a raw material, at least
(I) a copolymer represented by the following general formula [1];
(Ii) an epoxy group-containing silane compound represented by the following general formula [2];
(Iii) At least one metal oxide precursor selected from the group consisting of a compound represented by the following general formula [3] and a compound represented by the following general formula [4], hydrolysis of the metal oxide precursor At least one selected from the group consisting of a decomposition product and a condensate of the metal oxide precursor;
(Iv) an acid or base;
(V) a solvent,
For a total amount of 100% by mass of (i) to (iii),
For preparing an antifogging film, a coating solution for forming an antifogging film obtained by mixing at a ratio of (i) 10 to 80% by mass, (ii) 5 to 60% by mass, and (iii) 5 to 80% by mass is prepared. Coating solution preparation process,
(B) Applying the antifogging film-forming coating solution on the surface of the base material, applying the antifogging film-forming coating solution,
(C) The hardening process hardened | cured by exposing the coating film after the coating liquid application process for the said anti-fogging film formation to superheated steam.

(In the formula [1], R ¹ and R ² are a hydrogen group or a methyl group, R ³ is a hydrogen group or an alkyl group having 1 to 5 carbon atoms, and X is —C (═O). —NR ⁴ (wherein R ⁴ is an alkyl group having 1 to 4 carbon atoms), at least one group selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or an amide group, an amino group, and a sulfonic acid Y is a monovalent organic group composed of at least one group selected from the group consisting of a group and a hydroxyl group and an aliphatic hydrocarbon group, and Y is a carboxyl group or —R ⁵ —C (═O) —. R ⁵ is a group represented by OH, and R ⁵ represents a divalent aliphatic hydrocarbon group, or at least one group selected from the group consisting of an ester group, an ether group, and an amide group, and an aliphatic hydrocarbon group. A and b are a: b = 0.7-2. 5: is a number from 1.0 Note that the order of the repeating units of the formula [1] is not particularly limited)..
[R ⁶ (CH ₂ O) _c (CH ₂ ) _d ] _e Si (R ⁷ ) _f (Z ¹ ) _4-ef [2]
(In the formula [2], R ⁶ is at least one group selected from an epoxy group, a glycidoxy group, and a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, and R ⁷ is a carbon number. 1 to 3 alkyl groups, Z ¹ is at least one group selected from the group consisting of alkoxy groups and hydroxy groups, c and d are each 0 to 3, e is 1 or 2, f is 0 or 1.)
(R ⁸ ) _g M (Z ² ) _h-g [3]
(In the formula [3], R ⁸ is a monovalent organic group, Z ² is independently an alkoxy group, a hydroxy group, a halogen element, an oxygen element, a halide ion, NO ₃ ^— and CH ₃ COO ^—. At least one selected, M is at least one element selected from the group consisting of Si, Zr, Al and Ti, g is an integer of 0 to 3, h is 3 or 4, h -G is an integer of 1-4.)
(R ⁹ ) _j M (Z ³ ) _ij [4]
(In the formula [4], R ⁹ is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, Z ³ is an alkoxy group or a halogen element, and M is a group consisting of Si, Zr, Al and Ti. And j is an integer of 0 to 4, i is 3 or 4, and ij is an integer of 0 to 4.)

（式［５］で、Ｘ、ａ及びｂは式［１］と同様であり、ｍは０〜２、ｎは０〜３、ｓは１〜４、ｔは１〜４の数である。なお、式［５］中の繰り返し構造単位の順序は特に限定されない。） In the method for producing an antifogging article of the present invention, the copolymer represented by the general formula [1] is preferably a copolymer represented by the following general formula [5].

(In Formula [5], X, a, and b are the same as in Formula [1], m is 0-2, n is 0-3, s is 1-4, and t is 1-4. Note that the order of the repeating structural units in the formula [5] is not particularly limited.)

  Moreover, in the manufacturing method of the anti-fogging article | item of this invention, it is preferable that the weight average molecular weights of the copolymer represented by the said General formula [1] are 1,000-1,000,000.

In the method for producing an antifogging article of the present invention, the epoxy group-containing silane compound represented by the general formula [2] is preferably a compound represented by the following general formula [6].
^{_{R 10 (CH 2) k Si}} (CH 3) p (OR 11) 3-p [6]
(R ¹⁰ is a glycidoxy group, or a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, R ¹¹ is an alkyl group having 1 to 3 carbon atoms. K is 2 or 3. And p is 0 or 1.)

  In the method for producing an antifogging article of the present invention, the epoxy group-containing silane compound represented by the general formula [6] is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycol. It must be at least one selected from the group consisting of sidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. Is preferred.

In the method for producing an antifogging article of the present invention, when Y of the copolymer represented by the general formula [1] contains a carboxyl group,
In the coating solution preparation step for forming the antifogging film,
For 1 mol of carboxyl group
It is preferable to mix so that the epoxy group of the said epoxy group containing silane compound may be 0.2-3 mol amount.

In the method for producing an antifogging article of the present invention,
In the coating solution preparation step for forming the antifogging film,
A quaternary ammonium salt or a quaternary phosphonium salt may be further mixed as a raw material for the coating solution for forming an antifogging film.

In the method for producing an antifogging article of the present invention,
In the coating solution preparation step for forming the antifogging film,
It is preferable to further mix a curing agent as a raw material for the coating solution for forming an antifogging film.

In the method for producing an antifogging article of the present invention,
In the coating solution preparation step for forming the antifogging film,
It is preferable to further mix fine particles as a raw material for the coating solution for forming the antifogging film.

In the method for producing an antifogging article of the present invention,
After the coating solution preparation step for forming the antifogging film, before the coating solution coating step for forming the antifogging film,
You may perform operation which adjusts solid content concentration and viscosity of this coating liquid by concentrating a coating liquid or adding a solvent further.

In the method for producing an antifogging article of the present invention,
It is preferable that the said hardening process hardens | cures by exposing to 100-300 degreeC superheated steam.

（式［１］で、Ｒ^１及びＲ^２は、水素基又はメチル基であり、Ｒ^３は、水素基又は炭素数が１〜５のアルキル基であり、Ｘは、−Ｃ（＝Ｏ）−ＮＲ^４（ここで、Ｒ^４は炭素数が１〜４のアルキル基）、アミノ基、スルホン酸基及び水酸基からなる群から選ばれる少なくとも１つの基、又は、アミド基、アミノ基、スルホン酸基及び水酸基からなる群から選ばれる少なくとも１つの基と脂肪族炭化水素基とから構成された１価の有機基であり、Ｙは、カルボキシル基、又は、−Ｒ^５−Ｃ（＝Ｏ）−ＯＨで表される基であり、該Ｒ^５は、２価の脂肪族炭化水素基、又は、エステル基、エーテル基、アミド基からなる群から選ばれる少なくとも１つの基と脂肪族炭化水素基とから構成された２価の有機基である。ａとｂはａ：ｂ＝０．７〜２．５：１．０である数である。なお、式［１］中の繰り返し構造単位の順序は特に限定されない。）
［Ｒ^６（ＣＨ_２Ｏ）_ｃ（ＣＨ_２）_ｄ］_ｅＳｉ（Ｒ^７）_ｆ（Ｚ^１）_{４−ｅ−ｆ} ［２］
（式［２］で、Ｒ^６はエポキシ基、グリシドキシ基、及びエポキシ基と脂肪族炭化水素基とから構成された１価の有機基から選ばれる少なくとも１つの基であり、Ｒ^７は炭素数１〜３のアルキル基であり、Ｚ^１はアルコキシ基、及びヒドロキシ基からなる群から選ばれる少なくとも１つの基である。ｃ及びｄはそれぞれ０〜３であり、ｅは１又は２であり、ｆは０又は１である。）
（Ｒ^８）_ｇＭ（Ｚ^２）_ｈ−ｇ ［３］
（式［３］中、Ｒ^８は１価の有機基、Ｚ^２はそれぞれ独立にアルコキシ基、ヒドロキシ基、ハロゲン元素、酸素元素、ハロゲン化物イオン、ＮＯ_３ ⁻及びＣＨ_３ＣＯＯ⁻からなる群から選ばれる少なくとも１つであり、ＭはＳｉ、Ｚｒ、Ａｌ及びＴｉからなる群から選ばれる少なくとも１種の元素であり、ｇは０〜３の整数であり、ｈは３又は４であり、ｈ−ｇは１〜４の整数である。）
（Ｒ^９）_ｊＭ（Ｚ^３）_ｉ−ｊ ［４］
（式［４］中、Ｒ^９はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基、Ｚ^３はアルコキシ基又はハロゲン元素であり、ＭはＳｉ、Ｚｒ、Ａｌ及びＴｉからなる群から選ばれる少なくとも１種の元素であり、ｊは０〜４の整数であり、ｉは３又は４であり、ｉ−ｊは０〜４の整数である。） The present invention also provides:
As a raw material, at least,
(I) a copolymer represented by the following general formula [1];
(Ii) an epoxy group-containing silane compound represented by the following general formula [2];
(Iii) At least one metal oxide precursor selected from the group consisting of a compound represented by the following general formula [3] and a compound represented by the following general formula [4], hydrolysis of the metal oxide precursor At least one selected from the group consisting of a decomposition product and a condensate of the metal oxide precursor;
(Iv) an acid or base;
(V) a solvent,
For a total amount of 100% by mass of (i) to (iii),
It is a coating solution for forming an antifogging film obtained by mixing at a ratio of (i) 10 to 80% by mass, (ii) 5 to 60% by mass, and (iii) 3 to 80% by mass.

