JP2023118214A - Coating agent for forming anti-fog coating, method for manufacturing anti-fog article, and anti-fog article - Google Patents

Abstract

To provide a coating agent capable of forming an anti-fog coating with excellent antifogging properties, a method for manufacturing an anti-fog article allowing manufacture of anti-fog articles with excellent antifogging properties, and anti-fog articles having an anti-fog coating with excellent antifogging properties.SOLUTION: A coating agent for forming an anti-fog coating comprises (A) a polyisocyanate having two or more isocyanate groups, (H) a block polyisocyanate having two or more block isocyanate groups, (B) a polyol comprising an oxyethylene unit as a repeating unit and having two or more hydroxy groups in a molecule, and (L) a solvent. Also provided are an anti-fog article and a method for manufacturing the anti-fog article that employ the coating agent for forming an anti-fog coating.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to an antifogging film-forming coating agent, a method for producing an antifogging article, and an antifogging article.

In order to ensure the visibility of transparent substrates such as mirrors for bathrooms and washstands, window glass of automobiles and lenses of cameras, it is strongly desired to impart anti-fogging function to the surface of these substrates. ing.

Fogging that occurs on the main surface of a glass substrate such as a mirror or glass is caused by a dew condensation phenomenon in which countless minute water droplets are formed on the surface of the substrate. In order to prevent this fogging, there are hydrophilic coatings that form a uniform water film with countless minute water droplets on the substrate surface, and water-absorbing coatings that exhibit anti-fogging properties by incorporating water vapor and water droplets into the coating. is being investigated on a substrate.

Patent Document 1 describes an anti-fogging article having improved anti-fogging properties by using both a first isocyanate compound and a second isocyanate compound when forming an anti-fogging polyurethane film on a substrate. It is

Japanese Patent Application Laid-Open No. 2021-4350

In Patent Document 1, a first isocyanate compound that tends to make the crosslinked structure of polyurethane loose and a second isocyanate compound that tends to make the crosslinked structure of polyurethane coexist, and the isocyanate compound containing both has a predetermined average functional group number of isocyanate groups. The hardness of the polyurethane film is improved by making the range of

However, the present inventors have found that the combined use of an isocyanate compound and a blocked isocyanate compound can further improve the antifogging properties of a polyurethane film compared to the combined use of two types of isocyanate compounds.

The present disclosure has a coating agent capable of forming an anti-fogging coating with excellent anti-fogging properties, a method for producing an anti-fogging article capable of producing an anti-fogging article with excellent anti-fogging properties, and an anti-fogging coating with excellent anti-fogging properties. An object of the present invention is to provide an anti-fogging article.

The problem of the present disclosure is solved by the following configuration.
<1>
(A) a polyisocyanate having two or more isocyanate groups;
(H) a blocked polyisocyanate having two or more blocked isocyanate groups;
(B) a polyol comprising an oxyethylene unit as a repeating unit and having two or more hydroxy groups in the molecule;
(L) a solvent;
A coating agent for forming an antifogging film, comprising:
<2>
Furthermore, (C) an acrylic resin having two or more hydroxy groups in the molecule,
The coating agent for forming an antifogging film according to <1>, comprising:
<3>
The coating agent for forming an antifogging film according to <1> or <2>, further comprising (F) polytetramethylene ether glycol.
<4>
The coating agent for forming an antifogging film according to any one of <1> to <3>, further comprising (G) a short-chain polyol having a number average molecular weight of 60 to 200.
<5>
Any one of <1> to <4>, wherein the polyol (B) comprises (B1) polyethylene glycol and (B2) a copolymerized polyol comprising an oxyethylene unit and an oxypropylene unit as repeating units. A coating agent for forming an antifogging film.
<6>
The coating agent for forming an antifogging film according to any one of <1> to <5>, further comprising (D) a water repellent agent or (E) a hydrophilic agent.
<7>
The antifogging coating according to <6>, wherein the content of the water repellent agent (D) or hydrophilic agent (E) is 0.001 to 10.0% by mass with respect to 100% by mass of the urethane-forming component. Forming coating.
<8>
n ₍ NCO)/n(OH), which is the ratio of the total number n _(NCO) of isocyanate groups and blocked isocyanate groups in the urethane-forming component to the number n _{( OH)} of hydroxyl groups in the urethane-forming component, is 1. The coating agent for forming an antifogging film according to any one of <1> to <7>, which is 0 to 3.0.
<9>
For forming an antifogging film according to any one of <1> to <8>, wherein the content of the polyisocyanate (A) is 20 to 60% by mass with respect to 100% by mass of the urethane-forming component. Coating agent.
<10>
The coating agent for forming an antifogging film according to any one of <1> to <9>, wherein the mixing ratio of the polyisocyanate (A) and the blocked polyisocyanate (H) is 50:50 to 99:1.
<11>
A method for producing an antifogging article having a substrate and an antifogging coating, comprising:
A step (1) of applying the coating agent for forming an antifogging film according to any one of <1> to <10> to the surface of a substrate to form a coating film;
Step (2) of evaporating the solvent (L) from the coating film and curing the coating film to form an antifogging coating;
A method for manufacturing an anti-fogging article.
<12>
The method for producing an antifogging article according to <11>, wherein the substrate is a glass substrate.
<13>
The method for producing an antifogging article according to <12>, wherein the surface of the glass substrate is coated with a silane coupling agent.
<14>
<11> to <13>, wherein in the step (2), the isocyanate group of the polyisocyanate (A) reacts with the hydroxy group of the polyol (B) to form a polyurethane. A method for producing an antifogging article.
<15>
The method for producing an antifogging article according to any one of <11> to <14>, wherein in the step (2), the coating film is heated at 80 to 170°C.
<16>
An antifogging article having a substrate and an antifogging coating,
The anti-fogging coating is a coating containing a polyurethane resin, which is a cured product of the coating agent for forming an anti-fogging coating according to any one of <1> to <10>,
The film thickness of the antifogging coating is 5 μm to 50 μm,
Anti-fogging article.
<17>
The antifogging article according to <16>, wherein the substrate is a glass substrate.
<18>
The antifogging article according to <17>, wherein the surface of the glass substrate is coated with a silane coupling agent.
<19>
The antifogging article according to any one of <16> to <18>, wherein the antifogging coating has a pencil hardness of 2H or more.

