JP5423673B2 - Antifogging composition, kit for antifogging composition, antifogging article, and method for producing antifogging article - Google Patents

Description

  The present invention provides, for example, an antifogging film that is applied to a transparent hydrophilic substrate such as glass or plastic, and prevents the transparency of the hydrophilic substrate from being impaired even if fine water droplets adhere to the antifogging film. The present invention relates to an antifogging composition for forming, an antifogging composition kit for preparing the antifogging composition, an antifogging article, and a method for producing the antifogging article.

  For example, a transparent substrate such as glass or plastic has a so-called “cloudiness” in which when the surface of the substrate falls below the dew point temperature, fine water droplets adhere to the surface, and the transmitted light is scattered by the water droplets and the transparency is impaired. ”State. Various proposals have been made as means for preventing fogging.

  Specifically, (1) a method in which the surface of the substrate is treated with a surfactant to reduce the surface tension, and (2) a hydrophilic group is imparted to the substrate surface using a hydrophilic resin or a hydrophilic inorganic compound, (3) A method of reducing the atmospheric humidity on the surface of the substrate by providing a hygroscopic compound layer on the surface of the substrate, (4) The substrate surface is heated by installing a heater or the like on the substrate. A method for maintaining the dew point temperature or higher is known.

In the methods (1) and (2), a water film is formed on the surface of the formed film. Therefore, if the film is kept in a high humidity environment for a long period of time, the appearance is likely to change due to generation of distortion or water droplets. There was a case where the sticky feeling was felt somewhat uncomfortable.
On the other hand, in the method (3), since there is no water on the surface, the appearance does not change and the feeling of use is often popular. Furthermore, the method (3) is a particularly excellent method as a means for preventing fogging because it can exhibit the most excellent antifogging property without requiring running cost among the above methods.

According to the method using the hygroscopic compound layer of (3), a coating agent for forming a urethane resin having a surfactant and a trialkanolamine, which has both anti-fogging performance and wear resistance, and the coating agent An anti-fogging film is shown (Patent Document 1).
An article having an antifogging film in which a hydrophobic polymer segment is formed on a substrate, and a hydrophilic polymer segment considered to correspond to a hygroscopic compound layer is formed on the hydrophobic polymer segment, and A manufacturing method is shown (Patent Document 2).

Further, an antifogging agent composition and a vehicle lamp containing a block or graft copolymer composed of a hydrophobic polymer portion and a hydrophilic polymer portion are disclosed (Patent Document 3).
Furthermore, a method for producing an antifogging article having a silane coupling agent layer, a composition layer containing a hydrophobic monomer, and a composition layer containing a hydrophilic monomer on a substrate is shown (patent) Reference 4).

JP 2004-269851 A Japanese Patent No. 3700273 Japanese Patent No. 3216262 JP-A-8-27290

  However, in the technique of Patent Document 1, it is difficult to fix the surfactant to the substrate and the hygroscopicity is not sufficient, and thus it may be difficult to sufficiently maintain the antifogging performance for a long period of time.

In the technique of Patent Document 2, durability such as warm water resistance and moisture resistance of the two-layer film to be formed is not sufficient, and since the two-layer coating is applied, the mass-productivity may be inferior.
In the technique of Patent Document 3, there are cases where adhesion to the substrate is not sufficient, and durability such as warm water resistance and moisture resistance is not sufficient.
The technique of Patent Document 4 is a method in which two layers are applied and a curing process for curing them is performed twice, which may result in inferior mass productivity.
Therefore, an antifogging article having excellent antifogging performance and having various durability and mass productivity is desired.

  Accordingly, the present invention combines anti-fogging performance with durability and mass-productivity such as warm water resistance and moisture resistance in addition to excellent anti-fogging performance, and an anti-fogging article excellent in durability of the anti-fogging performance and simple production thereof. A method, an antifogging composition for forming the antifogging article, and a kit for the antifogging composition for preparing the antifogging composition are provided.

  The antifogging composition of the present invention is a composition for forming an antifogging film on a hydrophilic substrate, and comprises a low hygroscopic crosslinked polymer (A) and a highly hygroscopic crosslinked polymer (B) shown below. It is a composition characterized by including.

  Low hygroscopic cross-linked polymer (A): cross-linking polymerization reaction of polyepoxides (a1) having a water solubility of less than 20%, a curing agent (a2), and a silane coupling agent (a3) represented by the following formula (I) It is a polymer obtained by this. However, the mass ratio of the silane coupling agent (a3) to the total mass (100 mass%) of the polyepoxides (a1), the curing agent (a2), and the silane coupling agent (a3) is 7 mass% or more.

Highly hygroscopic crosslinked polymer (B): a polymer (B1) obtained by a crosslinking polymerization reaction of a polyepoxide (b1) having a water solubility of 100% and a curing agent (b2), and / or the polyepoxide (b1) And a curing agent (b2) and a polymer (B2) obtained by a cross-linking polymerization reaction between the silane coupling agent (b3) represented by the following formula (I). However, the silane coupling agent (b3) based on the total mass (100% by mass) of the polyepoxides (b1), the curing agent (b2), and the silane coupling agent (b3) used for the crosslinking polymerization reaction of the polymer (B2). ) Is 3 mass% or less.
_{^{R 1 - (CH 2) n}} -Si (R 2) m (R 3) 3-m ··· (I)
(In the formula, R ¹ is an alkyl group containing a glycidyl group, an amino group, or a (meth) acryloyloxy group, n is an integer of 1 to 3, R ² is a hydrolyzable group, and m is 1 And R ³ is an alkyl group having 1 to ³ carbon atoms.)
In the antifogging composition of the present invention, the mass ratio of the low hygroscopic crosslinked polymer (A) to the high hygroscopic crosslinked polymer (B) is preferably 30/70 to 70/30.
The curing agent (a2) and the curing agent (b2) are preferably polyamine compounds.

  The kit for an antifogging composition of the present invention is a kit for preparing any one of the above antifogging compositions, the liquid composition containing the low hygroscopic crosslinked polymer (A), and the high antifogging composition. And a liquid composition containing a hygroscopic crosslinked polymer (B).

The antifogging article of the present invention has a hydrophilic substrate and an antifogging film formed on the surface of the hydrophilic substrate, and the antifogging film is formed from any one of the antifogging compositions. And a saturated moisture absorption amount of the antifogging film is 20 mg / cm ³ or more.
The production method of the present invention is a method for producing an antifogging article having an antifogging film comprising a crosslinked resin layer on a hydrophilic substrate, wherein a liquid composition containing any one of the antifogging compositions is provided. It is a method including the process of apply | coating on the said hydrophilic base | substrate, and the process of heat-hardening and forming a crosslinked resin layer.

The anti-fogging composition of the present invention has excellent anti-fogging performance, in addition to durability such as warm water resistance and moisture resistance, and can form an anti-fogging film excellent in durability of the anti-fogging performance. it can. Moreover, according to this invention, the kit for anti-fogging compositions which prepares the said anti-fogging composition can be provided.
Further, the antifogging article of the present invention has durability and mass productivity such as warm water resistance and moisture resistance in addition to excellent antifogging performance, and can maintain the excellent antifogging performance for a long period of time.
Moreover, the manufacturing method of this invention can manufacture the said anti-fogging article | item easily.

<Anti-fogging composition>
The anti-fogging composition of the present invention is a composition for forming an anti-fogging film on a hydrophilic substrate, and has a low hygroscopic crosslinked polymer (A) and more hygroscopic than the low hygroscopic crosslinked polymer (A). And a highly hygroscopic crosslinked polymer (B) excellent in properties (also referred to as water absorption). Saturated moisture absorption of low hygroscopicity crosslinked polymer is preferably 10 mg / cm ³ or less, more preferably ^{5mg / cm 3, 1mg / cm} 3 or less is particularly preferred. On the other hand, the saturated moisture absorption amount of the highly hygroscopic crosslinked polymer is larger than the saturated moisture absorption amount of the low hygroscopic crosslinked polymer, preferably 20 mg / cm ³ or more, more preferably 45 mg / cm ³ or more.

[Low Hygroscopic Crosslinked Polymer (A)]
The low hygroscopic crosslinked polymer (A) is a polymer obtained by subjecting a polyepoxide (a1), a curing agent (a2), and a silane coupling agent (a3) to a crosslinking polymerization reaction. The cross-linking polymerization reaction of the low hygroscopic cross-linked polymer (A) is performed so that the cross-linking component remains to some extent.
With this remaining crosslinkable component, the antifogging composition comprising a crosslinked resin layer is formed by heat-curing the antifogging composition. A crosslinkable component means what included the crosslinkable group which polyepoxide (a1) has, the reactive group which a hardening | curing agent (a2) and a silane coupling agent (a3) have.

(Polyepoxides (a1))
The polyepoxides (a1) are polyepoxides having a water solubility of less than 20%.
The water solubility of the polyepoxides in the present invention is the water solubility determined as follows, and is a value before the crosslinking polymerization reaction.
A solution was prepared in a container with a ratio of the mass W2 of the polyepoxides to the mass W1 of distilled water (W1: W2) being 90:10, stirred at 25 ° C. for 5 minutes or more, and the solution was allowed to stand for 1 hour. After that, the polyepoxides separated from distilled water and precipitated or suspended are recovered, the mass W3 is measured, and the ratio of the polyepoxides dissolved in water according to the following formula is calculated as the water solubility.
Water solubility (%) = {(W2-W3) / W2} × 100
Polyepoxides are components that have an epoxy group as a crosslinkable group and become a crosslinkable resin by reaction with a curing agent.

The polyepoxide (a1) may have a crosslinkable group other than the epoxy group. As the crosslinkable group other than the epoxy group, a carboxy group and a hydroxyl group are preferable.
The average number of epoxy functional groups of the polyepoxides (a1) is 2 or more, and preferably 2 to 10.
Examples of the polyepoxides (a1) include those in which the water solubility of glycidyl compounds such as glycidyl ether compounds, glycidyl ester compounds, and glycidyl amine compounds is less than 20%. Of these, glycidyl ether compounds are preferred. As the glycidyl ether compound, a glycidyl ether of a bifunctional or higher alcohol is preferable, and a glycidyl ether of a trifunctional or higher alcohol is more preferable because durability and antifogging performance are improved. Further, these alcohols are preferably aliphatic alcohols, alicyclic alcohols, or sugar alcohols.

Specific examples include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, poly Specific examples include glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. Here, “poly” means that the average value is more than 2.
These polyepoxides (a1) may be used alone or in combination of two or more.
As the polyepoxides (a1), since an antifogging film comprising a crosslinked resin layer having particularly excellent crosslinking density is obtained, polyglycidyl ether of an aliphatic polyol having 6 or more hydroxyl groups (average glycidyl group per molecule) Is more than 5). Specific examples include sorbitol polyglycidyl ether.
The water solubility of the polyepoxides (a1) is affected by the ratio of the number of hydrophilic groups and the number of hydrophobic groups in the molecule. The more hydrophilic groups, the higher the water solubility, and the more hydrophobic groups, the lower the water solubility.

  Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonyl group, an amide group, an amino group, a quaternary ammonium base, and an oxyalkylene group. In addition, examples of the hydrophobic group include an epoxy group, a chloro group, and an alkyl group.

The water solubility of the polyepoxides (a1) shows a correlation (proportional relationship) with the value of the ratio P between the number of hydrophilic groups and the number of hydrophobic groups represented by the following formula. Therefore, the water solubility of the polyepoxides (a1) can be adjusted by adjusting the value of P.
P = (number of hydrophilic groups) / [(number of hydrophilic groups) + (number of hydrophobic groups)]
The amount of the hydrophilic group in the polyepoxides (a1) can be adjusted, for example, by adjusting the hydroxyl value. Moreover, the quantity of a hydrophobic group can be adjusted by adjusting content (mass%), such as a chloro group and an alkyl group, and an epoxy equivalent (WPE) in polyepoxides (a1).

  Specific examples of polyepoxides (a1) having a water solubility of less than 20% include Denacol EX-622 (trade name, sorbitol polyglycidyl ether, water solubility of less than 0.08%, manufactured by Nagase ChemteX Corporation). .

  The polyepoxide (a1) is preferably a linear polymer. The number of crosslinkable groups possessed by the polyepoxides (a1) may be any number as long as the antifogging performance and durability required in the present invention are satisfied, and 2 to 2 per molecule of the polyepoxides (a1). Six is preferable. Moreover, it is preferable that the molecular weights of polyepoxides (a1) are 500-50000 in a number average molecular weight.

  The mass ratio of the polyepoxides (a1) to the total mass (100% by mass) of the polyepoxides (a1), the curing agent (a2), and the coupling agent (a3) in the preparation of the low hygroscopic crosslinked polymer (A) is: Although it changes with kinds of hardening | curing agent (a2), it is preferable that it is 40-75 mass%.

  If the mass ratio of the polyepoxides (a1) is 40% by mass or more, a certain amount of the low hygroscopic component can be introduced into the crosslinked resin layer, so that sufficient warm water resistance, moisture resistance and the like can be easily imparted. If the mass ratio of the polyepoxides (a1) is 75% by mass or less, the curing agent (a2) and the coupling agent (a3) can be blended in an equivalent ratio of about 1.0, and the maximum degree of crosslinking can be realized. Sufficient durability is easily obtained.

(Curing agent (a2))
The curing agent (a2) is not particularly limited as long as it can undergo a crosslinking polymerization reaction, and a curing agent usually used for radical polymerization, ionic polymerization, polycondensation reaction, polyaddition reaction and the like can be used. Preferred curing agents (a2) are any of the following curing agents. The curing agent (a2-1) is suitable for polyaddition reaction, and the curing agent (a2-2) is suitable for ion polymerization.

  Curing agent (a2-1): a compound having a reactive group capable of reacting with the crosslinkable group of polyepoxides (a1), and reacting with polyepoxides (a1) to form a crosslinkable resin having a three-dimensional network structure Compound.

Curing agent (a2-2): A compound that promotes the formation of a crosslinkable resin having a three-dimensional network structure by catalyzing the crosslinking reaction of the polyepoxides (a1).
The reactive group of the curing agent (a2-1) is selected from reactive groups capable of reacting with the crosslinkable group according to the type of the crosslinkable group of the polyepoxides (a1) combined with the curing agent (a2-1). .
Examples of the reactive group of the curing agent (a2-1) include a vinyl group, an epoxy group, a styryl group, a (meth) acryloyloxy group, an amino group, a ureido group, a chloropropyl group, a mercapto group, a sulfide group, and an isocyanate. Groups, hydroxyl groups, carboxy groups, and acid anhydride groups.
Especially, since polyepoxide (a1) has an epoxy group as a crosslinkable group, it is preferable that the reactive group of a hardening | curing agent (a2-1) is a carboxy group, an amino group, an acid anhydride group, or a hydroxyl group.
Moreover, when the crosslinkable group of polyepoxide (a1) contains a hydroxyl group, it is preferable to use together the hardening | curing agent (a2-1) whose reactive group is an epoxy group or an isocyanate group. Moreover, when the crosslinkable group of polyepoxide (a1) contains a carboxy group, it is preferable to use together the hardening | curing agent (a2-1) whose reactive group is an amino group, and the reactive group is an epoxy group hardening | curing agent. It is more preferable to use (a2-1) in combination.

The number of reactive groups contained in one molecule of the curing agent (a2-1) is 1.5 or more on average, and preferably 2 to 4.
Two or more curing agents (a2-1) can be used in combination. For example, when the second curing agent (a2-1-2) is used in combination with the main first curing agent (a2-1-1), the reactivity of the second curing agent (a2-1-2). The group may react not only with the crosslinkable group of the polyepoxides (a1) but also with the reactive group of the first curing agent (a2-1-1). The second curing agent (a2-1-2) that reacts with the first curing agent (a2-1-1) is combined with the polyepoxides (a1) via the first curing agent (a2-1-1). Join. By using such a second curing agent (a2-1-2) in combination, the formation of a crosslinkable resin by the polyepoxides (a1) and the main first curing agent (a2-1-1) is promoted. be able to. At this time, the reactive group of the second curing agent (a2-1-2) may be the same as or different from the reactive group of the first curing agent (a2-1-1). . For example, when the first curing agent (a2-1-1) having an amino group is used as the curing agent (a2) for the polyepoxides (a1) having only an epoxy group, the second curing agent further having a hydroxyl group. By using (a2-1-2) or the second curing agent (a2-1-2) having an acid anhydride group in combination, the formation of the low hygroscopic crosslinked polymer (A) is promoted.

  Examples of the curing agent (a2-1) that can be used in the present invention include polyamine compounds, polycarboxylic acid compounds (including polycarboxylic acid anhydrides), polyol compounds, polyisocyanate compounds, and polyepoxy compounds. Is mentioned. These curing agents (a2-1) are selected according to the crosslinkable group of the polyepoxides (a1). Since the polyepoxide (a1) has at least an epoxy group, the curing agent (a2-1) is preferably a polyamine-based compound among the above compounds. Moreover, it is also preferable to use a polyol compound, a polycarboxylic anhydride, etc. together as a 2nd hardening | curing agent (a2-1-2) with the 1st hardening | curing agent (a2-1-1) of a polyamine type compound. In addition, when using a polyepoxy type compound as a hardening | curing agent (a2-1), the compound different from polyepoxides (a1) is selected.

  As the polyamine compound, an aliphatic polyamine compound or an alicyclic polyamine compound is preferable. Specific examples include, for example, ethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, isophoronediamine, mensendiamine, metaphenylenediamine, polypropylene glycol polyamine, polyethylene glycol polyamine, 3,9-bis (3-amino Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane.

  Examples of the polycarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, malic acid, citric acid, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.

  Examples of polyol compounds include polyhydric alcohol-ethylene oxide adducts, polyhydric alcohol-propylene oxide adducts, and polyester polyols.

  Examples of the polyisocyanate compound include hexamethylene diisocyanate and isophorone diisocyanate.

  Examples of the polyepoxy compound include glycidyl compounds such as glycidyl ether compounds, glycidyl ester compounds, and glycidyl amine compounds. Of these, glycidyl ether compounds are preferable, and aliphatic glycidyl ether compounds are more preferable. As the glycidyl ether compound, a glycidyl ether of a bifunctional or higher alcohol is preferable, and a glycidyl ether of a trifunctional or higher alcohol is more preferable because durability and antifogging performance are improved. Further, these alcohols are preferably aliphatic alcohols, alicyclic alcohols, or sugar alcohols.

Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, poly Specific examples include glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. Here, “poly” means that the average value is more than 2.
These hardening | curing agents (a2-1) may be used individually by 1 type, and may use 2 or more types together.

  The amount of the curing agent (a2-1) used in the low hygroscopic crosslinked polymer (A) is the number of crosslinkable groups of the polyepoxides (a1), the reactive group of the curing agent (a2-1), and the silane coupling. A ratio in which the total number of reactive groups in the agent (a3) is substantially equal is appropriate, and the equivalent ratio of the reactive groups to the crosslinkable groups is preferably about 0.8 to 1.2.

Moreover, the ratio of the crosslinkable group of the polyepoxides (a1) to the reactive group may be further increased as long as it is a crosslinkable group that may remain in the crosslinkable resin layer constituting the antifogging film. Similarly, if the reactive group of the curing agent (a2-1) can remain in the crosslinked resin layer constituting the antifogging film, the crosslinking group and silane coupling of the polyepoxides (a1) The ratio of the reactive group of the curing agent (a2-1) to the reactive group of the agent (a3) may be further increased.
As described above, the second curing agent (a2-1-2) can be used for adjusting the physical properties of the antifogging film in addition to crosslinking the crosslinkable component. For example, by using an acid anhydride compound that reacts with an amine compound that is the first curing agent (a2-1-1) as the second curing agent (a2-1-2), A hydrophilic bond reacted with an acid anhydride group can be provided to an antifogging film composed of a crosslinked resin layer. In this case, even if only one reactive group in the second curing agent (a2-1-2) is reacted, the function is exhibited.

  Moreover, if the 2nd hardening | curing agent (a2-1-2) can adjust the physical property of an anti-fogging film | membrane, it will couple | bond with polyepoxide (a1) and a 1st hardening | curing agent (a2-1-1). It may be a compound having only one reactive group. In this case, the compound having only one reactive group is a compound having no crosslinking function. When a compound having one reactive group is used as the second curing agent (a2-1-2) in addition to the first curing agent (a2-1-1), the amount is the first curing agent. The mass is preferably equal to or less than (a2-1-1), and more preferably 0.01 to 0.5 times mass. In addition, the 1st hardening | curing agent (a2-1-1) also affects the function of an anti-fogging film | membrane, and is essential between the 2nd hardening | curing agent (a2-1-2) at that point. There is no distinction.

When the curing agent (a2-1) is used as the curing agent (a2), the curing agent with respect to the total mass (100% by mass) of the polyepoxides (a1), the curing agent (a2-1), and the silane coupling agent (a3). The mass ratio of (a2-1) is preferably 15 to 50 mass%.
If the mass ratio of a hardening | curing agent (a2-1) is 15 mass% or more, sufficient crosslinking polymerization degree with polyepoxides (a1) will be implement | achieved, and it will become easy to obtain the outstanding durability. If the mass ratio of a hardening | curing agent (a2-1) is 50 mass% or less, it will be easy to prevent that an excessive hardening | curing agent (a2) will inhibit the whole crosslinking polymerization reaction and durability will fall.

  A hardening | curing agent (a2-2) is a substance which accelerates | stimulates the crosslinking reaction of a crosslinkable component, and the compound generally known as a polymerization catalyst can be used. Examples of the curing agent (a2-2) include dicyandiamides, organic acid dihydrazides, tris (dimethylaminomethyl) phenols, dimethylbenzylamines, phosphines, imidazoles, aromatic diazonium salts, aromatic sulfonium salts, Aromatic iodonium salts are mentioned. Of these, tris (dimethylaminomethyl) phenols, phosphines, aromatic sulfonium salts, or aromatic iodonium salts are preferable.