(In the formula [1], R ¹ and R ² are a hydrogen group or a methyl group, R ³ is a hydrogen group or an alkyl group having 1 to 5 carbon atoms, and X is —C (═O). —NR ⁴ (wherein R ⁴ is an alkyl group having 1 to 4 carbon atoms), at least one group selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or an amide group, an amino group, and a sulfonic acid Y is a monovalent organic group composed of at least one group selected from the group consisting of a group and a hydroxyl group and an aliphatic hydrocarbon group, and Y is a carboxyl group or —R ⁵ —C (═O) —. R ⁵ is a group represented by OH, and R ⁵ represents a divalent aliphatic hydrocarbon group, or at least one group selected from the group consisting of an ester group, an ether group, and an amide group, and an aliphatic hydrocarbon group. A and b are a: b = 0.7-2. 5: is a number from 1.0 Note that the order of the repeating units of the formula [1] is not particularly limited)..
[R ⁶ (CH ₂ O) _c (CH ₂ ) _d ] _e Si (R ⁷ ) _f (Z ¹ ) _4-ef [2]
(In the formula [2], R ⁶ is at least one group selected from an epoxy group, a glycidoxy group, and a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, and R ⁷ is a carbon number. 1 to 3 alkyl groups, Z ¹ is at least one group selected from the group consisting of alkoxy groups and hydroxy groups, c and d are each 0 to 3, e is 1 or 2, f is 0 or 1.)
(R ⁸ ) _g M (Z ² ) _h-g [3]
(In the formula [3], R ⁸ is a monovalent organic group, Z ² is independently an alkoxy group, a hydroxy group, a halogen element, an oxygen element, a halide ion, NO ₃ ^— and CH ₃ COO ^—. At least one selected, M is at least one element selected from the group consisting of Si, Zr, Al and Ti, g is an integer of 0 to 3, h is 3 or 4, h -G is an integer of 1-4.)
(R ⁹ ) _j M (Z ³ ) _ij [4]
(In the formula [4], R ⁹ is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, Z ³ is an alkoxy group or a halogen element, and M is a group consisting of Si, Zr, Al and Ti. And j is an integer of 0 to 4, i is 3 or 4, and ij is an integer of 0 to 4.)

（式［５］で、Ｘ、ａ及びｂは式［１］と同様であり、ｍは０〜２、ｎは０〜３、ｓは１〜４、ｔは１〜４の数である。なお、式［５］中の繰り返し構造単位の順序は特に限定されない。） In the antifogging film forming coating liquid of the present invention,
The copolymer represented by the general formula [1] is preferably a copolymer represented by the following general formula [5].

(In Formula [5], X, a, and b are the same as in Formula [1], m is 0-2, n is 0-3, s is 1-4, and t is 1-4. Note that the order of the repeating structural units in the formula [5] is not particularly limited.)

In the antifogging film forming coating liquid of the present invention,
The weight average molecular weight of the copolymer represented by the general formula [1] is preferably 1,000 to 1,000,000.

In the antifogging film forming coating liquid of the present invention,
The epoxy group-containing silane compound represented by the general formula [2] is preferably a compound represented by the following general formula [6].
^{_{R 10 (CH 2) k Si}} (CH 3) p (OR 11) 3-p [6]
(R ¹⁰ is a glycidoxy group, or a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, R ¹¹ is an alkyl group having 1 to 3 carbon atoms. K is 2 or 3. And p is 0 or 1.)

In the antifogging film forming coating liquid of the present invention,
The epoxy group-containing silane compound represented by the general formula [6] is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxy. It is preferably at least one selected from the group consisting of silane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.

In the antifogging film forming coating liquid of the present invention,
When Y of the copolymer represented by the general formula [1] contains a carboxyl group,
For 1 mol of carboxyl group
It is preferable that the epoxy group of the epoxy group-containing silane compound is mixed so as to have an amount of 0.2 to 3 mol.

In the antifogging film forming coating liquid of the present invention,
The raw material is preferably obtained by further mixing a quaternary ammonium salt or a quaternary phosphonium salt.

In the antifogging film forming coating liquid of the present invention,
It is preferable that the raw material is obtained by further mixing a curing agent.

In the antifogging film forming coating liquid of the present invention,
It is preferable that the raw material is obtained by further mixing fine particles.

  According to the present invention, it is possible to provide a method for producing an antifogging article using superheated steam for curing treatment and an antifogging article excellent in surface hardness, and a coating liquid for forming an antifogging film for obtaining the antifogging article. it can. As a result, it is possible to obtain an antifogging article having a surface hardness that can withstand actual use, which has been difficult to obtain in the past.

1. Coating solution preparation step for forming antifogging film (1) About copolymer represented by general formula [1] The copolymer represented by general formula [1] is a repeating structural unit having a group represented by X And a repeating structural unit having a group represented by Y (hereinafter, the copolymer represented by the general formula [1] may be simply referred to as “copolymer”). . The copolymer may be a random copolymer, a block copolymer, or an alternating copolymer.

  The copolymer may be obtained by copolymerizing monomers having copolymerizable groups, or may be obtained by copolymerizing oligomers having copolymerizable groups. Alternatively, it may be obtained by copolymerizing the above monomer and oligomer. Examples of the monomer that forms a repeating structural unit having a group represented by X include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N, N-di-n-propyl (meth) acrylamide. N, N-diiso-propyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) ) Acrylate, dibutylaminoethyl (meth) acrylate, dibutylaminopropyl (meth) acrylate, (meth) acryloylmorpholine, 1- (meth) acryloylpiperidin-2-one, 1-vinyl-2-pyrrolidone, 3-acryloyl-2 - Sazolidinone, t-butyl N-allylcarbamate, N- (2-hydroxymethyl) (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N-methylolacrylamide, dimethylaminoethyl (meth) acrylamide, Dimethylaminopropyl (meth) acrylamide, dimethylaminobutyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, diethylaminobutyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dipropylaminopropyl (Meth) acrylamide, dipropylaminobutyl (meth) acrylamide, dibutylaminoethyl (meth) acrylamide, dibutylaminopropyl (meth) a Kurylamide, dibutylaminobutyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide-t-butylsulfonic acid, vinylsulfone An acid etc. are mentioned. Moreover, as a monomer which forms the repeating structural unit which has the group represented by Y, (meth) acrylic acid, succinic acid mono (2-acryloyloxyethyl), (beta) -carboxyethyl (meth) acrylate, 3-butenoic acid 4-pentenoic acid, trans-3-pentenoic acid, trans-2-pentenoic acid, 5-hexenoic acid, trans-3-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 5-heptenoic acid, 6-heptene Examples include acid, 2-octenoic acid, trans-2-octenoic acid, 7-octenoic acid, 3-octenoic acid, 3-allyloxypropionic acid, and N-tigroylglycine. In addition, when obtaining the said copolymer using the oligomer which has a copolymerizable group, what was produced from the monomer which has the said copolymerizable group for this oligomer is preferable. The copolymer is synthesized by general polymerization.