According to the present disclosure, a coating agent capable of forming an anti-fogging coating with excellent anti-fogging properties, a method for producing an anti-fogging article capable of producing an anti-fogging article with excellent anti-fogging properties, and an anti-fogging coating with excellent anti-fogging properties It is possible to provide an antifogging article having

[Coating agent for forming anti-fogging film]
The coating agent for forming an antifogging film of the present disclosure is
(A) a polyisocyanate having two or more isocyanate groups;
(H) a blocked polyisocyanate having two or more blocked isocyanate groups;
(B) a polyol comprising an oxyethylene unit as a repeating unit and having two or more hydroxy groups in the molecule;
(L) a solvent;
Coating agent for forming an antifogging film <(A) a polyisocyanate having two or more isocyanate groups>
(A) A polyisocyanate having two or more isocyanate groups (also referred to as “polyisocyanate (A)”) will be described.

The polyisocyanate (A) serves as a skeleton component of the antifogging coating (also simply referred to as "coating"), and can impart water absorbency and hardness to the coating.

The polyisocyanate (A) is not particularly limited, and examples thereof include compounds having 2 to 5 isocyanate groups. Specific examples include hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and bis(methylcyclohexyl). diisocyanate, toluene diisocyanate, and the like. Furthermore, the polyisocyanate (A) is preferably a compound having 3 or more isocyanate groups, more preferably 3.2 or more.

Further, the polyisocyanate (A) may be a polymer (e.g., dimer, trimer, etc.), or at least one selected from the group consisting of an allophanate structure, an adduct structure, a biuret structure and an isocyanurate structure. It may have a seed structure. For example, it may be a dimer using hexamethylene diisocyanate as a starting material, a compound having an allophanate structure using hexamethylene diisocyanate as a starting material, or a compound having a biuret structure using hexamethylene diisocyanate as a starting material. When the polyisocyanate (A) is a polymer, the number average molecular weight is preferably 100-20,000, more preferably 150-5,000, and particularly preferably 200-2,000.

<(H) Blocked polyisocyanate having two or more blocked isocyanate groups>
The coating agent for forming an antifogging film of the present disclosure preferably further contains a blocked polyisocyanate having two or more (H) blocked isocyanate groups (also referred to as "blocked polyisocyanate (H)").
The blocked polyisocyanate (H) plays a role as a skeleton component of the antifogging coating and can improve the water absorption of the coating.

The blocked isocyanate group is a group in which the isocyanate group is protected with a blocking agent, and the blocking agent is dissociated by heat treatment to regenerate the isocyanate group. It is preferred that the antifogging coating be used without blocking, leaving blocked isocyanate groups in the antifogging coating.
Further, the blocked polyisocyanate (H) preferably has a dissociation temperature of 70°C to 150°C. The dissociation temperature can be determined by thermogravimetric analysis of the blocked polyisocyanate or measurement of the amount of carbon dioxide gas generated by the reaction between the dissociated isocyanate and water.

Although the reason why the coating agent for forming an anti-fogging film of the present disclosure improves water absorption by containing the blocked polyisocyanate (H) has not been elucidated, the present inventors have The amide bond of and the isocyanate group of the polyisocyanate (A) react to allophanatize or biuret to generate a high-molecular-weight polyisocyanate, which is contained in the high-molecular-weight polyisocyanate, derived from the polyisocyanate (A) It is presumed that the isocyanate group that forms reacts with the polyol (B) or the acrylic resin (C) to form a polyurethane having a large network structure, which improves the water absorbency.

The blocked polyisocyanate (H) is not particularly limited, and may be, for example, the isocyanate group of the above-described polyisocyanate (A) protected with a known blocking agent. Blocking agents include compounds having an oxime group (=NOH), a hydroxyl group (-OH) or an imino group (=NH).

Further, the blocked polyisocyanate (H) preferably has an amide bond (--NHCO--) in its molecule.

The number average molecular weight of the blocked polyisocyanate (H) is preferably 100-20,000, more preferably 150-5,000, and particularly preferably 200-2,000.

Block polyisocyanate (H) is commercially available, for example, DIC Barnok DB-980K, Barnok D-550, Asahi Kasei Duranate SBB-70P, Duranate SBN-70D, Duranate MF-K60B, Duranate MF- B60B etc. are mentioned.

<(B) Polyol Having Oxyethylene Units as Repeating Units and Having Two or More Hydroxy Groups in the Molecule>
(B) A polyol having an oxyethylene unit as a repeating unit and having two or more hydroxy groups in the molecule (also referred to as "polyol (B)") will be described.
The polyol (B) can impart water absorbency to the antifogging coating by having oxyethylene units as repeating units.

The polyol (B) is not particularly limited. It is preferable to include both (B2).

The copolymerized polyol (B2) is a polyether obtained by ring-opening polymerization of ethylene oxide and propylene oxide using a phosphazene compound, a Lewis acid compound or an alkali metal compound catalyst as an initiator, followed by block addition or random addition. Polyols can be used. Such polyols are commercially available, and examples thereof include "Toho Polyol PB-4000 (manufactured by Toho Chemical Industry Co., Ltd.)".

The molar ratio of oxyethylene units/oxypropylene units in the copolymerized polyol (B2) may be from 45/55 to 90/10, preferably from 70/30 to 80/20.

The number average molecular weight of the polyol (B) is preferably from 500 to 20,000, more preferably from 1,000 to 15,000, even more preferably from 1,500 to 12,000, and particularly preferably from 2,000 to 6,000.

<(L) Solvent>
(L) The solvent (also referred to as “solvent (L)”) will be described.
As the solvent (L), it is preferable to use an acetate solvent or ketones. Specifically, the acetate solvents include amyl acetate, allyl acetate, isoamyl acetate, isobutyl acetate, isopropyl acetate, ethyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, n-butyl acetate, s- butyl, propyl acetate, benzyl acetate, methyl acetate, methyl cyclohexyl acetate and the like. Ketones include acetylacetone, acetone, isophorone, ethyl-n-butyl ketone, diisobutyl ketone, diisopropyl ketone, diethyl ketone, cyclohexanone, di-n-propyl ketone, methyl oxide, methyl-n-amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, Methylcyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, methyl-n-heptyl ketone, diacetone alcohol, mixtures thereof and the like. Particularly preferred are isobutyl acetate, n-butyl acetate, s-butyl acetate, methyl ethyl ketone and diacetone alcohol.

<(C) Acrylic resin having two or more hydroxy groups in the molecule>
(C) An acrylic resin having two or more hydroxy groups in the molecule (also referred to as “acrylic resin (C)”) will be described.
The acrylic resin (C) is a copolymer of a hydroxyalkyl (meth)acrylate and a copolymerizable monomer such as an alkyl (meth)acrylate. is an ingredient.