  When using a hardening | curing agent (a2-2) as a hardening | curing agent (a2), it is preferable that the mass ratio of the hardening | curing agent (a2-2) with respect to polyepoxides (a1) is 2-15 mass%. If the mass ratio of a hardening | curing agent (a2-2) is 2 mass% or more, crosslinking polymerization reaction will fully advance and sufficient hygroscopicity and durability will be easy to be obtained. Moreover, if the mass ratio of the curing agent (a2-2) is 15% by mass or less, a residue remains in the crosslinked resin layer when the antifogging film is formed, and the antifogging film has an appearance such as yellowing. It is easy to prevent the problem from occurring.

(Silane coupling agent (a3))
The silane coupling agent (a3) is a silane coupling agent represented by the following formula (I).
_{^{R 1 - (CH 2) n}} -Si (R 2) m (R 3) 3-m ··· (I)
R ¹ in the silane coupling agent (a3) is an alkyl group containing a glycidyl group, an amino group, or a (meth) acryloyloxy group.
R ² is a hydrolyzable group. The hydrolyzable group is a group that becomes silanol (SiOH) by hydrolysis, and examples thereof include a chloro group, an alkoxy group, an acetoxy group, an isopropenoxy group, and an amino group.
R ³ is an alkyl group having 1 to ³ carbon atoms.
N is an integer of 1 to 3, and m is an integer of 1 to 3.

  Specific examples of the silane coupling agent (a3) include, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-amino Propyltrimethoxy Run, 3-ureidopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Among them, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane or 3-acryloxypropyltrimethoxysilane is preferred.

  Since the silane coupling agent (a3) has a group that easily binds to the hydrophilic substrate, in the antifogging film formed on the hydrophilic substrate, the closer to the hydrophilic substrate side, the lower the hygroscopic crosslinked polymer (A). It plays the role of adjusting the distribution of the low hygroscopic crosslinked polymer (A) so that the ratio becomes high. Thereby, since the hydrophilic base | substrate side of an anti-fogging film | membrane becomes a low hygroscopic property, adhesiveness with a hydrophilic base | substrate increases and durability of an anti-fogging film | membrane improves. At the same time, since the ratio of the highly hygroscopic crosslinked polymer (B) is increased on the antifogging film surface side, the antifogging performance is also improved.

  The silane coupling agent (a3) with respect to the total mass (100% by mass) of the polyepoxides (a1), the curing agent (a2), and the silane coupling agent (a3) used for the preparation of the low hygroscopic crosslinked polymer (A) The mass ratio should just be 7 mass% or more, and it is preferable that it is 7-30 mass%.

  When the mass ratio is 7% by mass or more, an antifogging composition capable of forming an antifogging film having excellent antifogging performance and durability can be obtained. Moreover, if the said mass ratio is 30 mass% or less, excess silane coupling agent (a3) will transfer in a highly hygroscopic crosslinked polymer (B), and a low hygroscopic crosslinked polymer (A) and The distribution of the highly hygroscopic crosslinked polymer (B) is lost, and it is easy to prevent the hygroscopicity and durability from being lowered.

(Production method)
As a method for producing the low hygroscopic crosslinked polymer (A), there is a method in which a polyepoxide (a1), a curing agent (a2), and a silane coupling agent (a3) are added to a solvent and mixed to cause a crosslinking polymerization reaction. preferable. Thereby, a low hygroscopic crosslinked polymer (A) is obtained as a liquid composition.
The solvent is not particularly limited as long as it is a solvent having good solubility of the polyepoxides (a1), the curing agent (a2), and the silane coupling agent (a3) and is inert to these components. . Specific examples include alcohols, acetate esters, ethers, ketones, and water.
As the solvent, diacetone alcohol, methyl ethyl ketone, butyl acetate, propylene carbonate, or diethylene glycol dimethyl ether is preferable.
A solvent may be used individually by 1 type and may use 2 or more types together.

Further, when a protic solvent is used as the solvent, when the antifogging film is formed from the obtained antifogging composition, depending on the type, the protic solvent reacts with the polyepoxide (a1) to form a crosslinked resin layer. May be difficult to form. Therefore, when using a protic solvent, it is preferable to select a solvent that does not easily react with the polyepoxides (a1). Examples of protic solvents that can be used include ethanol and isopropyl alcohol.
The amount of the solvent used is preferably 1 to 5 times the total mass of the polyepoxides (a1), the curing agent (a2), and the silane coupling agent (a3).
The cross-linking polymerization reaction of the low hygroscopic cross-linked polymer (A) is performed so that the cross-linking component remains to some extent.

The cross-linking polymerization reaction is preferably performed by stirring and mixing at 15 to 35 ° C. If the said temperature is 15 degreeC or more, sufficient reaction rate will be easy to be obtained. Moreover, if the said temperature is 35 degrees C or less, it will be easy to prevent that reaction advances too much.
Further, after the reaction, the obtained low hygroscopic crosslinked polymer (A) may be diluted with butyl acetate or the like, if necessary.
A more preferred method for producing the low hygroscopic crosslinked polymer (A) is to add the polyepoxides (a1) and the curing agent (a2) to the solvent in advance, stir and mix at 15 to 35 ° C., and then a silane coupling agent. In this method, (a3) is added, and the mixture is stirred and mixed at 15 to 35 ° C. to cause a crosslinking polymerization reaction. Thereby, the effect of the silane coupling agent (a3) is sufficiently exhibited, and an antifogging film excellent in antifogging performance and durability is easily obtained.

[Highly hygroscopic crosslinked polymer (B)]
The highly hygroscopic crosslinked polymer (B) is a polymer (B1) obtained by subjecting a polyepoxide (b1) and a curing agent (b2) to a crosslinking polymerization reaction, or / and a polyepoxide (b1) and a curing agent ( It is a polymer comprising a polymer (B2) obtained by a cross-linking polymerization reaction between b2) and a silane coupling agent (b3). The highly hygroscopic crosslinked polymer (B) may be either the polymer (B1) or the polymer (B2), or may be a mixture of the polymer (B1) and the polymer (B2). Although it is good, it is preferable that it is only a polymer (B1).
The cross-linking polymerization reaction of the polymer (B1) and the polymer (B2) is performed so that the cross-linkable component they have remains to some extent. With this remaining crosslinkable component, the antifogging composition comprising a crosslinked resin layer is formed by heat-curing the antifogging composition.

(Polyepoxides (b1))
The polyepoxide (b1) is a polyepoxide having a water solubility of 100%. The polyepoxide (b1) may have a crosslinkable group other than the epoxy group. As the crosslinkable group other than the epoxy group, a carboxy group or a hydroxyl group is preferable.
The average number of epoxy functional groups of the polyepoxides (b1) is 2 or more, and preferably 2 to 10.
Examples of the polyepoxides (b1) include those in which the water solubility of a glycidyl compound such as a glycidyl ether compound, a glycidyl ester compound, and a glycidyl amine compound is 100%. Of these, aliphatic glycidyl ether compounds are preferred.
Polyepoxides (b1) may be used alone or in combination of two or more.
The water solubility of the polyepoxides (b1) can be adjusted by adjusting the value of P represented by the following formula, as in the case of the polyepoxides (a1).
P = (number of hydrophilic groups) / [(number of hydrophilic groups) + (number of hydrophobic groups)]
The amount of the hydrophilic group in the polyepoxide (b1) can be adjusted, for example, by adjusting the hydroxyl value. Moreover, the quantity of a hydrophobic group can be adjusted by adjusting content (mass%), such as a chloro group and an alkyl group, and an epoxy equivalent (WPE) in polyepoxides (b1).

Specific examples of the polyepoxides (b1) include, for example, Denacol EX-1610 (trade name, aliphatic glycidyl ether compound, water solubility 100%, manufactured by Nagase ChemteX Corporation).
The polyepoxide (b1) is preferably a linear polymer. The number of crosslinkable groups of the polymer as the crosslinkable component may be any number as long as the antifogging performance and durability required in the present invention are satisfied, and 2 per molecule of the polyepoxide (b1). It is preferably ˜6. Moreover, it is preferable that the molecular weight of polyepoxides (b1) is 500-50000 in a number average molecular weight.

(Curing agent (b2))
As the curing agent (b2), the same ones as mentioned for the curing agent (a2) can be mentioned, and the preferred embodiments are also the same. Preferred curing agents (b2) are any of the following curing agents. The curing agent (b2-1) is suitable for polyaddition reaction, and the curing agent (b2-2) is suitable for ionic polymerization.

  Curing agent (b2-1): a compound having a reactive group capable of reacting with the crosslinkable group of polyepoxides (b1), and reacting with polyepoxides (b1) to form a crosslinkable resin having a three-dimensional network structure Compound.

Curing agent (b2-2): A compound that promotes the formation of a crosslinkable resin having a three-dimensional network structure by catalyzing the crosslinking reaction of the polyepoxides (b1).
The curing agent (b2) is preferably a polyamine compound that is the curing agent (b2-1).
The curing agent (b2-1) preferably has 2 to 8 reactive groups. When the number of reactive groups in the curing agent (b2-1) is within this range, an antifogging film having an excellent balance between antifogging performance and wear resistance is easily obtained.
When the second curing agent (b2-1-2) is used in addition to the first curing agent (b2-1-1), the second curing agent (b2-1-2) is a polyepoxide ( In addition to promoting the crosslinking reaction of b1), it can also be used for the purpose of adjusting the physical properties of the antifogging film formed on the hydrophilic substrate. For example, the hygroscopicity (also referred to as water absorption) of the antifogging film can be enhanced by the second curing agent (b2-1-2).

(Silane coupling agent (b3))
The same thing as a silane coupling agent (a3) is mentioned as a silane coupling agent (b3), A preferable aspect is also the same.
The polymer (B1) is obtained by a crosslinking polymerization reaction of the polyepoxides (b1) and the curing agent (b2).
The mass ratio of the polyepoxides (b1) to the total mass (100% by mass) of the polyepoxides (b1) and the curing agent (b2) used for the preparation of the polymer (B1) varies depending on the type of the curing agent (b2). It is preferable that it is 40-80 mass%.

If the mass proportion of the polyepoxides (b1) is 40% by mass or more, a certain amount of highly hygroscopic component can be introduced into the crosslinked resin layer, so that sufficient antifogging performance is easily imparted. Further, if the mass ratio of the polyepoxides (b1) is 80% by mass or less, the curing agent (b2) can be blended at an equivalent ratio of about 1.0, and the maximum degree of crosslinking can be realized. Easy to obtain.
When the curing agent (b2-1) is used as the curing agent (b2) in the preparation of the polymer (B1), the amount of the curing agent (b2-1) used depends on the number of crosslinkable groups in the polyepoxides (b1) and curing. The ratio in which the number of reactive groups in the agent (b2-1) is approximately equal is appropriate, and the equivalent ratio of the reactive groups to the crosslinkable groups is preferably about 0.8 to 1.2. However, when the 2nd hardening | curing agent (b2-1-2) exists, the equivalent ratio with respect to the crosslinkable group of the reactive group containing them mutually shall be about 0.8-1.2. Is appropriate. Further, the ratio of the crosslinkable group of the polyepoxides (b1) to the reactive group may be further increased as long as it is a crosslinkable group that can remain in the crosslinkable resin layer constituting the antifogging film. Similarly, if the reactive group of the curing agent (b2-1) can be left in the crosslinked resin layer constituting the antifogging film, the curing agent for the crosslinking group of the polyepoxides (b1) ( The proportion of the reactive group in b2-1) may be further increased.