In the copolymer, the group represented by X is a group that imparts water absorption to the film when the antifogging film is formed, and is a group that contributes to the development of antifogging properties. From the viewpoint of heat resistance, the group represented by X is preferably a group which is —C (═O) —NR ⁴ (where R ⁴ is an alkyl group having 1 to 4 carbon atoms). In the copolymer, the group represented by Y is a group that forms a cross-linkage with the epoxy group of the epoxy group-containing silane compound, and was excellent in the film when an antifogging film was formed. It is a group that imparts surface hardness, heat resistance, chemical resistance, and wear resistance. From the viewpoint of reactivity with the compatibility, the group represented by Y is, [- C (= O) -O-C s H 2s - {O-C (= O) -C t H 2t -} m] n A group represented by -C (= O) -OH (where m is 0 to 2, n is 0 to 3, s is 1 to 4, and t is 1 to 4) is preferable. (═O) —OH, —C (═O) OC ₂ H ₄ C (═O) —OH, —C (═O) OC ₂ H ₄ OC (═O) C ₂ H ₄ C (═O) — OH is preferable, and —C (═O) —OH is particularly preferable from the viewpoint of chemical resistance.

  In the copolymer, a and b in the general formula [1], which is the abundance ratio of the repeating structural unit having a group represented by X and the repeating structural unit having a group represented by Y, : B = 0.7 to 2.5: 1.0. When a is less than 0.7 times b (that is, a / b <0.7), a film having sufficient antifogging properties cannot be obtained, and a is more than 2.5 times b (ie 2.. In the case of 5 <a / b), since the cross-linking is reduced, the surface hardness is lowered when the antifogging film is formed. In order to achieve both practical antifogging properties and surface hardness, a: b = 1.0 to 2.0: 1.0 is more preferable.

  The weight average molecular weight of the copolymer represented by the general formula [1] is preferably 1,000 to 1,000,000. If the weight average molecular weight is less than 1,000, the chemical resistance tends to be weak, which is not preferable. On the other hand, if the weight average molecular weight is more than 1,000,000, the viscosity of the coating solution for forming an antifogging film tends to be high and the workability such as coating work tends to deteriorate, which is not preferable. The weight average molecular weight is more preferably 30,000 to 500,000.

(2) About epoxy group containing silane compound An epoxy group containing silane compound is a compound represented by following General formula [2].
[R ⁶ (CH ₂ O) _c (CH ₂ ) _d ] _e Si (R ⁷ ) _f (Z ¹ ) _4-ef [2]
(In the formula [2], R ⁶ is at least one group selected from an epoxy group, a glycidoxy group, and a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, and R ⁷ is a carbon number. 1 to 3 alkyl groups, Z ¹ is at least one group selected from the group consisting of alkoxy groups and hydroxy groups, c and d are each 0 to 3, e is 1 or 2, f is 0 or 1.)

The epoxy group in the epoxy group-containing silane compound is a group that forms a bridge with the group represented by Y of the copolymer represented by the general formula [1], and the epoxy group-containing silane compound Is a component that imparts excellent surface hardness, heat resistance, chemical resistance and wear resistance to the antifogging film. Further, the group represented by Z ¹ in the epoxy group-containing silane compound is a group that forms a siloxane bond or other metalloxane bond by a condensation reaction, and has an excellent surface when the antifogging film is formed. Gives hardness, stain resistance and adhesion. The contamination resistance means that when a contaminant is attached to the film surface, left for a certain period of time, and then wiped off, discoloration, blotting, and swelling due to the contaminant do not easily occur.

When the epoxy group-containing silane compound is a compound represented by the following general formula [6], the reactivity with the copolymer represented by the general formula [1] and the general formula [3] are represented. And at least one metal oxide precursor selected from the group consisting of compounds represented by the above general formula [4], hydrolyzate of the metal oxide precursor, and condensation of the metal oxide precursor The reactivity with at least one selected from the group consisting of products is good, and the effect of the leaving group upon hydrolysis on the membrane is small, which is more preferable.
^{_{R 10 (CH 2) k Si}} (CH 3) p (OR 11) 3-p [6]
(R ¹⁰ is a glycidoxy group, or a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, R ¹¹ is an alkyl group having 1 to 3 carbon atoms. K is 2 or 3. And p is 0 or 1.)

  Examples of the epoxy group-containing silane compound include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycid. Xylpropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. Among them, when the antifogging film is formed, surface hardness and adhesion to the substrate are improved. 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane are preferred.

  The antifogging film-forming coating solution of the present invention may contain a polyfunctional epoxysilane coupling agent as a raw material together with the epoxy group-containing silane compound. The polyfunctional epoxy silane coupling agent is a compound containing a plurality of epoxy groups or trialkoxysilyl groups in the molecule. For example, trade names “X-12-981” and “X-12” made by Shin-Etsu Silicone are used. -984 ", trade name" XIAMETER OFS-6040Silane "manufactured by Dow Corning Corporation.

In the raw material of the coating solution for forming the antifogging film, when Y of the copolymer represented by the general formula [1] contains a carboxyl group, the epoxy of the epoxy group-containing silane compound is used with respect to 1 mol of the carboxyl group. It is preferable to mix so that a group may be 0.2-3 mol amount. When the epoxy group is less than 0.2 mole amount relative to 1 mole amount of the carboxyl group, unreacted carboxyl groups remain in the resulting antifogging film, and the alkali resistance of the antifogging film tends to be reduced. There is not preferable. Moreover, the acid resistance of the anti-fogging film | membrane which can increase the bonding site | part formed by reaction of epoxy groups as the said epoxy group exceeds 3 mol amount with respect to 1 mol amount of said carboxyl groups tends to fall. There is not preferable. It is more preferable that the epoxy group is mixed in an amount of 0.5 to 2 mol relative to 1 mol of the carboxyl group.
In addition, when the polyfunctional epoxysilane coupling agent is used as a raw material together with the epoxy group-containing silane compound, Y is mixed with the copolymer represented by the general formula [1] containing a carboxyl group. However, it is preferable that the epoxy group of the epoxy group-containing silane compound is 0.2 to 3 mole amount relative to 1 mole amount of the carboxyl group. Furthermore, it is preferable that the total amount of the epoxy group of the epoxy group-containing silane compound and the epoxy group of the polyfunctional epoxysilane coupling agent is 0.2 to 3 moles relative to 1 mole of the carboxyl group.

(3) Metal Oxide Precursor, Hydrolyzate of Metal Oxide Precursor, Condensate of Metal Oxide Precursor The coating solution for forming an antifogging film of the present invention has the following general formula [3 And at least one metal oxide precursor selected from the group consisting of a compound represented by the following general formula [4], a hydrolyzate of the metal oxide precursor, and the metal oxide It contains at least one selected from the group consisting of condensates of precursors.
(R ⁸ ) _g M (Z ² ) _h-g [3]
(In the formula [3], R ⁸ is a monovalent organic group, Z ² is independently an alkoxy group, a hydroxy group, a halogen element, an oxygen element, a halide ion, NO ₃ ^— and CH ₃ COO ^—. At least one selected, M is at least one element selected from the group consisting of Si, Zr, Al and Ti, g is an integer of 0 to 3, h is 3 or 4, h -G is an integer of 1-4.)
(R ⁹ ) _j M (Z ³ ) _ij [4]
(In the formula [4], R ⁹ is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, Z ³ is an alkoxy group or a halogen element, and M is a group consisting of Si, Zr, Al and Ti. And j is an integer of 0 to 4, i is 3 or 4, and ij is an integer of 0 to 4.)

  At least one metal oxide precursor selected from the group consisting of the compound represented by the general formula [3] and the compound represented by the general formula [4], and a hydrolyzate of the metal oxide precursor , And at least one selected from the group consisting of condensates of the metal oxide precursor reacts with the epoxy group-containing silane compound and the like, and itself becomes a part of the obtained antifogging film, This film imparts excellent surface hardness, stain resistance and adhesion.

In the above general formula [3], h is 4 when M is Si. Examples of the compound when g is 0 include tetraethoxysilane, tetramethoxysilane, and tetrachlorosilane. Examples of the compound when g is 1 include monomethyltriethoxysilane, monomethyltrimethoxysilane, monomethyltrichlorosilane, ( 3-aminopropyl) trimethoxysilane and the like, and examples of the compound when g is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane and the like. Among these, it is particularly preferable to use an alkoxysilane represented by the general formula Si (Z ² ) ₄ since the hardness of the coating becomes good.

In the general formula [3], when M is Zr, h is 3. Examples of the compound when g is 0 include at least one zirconium oxide precursor selected from the group consisting of compounds represented by the general formula [7].
ZrO (Z ² ) ₂ [7]
(In formula [7], Z ² is Cl ⁻ , NO ₃ ^— or CH ₃ COO ^— .)
Examples of the zirconium oxide precursor represented by the general formula [7] include zirconium oxychloride, zirconium oxynitrate, and zirconium oxyacetate.