Specific examples of the acrylic resin (C) include hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, and N-methylolacrylamide. , styrene, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, acrylo-tolyl, methacrylonitrile, methyl acrylate, ethyl acrylate, acrylate-n- Examples include those obtained by copolymerization with butyl, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and the like.

In addition, amino group-containing monomers such as 2-dimethylaminoethyl methacrylate and tert-butylaminoethyl methacrylate, glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate, amino group-containing monomers such as acrylamide and methacrylamide, and acrylic acid. , methacrylic acid, maleic anhydride, crotonic acid, fumaric acid, itaconic acid, or the like, or those obtained by copolymerizing fumaric acid esters, itaconic acid esters, etc. with the hydroxyl group-containing monomers. can.

The acrylic resin (C) preferably has a number average molecular weight of 500 or more, more preferably 5,000 to 25,000, even more preferably 8,000 to 25,000, and particularly preferably 12,000 to 20,000.

A commercial item can also be used for the acrylic resin (C).
Examples of commercially available acrylic resins (C) include "Acrydic 47-538-BA (manufactured by DIC Corporation)".

<(D) water repellent>
The coating agent for forming an antifogging film of the present disclosure may contain (D) a water repellent agent (also referred to as “water repellent agent (D)”).
The water repellent (D) is a component that imparts antifouling properties to the antifogging coating.
The water repellent (D) is not particularly limited, but preferably contains at least one compound selected from the group consisting of (D1), (D2) and (D3) below.

(D1) has at least one group selected from the group consisting of a hydroxy group, a functional group that produces a hydroxy group by hydrolysis, a carboxy group, an amino group, and an isocyanate group, and a dialkylsiloxane moiety (SiR ₂ O, R is Linear polydialkylsiloxane (also referred to as “compound (D1)”) having an average number of 5 to 400 linear or branched alkyl groups each independently representing a linear or branched alkyl group having 1 to 10 carbon atoms. )
(D2) a fluoroalkylsilane having at least one group selected from the group consisting of a hydroxy group, a functional group that produces a hydroxy group upon hydrolysis, a carboxy group, an amino group, and an isocyanate group, and having a fluorocarbon moiety (“Compound (D2)".)
(D3) a perfluoropolyether having at least one group selected from the group consisting of a hydroxy group, a functional group that produces a hydroxy group upon hydrolysis, a carboxy group, an amino group, and an isocyanate group, and having a fluorocarbon moiety (" Also referred to as "compound (D3)".)
Examples of the functional group that produces a hydroxy group upon hydrolysis in the compounds (D1), (D2) and (D3) include an alkoxy group, preferably a linear or branched alkoxy group having 1 to 6 carbon atoms, specifically Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

(Compound (D1))
Since compound (D1) has a dialkylsiloxane moiety with excellent lubricity, it can impart antifouling properties to the film.
In the compound (D1), the average number of dialkylsiloxane moieties (SiR ₂ O) is preferably 20 to 50 in order to obtain a film having better antifouling properties and durability.
R of SiR ₂ O is preferably a methyl group or an ethyl group, more preferably a methyl group.
As the compound (D1), for example, polydimethylsiloxane represented by the following general formula [1] is preferably used.

一般式［１］中、Ｘ^１及びＸ^２は、それぞれ独立に、一価もしくは二価の官能基を表す。ａ及びｂは、それぞれ独立に、０～３の整数であり、ｎは１０～４００の整数である。ただし、ａ＋ｂは１以上であり、Ｘ^１及びＸ^２の少なくとも１つは、ヒドロキシ基、加水分解でヒドロキシ基を生じる官能基、カルボキシ基、アミノ基、及びイソシアネート基からなる群より選択される少なくとも１つである。

In general formula [1], X ¹ and X ² each independently represent a monovalent or divalent functional group. a and b are each independently an integer of 0-3, and n is an integer of 10-400. However, a + b is 1 or more, and at least one of X ¹ and X ² is at least selected from the group consisting of a hydroxy group, a functional group that produces a hydroxy group by hydrolysis, a carboxy group, an amino group, and an isocyanate group. is one.

Specific examples of monovalent or divalent functional groups represented by X ¹ and X ² include a hydroxy group, an amino group, an epoxy group, a carboxy group, an acryloyl group, an allyl group, a mercapto group, and -C(=O)-OR. ¹ group (R ¹ represents a linear or branched saturated alkyl group having 1 to 4 carbon atoms), -O-C(=O)R ¹ group (R ¹ is -C(=O)-OR ¹ group R ¹ ), -A ¹ -B ¹ group (A ¹ represents a divalent organic group, B ¹ is a hydroxy group, amino group, epoxy group, -C(=O)-OR ¹ group ( R ¹ represents a linear or branched saturated alkyl group having 1 to 4 carbon atoms) or -O-C(=O)R ¹ group (R ¹ is -C(=O)-OR ¹ group of R ¹ )), -A ¹ -C (A ² ) (A ³ B ² ) (A ⁴ B ³ ) group (A ¹ represents a divalent organic group, A ² represents a hydrogen atom or a monovalent A ³ and A ⁴ each independently represent a divalent organic group, B ² or B ³ each independently represents a hydroxy group, an amino group, an epoxy group, a carboxy group, an acryloyl group , allyl group, mercapto group, -C(=O)-OR ¹ group (R ¹ represents a linear or branched saturated alkyl group having 1 to 4 carbon atoms) or -OC(=O)R ¹ group (R ¹ is the same as R ¹ of -C(=O)-OR ¹ group).

(Compound (D2))
The fluorocarbon moiety in compound (D2) is preferably _CF2 or _CF3 .
As the compound (D2), a fluoroalkylsilane having a functional group at one end represented by the following general formula [2], or a fluoroalkyl having a functional group at both ends represented by the following general formula [3] Silane is preferably used.

一般式［２］中、Ｙ^１は、それぞれ独立に、一価の官能基を表す。ｐは１～３の整数であり、官能基の数を表す。ｍは２～６の整数である。ただし、少なくとも１つのＹ^１は、ヒドロキシ基、加水分解でヒドロキシ基を生じる官能基、カルボキシ基、アミノ基、及びイソシアネート基からなる群より選択される少なくとも１つを表す。

In general formula [2], each Y ¹ independently represents a monovalent functional group. p is an integer of 1 to 3 and represents the number of functional groups. m is an integer of 2-6. However, at least one ^Y1 represents at least one selected from the group consisting of a hydroxy group, a functional group that produces a hydroxy group upon hydrolysis, a carboxy group, an amino group, and an isocyanate group.