  When the curing agent (b2-1) is used as the curing agent (b2) for the preparation of the polymer (B1), the curing agent based on the total mass (100% by mass) of the polyepoxides (b1) and the curing agent (b2-1) to be used. The mass ratio of (b2-1) is preferably 20 to 60 mass%.

  If the mass ratio of the curing agent (b2-1) is 20% by mass or more, it is easy to achieve a sufficient degree of crosslinking polymerization with the polyepoxides (b1) and achieve both excellent antifogging performance and durability. become. If the mass ratio of a hardening | curing agent (b2-1) is 60 mass% or less, it will be easy to prevent that an excessive hardening | curing agent (b2) inhibits the whole crosslinking polymerization reaction and durability falls.

When the curing agent (b2-2) is used as the curing agent (b2) in the preparation of the polymer (B1), the mass ratio of the curing agent (b2-2) to the polyepoxides (b1) is 2 to 15 mass%. It is preferable. If the mass ratio of a hardening | curing agent (b2-2) is 2 mass% or more, crosslinking polymerization reaction will fully advance and sufficient hygroscopicity and durability will be easy to be obtained. Further, if the mass ratio of the curing agent (b2-2) is 15% by mass or less, a residue remains in the crosslinked resin layer when the antifogging film is formed, and the antifogging film has an appearance such as yellowing. It is easy to prevent the problem from occurring.
The polymer (B2) is obtained by a crosslinking polymerization reaction between the polyepoxides (b1) and the curing agent (b2) and the silane coupling agent (b3).
When the curing agent (b2-1) is used as the curing agent (b2) in the preparation of the polymer (B2), the amount of the curing agent (b2-1) used is the number of crosslinkable groups in the polyepoxides (b1), A ratio in which the total number of reactive groups of the curing agent (b2-1) and reactive groups of the silane coupling agent (b3) is approximately equal is appropriate, and the equivalent ratio of the reactive groups to the crosslinkable groups is 0. It is preferably about 8 to 1.2.
Further, the ratio of the crosslinkable group of the polyepoxides (b1) to the reactive group may be further increased as long as it is a crosslinkable group that can remain in the crosslinkable resin layer constituting the antifogging film. Similarly, if the reactive group of the curing agent (b2-1) can remain in the crosslinked resin layer constituting the antifogging film, the crosslinkable group and silane coupling of the polyepoxides (b1) The ratio of the reactive group of the curing agent (b2-1) to the reactive group of the agent (b3) may be further increased.

When the curing agent (b2-1) is used as the curing agent (b2) in the preparation of the polymer (B2), the total mass of the polyepoxides (b1), the curing agent (b2-1), and the silane coupling agent (b3). It is preferable that the mass ratio of the hardening | curing agent (b2-1) with respect to (100 mass%) is 20-60 mass%.
If the mass ratio of the curing agent (b2-1) is 20% by mass or more, it is easy to achieve a sufficient degree of crosslinking polymerization with the polyepoxides (b1) and achieve both excellent antifogging performance and durability. become. If the mass ratio of a hardening | curing agent (b2-1) is 60 mass% or less, it will be easy to prevent that an excessive hardening | curing agent (b2) inhibits the whole crosslinking polymerization reaction and durability falls.
When the curing agent (b2-2) is used as the curing agent (b2) in the preparation of the polymer (B2), the mass ratio of the curing agent (b2-2) to the polyepoxides (b1) is 2 to 15 mass%. It is preferable. If the mass ratio of a hardening | curing agent (b2-2) is 2 mass% or more, crosslinking polymerization reaction will fully advance and sufficient hygroscopicity and durability will be easy to be obtained. Moreover, if the mass ratio of a hardening | curing agent (b2-2) is 15 mass% or less, a residue will remain in the crosslinkable resin obtained, and the appearance problems, such as yellowing, generate | occur | produce in an anti-fogging film | membrane. Easy to prevent.

The mass ratio of the silane coupling agent (b3) to the total mass (100 mass%) of the polyepoxides (b1), the curing agent (b2-1), and the silane coupling agent (b3) used for the preparation of the polymer (B2) Is preferably 3% by mass or less.
When the mass ratio is 3% by mass or less, the ratio of the low hygroscopic crosslinked polymer (A) is higher as it is closer to the hydrophilic substrate side, and the ratio of the polymer (B2) is higher as it is closer to the antifogging film surface. Thus, since adjustment of the distribution of the polymer (B2) is not hindered, an antifogging composition capable of forming an antifogging film having both excellent antifogging performance and durability is obtained. Further, if the amount of the silane coupling agent (b3) used is not excessive, it is easy to prevent the antifogging film from being colored due to oxidation or the like when exposed to a high temperature.

(Production method)
As the method for producing the highly hygroscopic crosslinked polymer (B), the same method as that for the low hygroscopic crosslinked polymer (A) can be used. That is, the method for producing the polymer (B1) is preferably a method in which the polyepoxides (b1) and the curing agent (b2) are added to a solvent, and the mixture is stirred and mixed to cause a crosslinking polymerization reaction. The polymer (B2) is preferably produced by adding a polyepoxide (b1), a curing agent (b2), and a silane coupling agent (b3) in a solvent, followed by stirring and mixing to cause a crosslinking polymerization reaction. .

Examples of the solvent include the same solvents as those mentioned for the low hygroscopic crosslinked polymer (A). As the solvent, t-butanol, diacetone alcohol, methyl ethyl ketone, butyl acetate, propylene carbonate, or diethylene glycol dimethyl ether is preferable.
A solvent may be used individually by 1 type and may use 2 or more types together.
The amount of the solvent used in producing the polymer (B1) is preferably 1 to 5 times the total mass of the polyepoxides (b1) and the curing agent (b2). Moreover, the amount of the solvent used for producing the polymer (B2) is 1 to 5 times the total mass of the polyepoxides (b1), the curing agent (b2), and the silane coupling agent (b3). Preferably there is.
The cross-linking polymerization reaction of the highly hygroscopic cross-linked polymer (B) is performed so that the cross-linking component remains to some extent.

The crosslinking polymerization reaction is preferably performed by stirring and mixing at 20 to 60 ° C. If the said temperature is 20 degreeC or more, sufficient reaction rate will be easy to be obtained. Moreover, if the said temperature is 60 degrees C or less, it will be easy to prevent that reaction advances too much.
Further, after the reaction, the obtained highly hygroscopic crosslinked polymer (B) may be diluted with butyl acetate or the like, if necessary.

The antifogging composition of the present invention is a composition comprising the low-hygroscopic crosslinked polymer (A) and the highly hygroscopic crosslinked polymer (B) described above. 1 type may be sufficient as a low hygroscopic crosslinked polymer (A), and 2 or more types may be sufficient as it. Moreover, only 1 type may be sufficient about a highly hygroscopic crosslinked polymer (B), and 2 or more types may be sufficient as it.
The ratio (Ma / Mb) of the low hygroscopic crosslinked polymer (A) [mass: Ma (g)] and the highly hygroscopic crosslinked polymer (B) [mass: Mb (g)] in the antifogging composition is 30/70 to 70/30. When the ratio (Ma / Mb) is within the above range, an antifogging film having both excellent antifogging performance and durability can be easily formed.

  Moreover, it is preferable that the antifogging composition of this invention contains the filler other than the low hygroscopic crosslinked polymer (A) and the high hygroscopic crosslinked polymer (B). By including the filler, the mechanical strength and heat resistance of the antifogging film comprising the formed crosslinked resin layer can be increased, and the curing shrinkage of the resin during the crosslinking polymerization reaction can be reduced.

As the filler, a filler made of a metal oxide is preferable. Examples of the metal oxide include silica, alumina, titania, and zirconia. Among these, silica is preferable. Examples of such a filler include Snowtex IPA-ST (manufactured by Nissan Chemical Industries).
In addition to the filler, a filler made of ITO (Indium Tin Oxide) can also be used. Since ITO has infrared absorptivity, heat ray absorptivity can be imparted to the antifogging film. Therefore, if a filler made of ITO is used, in addition to hygroscopicity, an antifogging effect due to heat ray absorption can be expected.

  The filler is preferably particulate. The average particle size of the filler is preferably 0.01 to 0.3 μm, and more preferably 0.01 to 0.1 μm. Moreover, it is preferable that the compounding quantity of a filler is 1-20 mass% with respect to the total mass of polyepoxides and a hardening | curing agent, and it is more preferable that it is 1-10 mass%. When the blending amount of the filler is 1% by mass or more, it is easy to suppress a reduction in the curing shrinkage reduction effect of the polyepoxides. Further, if the blending amount of the filler is 20% by mass or less, a sufficient space for water absorption can be secured, and excellent antifogging performance can be easily obtained.

  In addition, when an antifogging composition is applied to the surface of a hydrophilic substrate and dried to form an antifogging film, the wettability of the antifogging composition makes the coating thickness non-uniform, resulting in perspective distortion. There is a case. In order to make the thickness of the coating film uniform, it is preferable to add a leveling agent. Examples of the leveling agent include a silicone leveling agent, a fluorine leveling agent, and an acrylic leveling agent, and among them, a silicone leveling agent is preferable.

  Examples of the silicone leveling agent include amino-modified silicone, carbonyl-modified silicone, epoxy-modified silicone, polyether-modified silicone, and alkoxy-modified silicone. Moreover, as a silicone type leveling agent, an amino modified silicone or a polyether modified silicone is preferable.

  In addition, it is also preferable to add a silicone leveling agent having an oxyalkylene chain such as an oxyethylene chain or an oxypropylene chain from the viewpoint of imparting hydrophilicity to the antifogging film and improving the antifogging performance.

By adding 0.02 to 1% by mass of the silicone leveling agent with respect to the mass of the antifogging composition, the wettability can be improved and the thickness of the coating film can be made uniform. Moreover, since the addition amount of a silicone type leveling agent is easy to prevent the cloudiness of a coating film, it is preferable that it is 0.02-0.30 mass% with respect to the mass of an anti-fogging composition, 0.02- More preferably, it is 0.10% by mass.
The antifogging composition of the present invention may contain a surfactant.
As the surfactant, any of a nonionic surfactant, a cationic surfactant, a betaine surfactant, and an anionic surfactant may be used. If the surfactant is a surfactant having an oxyalkylene chain such as an oxyethylene chain or an oxypropylene chain, hydrophilicity can be imparted to the formed antifogging film, and the antifogging performance is improved.