In the general formula [4], when M is Zr, i is 4 and j is 0 to 4. Examples of the oxide precursor include at least one zirconium oxide precursor selected from the group consisting of compounds represented by the general formula [8].
(R ¹² ) _r Zr (Z ³ ) _4-r [8]
(Wherein ^{[8], R 12} is acetyl acetonate group, ^{Z 3} is an alkoxyl group or a halogen having 2 to 4 carbon atoms, r is an integer of 0-4.)
In the zirconium oxide precursor represented by the general formula [8], examples of the compound when r is 0 include tetraisopropoxyzirconium, tetranormalbutoxyzirconium, and tetraethoxyzirconium. These correspond to compounds in which i in the general formula [4] is 4 and j is 0. Examples of the compound where r is 4 include zirconium tetraacetylacetonate. These correspond to compounds in which i in the general formula [4] is 4 and j is 4.

In the general formula [4], when M is Al, i is 3 and j is 0 to 3. Examples of the compound in the case where j is 0 include aluminum alkoxides, and specific examples include aluminum ethoxide, aluminum isopropoxide, aluminum-n-butoxide, aluminum-sec-butoxide, and aluminum-tert-butoxide. Can be mentioned. Examples of the compound when j is 1 include aluminum ethyl acetoacetate diisopropylate, aluminum dinormal butoxy monoethyl acetoacetate and the like. Examples of the compound in the case where j is 3 include aluminum trisacetylacetonate, aluminum trisethylacetoacetate, aluminum bisethylacetoacetate / monoacetylacetonate, and the like. Among these, aluminum ethyl acetoacetate / diisopropylate represented by R ¹³ Al (Z ³ ) ₂ , aluminum dinormalbutoxy monoethyl acetoacetate and the like are preferable.

  In the above general formula [3], h is 4 when M is Ti. Examples of the compound when g is 0 include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, and tetraisobutoxy titanium. Examples of the compound when g is 2 include diisopropoxybis (acetylacetonate) titanium, diisopropoxybis (ethylacetoacetate) titanium and the like.

  In addition, examples of the hydrolyzate of the metal oxide precursor exemplified above include those obtained by hydrolyzing part or all of them. Examples of the condensate of the metal oxide precursors exemplified above include those obtained by condensing some of them.

(4) About acid or base The above acid or base promotes hydrolysis and polycondensation reaction of the compounds represented by the general formulas [2], [3], [4] and [6]. , Itself may be a part of the anti-fogging film. Examples of the acid include organic acids and inorganic acids, and examples include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, sulfonic acid, maleic acid, and the like, and among these, hydrochloric acid, nitric acid, and acetic acid are more preferable. Examples of the base include ammonia, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine, pyridine, piperidine, and triethylamine, and among them, ammonia and pyridine are preferable. . The amount of the acid or base added is not particularly limited as long as it is an amount effective for promoting the hydrolysis and polycondensation reactions, but it is limited to 1 mol amount of the hydrolyzable group. It is preferable that it is 0.0001-10 mol amount with respect to it. When the addition amount is less than 0.0001 molar amount, hydrolysis and polycondensation reaction may be insufficient, which is not preferable. On the other hand, when the amount exceeds 10 mol, it is not preferable because cracks may be generated in the resulting coating or the hydrolysis resistance of the resulting coating may be poor. The addition amount of the acid or base is more preferably 0.001 to 5 mol relative to 1 mol of the hydrolyzable group. Moreover, since the surface hardness of the obtained anti-fogging film tends to be better when the acid is used than when the base is used, it is more preferable to use the acid.

(5) Solvent Examples of the solvent include water, methyl alcohol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, 1,2-propanediol, cyclohexanol, N, N-dimethylformamide, dimethyl sulfoxide and the like. It is done. From the viewpoints of compatibility and safety, ethyl alcohol is preferred. Moreover, it is good also as a mixed solvent using a some solvent.

(6) Other raw materials As a raw material of the coating solution for forming an antifogging film of the present invention, a quaternary ammonium salt or a quaternary phosphonium salt may be further mixed. The quaternary ammonium salt or quaternary phosphonium salt promotes a crosslinking reaction between the carboxyl group of the copolymer represented by the general formula [1] and the epoxy group of the epoxy group-containing silane compound. Yes, it may itself be a part of the antifogging film.

  Examples of the quaternary ammonium salt include triethylbenzylammonium chloride, trimethylcetylammonium bromide, tetrabutylammonium bromide, trimethylbenzylammonium chloride and the like. The quaternary phosphonium salts include tetrabutylphosphonium bromide, butyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, methyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetraparamethyl. Examples thereof include phenyl borate, tetraphenylphosphonium thiocyanate, and tetrabutylphosphonium decanoate. Among them, ethyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, and the like, which are excellent in heat resistance and the effect of promoting the crosslinking reaction, are preferable.

  The quaternary ammonium salt or quaternary phosphonium salt is preferably added in an amount of 0.1 to 10 moles per mole of the epoxy group-containing silane compound. When the addition amount is less than 0.1 mol, the crosslinking reaction promoting effect tends to be small, and the surface hardness, heat resistance, acid resistance, and alkali resistance of the resulting antifogging film may be lowered. On the other hand, even if the added amount exceeds 10 mol, the crosslinking reaction promoting effect does not change so much, which is not preferable from the viewpoint of cost.

  The raw material of the coating solution for forming an antifogging film of the present invention may further contain a curing agent. The curing agent accelerates the reaction of the epoxy group and accelerates the curing of the coating film in the curing step described later, and may itself be a part of the antifogging film. Examples of the curing agent include amine compounds, imidazole compounds, and organometallic compounds. A plurality of curing agents may be added. Among the above curing agents, polyoxyalkylene triamine (for example, trade name “T403 manufactured by Mitsui Chemicals Fine Co., Ltd.” is obtained because the epoxy group reactivity promoting effect, the heat resistance of the antifogging film after curing, and the surface hardness are improved. , Etc.), polyoxyalkylene diamines (for example, trade name “D230” manufactured by Mitsui Chemicals Fine Co., Ltd.), and dibutyltin diacetate and bis (acetoxydibutyltin) oxide that favorably accelerate the curing of the coating film in the curing process , Dibutyltin bis (acetylacetonate), dibutyltin bis (maleic acid monobutyl ester), dioctyltin bis (maleic acid monobutyl ester), diisopropoxytitanium bis (acetylacetonate), titanium tetra (acetylacetonate), diocta Noxytitanium dioctanoate, diisotop Pokishichitanbisu (ethylacetoacetate) and the like are preferable.

  Further, the raw material of the coating solution for forming an antifogging film of the present invention may further contain fine particles. When fine particle components such as inorganic fine particles and organic fine particles are contained, the presence of the fine particle components in the resulting anti-fogging film may cause liquid contaminants attached to a part of the anti-fogging film surface. Even if it is absorbed and taken in, the film expansion of the part to which the contaminant has adhered is suppressed, so the difference in film thickness from the part to which the substance has not adhered is difficult to increase. This is preferable because visual distortion is less likely to occur. The fine particles are preferably colloidal particles uniformly dispersed in the liquid. For example, “Methanol Silica Sol”, “MA-ST-MS”, “IPA-ST”, “IPA-ST-MS” manufactured by Nissan Chemical Co., Ltd. ”,“ IPA-ST-L ”,“ IPA-ST-ZL ”,“ IPA-ST-UP ”,“ EG-ST ”,“ NPC-ST-30 ”,“ MEK-ST ”,“ MEK-ST ” -MS "," MIBK-ST "," XBA-ST "," PMA-ST "," DMAC-ST "," ST-20 "," ST-30 "," ST-40 "," ST-C ”,“ ST-N ”,“ ST-O ”,“ ST-S ”,“ ST-50 ”,“ ST-20L ”,“ ST-OL ”,“ ST-XS ”,“ ST-XL ”, "ST-YL", "ST-ZL", "QAS-40", "LSS-35", "LSS- 5, “ST-UP”, “ST-OUP”, “ST-AK”, “AT-20”, “AT-30”, “AT-40”, “AT-50”, “AT-50” manufactured by ADEKA “AT-20N”, “AT-20A”, “AT-30A”, “AT-20Q”, “AT-300”, “AT-300S”, “PL-1”, “PL-3” manufactured by Fuso Chemical Industries, Ltd. ”,“ PL-70 ”,“ PL-20 ”,“ PL-1-PA ”,“ PL-1-MA ”, and the like. The fine particles preferably have an average particle size of 5 to 100 nm obtained by measuring the particle size by the BET method. If it is less than 5 nm, the effect of reducing the film expansion tends to be small, such being undesirable. If it exceeds 100 nm, it functions as a light scattering center and tends to increase the haze of the film, which is not preferable. More preferably, it is 10-80 nm. Moreover, it is preferable to contain the microparticles | fine-particles contained in an antifogging film so that it may become 50 mass parts or less by solid content with respect to 100 mass parts of solid content of an antifogging film. If it exceeds 50 parts by mass, the water absorption of the resulting antifogging film tends to decrease, such being undesirable. A more preferable content of the fine particles is 3 to 30 parts by mass with respect to 100 parts by mass of the solid content of the antifogging film.