一般式［３］中、Ｙ^２及びＹ^３は、それぞれ独立に、一価の官能基を表す。ｍは２～６の整数であり、フルオロカーボン部位の数を表す。ｑ及びｒは、それぞれ独立に、１～３の整数であり、一価の官能基の数を表す。ただし、Ｙ^２及びＹ^３の少なくとも１つは、ヒドロキシ基、加水分解でヒドロキシ基を生じる官能基、カルボキシ基、アミノ基、及びイソシアネート基からなる群より選択される少なくとも１つを表す。

In general formula [3], Y ² and Y ³ each independently represent a monovalent functional group. m is an integer from 2 to 6 and represents the number of fluorocarbon moieties. q and r are each independently an integer of 1 to 3 and represent the number of monovalent functional groups. However, at least one of ^Y2 and ^Y3 represents at least one selected from the group consisting of a hydroxy group, a functional group that produces a hydroxy group upon hydrolysis, a carboxy group, an amino group, and an isocyanate group.

Compound (D2) has a fluorocarbon moiety that has excellent antifouling properties and removability against fouling components such as sebum components, fingerprints, and water stains, as well as durability, so it is effective in improving the antifouling properties and durability of the obtained film. play.

In addition, a perfluoroalkyl group (CF ₃ (CF ₂ ) _t-1 -) or a perfluoroalkylene group (-(CF ₂ ) _u -) having 2 to 6 fluorocarbon moieties in the molecule of the compound (D2) is preferred. Increasing the number of fluorocarbon moieties increases the durability of the resulting antifouling coating. t and u represent integers, and the "-" indicates a bond.

(Compound (D3))
The fluorocarbon moiety in compound (D3) is preferably _CF2 or _CF3 .
As the compound (D3), one represented by any one of the following general formulas [4] to [6] is preferable.

一般式［４］中、Ｒｆ１は、式：－Ｃ_ｐＦ_２ｐＯ－（ｐは１～６の整数である。）で表される構造、または、－Ｃ_ｑＦ_２ｑ－（ｑは１～８の整数である。）で表される構造である。Ｚは、それぞれ独立に、炭素数１～６の直鎖もしくは分岐鎖のアルコキシ基を表し、具体的な基は、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等である。Ｒは炭素数が１～１０のアルキル基であり、ａは１～３の整数である。ｎ及びｎ’はそれぞれ１～５の整数、ｍ及びｍ’はそれぞれ０～２の整数である。

In general formula [4], Rf1 is a structure represented by the formula: -C _p F _2p O- (p is an integer of 1 to 6), or -C _q F _2q - (q is 1 to is an integer of 8.). Each Z independently represents a linear or branched alkoxy group having 1 to 6 carbon atoms, and specific groups include methoxy, ethoxy, propoxy, isopropoxy and butoxy. R is an alkyl group having 1 to 10 carbon atoms, and a is an integer of 1 to 3. n and n' are each integers of 1 to 5; m and m' are each integers of 0 to 2;

一般式［５］中、ｒは１～２００の整数を表す。Ｚは、それぞれ独立に、炭素数１～６の直鎖もしくは分岐鎖のアルコキシ基を表し、具体的な基は、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等である。

In general formula [5], r represents an integer of 1-200. Each Z independently represents a linear or branched alkoxy group having 1 to 6 carbon atoms, and specific groups include methoxy, ethoxy, propoxy, isopropoxy and butoxy.

一般式［６］中、ｓは１～１００の整数を表し、ｔは１～１０の整数を表す。Ｚは、それぞれ独立に、炭素数１～６の直鎖もしくは分岐鎖のアルコキシ基を表し、具体的な基は、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等である。

In general formula [6], s represents an integer of 1-100, and t represents an integer of 1-10. Each Z independently represents a linear or branched alkoxy group having 1 to 6 carbon atoms, and specific groups include methoxy, ethoxy, propoxy, isopropoxy and butoxy.

Similarly to compound (D2), compound (D3) has antifouling properties and removability against staining components such as sebum components, fingerprints, and water stains, and has a fluorocarbon moiety that is excellent in durability. Effective in improving stain resistance and durability.

<(E) hydrophilic agent>
The coating agent for forming an antifogging film of the present disclosure may contain (E) a hydrophilic agent (also referred to as “hydrophilic agent (E)”).
Although the hydrophilic agent (E) is not particularly limited, a compound represented by any one of the following general formulas [7] to [9] is preferred.

［一般式［７］中、Ｘは単結合、置換基を有していてもよい炭素数１～１０のアルキレン基、または置換基を有していてもよい炭素数６～１８のアリーレン基のいずれかを示し、Ｙは単結合、エステル結合、アミド結合、スルホン酸エステル結合、スルホン酸アミド結合、エーテル結合のいずれかを示す。ただし、Ｘが単結合の場合は、ＹもＸと一緒になって単結合となる。また、ｎは２～２２の自然数である。］

[In general formula [7], X is a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or an arylene group having 6 to 18 carbon atoms which may have a substituent. Y represents either a single bond, an ester bond, an amide bond, a sulfonate ester bond, a sulfonate amide bond, or an ether bond. However, when X is a single bond, Y also becomes a single bond together with X. Also, n is a natural number from 2 to 22. ]

［一般式［８］中、Ｘは単結合、置換基を有していてもよい炭素数１～１０のアルキレン基、または置換基を有していてもよい炭素数６～１８のアリーレン基のいずれかを示し、Ｙは単結合、エステル結合、アミド結合、スルホン酸エステル結合、スルホン酸アミド結合、エーテル結合のいずれかを示す。ただし、Ｘが単結合の場合は、ＹもＸと一緒になって単結合となる。また、ｎは２～２２の自然数である。］

[In the general formula [8], X is a single bond, an alkylene group having 1 to 10 carbon atoms which may have a substituent, or an arylene group having 6 to 18 carbon atoms which may have a substituent. Y represents either a single bond, an ester bond, an amide bond, a sulfonate ester bond, a sulfonate amide bond, or an ether bond. However, when X is a single bond, Y also becomes a single bond together with X. Also, n is a natural number from 2 to 22. ]

［一般式［９］中、Ｒは炭素数１０～２２の直鎖、分岐鎖、または環状のアルキル基である。］
一般式［７］や一般式［８］の含フッ素化合物は本開示の防曇性物品に対して防汚性の機能を付与し、また、界面活性剤としても作用する。更に、これらの界面活性剤は、水酸基、メルカプト基、アミノ基等のイソシアネート反応性基を有しないものである。なお、防汚性とは、皮脂成分、指紋、水垢等の汚れ成分に対する耐汚染性および汚れ成分に対する除去性をいう。

[In general formula [9], R is a linear, branched or cyclic alkyl group having 10 to 22 carbon atoms. ]
The fluorine-containing compounds represented by general formula [7] and general formula [8] impart an antifouling function to the antifogging article of the present disclosure, and also act as a surfactant. Furthermore, these surfactants are free of isocyanate-reactive groups such as hydroxyl groups, mercapto groups and amino groups. Here, the antifouling property refers to the staining resistance to staining components such as sebum components, fingerprints and water stains, and the removability of the staining components.