<Anti-fogging composition kit>
The kit for an antifogging composition of the present invention is a kit for preparing the antifogging composition of the present invention, and is a liquid composition containing a low hygroscopic crosslinked polymer (A) (hereinafter referred to as liquid composition A). And a liquid composition containing the highly hygroscopic crosslinked polymer (B) (hereinafter referred to as “liquid composition B”).
In the kit for anti-fogging composition of the present invention, the low-hygroscopic crosslinked polymer (A) and the highly hygroscopic crosslinked polymer (B) were produced by the above-described production methods, which were designated as liquid compositions A and B, respectively. It can be prepared by diluting the product with butyl acetate or the like as necessary.
The liquid composition A and the liquid composition B may contain the filler, leveling agent, surfactant, and the like as necessary.

  The low hygroscopic crosslinked polymer (A) and the low hygroscopic crosslinked polymer (B) of the present invention may cause a curing reaction depending on the storage environment. Therefore, it is preferable to prepare an antifogging composition by mixing it immediately before use as much as possible, as a kit for an antifogging composition.

The content of the low hygroscopic crosslinked polymer (A) in the liquid composition A (100% by mass) is preferably 10 to 40% by mass. When the content of the low hygroscopic crosslinked polymer (A) is 10% by mass or more, it is easy to prepare an antifogging composition that forms an antifogging film having excellent antifogging performance and durability. Moreover, if content of a low hygroscopic crosslinked polymer (A) is 40 mass% or less, it will be easy to suppress that a low hygroscopic crosslinked polymer (A) raise | generates hardening reaction in the liquid composition A.
The content of the highly hygroscopic crosslinked polymer (B) in the liquid composition B (100% by mass) is preferably 10 to 40% by mass. When the content of the highly hygroscopic crosslinked polymer (B) is 10% by mass or more, it is easy to prepare an antifogging composition that forms an antifogging film having excellent antifogging performance and durability. Moreover, if content of a highly hygroscopic crosslinked polymer (B) is 40 mass% or less, it will be easy to suppress that a highly hygroscopic crosslinked polymer (B) raise | generates hardening reaction in the liquid composition B.

<Anti-fogging article>
The antifogging article of the present invention has a hydrophilic substrate and an antifogging film formed on the surface of the hydrophilic substrate.
[Hydrophilic substrate]
The hydrophilic substrate is a substrate having a water contact angle of 20 ° or less.
The hydrophilic substrate is preferably a substrate made of glass, plastic, metal, ceramics, or a combination thereof (composite material, laminated material, etc.), more preferably a transparent substrate made of glass or plastic, or a mirror. . As the glass, soda lime glass is particularly preferable.
The shape of the hydrophilic substrate may be a flat plate, or the entire surface or a part thereof may have a curvature. The thickness of the hydrophilic substrate can be appropriately selected depending on the use of the antifogging article, and is generally preferably 1 to 10 mm.
The hydrophilic substrate preferably has a reactive group on the surface. As the reactive group, a hydrophilic group is preferable, and as the hydrophilic group, a hydroxyl group is preferable. Also, the surface of the substrate can be made hydrophilic by subjecting the substrate to oxygen plasma treatment, corona discharge treatment, ozone treatment, etc. to decompose and remove organic substances adhering to the surface or to form a fine uneven structure on the surface. Good. Glass and metal oxide usually have a hydroxyl group on the surface.
In addition, the hydrophilic substrate is provided with a metal oxide thin film such as silica, alumina, titania, zirconia or an organic group-containing metal oxide thin film on the surface of glass or the like for the purpose of improving adhesion with the antifogging film. But you can.

The metal oxide thin film can be formed by a sol-gel method using a metal compound having a hydrolyzable group. As the metal compound, tetraalkoxysilane, tetraisocyanatesilane, or oligomers thereof are preferable.
The organic group-containing metal oxide thin film can be obtained by treating the substrate surface with an organometallic coupling agent. As the organometallic coupling agent, a silane coupling agent for surface treatment, a titanium coupling agent, an aluminum coupling agent and the like can be used, and a silane coupling agent is preferably used.

[Anti-fogging film]
The antifogging film of the present invention is a film composed of a crosslinked resin layer formed from the above-described antifogging composition. The crosslinked resin layer is a layer made of a non-linear polymer having a three-dimensional network structure.
In the anti-fogging film, the closer to the hydrophilic substrate side, the higher the proportion of the low hygroscopic crosslinked polymer (A), and the closer to the antifogging film surface side, the higher the proportion of the highly hygroscopic crosslinked polymer (B). It is high. Thereby, it is possible to achieve both excellent anti-fogging performance and durability.
The saturated moisture absorption amount of the antifogging film is 20 mg / cm ³ or more. The saturation moisture absorption amount of the antifogging is preferably 45~150mg / cm ^3, further preferably 60 to 100 mg / cm ^3. When the saturated moisture absorption amount is 20 mg / cm ³ or more, high antifogging performance is obtained. On the other hand, if the saturated moisture absorption amount is 150 mg / cm ³ or less, it is easy to prevent the durability and adhesion during moisture absorption from being lowered.

The film thickness of the antifogging film is 1.0 μm or more, preferably 5 μm or more, and more preferably 10 μm or more. If the film thickness of the antifogging film is 1.0 μm or more, it becomes easy to secure a necessary saturated moisture absorption amount for the entire antifogging film. On the other hand, from the viewpoint of preventing the durability of the antifogging film from being lowered, the thickness of the antifogging film is preferably 50 μm or less, and more preferably 30 μm or less.
Since the saturated moisture absorption amount of the antifogging film is proportional to the amount of hydrophilic groups in the crosslinked resin layer constituting the antifogging film, it can be controlled by adjusting the amount of hydrophilic groups. The amount of the hydrophilic group in the crosslinked resin layer can be adjusted by adjusting the amount of the hydrophilic group (for example, hydroxyl value) contained in the polyepoxides and the curing agent. When a hydrophilic group is formed by a crosslinking reaction, the saturated moisture absorption can be controlled by adjusting the number of functional groups and the degree of crosslinking of the crosslinking component and the curing agent.
The saturated moisture absorption amount also depends on the degree of crosslinking in the crosslinked resin layer. If the number of cross-linking points contained in the cross-linked resin layer per unit amount is large, the cross-linked resin layer has a dense three-dimensional network structure, and the space for water retention is reduced, so that the hygroscopic property is lowered. On the other hand, if there are few crosslinking points contained per unit amount, the space for water retention will become large and it will be thought that moisture absorption becomes high. The glass transition point of the crosslinkable resin is closely related to the number of crosslink points in the crosslinkable resin. In general, a resin having a high glass transition point is considered to have a large number of crosslink points per unit amount.
Therefore, in order to increase the antifogging performance, it is preferable to lower the glass transition point of the highly hygroscopic crosslinked polymer (B), and in order to increase the durability, the glass transition of the low hygroscopic crosslinked polymer (A). It is better to raise the point.

  From the above, the glass transition point of the highly hygroscopic crosslinked polymer (B) is preferably 10 to 200 ° C, and more preferably 30 to 150 ° C. Moreover, it is preferable that the glass transition point of a low hygroscopic crosslinked polymer (A) is 50-200 degreeC, and it is more preferable that it is 90-150 degreeC. When the glass transition point of the low hygroscopic crosslinked polymer (A) and the high hygroscopic crosslinked polymer (B) is within the above range, it is easy to achieve both antifogging performance and durability at a high level.

The glass transition point is a value measured according to JIS K7121. Specifically, a film was formed on the substrate with the low hygroscopic crosslinked polymer (A) or the high hygroscopic crosslinked polymer (B), and this was left in an environment of 20 ° C. and 50% relative humidity for 1 hour. Thereafter, the value is measured using a differential scanning calorimeter. However, the heating rate at the time of measurement shall be 10 degrees C / min.
In addition, when the moisture absorption amount exceeds the limit amount of the crosslinked resin layer, the antifogging article should have a water film rather than being cloudy depending on the application (such as when used in a bathroom vanity). There is also. Therefore, it is preferable that the crosslinked resin layer contains a surfactant. As a method of including a surfactant in the crosslinked resin layer, a method of adding a surfactant to the antifogging composition, a method of adding a surfactant after coating the antifogging composition on a hydrophilic substrate, and the like. Examples include a method of further applying the composition and performing heat curing, and the latter is preferable from the viewpoint of more excellent effects. The surfactant used for this purpose preferably has a reactive group. By having the reactive group, the surfactant becomes a part of the crosslinked resin layer, and the effect becomes higher.
The antifogging film preferably has a change in haze value of 20% or less before and after the test according to the abrasion resistance test conducted according to JIS R 3212.

<Method for producing antifogging article>
As a method for producing the antifogging article of the present invention, a method (1) of reacting a liquid composition containing the antifogging composition on a hydrophilic substrate, molding the antifogging composition into a film, The method (2) etc. which bond this film and a hydrophilic base | substrate are mentioned. Among them, the method (1) is preferable because a good appearance can be maintained when an antifogging film is provided on the surface of a hydrophilic substrate having a large area or during industrial mass production.

Hereinafter, the method (1) will be described in detail.
Method (1) is a method for producing an antifogging article having an antifogging film comprising a crosslinked resin layer on a hydrophilic substrate, and is a liquid composition containing the antifogging composition of the present invention (hereinafter referred to as liquid composition). This is a method including an application step of applying a product C) onto a hydrophilic substrate and a curing step of forming a crosslinked resin layer by heat curing. In the curing step, the crosslinkable groups of the polyepoxides (a1) and polyepoxides (b1) remaining in the low hygroscopic crosslinked polymer (A) and the high hygroscopic crosslinked polymer (B) are cured by a crosslinking reaction. A crosslinked resin layer is formed.

  In the application step, the liquid composition C is applied to the surface of the hydrophilic substrate. The liquid composition C preferably contains a solvent in order to improve the coating workability. Therefore, the low hygroscopic cross-linked polymer (A) and the high hygroscopic cross-linked polymer (B) are prepared as a liquid composition containing a solvent as in the above-described method, and mixed after being diluted as necessary. It is preferable to obtain an antifogging composition containing a solvent as the liquid composition C.

Examples of the method for applying the liquid composition C onto the hydrophilic substrate surface include spin coating, dip coating, spray coating, flow coating, and die coating. Among these, spray coating, flow coating, and die coating are preferable.
The thickness of the coating film obtained by applying the liquid composition C is preferably 5 to 100 μm.

  In the curing step, the crosslinked resin layer is formed by heat curing the coating film of the liquid composition C. This crosslinking reaction may be accompanied by a bond forming reaction with the hydrophilic substrate surface. From the viewpoint of durability of the resulting antifogging article, the crosslinking reaction is preferably accompanied by a bond forming reaction with the surface of the hydrophilic substrate.