  Further, the coating solution for forming an antifogging film of the present invention includes a known surfactant, antioxidant, ultraviolet absorber, light stabilizer, infrared absorber, flame retardant, and the like, as long as the object of the present invention is not impaired. Components such as an antihydrolysis agent, an antifungal agent, inorganic fine particles such as oxide fine particles, and organic fine particles may be contained. Further, the coating solution for forming an antifogging film of the present invention may contain a leveling agent as a raw material. When the leveling agent is contained, the surface smoothness of the coating film is improved when the antifogging film-forming coating solution is applied to the substrate, so that the surface of the coating film obtained as a result is easily smooth. Thus, when the surface is a smooth coating, there is little catching on the surface of the film when evaluating the surface hardness, and thus a more excellent surface hardness may be achieved. Examples of the leveling agent include a silicon-based surface conditioner and an acrylic-based surface conditioner. For example, BYK306, BYK307, BYK333, BYK337, BYK345, BYK346, BYK347, and the like manufactured by BYK Chemie Japan are listed. Of these, silicon-based surface conditioners such as BYK306, BYK307, and BYK333 are preferable. The above components are originally represented by the copolymer represented by the general formula [1], the epoxy group-containing silane compound, the compound represented by the general formula [3], and the general formula [4]. At least one metal oxide precursor selected from the group consisting of the above compounds, at least one selected from the group consisting of hydrolysates of the metal oxide precursors, and condensates of the metal oxide precursors, It may be contained in an acid or base or a solvent, or may be added in the coating solution preparation step for forming an antifogging film or in a subsequent operation, so as not to affect the reaction. It is preferable that it is added in the coating liquid preparation process for antifogging film formation and subsequent operation.

(7) About conditions of coating liquid preparation process for antifogging film formation In the coating liquid preparation process for antifogging film formation, the conditions at the time of mixing the raw material mentioned above are not specifically limited, The liquid temperature of a liquid mixture is 0 degreeC or more. It is preferably carried out at a temperature equal to or lower than the boiling point of the solvent. When it is carried out in a closed container, it may be in a pressurized state. In addition, the boiling point of said solvent means the boiling point of the solvent with most content in a mixed solvent, when this solvent is a mixed solvent. Although said mixing time is not specifically limited, It is preferable to carry out for about 1 minute-24 hours.

In the coating solution preparation step for forming the antifogging film, as a raw material, at least,
(I) a copolymer represented by the above general formula [1];
(Ii) an epoxy group-containing silane compound represented by the general formula [2],
(Iii) At least one metal oxide precursor selected from the group consisting of the compound represented by the general formula [3] and the compound represented by the general formula [4], and hydrolysis of the metal oxide precursor At least one selected from the group consisting of a decomposition product and a condensate of the metal oxide precursor;
(Iv) an acid or base;
(V) a solvent,
For a total amount of 100% by mass of (i) to (iii),
A coating solution for forming an antifogging film is prepared by mixing at a ratio of (i) 10 to 80% by mass, (ii) 5 to 60% by mass, and (iii) 3 to 80% by mass.
For a total amount of 100% by mass of (i) to (iii),
When (i) is less than 10% by mass, the antifogging property of the antifogging film is insufficient.
When (i) exceeds 80% by mass, the surface hardness of the antifogging film is insufficient.
(I) is preferably 25 to 75% by mass.
When (ii) is less than 5% by mass, the surface hardness of the antifogging film is insufficient.
When (ii) exceeds 60% by mass, the surface hardness or antifogging property of the antifogging film is insufficient.
(Ii) is preferably 10 to 50% by mass.
When (iii) is less than 3% by mass, the surface hardness of the antifogging film is insufficient.
When (iii) exceeds 80% by mass, the antifogging property of the antifogging film is insufficient.
(Iii) is preferably 5 to 70% by mass.

  In addition, after the above-described antifogging film forming coating liquid preparation step and before the antifogging film forming coating liquid coating step, the coating liquid is concentrated or further added with a solvent, whereby the coating liquid is added. You may perform operation which adjusts solid content concentration and viscosity of.

  In order to adjust the solid content concentration and the viscosity, the solvent to be added may be the same as described in the coating solution preparation step for forming the antifogging film.

  By the operation after the above-described coating solution preparation step for forming an antifogging film, a coating solution for forming an antifogging film whose solid content concentration and viscosity are adjusted is obtained. It is preferable that the solid content concentration of the coating solution for forming an antifogging film is 10 to 60% by mass. When the solid content is within the range, the film thickness of the antifogging film can be easily controlled when the antifogging film is formed. The viscosity of the coating solution for forming an antifogging film is preferably 20 to 200 mPa · s at 25 ° C. in a measuring method based on, for example, JIS Z 8803. When the viscosity is within the range, the leveling property of the coating film is good in the coating solution coating step for forming an antifogging film, which will be described later, and as a result, the film forming property is good. In addition, well-known methods, such as heating concentration and deaeration concentration, are mentioned as concentration which may be performed by operation after said coating liquid preparation process for anti-fogging film formation. In addition, when the coating solution for forming an antifogging film having the above-described solid content concentration and viscosity is obtained in the coating solution forming process for forming an antifogging film, the subsequent concentration or further solvent is used. You may abbreviate | omit the operation which adjusts solid content concentration and a viscosity by adding.

2. The antifogging article of the present invention is an antifogging article having a base material and an antifogging film formed on the surface of the base material, and at least the composition as described above. An antifogging film forming coating solution, an antifogging film forming coating solution preparing step, applying the antifogging film forming coating solution onto the substrate surface, an antifogging film forming coating solution step, It is obtained through a curing process in which the coating film after the coating liquid coating process for forming a cloudy film is cured by exposure to superheated steam. Since the anti-fogging film of the present invention has good adhesion to the base material, there is no need to previously provide a primer layer on the base material, which has the advantage that the configuration can be simplified. However, the antifogging article may be an antifogging article having a base material, a primer layer formed on the surface of the base material, and an antifogging film formed on the surface of the primer layer. Forming a primer layer comprising a silane coupling agent on the surface, forming a primer layer, applying the antifogging film forming coating liquid on the primer layer, applying an antifogging film forming liquid, and the antifogging film It may be obtained through a curing step in which the coating film after the forming coating solution coating step is cured by exposure to superheated steam.

  Examples of the substrate include those having light transmittance, light reflectivity, or glossiness, and the visibility, appearance, and design properties are significantly impaired by fogging.

  As a typical base material having optical transparency, glass is used. The glass is a plate glass usually used for automobiles, architectural and industrial glasses, and is a plate glass by a float method, a duplex method, a roll-out method, etc., and the production method is not particularly limited. As glass types, it can be used for various colored glasses such as clear, green and bronze, various functional glasses such as UV, IR cut glass and electromagnetic shielding glass, netted glass, low expansion glass, zero expansion glass and fireproof glass. Examples thereof include glass, tempered glass, glass similar to them, laminated glass, and multilayer glass. In addition to the above plate glass, for example, a resin film such as polyethylene terephthalate, a resin plate such as polycarbonate and acrylic, and the like can also be mentioned.

  Moreover, as a typical base material having light reflectivity, a mirror, a metal, a metal-plated article, and the like can be given.

  Moreover, as a typical base material having gloss, a metal, a metal-plated article, ceramics, and the like can be given.

  Various molded bodies, such as a flat plate and a bending board, can be used for said base material. The plate thickness is not particularly limited, but is preferably 1.0 mm or more and 10 mm or less. For example, the window material for a vehicle is preferably 1.0 mm or more and 5.0 mm or less. In addition, it is preferable that the base material is cleaned in advance and dried to have a clean surface.