In the present disclosure, the fluorine-containing surfactant represented by the general formula [7] and the quaternary ammonium salt represented by the general formula [9] are preferable from the viewpoint of not reducing the hydrophilicity and hardness.

In the quaternary ammonium salt represented by the general formula [9], R is preferably a linear, branched or cyclic alkyl group having 15 to 22 carbon atoms, and a linear, branched or cyclic alkyl group having 16 to 20 carbon atoms. or more preferably a cyclic alkyl group.

A surfactant that is solid at room temperature (eg, the quaternary ammonium salt) may crystallize a small amount of the surfactant present on the surface of the film, making the film cloudy. Therefore, surfactants that are liquid at room temperature (for example, fluorine-containing surfactants represented by general formula [7]) are more preferable. Further, in the fluorine-containing surfactant represented by the general formula [7], in the general formula [7], X and Y are preferably single bonds, and n is preferably a natural number of 8 to 16. , 9 to 13 natural numbers.

<(F) Polytetramethylene ether glycol>
The coating agent for forming an antifogging film of the present disclosure may further contain (F) polytetramethylene ether glycol (also referred to as "polytetramethylene ether glycol (F)"). The number average molecular weight of the polytetramethylene ether glycol (F) is preferably 100-4000, more preferably 500-2000, particularly preferably 800-1200.

<(G) Short-chain polyol having a number average molecular weight of 60 to 200>
The coating agent for forming an antifogging film of the present disclosure may further contain (G) a short-chain polyol having a number average molecular weight of 60 to 200 (also referred to as “short-chain polyol (G)”).

The short chain polyol (G) is a polyol having a short chain length and having a number average molecular weight in the range of 60-200.

By containing the short-chain polyol (G), the hardness of the coating is likely to be improved. The number of hydroxyl groups per molecule of the short-chain polyol (G) may be 2 or 3.

Examples of short-chain polyols (G) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 , 3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol , triethylene glycol, glycerin, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 1,2,6-hexanetriol, alkyl polyols such as 2,2′-thiodiethanol, diethanolamine, triethanol Examples include alkanolamines such as amines, and they can be used alone, as a mixture, or as a copolymer having a number average molecular weight in the range of 60-200.

Among these, ethylene glycol and triethylene glycol are preferable from the viewpoint of improving the hardness of the film, and 1,2-propanediol, 1,2-butanediol, 1,3-butanediol and 2,3-butanediol are preferred. Such short-chain polyols having secondary or tertiary hydroxyl groups, which are less active than primary hydroxyl groups, are preferable from the viewpoint of the stability of the coating solution (prolonged pot life).

<Urethane-forming component>
As used herein, the term “urethane-forming component” refers to, among the components contained in the coating agent for forming an anti-fogging film of the present disclosure, components that are raw materials for forming polyurethane, water repellent (D) and All the components except the hydrophilic agent (E).

Typically, the "urethane-forming component" includes polyisocyanate (A), blocked polyisocyanate (H), polyol (B), acrylic resin (C), Represents polytetramethylene ether glycol (F) and short-chain polyol (G).

The coating agent for forming an antifogging film of the present disclosure contains polyisocyanate (A), blocked polyisocyanate (H), and polyol (B), acrylic resin (C), polytetramethylene ether glycol (F), And when the short-chain polyol (G) is not contained, the "urethane-forming component" is the polyisocyanate (A), the blocked polyisocyanate (H), and the polyol (B).
In other cases as well, the "urethane-forming component" is considered in the same manner as above.

<Content of each component>
The content of the polyisocyanate (A) in the coating agent for forming an antifogging film of the present disclosure is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, based on 100% by mass of the urethane-forming component. more preferably 30 to 50% by mass.

The content of the blocked polyisocyanate (H) in the coating agent for forming an antifogging film of the present disclosure is preferably 2 to 25% by mass, more preferably 5 to 20% by mass, based on 100% by mass of the urethane-forming component. is more preferable, and 5 to 15% by mass is even more preferable.

The mixing ratio of polyisocyanate (A) and blocked polyisocyanate (H) in the coating agent for forming an antifogging film of the present disclosure (the ratio of isocyanate groups derived from polyisocyanate and isocyanate groups derived from blocked polyisocyanate to all isocyanate groups) ratio) is preferably 50:50 to 99:1, more preferably 70:30 to 95:5, even more preferably 75:25 to 93:7.

The content of the polyol (B) in the coating agent for forming an antifogging film of the present disclosure is preferably 25 to 65% by mass, more preferably 30 to 60% by mass, based on 100% by mass of the urethane-forming component. is more preferable, and 40 to 55% by mass is even more preferable.

The content of the solvent (L) in the antifogging film-forming coating agent of the present disclosure is, for example, such that the solid content concentration in the antifogging film-forming coating agent of the present disclosure is 10 to 50% by mass. , can be adjusted. The solid content is all components except the solvent (L) from all the components in the coating agent for forming an antifogging film of the present disclosure, and the solid content concentration is the concentration (content) of the solid content. is.

When the coating agent for forming an antifogging film of the present disclosure contains a water repellent agent (D) or a hydrophilic agent (E), the water repellent agent (D) in the coating agent for forming an antifogging film of the present disclosure or The content of the hydrophilic agent (E) is preferably 0.001 to 10.0% by mass, more preferably 0.005 to 5.0% by mass, relative to 100% by mass of the urethane-forming component. , more preferably 0.01 to 3.0% by mass.