The conditions for heat curing can be carried out, for example, by holding a hydrophilic substrate having a coating film at 100 to 300 ° C. for 1 minute to 1 hour using an infrared heating furnace or the like. Moreover, it can implement also by irradiating an ultraviolet-ray or visible light using a metal halide lamp, a high pressure mercury lamp, a halogen lamp etc. In this case, the integrated light quantity is preferably 10 to 1000 mJ / cm ² .
When the surfactant is included in the crosslinked resin layer, the surfactant may be included in the liquid composition C, and the crosslinked resin layer may be formed using the above method. The method of performing a hardening process after apply | coating the liquid composition containing surfactant further after this may be sufficient.
By the method described above, an antifogging article in which an antifogging film composed of a crosslinked resin layer is formed on a hydrophilic substrate is obtained.

  In general, when a hygroscopic cross-linked resin layer is formed on the surface of a substrate, the antifogging performance that is manifested by moisture absorption correlates with the hygroscopicity of the formed cross-linked resin layer. The higher the hygroscopicity of the cross-linked resin layer, the longer the effect of reducing the atmospheric humidity on the surface of the cross-linked resin layer formed on the substrate surface, and the higher the antifogging performance. The hygroscopic crosslinked resin layer expands when absorbing moisture and contracts when releasing moisture. Therefore, the hygroscopic crosslinked resin layer having high anti-fogging performance repeats large expansion and contraction, and interface stress accumulates at the bonding interface between the substrate and the hygroscopic crosslinked resin layer, and the adhesiveness tends to decrease. In some cases, the hygroscopic crosslinked resin layer may peel off.

  Moreover, a crosslinked resin layer takes in the alkali ion and acidic ion which originate in a washing | cleaning agent and drinking water with water at the time of moisture absorption. When alkali ions or acidic ions move to the adhesion interface between the substrate and the crosslinked resin layer, the bond between the reactive group on the substrate surface and the crosslinkable resin in the crosslinked resin layer is broken, and the crosslinked resin layer is peeled off or decomposed. There is a case. Further, when the substrate is soda lime glass, when the hygroscopic crosslinked resin layer takes in water and the water moves to the adhesion interface, an alkaline component comes out from the substrate, which causes the same problem.

On the other hand, the crosslinked resin layer constituting the antifogging film in the present invention is hydrophilic because the ratio of the low hygroscopic crosslinked polymer (A) on the hydrophilic substrate side is high due to the effect of the silane coupling agent (a3). The saturated moisture absorption in the vicinity of the substrate is small, and the degree of expansion / contraction is small. Therefore, the adhesiveness between the crosslinked resin layer and the hydrophilic substrate is high. In addition, since the ratio of the low hygroscopic crosslinked polymer (A) on the hydrophilic substrate side is high, it inhibits alkali ions, acidic ions, etc. taken together with water from coming between the crosslinked resin layer and the hydrophilic substrate. It is possible to prevent the bond between the hydrophilic substrate and the antifogging film from being broken. Similarly, since water can be prevented from transferring between the crosslinked resin layer and the hydrophilic substrate, even if the hydrophilic substrate is glass, the antifogging film is peeled off from the hydrophilic substrate by an alkali component, etc. The problem of almost disappears.
Furthermore, in the present invention, since the ratio of the highly hygroscopic crosslinked polymer (B) is increased on the surface side of the antifogging film at the same time, the surface side of the antifogging film becomes highly hygroscopic and can exhibit high antifogging performance.

Since the anti-fogging composition of the present invention mixes the low-hygroscopic crosslinked polymer (A) and the highly hygroscopic crosslinked polymer (B) as a polymer, the compatibility thereof decreases to some extent. The distribution as described above in the antifogging film can be generated by utilizing the effect of the ring agent.
In addition, since polyepoxides are used in the antifogging composition in the present invention, a hydroxyl group is generated by a crosslinking reaction, so that the antifogging performance excellent in the antifogging film can be exhibited.
Further, the antifogging film in the present invention does not have a two-layer configuration of a low hygroscopic crosslinked resin layer and a highly hygroscopic crosslinked resin layer, and has no interface in the antifogging film. Since the generation of stress can be suppressed, the durability is excellent.
From the above, the antifogging article of the present invention in which an antifogging film is formed on a hydrophilic substrate using the antifogging composition of the present invention has both excellent antifogging performance and durability.

  The antifogging article of the present invention does not necessarily have to be provided with an antifogging film composed of a crosslinked resin layer on the entire surface of the hydrophilic substrate. For example, the antifogging film may be formed on a part of the substrate surface. The antifogging film of the present invention is not limited to a single layer, and may be composed of a plurality of layers as long as it satisfies the conditions of the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
The water solubility of the polyepoxides used in this example was calculated by the method shown below.
[Water solubility]
A solution was prepared in a container with a ratio of the mass W2 of the polyepoxides to the mass W1 of distilled water (W1: W2) being 90:10 and stirred at 25 ° C. for 5 minutes or more. The solution is allowed to stand for 1 hour, and then the precipitated or suspended polyepoxides separated from distilled water are collected, the mass W3 is measured, and the ratio of the polyepoxides dissolved in water is calculated according to the following formula to calculate the water solubility. did.
Water solubility (%) = {(W2-W3) / W2} × 100

<Evaluation method>
Evaluation of the antifogging composition and the antifogging article in this example was performed as follows.

[Measurement of film thickness]
After the antifogging article is left in an environment of 25 ° C. and 50% relative humidity for 1 hour, the film thickness of the antifogging film comprising a crosslinked resin layer is measured using a stylus type surface shape measuring device DEKTAK3030 (manufactured by ULVAC). The step was measured.

[Measurement of saturated moisture absorption]
The saturation moisture absorption was measured for the entire antifogging film composed of the crosslinked resin layer.
First, a cross-linked resin layer was provided on the substrate, which was left in an environment of 25 ° C. and a relative humidity of 50% for 1 hour, and then the surface was placed on a hot water bath at 40 ° C. to cause cloudiness or distortion due to a water film. Immediately afterwards, the total water content (Q1) was measured using a trace moisture meter.
Separately, the moisture content (Q2) of the substrate itself in which the crosslinked resin layer is not formed is measured in the same procedure, and the value obtained by subtracting the moisture content (Q2) from the moisture content (Q1) is the volume of the crosslinkable resin. The value obtained by dividing the value by the amount was defined as the saturated moisture absorption amount.

The moisture content was measured with a micro moisture meter FM-300 (manufactured by Kett Science Laboratory). The test sample was heated at 120 ° C., and the moisture released from the test sample was adsorbed on the molecular sieve in the micro moisture meter, and the mass change of the molecular sieve was taken as the moisture content.
The end point of the measurement was the time when the amount of change in the molecular sieves per minute became 0.02 mg or less. The saturated moisture absorption was evaluated as follows: 3.3 cm × 10 cm × 5 mm thick mirror substrate, 3.3 cm × 10 cm × 100 μm thick PET (polyethylene terephthalate) substrate, 50 mmΦ × 3 mm aluminum substrate, and 3.3 cm × 10 cm × sample prepared using a soda lime glass substrate having a thickness of 2 mm (comparative) (area of cross-linked resin layer 33cm ^2.) it was carried out by.

[Evaluation of anti-fogging performance]
The surface of an antifogging film of an antifogging article left in an environment of 25 ° C. and 50% relative humidity for 1 hour is placed on a 40 ° C. hot water bath, and the antifogging time (minutes) until the water film is observed and cloudiness. The anti-fogging time (minutes) until was observed was measured. A normal substrate not subjected to an antifogging process (a mirror substrate having no antifogging film, a soda lime glass substrate, a PET substrate, an aluminum substrate) was fogged in 0.01 to 0.08 minutes.
The antifogging performance required for the antifogging film varies depending on the application. In this example, the time until either one of water film or cloudiness is recognized is 0.3 minutes or more practically, 0.5 minutes or more is preferable, and 1 minute or more is more preferable. .

[Evaluation of anti-fog retention]
On the surface of the anti-fogging film of the anti-fogging article, a Nell cloth (cotton No. 300) containing distilled water (1 mL) was reciprocated 5000 times with a load of 4.9 N / 4 cm ² , and then warm water at 40 ° C. We put on bath and evaluated based on the following evaluation criteria.
(Double-circle): There was no change in external appearance and the anti-fogging time was 1 minute or more.
◯: There was no change in appearance, and the antifogging time was 0.3 minutes or more and less than 1 minute.
X: At least one of whether the appearance was changed or the antifogging time was less than 0.3 minutes was observed.

[Evaluation of dry cloth friction resistance]
The anti-fogging film surface of the anti-fogging article was reciprocated 5000 times using a flannel cloth (cotton No. 300) under a load of 14.7 N / 4 cm ² and then put on a warm water bath at 40 ° C. Evaluation based on the evaluation criteria.
(Double-circle): There was no change in external appearance and the anti-fogging time was 1 minute or more.
◯: There was no change in appearance, and the antifogging time was 0.3 minutes or more and less than 1 minute.
X: At least one of whether the appearance was changed or the antifogging time was less than 0.3 minutes was observed.

[Evaluation of hot water resistance]
The antifogging article was immersed in distilled water at 60 ° C. for 10 days, dried at room temperature, and evaluated based on the following evaluation criteria.
(Double-circle): There was no change in external appearance and the anti-fogging time was 1 minute or more.
◯: There was no change in appearance, and the antifogging time was 0.3 minutes or more and less than 1 minute.
Δ: The appearance was slightly changed but at a practical level, and the antifogging time was 0.3 minutes or more and less than 1 minute.
X: At least one of whether the appearance was changed or the antifogging time was less than 0.3 minutes was observed.

[Evaluation of moisture resistance]
The antifogging article was left in a constant temperature and humidity chamber adjusted to 60 ° C. and relative humidity 95% for 14 days, cleaned on the surface and then put on a 40 ° C. hot water bath, and evaluated based on the following evaluation criteria. .
(Double-circle): There was no change in external appearance and the anti-fogging time was 1 minute or more.
◯: There was no change in appearance, and the antifogging time was 0.3 minutes or more and less than 1 minute.
X: At least one of whether the appearance was changed or the antifogging time was less than 0.3 minutes was observed.

[Evaluation of contamination resistance]
On the surface of the antifogging film of the antifogging article, 0.5 mL of a commercially available gargle liquid (Isodine gargle liquid, manufactured by Meiji Seika Co., Ltd.) was dropped and left at room temperature for 3 hours, washed with water and dried at room temperature for 2 days. It put on 40 degreeC warm water bath, and evaluated visually based on the following evaluation criteria.
(Double-circle): There was no change in an external appearance and coloring was hardly recognized.
○: No change in appearance, and coloring was observed.
×: Change in appearance was observed.