  Examples of the compound forming the primer layer include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N Examples include silane coupling agents such as 2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  As a method of applying the antifogging film forming coating liquid on the substrate in the antifogging film forming coating liquid coating step, dip coating, flow coating, spin coating, roll coating, spray coating, nozzle coating, Known methods such as screen printing, flexographic printing, hand-coating method, ink jet method and the like can be mentioned.

  The substrate may be held at a temperature of 10 to 300 ° C. after the coating solution coating step for forming the antifogging film and before the curing step, and the coating film may be dried in advance to be in a tack-free state. Hereinafter, this process is referred to as “drying process”. If the coating film is tack-free by the drying process, even if water droplets adhere to the coating film surface due to condensation when the substrate is exposed to superheated steam in the subsequent curing process, the smoothness of the coating film obtained Is preferable because it is difficult to damage. Furthermore, it is more preferable that the surface temperature of the substrate is raised to 100 ° C. or higher in the drying step and then the substrate is exposed to superheated steam in the curing step because condensation hardly occurs on the coating film surface. However, it is not preferable to perform the drying step at a temperature higher than 300 ° C. because the material itself forming the antifogging film may be deteriorated.

  The drying step may be performed while being held in a laboratory environment or may be performed while being held in a heating environment. The heating method is not particularly limited, and examples thereof include a method of heating in a hot air circulating furnace, heating by infrared rays, heating by microwaves, and the like, and these may be combined. Moreover, you may implement a drying process in the apparatus same as the apparatus used by the hardening process of a post process. If it is the method of performing a drying process and a hardening process continuously, it will be easy to transfer to a hardening process, maintaining the surface temperature of the base material at the time of heating at a drying process.

3. Curing Step The method of curing the coating film in the curing step is a method of exposing the coating film to superheated steam. As the superheated steam, it is possible to use water or a liquid such as a mixed liquid of water and alcohol heated to a boiling point or higher (equal boiling point in the case of a mixed liquid). Among these, superheated steam is preferable from the viewpoint of safety and environmental load. Since the temperature of the base material and the amount of vapor to be brought into contact with the coating surface are likely to be stable, it is preferable to perform the curing step in the chamber. The temperature of the superheated steam is preferably 100 to 300 ° C. If it is less than 100 ° C., the curing rate is slow and the curing tends to take time, which is not preferable. On the other hand, if it exceeds 300 ° C., the material for forming the antifogging film itself may deteriorate, which is not preferable. More preferably, it is 100-200 degreeC. Further, the pressure of the superheated steam to be supplied is preferably from atmospheric pressure to 0.5 MPa, and more preferably from atmospheric pressure to 0.2 MPa.

4). Antifogging article The thickness of the antifogging film of the antifogging article of the present invention is preferably 5 to 100 µm. If it is less than 5 μm, there is a tendency that sufficient water absorption performance is not imparted to the antifogging film, which is not preferable. On the other hand, if it exceeds 100 μm, optical distortion is likely to occur in the antifogging film, and productivity may be lowered, which is not preferable.

  The pencil hardness based on JIS K 5600 on the antifogging film surface of the present invention is preferably 3H or more. If it is 3H or more, it can be said that the antifogging film has a surface hardness that can withstand actual use. More preferably, it is 4H or more.

It is preferable that the water absorption of the unit area at the time of water absorption saturation of the antifogging film of the antifogging article of the present invention is 0.1 to 5 mg / cm ² . When the amount of water absorption is within the above range, the antifogging film has sufficient water absorption performance, and thus the antifogging article having the antifogging film tends to exhibit sufficient antifogging properties. Further, the antifogging film tends to have good surface hardness. More preferably, the water absorption is 0.1 to 3 mg / cm ² .

  Hereinafter, the present invention will be described specifically by way of examples. In addition, quality evaluation was performed by the method shown below for the anti-fogging articles (hereinafter sometimes referred to as “samples”) obtained in the examples and comparative examples.

[Thickness of anti-fogging film]
The film thickness of the antifogging film formed on the substrate was measured using a stylus type surface roughness meter (manufactured by Kosaka Laboratory, Surfcoder ET-4000A).

[Pencil hardness]
The pencil hardness of the antifogging film was measured according to JIS K 5600. The pencil hardness is from the softest (low hardness) “6B” to “6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H,. In this order, the level of harder (higher hardness) is set, and it can be said that the higher the pencil hardness (the higher the hardness), the better the surface hardness. In particular, when the pencil hardness of the antifogging film is 3H or more, it can be said that the antifogging film has a surface hardness that can withstand actual use.

[35 ° C water vapor defogging]
A sample was placed on the top of a tank filled with 35 ° C. saturated steam with the antifogging film surface facing the tank, and the time until cloudiness occurred was measured. From the viewpoint of achieving a good balance between the antifogging property and the surface hardness of the antifogging film, it is preferable that the time until fogging is 10 to 40 seconds in the test.

[Unit area water absorption at the time of water absorption saturation of the anti-fogging film]
The mass (a) of the antifogging article after being held in a drying furnace at a temperature of 80 ° C. for 2 hours is measured, and 35 ° C. saturated water vapor is brought into contact with the antifogging film for 60 minutes to cause fogging on the entire surface exposed to the vapor. The antifogging film was saturated with water absorption. Then, after wiping off the water droplets on the antifogging film surface, the mass (b) of the antifogging article was measured. The value obtained by the calculation formula of “(b−a) / steam exposure area” was defined as the unit area water absorption at the time of water absorption saturation of the antifogging film. The value (a) here corresponds to that in a state where the antifogging film does not absorb water. If the water absorption of the unit area is 0.1 to 5 mg / cm ² , the antifogging article tends to exhibit sufficient antifogging properties, and the antifogging film tends to have good surface hardness.

[Example 1]
(Preparation of base material)
As the substrate, float glass having a thickness of 3 mm and 100 mm square was used. The surface of the substrate was polished with ceria fine particles, washed by brushing and dried.
(Preparation process for coating solution for forming antifogging film)
First, a copolymer represented by the general formula [1] was synthesized. N, N-diethylacrylamide (hereinafter sometimes referred to as “DEAA”) and acrylic acid (hereinafter sometimes referred to as “AA”) are used as raw materials, and DEAA / AA = 1.4 in molar ratio. /1.0 to give a copolymer having a weight average molecular weight of 90,000 (copolymer represented by the above general formula [1]). In the copolymer, the group represented by X in the general formula [1] corresponds to a —C (═O) N (C ₂ H ₅ ) ₂ group, and the group represented by Y corresponds to a carboxyl group. . A and b in the general formula [1] are abundance ratios of a repeating structural unit having a —C (═O) N (C ₂ H ₅ ) ₂ group and a repeating structural unit having a carboxyl group, and were used as raw materials. _{-C (= O) N (C} 2 H 5) can be calculated by the molar ratio of AA with DEAA a carboxyl group having ₂ group, a: b = 1.4: 1.0.
Next, 1.70 g of 3-glycidyloxypropyltrimethoxysilane (hereinafter sometimes referred to as “GPTMS”) as the compound represented by the general formula [2] with respect to 1.50 g of the copolymer. 1.04 g of tetraethoxysilane (hereinafter sometimes referred to as “TEOS”) as the compound represented by the above general formula [3], 0.21 g of 1N HNO _3, and butyltriphenyl as the quaternary phosphonium salt Add 0.02 g of phosphonium bromide (hereinafter sometimes referred to as “BTPPB”), add 4.30 g of methanol (hereinafter sometimes referred to as “MeOH”) as a solvent, and in a sealed container at room temperature. Stir for 2 hours. In addition, (i) the copolymer represented by the general formula [1], (ii) the epoxy group-containing silane compound represented by the general formula [2], and (iii) the general formula [3] (I) was 50 mass%, (ii) was 40 mass%, and (iii) was 10 mass% with respect to 100 mass% of the total amount of the compound represented. Further, (iv) was 0.005 mol when the hydrolyzable group contained in the coating solution was 1 mol.
Further, 0.08 g of BYK333 was added as a leveling agent to prepare a coating solution for forming an antifogging film. The resulting antifogging film-forming coating solution had a solid content concentration of 33% by mass, and the viscosity at 25 ° C. was 80 mPa · s in the measuring method based on JIS Z 8803.
(Anti-fogging film forming coating solution coating process to curing process)
The coating solution for forming an antifogging film prepared above was applied onto the substrate by a spin coating method. The substrate was placed in an electric furnace maintained at 150 ° C. for 15 minutes, and the coating film was dried to a tack-free state (drying process), and then exposed to superheated steam at 180 ° C. for 15 minutes at atmospheric pressure. An antifogging film was formed by curing to obtain an antifogging article.