When the coating agent for forming an antifogging film of the present disclosure contains polytetramethylene ether glycol (F), the content of polytetramethylene ether glycol (F) in the coating agent for forming an antifogging film of the present disclosure is preferably 5 to 15% by mass, more preferably 8 to 12% by mass, based on 100% by mass of the urethane-forming component.

When the coating agent for forming an antifogging film of the present disclosure contains a short-chain polyol (G), the content of the short-chain polyol (G) in the coating agent for forming an antifogging film of the present disclosure is It is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and even more preferably 3 to 8% by mass, based on 100% by mass of the component.

<n _(NCO) /n _(OH) >
n _(NCO) /n, which is the ratio of the number n _(NCO) of isocyanate groups in the urethane-forming component and the number n _(OH) of hydroxyl groups in the urethane-forming component in the coating agent for forming an antifogging film of the present disclosure _(OH) is preferably 1.0 to 3.0, more preferably 1.1 to 2.5, even more preferably 1.2 to 2.0.
The number of blocked isocyanate groups is also included in the number n of isocyanate groups (NCO).

<Other components and their content>
The coating agent for forming an anti-fogging film of the present disclosure is cured to increase the curing speed when forming an anti-fogging film by curing the coating film formed by applying the coating agent for forming an anti-fogging film. It may contain a catalyst.

When the coating agent for forming an antifogging film of the present disclosure contains a curing catalyst, the content of the curing catalyst in the coating agent for forming an antifogging film of the present disclosure is It is preferably 0.001 to 0.5% by mass.

Examples of curing catalysts include organic metal compounds such as organic tin compounds, organic titanium compounds, organic zirconium compounds and organic bismuth compounds, and amine compounds.

The coating agent for forming an antifogging film of the present disclosure may contain a leveling agent that promotes the smoothness of the coating film on the substrate.

When the coating agent for forming an anti-fogging film of the present disclosure contains a leveling agent, the content of the leveling agent in the coating agent for forming an anti-fogging film of the present disclosure is It is preferably 0.01 to 0.50% by mass with respect to the coating agent.

The coating agent for forming an antifogging film of the present disclosure may contain additives that improve the heat resistance, weather resistance, and water resistance of the coating film.

Examples of the additives include hindered amine-based light stabilizers, benzotriazole-based ultraviolet absorbers, hindered phenol-based antioxidants, carbodiimide-based hydrolysis inhibitors, and the like. The above additives may be used singly or in combination.

When the coating agent for forming an anti-fogging film of the present disclosure contains the above additive, the content of the additive in the coating agent for forming an anti-fogging film of the present disclosure is 0.2 to 10.0% by mass, more preferably 0.5 to 2.0% by mass.

The application of the coating agent for forming an anti-fogging film of the present disclosure is not particularly limited. Glass or mirrors, specifically rearview mirrors, door mirrors, etc., and other openings such as glasses, camera lenses, goggles, helmet shields, refrigerated showcases, freezer showcases, testing machines, precision equipment cases, etc. Examples include observation windows, road reflectors, displays of mobile communication devices such as mobile phones, and the like.

[Method for producing antifogging article]
The manufacturing method of the anti-fogging article of the present disclosure comprises:
A method for manufacturing an antifogging article having a substrate and an antifogging coating, comprising:
a step (1) of applying the coating agent for forming an antifogging film of the present disclosure to the surface of a substrate to form a coating film;
Step (2) of evaporating the solvent (L) from the coating film and curing the coating film to form an antifogging coating;
A method for manufacturing an antifogging article, comprising:
An antifogging article is obtained by performing the above step (1) and the above step (2) in this order.

<Base material>
As the base material, a plate-like one is preferably used, and glass is typically used. The glass is plate glass made of soda-lime glass, which is commonly used for automotive, architectural, and industrial glass, and is plate glass produced by the float method, duplex method, roll-out method, or the like, and the manufacturing method is not particularly limited.

Glass types include various colored glasses such as clear, green, bronze, etc., various functional glasses such as UV, IR cut glass, electromagnetic shielding glass, and fireproof glass such as wired glass, low expansion glass, and zero expansion glass. Various glass products such as glass, tempered glass and similar glass, laminated glass and multi-layer glass, mirrors produced by the silver coating method or vacuum film forming method, and flat plates and bent plates can be used.

The plate thickness of the substrate is not particularly limited, but is preferably 1 mm or more and 10 mm or less, and particularly preferably 1 mm or more and 5 mm or less.

The formation of the antifogging coating on the surface of the substrate may be carried out on only one side of the substrate, or on both sides depending on the application. Moreover, the formation of the antifogging coating may be performed on the entire surface of the base material or on a part of the base material surface.

The surface of the glass substrate is preferably coated with a primer component such as a silane coupling agent in order to improve the adhesion between the glass substrate and the antifogging coating. When applying the silane coupling agent to the substrate, the silane coupling agent may be diluted with alcohol, water, or the like to about 0.05 to 2.0% by mass. Examples of the silane coupling agent include aminosilane, mercaptosilane and epoxysilane. Silane coupling agents having an amino group are particularly preferred, and γ-glycidoxypropyltrimethoxy, γ-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane and the like are particularly preferred. Thus, the step of applying a solution containing the above coupling agent to the base material is a particularly preferable embodiment in which the adhesiveness between the base material and the coating is improved.

It is preferable that the base material is a glass base material and that a silane coupling agent having an amino group is applied to the surface of the glass base material.

The substrate may be a resin film such as polyethylene terephthalate, a resin such as polycarbonate, or the like, in addition to the glass substrate. An anti-fogging article may be obtained by forming the anti-fogging film on the surface of these resinous transparent substrates, and the article may be attached to a glass substrate.

<Step (1)>
Step (1) is a step of applying the coating agent for forming an antifogging film of the present disclosure to the surface of a substrate to form a coating film.
Before the step (1), the base material described above and the coating agent for forming the antifogging film of the present disclosure described above are prepared.
The coating agent for forming an antifogging film of the present disclosure can be applied to a substrate by known means such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, and flexographic printing. .

<Step (2)>
Step (2) is a step of evaporating the solvent (L) from the coating film and curing the coating film to form an antifogging coating.

Curing the coating specifically refers to reacting raw materials in the coating to form polyurethane and to solidify the coating.

In step (2), it is preferred that the isocyanate groups of the polyisocyanate (A) react with the hydroxy groups of the polyol (B) to form a polyurethane.

In step (2), the film is left at room temperature or heat-treated at 170° C. or less to cure the coating film and evaporate the solvent (L), thereby solidifying the coating film to form an antifogging coating.