<Manufacture of antifogging composition>
Table 1 shows the physical properties of the polyepoxides used in the production of the antifogging composition. However, WPE in Table 1 is an epoxy equivalent, hydrophilic groups are a hydroxyl group (OH group) and an oxyalkylene group, and hydrophobic groups are an epoxy group, a chloro group (Cl group), and an alkyl group. Moreover, the symbol of the kind of polyepoxides in Table 1 has the following meaning.
EX622: Sorbitol polyglycidyl ether, trade name: Denacol EX-622, manufactured by Nagase ChemteX Corporation EX321: Trimethylolpropane polyglycidyl ether, trade name: Denacol EX-321, manufactured by Nagase ChemteX Corporation EX314: Glycerol polyglycidyl ether, commodity Name: Denacol EX-314, manufactured by Nagase ChemteX Corporation EX1610: Aliphatic glycidyl ether compound, Product name: Denacol EX-1610, manufactured by Nagase ChemteX Corporation

[Production Example 1]
In a glass container in which a stirrer and a thermometer are set, 7.47 g of diacetone alcohol (manufactured by Junsei Chemical Co., Ltd.), 0.11 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.), sorbitol polyglycidyl as polyepoxides (a1) 5.94 g of ether (water solubility less than 0.08%, Denacol EX-622, manufactured by Nagase ChemteX Corp.) and 1.88 g of polyoxyalkylene triamine (Jefamine T403, manufactured by Huntsman Corp.) as a curing agent (a2) And stirred at 25 ° C. for 10 minutes. Next, 0.90 g of 3-aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) is added as a silane coupling agent (a3), stirred at 25 ° C. for 20 minutes, and diluted 3-fold with butyl acetate. Thus, a low hygroscopic crosslinked polymer (A-1) was obtained. Denacol EX-622 has an epoxy equivalent of 191 g / mol and a hydroxyl value of 67 mg KOH / g (1.19 meq / g).
Further, in a glass container in which a stirrer and a thermometer are set, 19.59 g of t-butanol (manufactured by Junsei Kagaku), 2.17 g of Jeffamine T403 (manufactured by Huntsman) as a curing agent (b2), polyepoxides As (b1), 5.32 g of an aliphatic glycidyl ether compound (water solubility: 100%, Denacol EX-1610, manufactured by Nagase ChemteX Corporation) was added, stirred at 25 ° C. for 15 minutes, and then stirred at 50 ° C. for 1 hour. . After the stirring, the mixture was cooled to room temperature and diluted 1.5 times with butyl acetate to obtain a highly hygroscopic crosslinked polymer (B1-1). The epoxy equivalent of Denacol EX-1610 is 170 g / mol. The obtained low hygroscopic crosslinked polymer (A-1) and high hygroscopic crosslinked polymer (B1-1) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic crosslinked polymer (A-1) and 10 g of the high hygroscopic crosslinked polymer (B1-1) are added and stirred at 25 ° C. for 10 minutes to prevent fogging. Sex composition (Z-1) was obtained.

[Production Example 2]
In a glass container in which a stirrer and a thermometer are set, 10.92 g of diacetone alcohol (made by Junsei Kagaku Co., Ltd.) and 5.94 g of Denacol EX-622 (manufactured by Nagase ChemteX Corp.) as a polyepoxide (a1) are cured. As an agent (a2), 5.72 g of hydrogenated methyl nadic acid anhydride (HNA-100, manufactured by Shin Nippon Rika Co., Ltd.) was added and stirred at 25 ° C. for 1 hour. Next, 0.90 g of 3-glycidoxypropyltrimethoxysilane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) is added as a silane coupling agent (a3), stirred at 25 ° C. for 1 hour, and tripled with butyl acetate. Dilution was performed to obtain a low hygroscopic crosslinked polymer (A-2).
Further, a highly hygroscopic crosslinked polymer (B1-1) was obtained in the same manner as in Production Example 1. The obtained low hygroscopic crosslinked polymer (A-2) and high hygroscopic crosslinked polymer (B1-1) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic crosslinked polymer (A-2) and 10 g of the high hygroscopic crosslinked polymer (B1-1) are placed and stirred at 25 ° C. for 10 minutes to prevent fogging. Sex composition (Z-2) was obtained.

[Production Example 3]
A low hygroscopic crosslinked polymer (A-2) was obtained in the same manner as in Production Example 2.
In a glass container with a stirrer and thermometer, 28.97 g of diacetone alcohol (manufactured by Junsei Chemical Co., Ltd.) and hydrogenated methylnadic acid anhydride (HNA-100, Shin Nippon Rika Co., Ltd.) as a curing agent (b2) 5.76 g of Denapor EX-1610 (manufactured by Nagase ChemteX Corporation) as a polyepoxide (b1) was added and stirred at 25 ° C. for 15 minutes and then stirred at 50 ° C. for 1 hour. After the stirring, the mixture was cooled to room temperature and diluted 1.5 times with butyl acetate to obtain a highly hygroscopic crosslinked polymer (B1-2). The obtained low hygroscopic crosslinked polymer (A-2) and high hygroscopic crosslinked polymer (B1-2) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic crosslinked polymer (A-2) and 10 g of the high hygroscopic crosslinked polymer (B1-2) are placed and stirred at 25 ° C. for 10 minutes to prevent fogging. Sex composition (Z-3) was obtained.

[Production Examples 4 to 7]
Prevention was carried out in the same manner as in Production Example 4 except that the ratio of the low hygroscopic crosslinked polymer (A-1) and the highly hygroscopic crosslinked polymer (B1-1) (total mass 20 g) was changed as shown in Table 2. The cloudy composition (Z-4) to the antifogging composition (Z-7) were obtained.

[Production Example 8]
A low hygroscopic crosslinked polymer (A-1) was obtained in the same manner as in Production Example 1.
Further, in a glass container in which a stirrer and a thermometer are set, 19.59 g of t-butanol (manufactured by Junsei Kagaku), 2.17 g of Jeffamine T403 (manufactured by Huntsman) as a curing agent (b2), polyepoxides As (b1), 5.32 g of Denacor EX-1610 (manufactured by Nagase ChemteX Corporation) was added, stirred at 25 ° C. for 10 minutes, and then stirred at 50 ° C. for 1 hour. Next, 0.20 g of KBM903 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a silane coupling agent (b3), and the mixture was stirred at 25 ° C. for 15 minutes. After completion of the stirring, the mixture was cooled to room temperature and diluted 1.5 times with butyl acetate to obtain a highly hygroscopic crosslinked polymer (B2-1). The obtained low hygroscopic crosslinked polymer (A-1) and high hygroscopic crosslinked polymer (B2-1) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic crosslinked polymer (A-1) and 10 g of the high hygroscopic crosslinked polymer (B2-1) are added and stirred at 25 ° C. for 10 minutes to prevent fogging. Sex composition (Z-8) was obtained.

[Production Example 9]
A highly hygroscopic crosslinked polymer (B2′-1) was prepared in the same manner as in Production Example 8 except that the amount of KBM903 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent (b3), was 0.30 g. The obtained low hygroscopic crosslinked polymer (A-1) and high hygroscopic crosslinked polymer (B2′-1) were used as an antifogging composition kit, and the antifogging composition (Z-9) was obtained. Got.

[Production Example 10]
A low hygroscopic crosslinked polymer (A′-1) was prepared in the same manner as in Production Example 1 except that the amount of KBM903 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent (a3), was 0.50 g. Obtained.
Further, a highly hygroscopic crosslinked polymer (B1-1) was obtained in the same manner as in Production Example 1. The obtained low hygroscopic crosslinked polymer (A′-1) and high hygroscopic crosslinked polymer (B1-1) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic cross-linked polymer (A′-1) and 10 g of the high hygroscopic cross-linked polymer (B1-1) are placed and stirred at 25 ° C. for 10 minutes. A cloudy composition (Z-10) was obtained.

[Production Example 11]
In a glass container in which a stirrer and a thermometer are set, 6.69 g of diacetone alcohol (manufactured by Junsei Kagaku Co., Ltd.), 0.11 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.), and Denacol EX- as polyepoxides (a1) 622 (manufactured by Nagase ChemteX Corp.) and 5.88 g of Jeffermin T403 (manufactured by Huntsman Corp.) as a curing agent (a2) were added and stirred at 25 ° C. for 2 hours. Subsequently, it diluted 3 times with butyl acetate, and the low hygroscopic crosslinked polymer (A'-2) was obtained.
Further, a highly hygroscopic crosslinked polymer (B1-1) was obtained in the same manner as in Production Example 1. The obtained low hygroscopic crosslinked polymer (A′-2) and high hygroscopic crosslinked polymer (B1-1) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic crosslinked polymer (A′-2) and 10 g of the high hygroscopic crosslinked polymer (B1-1) are placed and stirred at 25 ° C. for 10 minutes to prevent A cloudy composition (Z-11) was obtained.

[Production Example 12]
In a glass container in which a stirrer and a thermometer are set, 6.09 g of diacetone alcohol (manufactured by Junsei Chemical Co., Ltd.), 0.11 g of distilled water (manufactured by Wako Pure Chemical Industries, Ltd.), other than polyepoxides (a1) 4.35 g of trimethylolpropane polyglycidyl ether (27% water solubility, Denacol EX-321, manufactured by Nagase ChemteX Corp.) as polyepoxides and 1.88 g of Jeffamine T403 (manufactured by Huntsman Corp.) as curing agent (a2) And stirred at 25 ° C. for 10 minutes. Next, 0.90 g of KBM903 (manufactured by Shin-Etsu Chemical Co., Ltd.) is added as a silane coupling agent, stirred at 25 ° C. for 20 minutes, diluted three-fold with butyl acetate, and a low hygroscopic crosslinked polymer (A '-3) was obtained. The epoxy equivalent of Denacol EX-321 is 140 g / mol.
Further, a highly hygroscopic crosslinked polymer (B1-1) was obtained in the same manner as in Production Example 1. The obtained low hygroscopic crosslinked polymer (A′-3) and high hygroscopic crosslinked polymer (B1-1) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic cross-linked polymer (A′-3) and 10 g of the high hygroscopic cross-linked polymer (B1-1) are added and stirred at 25 ° C. for 10 minutes to prevent A cloudy composition (Z-12) was obtained.

[Production Example 13]
A low hygroscopic crosslinked polymer (A-1) was obtained in the same manner as in Production Example 1, except that the amount of diacetone alcohol used was 6.09 g.
In a glass container in which a stirrer and a thermometer are set, 17.46 g of t-butanol (manufactured by Junsei Chemical Co., Ltd.) and glycerol polyglycidyl ether (water solubility 64%, Denacol) as other polyepoxides other than polyepoxides (b1) 4.51 g of EX-314 (manufactured by Nagase ChemteX Corp.) and 2.17 g of Jeffermin T403 (manufactured by Huntsman Corp.) as a curing agent (b2) were stirred for 15 minutes at 25 ° C., then 1 at 50 ° C. Stir for hours. After the stirring, the mixture was cooled to room temperature and diluted 1.5 times with butyl acetate to obtain a highly hygroscopic crosslinked polymer (B1′-1). The epoxy equivalent of Denacol EX-314 is 144 g / mol. The obtained low hygroscopic crosslinked polymer (A-1) and high hygroscopic crosslinked polymer (B1′-1) were used as a kit for an antifogging composition.
In a glass container in which a stirrer is set, 10 g of the low hygroscopic crosslinked polymer (A-1) and 10 g of the high hygroscopic crosslinked polymer (B1′-1) are added, and the mixture is stirred for 10 minutes at 25 ° C. A cloudy composition (Z-13) was obtained.