  For each example and comparative example, Table 1 shows the coating solution for forming the antifogging film and the preparation conditions of the antifogging article, and Table 2 shows the quality evaluation results of the obtained antifogging articles.

[Examples 2 to 12]
A copolymer represented by the general formula [1] used in the coating solution preparation step for forming an antifogging film in Example 1 (X group, Y group, a: b ratio, weight average molecular weight of the compound), general The epoxy group-containing silane compound represented by the formula [2], the molar amount of the epoxy group relative to 1 molar amount of the carboxyl group, the metal oxide precursor, the hydrolyzate of the metal oxide precursor, and the metal oxide precursor At least one selected from the group consisting of condensates of the body, acid or base, solvent, and the superheated steam temperature in the curing process of the antifogging film were changed. Articles were prepared and evaluated.

In the table, the repeating structure in which the X group is represented by “—C (═O) N (CH ₃ ) ₂ ” is a structure formed using N, N-dimethylacrylamide as a raw material, and the Y group Is represented by “—C (═O) OC ₂ H ₄ O (C═O) C ₂ H ₄ C (═O) OH”, and succinic acid mono (2-acryloyloxyethyl) is used as a raw material. “(ECH) ETMS” means 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, “MTES” means methyltriethoxysilane, and “IPA” means isopropyl. Means alcohol.

[Example 13]
Except that the quaternary phosphonium salt and the leveling agent were not used as raw materials for the coating solution for forming the antifogging film of Example 1, and MeOH was further added to the resulting coating solution to adjust the solid content concentration and viscosity. An antifogging article was prepared and evaluated in the same manner as in Example 1. In addition, the solid content concentration of the obtained coating solution for forming an antifogging film was 23% by mass, and the viscosity at 25 ° C. was 60 mPa · s in the measuring method based on JIS Z 8803.

[Example 14]
An antifogging article was prepared and evaluated in the same manner as in Example 1 except that the quaternary phosphonium salt was not used as a raw material for the coating solution for forming the antifogging film of Example 1.

[Example 15]
Example 1 except that the leveling agent was not used as a raw material for the coating solution for forming an antifogging film of Example 1, and MeOH was further added to the resulting coating solution to adjust the solid content concentration and viscosity. An antifogging article was prepared and evaluated in the same manner. In addition, the solid content concentration of the obtained coating solution for forming an antifogging film was 23% by mass, and the viscosity at 25 ° C. was 60 mPa · s in the measuring method based on JIS Z 8803.

[Comparative Example 1]
An antifogging article was prepared and evaluated in the same manner as in Example 1 except that the copolymer represented by the general formula [1] was not used. Cracks were partially generated in the antifogging film of the obtained antifogging article. Moreover, antifogging property could not be confirmed with the antifogging film.

[Comparative Example 2]
Attempts were made to produce an antifogging article by the same operation as in Example 1 except that a compound having a ratio of a: b of the compound of 0: 1 was used as the copolymer represented by the general formula [1]. And evaluated. The resulting antifogging article was insufficient in antifogging properties.

[Comparative Example 3]
As the copolymer represented by the general formula [1], an antifogging article was prepared in the same manner as in Example 1 except that a compound having an a: b ratio of 1: 0 was used. And evaluated. The antifogging film of the obtained antifogging article had insufficient pencil hardness.

[Comparative Example 4]
An antifogging article was prepared and evaluated in the same manner as in Example 1 except that the epoxy group-containing silane compound represented by the general formula [2] was not used. The antifogging film of the obtained antifogging article had insufficient pencil hardness.

[Comparative Example 5]
An antifogging article was prepared and evaluated in the same manner as in Example 1 except that the compound represented by the general formula [3] was not used. The antifogging film of the obtained antifogging article had insufficient pencil hardness.

[Comparative Example 6]
An attempt was made to produce an antifogging article by the same operation as in Example 1 except that no acid was used. However, the hydrolysis reaction and the polycondensation reaction are insufficient, the compatibility of the raw material components is not obtained, and the coating solution for forming the antifogging film is a non-uniform solution. The film of the obtained anti-fogging article was also cloudy and could not be evaluated for quality.

[Comparative Example 7]
An attempt was made to produce an antifogging article by the same operation as in Example 1 except that the heating with 180 ° C. was carried out in an electric furnace for 15 minutes after the drying step without curing with superheated steam. The antifogging film of the obtained antifogging article had insufficient pencil hardness.

As is clear from Tables 1 and 2, in Examples 1 to 15 in which the coating solution for forming an antifogging film having the composition described above was used and curing with superheated steam was performed, the antifogging article obtained was prevented It was found that the anti-fogging property and surface hardness of the cloud film were excellent.
In addition, in the coating solution for forming an antifogging film, Example 1 in which an acid (1N HNO ₃ or 1N CH ₃ COOH) is used as an acid or a base rather than Example 12 in which a base (1N NH ₃ ) is used. Example 9 was found to have better surface hardness.
Further, as a raw material of the coating solution for forming an antifogging film, Example 1 using a quaternary phosphonium salt has better surface hardness than Examples 13 and 14, which did not use a quaternary phosphonium salt. I found out.
Moreover, as a raw material of the coating liquid for forming an antifogging film, Example 1 using a leveling agent has a surface hardness superior to that of Examples 13 and 15 in which a leveling agent is not used. all right.
In Examples 13 and 15, since the coating solution was diluted, the solid content concentration was lower than that in Example 1 and the viscosity was small. Therefore, the film thickness of the obtained antifogging film was thin (10 μm). As a result, although it appears that the antifogging property is low, the antifogging properties of Examples 13 and 15 are comparable to the antifogging property of Example 1 when converted to the same film thickness of 15 μm as Example 1. It is.

  On the other hand, in Comparative Examples 1 to 6 in which a coating liquid deviating from the composition described above was prepared and an antifogging article was attempted to be produced using the coating liquid, the resulting film had poor antifogging properties and surface hardness. It was inferior because it was sufficient or the film obtained was cloudy.

Moreover, in the comparative example 7 which did not harden | cure by superheated steam, the surface hardness of the film obtained was inadequate and was inferior.

Claims (20)

A method for producing an antifogging article having an antifogging film formed by applying a coating solution for forming an antifogging film on the surface of the base material and the base material, and curing the coated film after coating,
The manufacturing method of the anti-fogging article | item characterized by having the following processes at least.
(A) As a raw material, at least
(I) a copolymer represented by the following general formula [1];
(Ii) an epoxy group-containing silane compound represented by the following general formula [2];
(Iii) At least one metal oxide precursor selected from the group consisting of a compound represented by the following general formula [3] and a compound represented by the following general formula [4], hydrolysis of the metal oxide precursor At least one selected from the group consisting of a decomposition product and a condensate of the metal oxide precursor;
(Iv) an acid or base;
(V) a solvent,
For a total amount of 100% by mass of (i) to (iii),
(I) 10-80 mass%, (ii) 5-60 mass%, (iii) The antifogging film formation coating liquid prepared by mixing in the ratio of 3-80 mass% is obtained. Coating solution preparation process,
(B) A coating liquid application step for forming an antifogging film, wherein the coating liquid for forming an antifogging film is applied to the surface of a substrate.
(C) A curing step in which the coating film after the coating solution coating step for forming the antifogging film is cured by exposing it to superheated steam.