In order to promote curing of the coating film, heating is preferably performed at 80 to 170°C, more preferably at 100 to 165°C, and even more preferably at 120 to 160°C.

[Anti-fogging article]
The anti-fogging article of the present disclosure is
An antifogging article having a substrate and an antifogging coating,
The antifogging coating is a coating containing polyurethane, which is a cured product of the coating agent for forming an antifogging coating of the present disclosure,
The film thickness of the antifogging coating is 5 μm to 50 μm,
It is an antifogging article.

The base material of the antifogging article is as described in [Method for producing antifogging article]. In particular, it is preferable that the base material is a glass base material, and that the surface of the glass base material is coated with a silane coupling agent having an amino group.

The thickness of the antifogging coating is 5 μm to 50 μm, preferably 10 μm to 45 μm, more preferably 15 μm to 40 μm, particularly preferably 20 μm to 30 μm.

The pencil hardness of the antifogging coating is preferably 2H or more, more preferably 3H or more.

Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples.

In the present examples and comparative examples, a coating agent (coating solution) for forming an antifogging film for producing an antifogging article was prepared, and the coating film made of the coating solution applied on the substrate was heat-treated, An antifog article was produced by curing to an antifog coating. The method for preparing the coating liquid and the method for producing the antifogging article are as described below. Next, the obtained antifogging article was subjected to quality evaluation by the method shown below.

[Thickness of anti-fogging coating]: The thickness of the anti-fogging coating is measured by making a cut in the surface of the anti-fogging coating with a cutter, and using a surface roughness meter (Kosaka research Measured with Surfcorder ET-4000A manufactured by Shosha Co., Ltd., and the average value of 5 points was taken as the film thickness of the antifogging coating.

[Appearance evaluation]: The appearance, permeability, and presence or absence of cracks of the antifogging coating were visually evaluated.

[Anti-fogging property]: The surface of the anti-fogging coating film of the anti-fogging article is exposed to saturated steam at 15°C in a room with a temperature of 10°C and a humidity of 30%. The anti-fogging time of the anti-fogging coating film is defined as the time when the surface of the anti-fogging coating film begins to fog, and the anti-fogging time exceeding 7 minutes and 30 seconds is passed (○), and the one of 7 minutes and 30 seconds or less is unsatisfactory. It was set as pass (x).

[Pencil hardness]: In accordance with JIS K 5600 Paint general test method (1999), the surface of the anti-fogging coating film was scratched twice with a pencil loaded with a load of 750 g. The hardness of the pencil that was absent was taken as the pencil hardness of the antifogging coating film. 2H or more was set as a pass (O), and H or less was set as a failure (X).

[Example 1]
(1) Preparation of Coating Agent for Forming Antifogging Film As the polyisocyanate (A), a biuret-type polyisocyanate of hexamethylene diisocyanate (trade name “Desmodur N3200A” manufactured by Sumika Covestro Urethane, functional group number 3.3) was used. 16.19 g was prepared. Let this be drug A.

As a blocked polyisocyanate (H), 3.87 g of an isocyanurate-type blocked isocyanate (trade name “Barnock DB-980K” manufactured by DIC, having more than 3 functional groups) was prepared. Let this be medicine B.

The mixing ratio of polyisocyanate (A) and blocked polyisocyanate (H) was 9:1.

Also, each component described below was mixed in the amounts specified below to obtain a total amount of drug C of 82.17 g.
<Solvent (L)>
Mixture of isobutyl acetate and diacetone alcohol; 53.92 g, acetylacetone; 1.8 g
<Polyol (B)>
Oxyethylene/oxypropylene copolymer polyol having a number average molecular weight of 4000 (trade name “Toho Polyol PB-4000”; manufactured by Toho Chemical Industry Co., Ltd.); 9.20 g,
1.25 g polyethylene glycol with a number average molecular weight of 1000;
Polytetramethylene ether glycol with a number average molecular weight of 1000; 4.18g
<Acrylic resin (C)>
Mixed solution containing 45.0% by mass of acrylic polyol having a number average molecular weight of 18,000 (trade name “Acrydic 47-538-BA”; manufactured by DIC Corporation); 9.29 g
<Short chain polyol (G)>
2,3-butanediol (manufactured by Tokyo Kasei); 2.09 g
<Leveling agent>
Organically modified silicone substrate wetting agent KL-400HF (manufactured by Kyoeisha Chemical Co., Ltd.); 0.03 g
<Light stabilizer>
Hindered amine light stabilizer ADEKA STAB LA-72 (manufactured by ADEKA); 0.40 g
In the drug C, the oxyethylene/oxypropylene copolymer polyol, polyethylene glycol, acrylic polyol, 2,3-butanediol, and polytetramethylene ether glycol have a solid content ratio (hereinafter, “EOPO:PEG1000:AP: 2,3-BD:PTMG ratio”) and was “EOPO:PEG1000:AP:2,3-BD:PTMG=44:6:20:10:20”.

102.27 g of coating liquid was prepared by mixing the above-described agents A, B, and C, and adding 0.04 g of dibutyltin dilaurate (hereinafter also referred to as DBTDL) as a curing catalyst.

The urethane-forming component in the coating solution was 40% by mass when the total amount of the coating agent for forming the antifogging film (coating solution) was 100% by mass.

The amount of the leveling agent was 0.0003 times the total amount of the coating liquid in mass ratio.

The ratio n _{(NCO)/n(OH) of the number n(NCO) of isocyanate groups in the urethane-forming component to the number n(OH )} of hydroxyl groups in the urethane-forming component was 1.5.

The content of polyisocyanate (A) in the coating liquid was 40.5% by mass with respect to 100% by mass of the urethane-forming component.

(2) Preparation of Substrate A mirror was prepared by forming a silver film on the back surface of a rectangular soda-lime glass plate having a size of 200 mm×300 mm×5 mm (thickness) by a conventional method. A mixed solution of 89 g of ion-exchanged water, 10 g of propanol, and 1 g of 3-(2-aminoethylamino)propyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a silane coupling agent, was prepared. The mixed solution is applied by wiping the glass surface of the mirror with a wiper (trade name “BENCOT”, model M-1, 50 mm×50 mm, manufactured by Ozu Sangyo) made of cellulose fibers impregnated with the mixed solution, Then, it was washed with water, and a mirror on which a primer layer (the layer containing the silane coupling agent) was formed was prepared as a substrate.