<Manufacture of anti-fogging articles>
Using the antifogging composition obtained in the production examples, antifogging films were formed on various substrates and evaluated.
[Example 1]
In a glass container in which a stirrer is set, 83.46 g of butyl acetate, 15.00 g of diacetone alcohol, and 1.54 g of acryloyloxy group-containing nonionic surfactant (ER10, manufactured by Adeka) as a surfactant are placed. The mixture was stirred at 25 ° C. for 10 minutes to obtain a surfactant composition (X).
As a hydrophilic substrate, a clean mirror substrate (water contact angle 5 °, 100 mm × 200 mm × thickness 5 mm), which was polished and cleaned with cerium oxide, was used, and the surface of the mirror substrate was obtained in Production Example 1. The antifogging composition (Z-1) was applied by spray coating. Then, surfactant composition (X) was apply | coated by spray coating, and it hold | maintained for 5 minutes with the infrared heating furnace set to 360 degreeC, and obtained the antifogging article | item which has a crosslinked resin layer.

[Example 2]
As a hydrophilic substrate, a clean PET substrate (water contact angle 15 °, 210 mm × 297 mm × thickness 100 μm, HS-100, manufactured by Teijin DuPont Films Ltd.) which has been treated with UV ozone gas after removing surface contaminants with acetone. The antifogging composition (Z-1) obtained in Production Example 1 was applied to the surface of the PET substrate by spray coating. Then, surfactant composition (X) was apply | coated by spray coating, and it hold | maintained for 5 minutes with the infrared heating furnace set to 360 degreeC, and obtained the antifogging article | item which has a crosslinked resin layer.

[Example 3]
As a hydrophilic substrate, a clean aluminum substrate (water contact angle 5 °, 50 mmφ × thickness 3 mm) obtained by removing surface contaminants with acetone and subjected to UV ozone gas treatment was used on the surface of the aluminum substrate in Production Example 1. The obtained antifogging composition (Z-1) was applied by spin coating.
Then, surfactant composition (X) was apply | coated by spin coating, and it hold | maintained for 5 minutes with the infrared heating furnace set to 360 degreeC, and obtained the antifogging article which has a crosslinked resin layer.

[Example 4]
As a hydrophilic substrate, a clean mirror substrate (water contact angle 5 °, 100 mm × 200 mm × thickness 5 mm), which was polished and cleaned with cerium oxide, was used, and the surface of the mirror substrate was obtained in Production Example 1. The antifogging composition (Z-1) was applied by spray coating. Then, it hold | maintained for 5 minutes with the infrared heating furnace set to 360 degreeC, and obtained the anti-fogging article | item which has a crosslinked resin layer.

[Examples 5 to 8]
As a hydrophilic substrate, a clean mirror substrate (water contact angle of 5 ° or less, 100 mm × 200 mm × thickness 5 mm), which has been polished and washed with cerium oxide and dried, is shown in Table 3 on the surface of the mirror substrate. Thus, the antifogging composition obtained in the production example was applied by spray coating. Subsequently, the surfactant composition (X) was applied by spray coating, and held in an infrared heating furnace set at 360 ° C. for 5 minutes to obtain antifogging articles each having a crosslinked resin layer.

[Example 9]
An antifogging article having a crosslinked resin layer was obtained in the same manner as in Example 4 except that the antifogging composition (Z-8) was used.

[Examples 10 and 11]
An antifogging article having a crosslinked resin layer was obtained in the same manner as in Examples 5 to 8 except that the antifogging composition was used as shown in Table 3.

[Comparative Examples 1 and 2]
An antifogging article having a crosslinked resin layer was obtained in the same manner as in Example 4 except that the antifogging compositions (Z-9) and (Z-10) were used.

[Comparative Examples 3 to 5]
As a hydrophilic substrate, a clean mirror substrate (water contact angle of 5 ° or less, 100 mm × 200 mm × thickness 5 mm), which was polished and washed with cerium oxide and dried, was used on the surface of the mirror substrate. The antifogging compositions (Z-11) to (Z-13) obtained in 13 were applied by spray coating. Then, surfactant composition (X) was apply | coated by spray coating, and it hold | maintained for 5 minutes with the infrared heating furnace set to 360 degreeC, and obtained the antifogging article | item which has a crosslinked resin layer.

[Comparative Example 6]
The antifogging composition (Z-1) obtained in Production Example 1 was applied by spray coating on the surface of a mirror substrate (water contact angle 42 °, 100 mm × 200 mm × thickness 5 mm) whose surface was not washed. Then, surfactant composition (X) was apply | coated by spray coating, and it hold | maintained for 5 minutes with the infrared heating furnace set to 360 degreeC, and obtained the antifogging article | item which has a crosslinked resin layer. A part of the repellent pattern was seen in the crosslinked resin layer.
Table 3 shows the evaluation results of the antifogging articles obtained in Examples 1 to 11 and Comparative Examples 1 to 6.

As shown in Table 3, the antifogging articles of Examples 1 to 9 using the antifogging composition of the present invention are excellent in antifogging performance, and the durability of the antifogging performance (antifogging maintenance property), Excellent durability such as dry cloth rub resistance, warm water resistance, moisture resistance, and stain resistance. The antifogging composition of the present invention is a composition comprising a low hygroscopic crosslinked polymer (A) and a highly hygroscopic crosslinked polymer (B), and can be formed as a single-layer antifogging film. It was also excellent in performance.
In addition, the antifogging articles of Examples 10 and 11 both had an antifogging time of 1 minute or more and were excellent in the sustainability of the antifogging performance. Further, in both Examples 10 and 11, there was no practical problem with the durability of the antifogging film. In Example 11, although the appearance defect was observed with warm water resistance, the appearance was present only on the film surface observed in the comparative example, with only a part being seen from the end of the antifogging film. Unlike the defect, it was at a practical level. From the results of Examples 10 and 11 and the results of Examples 1 to 9, the antifogging composition of the present invention is a low-hygroscopic crosslinked polymer (A) [mass: Ma (g) in the antifogging composition. ] And the highly hygroscopic crosslinked polymer (B) [mass: Mb (g)] ratio (Ma / Mb) is 30/70 to 70/30, more excellent antifogging performance and durability Was found to be easy to obtain.

On the other hand, in Comparative Example 1 in which the amount of the silane coupling agent contained in the highly hygroscopic crosslinked polymer was large, the antifogging maintenance property was inferior to that of the Example. Further, in Comparative Example 2 in which the amount of the silane coupling agent contained in the low hygroscopic crosslinked polymer is small, the antifogging maintenance property is similarly inferior to the Examples. Further, in Comparative Example 3 in which the silane coupling agent was not contained in the low hygroscopic crosslinked polymer, the antifogging maintenance property, dry cloth friction resistance, warm water resistance, and moisture resistance were inferior.
Further, in Comparative Example 4 in which a polyepoxide having a water solubility of 20% or more was used for the low hygroscopic crosslinked polymer, the water resistance and moisture resistance were inferior. Further, Comparative Example 5 using a polyepoxide having a water solubility of less than 100% for the highly hygroscopic crosslinked polymer was inferior in antifogging maintenance property and dry cloth friction resistance, and inferior in antifogging performance.

  Moreover, in the comparative example 6 which did not use a hydrophilic base | substrate, it was inferior to anti-fogging maintenance property, dry cloth friction resistance, warm water, a weather resistance, and moisture resistance.

The anti-fogging article of the present invention can be used for, for example, window glass for transportation equipment (automobile, railway, ship, airplane, etc.), refrigerated showcase, vanity mirror, bathroom mirror, optical equipment and the like.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2008-152921 filed on June 11, 2008 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (10)

A composition for forming an antifogging film on a hydrophilic substrate, comprising the following low hygroscopic crosslinked polymer (A) and highly hygroscopic crosslinked polymer (B): object.
Low hygroscopic cross-linked polymer (A): cross-linking polymerization reaction of polyepoxides (a1) having a water solubility of less than 20%, a curing agent (a2), and a silane coupling agent (a3) represented by the following formula (I) It is a polymer obtained by this. However, the mass ratio of the silane coupling agent (a3) to the total mass (100 mass%) of the polyepoxides (a1), the curing agent (a2), and the silane coupling agent (a3) is 7 mass% or more.
Highly hygroscopic crosslinked polymer (B): a polymer (B1) obtained by a crosslinking polymerization reaction of a polyepoxide (b1) having a water solubility of 100% and a curing agent (b2), and / or the polyepoxide (b1) And a curing agent (b2) and a polymer (B2) obtained by a cross-linking polymerization reaction between the silane coupling agent (b3) represented by the following formula (I). However, the silane coupling agent (b3) based on the total mass (100% by mass) of the polyepoxides (b1), the curing agent (b2), and the silane coupling agent (b3) used for the crosslinking polymerization reaction of the polymer (B2). ) Is 3 mass% or less.
_{^{R 1 - (CH 2) n}} -Si (R 2) m (R 3) 3-m ··· (I)
(In the formula, R ¹ is an alkyl group containing a glycidyl group, an amino group, or a (meth) acryloyloxy group, n is an integer of 1 to 3, R ² is a hydrolyzable group, and m is 1 And R ³ is an alkyl group having 1 to ³ carbon atoms.)   The antifogging composition of Claim 1 whose mass ratio of the said low hygroscopic crosslinked polymer (A) and the said highly hygroscopic crosslinked polymer (B) is 30 / 70-70 / 30.   The antifogging composition according to claim 1 or 2, wherein the curing agent (a2) and the curing agent (b2) are polyamine compounds.   The antifogging composition according to any one of claims 1 to 3, wherein the polyepoxide (a1) is a polyglycidyl ether of an aliphatic polyol having 6 or more hydroxyl groups.   The antifogging composition according to any one of claims 1 to 4, wherein the polyepoxide (b1) is an aliphatic glycidyl ether compound.   The silane coupling agent (a3) is 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyl The antifogging composition according to any one of claims 1 to 5, which is dimethoxysilane or 3- (meth) acryloxypropyltrimethoxysilane. A kit for preparing the antifogging composition according to any one of claims 1 to 6,
A kit for an antifogging composition, comprising: a liquid composition containing the low hygroscopic crosslinked polymer (A); and a liquid composition containing the high hygroscopic crosslinked polymer (B). A crosslinked resin layer comprising a hydrophilic substrate and an antifogging film formed on the surface of the hydrophilic substrate, wherein the antifogging film is formed from the antifogging composition according to any one of claims 1 to 6. And an anti-fogging article having a saturated moisture absorption of 20 mg / cm ³ or more.   The antifogging article according to claim 8, wherein the crosslinked resin layer contains a surfactant. A method for producing an antifogging article having an antifogging film comprising a crosslinked resin layer on a hydrophilic substrate,
An antifogging property comprising a step of applying a liquid composition comprising the antifogging composition according to any one of claims 1 to 6 on the hydrophilic substrate, and a step of forming a crosslinked resin layer by heat curing. Article manufacturing method.