(In the formula [1], R ¹ and R ² are a hydrogen group or a methyl group, R ³ is a hydrogen group or an alkyl group having 1 to 5 carbon atoms, and X is —C (═O). —NR ⁴ (wherein R ⁴ is an alkyl group having 1 to 4 carbon atoms), at least one group selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or an amide group, an amino group, and a sulfonic acid Y is a monovalent organic group composed of at least one group selected from the group consisting of a group and a hydroxyl group and an aliphatic hydrocarbon group, and Y is a carboxyl group or —R ⁵ —C (═O) —. R ⁵ is a group represented by OH, and R ⁵ represents a divalent aliphatic hydrocarbon group, or at least one group selected from the group consisting of an ester group, an ether group, and an amide group, and an aliphatic hydrocarbon group. A and b are a: b = 0.7-2. 5: is a number from 1.0 Note that the order of the repeating units of the formula [1] is not particularly limited)..
[R ⁶ (CH ₂ O) _c (CH ₂ ) _d ] _e Si (R ⁷ ) _f (Z ¹ ) _4-ef [2]
(In the formula [2], R ⁶ is at least one group selected from an epoxy group, a glycidoxy group, and a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, and R ⁷ is a carbon number. 1 to 3 alkyl groups, Z ¹ is at least one group selected from the group consisting of alkoxy groups and hydroxy groups, c and d are each 0 to 3, e is 1 or 2, f is 0 or 1.)
(R ⁸ ) _g M (Z ² ) _h-g [3]
(In the formula [3], R ⁸ is a monovalent organic group, Z ² is independently an alkoxy group, a hydroxy group, a halogen element, an oxygen element, a halide ion, NO ₃ ^— and CH ₃ COO ^—. At least one selected, M is at least one element selected from the group consisting of Si, Zr, Al and Ti, g is an integer of 0 to 3, h is 3 or 4, h -G is an integer of 1-4.)
(R ⁹ ) _j M (Z ³ ) _ij [4]
(In the formula [4], R ⁹ is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, Z ³ is an alkoxy group or a halogen element, and M is a group consisting of Si, Zr, Al and Ti. And j is an integer of 0 to 4, i is 3 or 4, and ij is an integer of 0 to 4.) The method for producing an antifogging article according to claim 1, wherein the copolymer represented by the general formula [1] is a copolymer represented by the following general formula [5].

(In Formula [5], X, a, and b are the same as in Formula [1], m is 0-2, n is 0-3, s is 1-4, and t is 1-4. Note that the order of the repeating structural units in the formula [5] is not particularly limited.) The method for producing an antifogging article according to claim 1 or 2, wherein the copolymer represented by the general formula [1] has a weight average molecular weight of 1,000 to 1,000,000. The method for producing an antifogging article according to any one of claims 1 to 3, wherein the epoxy group-containing silane compound represented by the general formula [2] is a compound represented by the following general formula [6].
^{_{R 10 (CH 2) k Si}} (CH 3) p (OR 11) 3-p [6]
(R ¹⁰ is a glycidoxy group, or a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, R ¹¹ is an alkyl group having 1 to 3 carbon atoms. K is 2 or 3. And p is 0 or 1.) The epoxy group-containing silane compound represented by the general formula [6] is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxy. The method for producing an antifogging article according to claim 4, which is at least one selected from the group consisting of silane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. When Y of the copolymer represented by the general formula [1] contains a carboxyl group,
In the coating solution preparation step for forming the antifogging film,
For 1 mol of carboxyl group
The method for producing an antifogging article according to any one of claims 1 to 5, wherein the epoxy group of the epoxy group-containing silane compound is mixed so as to have an amount of 0.2 to 3 mol. In the coating solution preparation step for forming the antifogging film,
The method for producing an antifogging article according to any one of claims 1 to 6, wherein a quaternary ammonium salt or a quaternary phosphonium salt is further mixed as a raw material of the coating solution for forming an antifogging film. In the coating solution preparation step for forming the antifogging film,
The method for producing an antifogging article according to any one of claims 1 to 7, further comprising mixing a curing agent as a raw material for the coating liquid for forming an antifogging film. In the coating solution preparation step for forming the antifogging film,
The method for producing an antifogging article according to any one of claims 1 to 8, wherein fine particles are further mixed as a raw material for the coating liquid for forming an antifogging film. After the antifogging film forming coating liquid preparation step, before the antifogging film forming coating liquid coating step,
The production of an antifogging article according to any one of claims 1 to 9, wherein the operation of adjusting the solid content concentration and viscosity of the coating solution is performed by concentrating the coating solution or further adding a solvent. Method. The method for producing an antifogging article according to any one of claims 1 to 10, wherein the curing step is curing by exposure to superheated steam at 100 to 300 ° C. As a raw material, at least,
(I) a copolymer represented by the following general formula [1];
(Ii) an epoxy group-containing silane compound represented by the following general formula [2];
(Iii) At least one metal oxide precursor selected from the group consisting of a compound represented by the following general formula [3] and a compound represented by the following general formula [4], hydrolysis of the metal oxide precursor At least one selected from the group consisting of a decomposition product and a condensate of the metal oxide precursor;
(Iv) an acid or base;
(V) a solvent,
For a total amount of 100% by mass of (i) to (iii),
A coating solution for forming an antifogging film obtained by mixing at a ratio of (i) 10 to 80% by mass, (ii) 5 to 60% by mass, and (iii) 3 to 80% by mass.

(In the formula [1], R ¹ and R ² are a hydrogen group or a methyl group, R ³ is a hydrogen group or an alkyl group having 1 to 5 carbon atoms, and X is —C (═O). —NR ⁴ (wherein R ⁴ is an alkyl group having 1 to 4 carbon atoms), at least one group selected from the group consisting of an amino group, a sulfonic acid group, and a hydroxyl group, or an amide group, an amino group, and a sulfonic acid Y is a monovalent organic group composed of at least one group selected from the group consisting of a group and a hydroxyl group and an aliphatic hydrocarbon group, and Y is a carboxyl group or —R ⁵ —C (═O) —. R ⁵ is a group represented by OH, and R ⁵ represents a divalent aliphatic hydrocarbon group, or at least one group selected from the group consisting of an ester group, an ether group, and an amide group, and an aliphatic hydrocarbon group. A and b are a: b = 0.7-2. 5: is a number from 1.0 Note that the order of the repeating units of the formula [1] is not particularly limited)..
[R ⁶ (CH ₂ O) _c (CH ₂ ) _d ] _e Si (R ⁷ ) _f (Z ¹ ) _4-ef [2]
(In the formula [2], R ⁶ is at least one group selected from an epoxy group, a glycidoxy group, and a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, and R ⁷ is a carbon number. 1 to 3 alkyl groups, Z ¹ is at least one group selected from the group consisting of alkoxy groups and hydroxy groups, c and d are each 0 to 3, e is 1 or 2, f is 0 or 1.)
(R ⁸ ) _g M (Z ² ) _h-g [3]
(In the formula [3], R ⁸ is a monovalent organic group, Z ² is independently an alkoxy group, a hydroxy group, a halogen element, an oxygen element, a halide ion, NO ₃ ^— and CH ₃ COO ^—. At least one selected, M is at least one element selected from the group consisting of Si, Zr, Al and Ti, g is an integer of 0 to 3, h is 3 or 4, h -G is an integer of 1-4.)
(R ⁹ ) _j M (Z ³ ) _ij [4]
(In the formula [4], R ⁹ is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, Z ³ is an alkoxy group or a halogen element, and M is a group consisting of Si, Zr, Al and Ti. And j is an integer of 0 to 4, i is 3 or 4, and ij is an integer of 0 to 4.) The coating solution for forming an antifogging film according to claim 12, wherein the copolymer represented by the general formula [1] is a copolymer represented by the following general formula [5].

(In Formula [5], X, a, and b are the same as in Formula [1], m is 0-2, n is 0-3, s is 1-4, and t is 1-4. Note that the order of the repeating structural units in the formula [5] is not particularly limited.) The coating solution for forming an antifogging film according to claim 12 or 13, wherein the copolymer represented by the general formula [1] has a weight average molecular weight of 1,000 to 1,000,000. The coating solution for forming an antifogging film according to any one of claims 12 to 14, wherein the epoxy group-containing silane compound represented by the general formula [2] is a compound represented by the following general formula [6].
^{_{R 10 (CH 2) k Si}} (CH 3) p (OR 11) 3-p [6]
(R ¹⁰ is a glycidoxy group, or a monovalent organic group composed of an epoxy group and an aliphatic hydrocarbon group, R ¹¹ is an alkyl group having 1 to 3 carbon atoms. K is 2 or 3. And p is 0 or 1.) The epoxy group-containing silane compound represented by the general formula [6] is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxy. The coating solution for forming an antifogging film according to claim 15, which is at least one selected from the group consisting of silane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane. When Y of the copolymer represented by the general formula [1] contains a carboxyl group,
For 1 mol of carboxyl group
The coating solution for forming an antifogging film according to any one of claims 12 to 16, wherein the epoxy group of the epoxy group-containing silane compound is mixed so that an amount of the epoxy group is 0.2 to 3 mol. The coating solution for forming an antifogging film according to any one of claims 12 to 17, which is obtained by further mixing a quaternary ammonium salt or a quaternary phosphonium salt as a raw material. The coating solution for forming an antifogging film according to any one of claims 12 to 18, which is obtained by further mixing a curing agent as a raw material. The coating solution for forming an antifogging film according to any one of claims 12 to 19, which is obtained by further mixing fine particles as a raw material.