(3) Manufacture of antifogging article The coating solution is applied by spin coating to the surface of the base material on which the primer layer is formed to form a coating film, and then heat-treated at about 160°C for about 10 minutes. Thus, an antifogging article having an antifogging film having a thickness of 25 μm was obtained. The evaluation results of the antifogging article of this example were good as shown in Table 1.

[Example 2]
An antifogging article was obtained in the same manner as in Example 1, except that the film thickness of the antifogging coating was changed to 35 μm. The evaluation results of the antifogging article of this example were good as shown in Table 1.

[Example 3]
An antifogging article was obtained in the same manner as in Example 1, except that n _(NCO) /n _(OH) was changed to 1.8. The evaluation results of the antifogging article of this example were good as shown in Table 1.

[Example 4]
An antifogging article was obtained in the same manner as in Example 1, except that the mixing ratio of polyisocyanate (A) and blocked polyisocyanate (H) was changed to 8:2. The evaluation results of the antifogging article of this example were good as shown in Table 1.

[Example 5]
An anti-fogging article was obtained in the same manner as in Example 1, except that an adduct-type blocked isocyanate (trade name "Barnock D-550" manufactured by DIC) was used as the blocked polyisocyanate (H). The evaluation results of the antifogging article of this example were good as shown in Table 1.

[Example 6]
As the water repellent (D), one end diol-modified polydimethylsiloxane (trade name "X-22-176DX" manufactured by Shin-Etsu Chemical Co., Ltd.) was added in an amount of 0.01% by mass based on the urethane-forming component. A similar operation was performed to obtain an antifogging article. The evaluation results of the antifogging article of this example were good as shown in Table 1.

[Example 7]
The same operation as in Example 1 was performed except that Phtergent 212M (manufactured by NEOS Corporation), a one-end hexafluoropropene-modified polyoxyethylene compound, was added as a hydrophilic agent (E) in an amount of 3% by mass of the urethane-forming component. A cloudy article was obtained. The evaluation results of the antifogging article of this example were good as shown in Table 1.

[Comparative Example 1]
An antifogging article was obtained in the same manner as in Example 1, except that the blocked polyisocyanate (H) was not used. As shown in Table 1, the evaluation result of the antifogging article of this comparative example was that the antifogging property was inferior to that of the example.

[Comparative Example 2]
An antifogging article was obtained in the same manner as in Example 1, except that the polyisocyanate (A) was not used. The antifogging article of this comparative example did not cure as a film and was inferior to the examples.

[Comparative Example 3]
In place of the blocked polyisocyanate (H), an allophanate-type polyisocyanate of hexamethylene diisocyanate (trade name “Desmodur N3580BA” manufactured by Sumika Covestro Urethane Co., Ltd., functional group number 4.5), which is the polyisocyanate (A), was used as the second isocyanate instead of the blocked polyisocyanate (H). An antifogging article was obtained in the same manner as in Example 1 except that 5) was used. The antifogging property of the antifogging article of this comparative example was inferior to that of the examples. The mixing ratio of the first isocyanate and the second isocyanate was 9:1.

Claims (19)

(A) a polyisocyanate having two or more isocyanate groups;
(H) a blocked polyisocyanate having two or more blocked isocyanate groups;
(B) a polyol comprising an oxyethylene unit as a repeating unit and having two or more hydroxy groups in the molecule;
(L) a solvent;
A coating agent for forming an antifogging film, comprising: Furthermore, (C) an acrylic resin having two or more hydroxy groups in the molecule;
The coating agent for forming an antifogging film according to claim 1, comprising: 3. The coating agent for forming an antifogging film according to claim 1, further comprising (F) polytetramethylene ether glycol. The coating agent for forming an antifogging film according to any one of claims 1 to 3, further comprising (G) a short-chain polyol having a number average molecular weight of 60 to 200. The polyol (B) comprises (B1) polyethylene glycol, and (B2) a copolymer polyol comprising an oxyethylene unit and an oxypropylene unit as repeating units. A coating agent for forming a cloudy film. The coating agent for forming an antifogging film according to any one of claims 1 to 5, further comprising (D) a water repellent agent or (E) a hydrophilic agent. 7. The antifogging coating according to claim 6, wherein the water repellent agent (D) or hydrophilic agent (E) content is 0.001 to 10.0% by mass with respect to 100% by mass of the urethane-forming component. Forming coating. n ₍ NCO)/n(OH), which is the ratio of the total number n _(NCO) of isocyanate groups and blocked isocyanate groups in the urethane-forming component to the number n _{( OH)} of hydroxyl groups in the urethane-forming component, is 1. The coating agent for forming an antifogging film according to any one of claims 1 to 7, wherein the ratio is 0 to 3.0. The coating agent for forming an antifogging film according to any one of claims 1 to 8, wherein the content of the polyisocyanate (A) is 20 to 60% by mass with respect to 100% by mass of the urethane-forming component. . 10. The coating agent for forming an antifogging film according to any one of claims 1 to 9, wherein the mixing ratio of the polyisocyanate (A) and the blocked polyisocyanate (H) is 50:50 to 99:1. A method for producing an antifogging article having a substrate and an antifogging coating, comprising:
A step (1) of applying the coating agent for forming an antifogging film according to any one of claims 1 to 10 to the surface of a substrate to form a coating film;
Step (2) of evaporating the solvent (L) from the coating film and curing the coating film to form an antifogging coating;
A method for manufacturing an anti-fogging article. 12. The method for manufacturing an antifogging article according to claim 11, wherein said substrate is a glass substrate. 13. The method for producing an antifogging article according to claim 12, wherein the surface of the glass substrate is coated with a silane coupling agent. The antifogging according to any one of claims 11 to 13, wherein in the step (2), the isocyanate groups of the polyisocyanate (A) react with the hydroxy groups of the polyol (B) to form polyurethane. method of manufacturing a sexual product. The method for producing an antifogging article according to any one of claims 11 to 14, wherein in the step (2), the coating film is heated at 80 to 170°C. An antifogging article having a substrate and an antifogging coating,
The antifogging coating is a coating containing a polyurethane resin, which is a cured product of the coating agent for forming an antifogging coating according to any one of claims 1 to 10,
The film thickness of the antifogging coating is 5 μm to 50 μm,
Anti-fogging article. 17. The anti-fogging article according to claim 16, wherein said substrate is a glass substrate. 18. The antifogging article according to claim 17, wherein the surface of said glass substrate is coated with a silane coupling agent. The antifogging article according to any one of claims 16 to 18, wherein the antifogging coating has a pencil hardness of 2H or more.