JP2002161241A - Antifogging composition for coating surface and antifogging surface-coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new antifogging composition for coating the surface having excellent clear visibility (transparency), durability and abrasion resistance and capable of always sustaining stable high antifogging effect even in the environment at high temperature and high humidifies (e.g. an expired air or steam) and to obtain a new antifogging surface-coated product. SOLUTION: This antifogging composition for coating the surface is characterized in that the composition is obtained from (A) an organic compound having functional groups [except an SiOR1 group (R1 group denotes a hydrogen atom or a 1-4C alkyl group)], (B) an organic compound having a functional group reactive with that possessed by the organic compound (A) and the SiOR1 group (R1 is the same as that described above) and/or its hydrolyzate condensate, (C) a solvent and, further as necessary, (D) an organometallic compound represented by the general formula R2mM(OR3)n (wherein, M is a metallic element; R2 is a 1-4C alkyl group or a 1-4C alkyl group having a functional group unreactive with amino group; R3 is a hydrogen atom or a 1-4C alkyl group; n is an integer of >=1; and m+n coincides with the valence of the metallic element).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel antifogging surface coating composition and an antifogging surface coating.

[0002]

2. Description of the Related Art The phenomenon that the surface of glass and other articles is fogged is
Fine water droplets adhere to and condense on the surface, and the water droplets are generated due to irregular reflection of light. This fogging is a problem that causes a remarkable decrease in the performance of optical components such as eyeglasses, goggles, and optical lenses, and is a problem in design and design in architectural window glasses and mirrors. As a glass, a decrease in the field of view is caused, which is a major safety problem.

[0003] As a method of solving such a problem, a surfactant is applied (for example, Japanese Patent Publication No. 52-47926), and a coating mainly comprising a hydrophilic and water-absorbing resin (for example,
JP-A-6-220428), immobilization of hydrophilic molecules (for example, JP-A-4-328701), surface roughening (for example, JP-A-61-91042) and the like.

[0004]

However, in the method of applying a surfactant, there are problems that the antifogging effect is low in persistence and only a temporary effect is obtained, and that visibility is reduced due to glare and whitening. . The coating method mainly comprising a hydrophilic / water-absorbing resin has problems such as low abrasion resistance and low durability. The hydrophilic molecule fixing method has problems that the antifogging performance is not always sufficient, that the method is easily stained, and that the durability of the antifogging effect is low. The surface roughening method is mainly manufactured by using etching with hydrofluoric acid, but has a problem such as a low antifogging effect against breath or steam.

[0005] Therefore, an object of the present invention is to provide an excellent visibility (transparency), durability, and abrasion resistance in view of the above-mentioned prior art, and even in an environment of high temperature and high humidity (for example, On the other hand, the present invention provides a novel antifogging surface coating composition and an antifogging surface coating which can always stably maintain a high antifogging effect.

[0006]

These objects are attained by the following (1) to (3).

(1) An organic compound (A) having a functional group [however, except for a SiOR ¹ group (R ¹ group represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)]; A compound obtained from an organic compound (B) having a functional group capable of reacting with a functional group contained in A) and a SiOR ¹ group (R ¹ is the same as described above) and / or a hydrolysis condensate thereof, and a solvent (C). A composition for surface coating for anti-fog comprising:

(2) Further, the following general formula (I) R ² _mM (OR ³ ) _n (I) (wherein, M is a metal element, R ² is an alkyl group having 1 to 4 carbon atoms or amino group) An alkyl group having 1 to 4 carbon atoms having a functional group that does not react with the group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 or more, and m + n is the valence of the metal element M The composition for antifogging surface coating according to the above (1), which is obtained by adding an organometallic compound (D) represented by the formula (1):

(3) The above-mentioned (1) or (2)
An anti-fogging surface coating obtained by coating the anti-fogging surface coating composition described in 1. above.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The antifogging surface coating composition of the present invention comprises a functional group (excluding a SiOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)). And an organic compound (B) having a functional group capable of reacting with a functional group of the organic compound (A) and a SiOR ¹ group (R ¹ is as defined above) and / or a hydrolyzate thereof. It is obtained by mixing or reacting the decomposition condensate with the solvent (C). Preferably, the composition for surface coating for antifogging of the present invention further comprises the following general formula (I) R ² _mM (OR ³ ) _n (I) (wherein, M is a metal element and R ² is An alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a functional group which does not react with an amino group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or more. And m + n coincides with the valency of the metal element M.), and the mixture is mixed or reacted.

The antifogging surface coating composition having the above-mentioned structure imparts sufficient strength and hardness to an antifogging surface coating obtained by coating the composition on a substrate, and provides excellent transparency. Performance, durability, weather resistance, impact resistance, heat resistance, flexibility,
It has been clarified by the inventors of the present invention over many years of research that they can exhibit moisture resistance, solvent resistance, light resistance, water resistance, flexibility, gas barrier properties, and the like.
No. 8 has been proposed, but as a result of further intensive studies by the present inventors, it has been found that more excellent anti-fogging properties can be exhibited. This is a new use development that cannot be achieved. In particular, they have found that these effects can be further enhanced by using the organometallic compound (D) represented by the general formula (I). Therefore, multi-functionality (transparency, durability, weather resistance, impact resistance, heat resistance, flexibility, moisture resistance, solvent resistance, light resistance, water resistance, etc.) , Flexibility, gas barrier properties, etc.), sufficient strength and hardness, and excellent antifogging properties, so that it can be suitably used, as well as for construction, vehicles, optical components, industrial, and agriculture. It can be widely applied to various uses for which anti-fog properties are required, such as glass products (lenses, mirrors, windows, etc.) and plastic products (films and sheets), which are used for daily necessities, houses, and medical use.

Hereinafter, the present invention will be described in detail.

The organic compound (A), which is one of the main components of the antifogging surface coating composition of the present invention, is an SiOR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). Is an organic compound having a functional group other than Since it does not have such a SiOR ¹ group, it does not participate in the hydrolysis condensation reaction of the organic compound (B) or the organometallic compound (D). An antifogging surface coating obtained by coating a substrate with an antifogging surface coating composition containing an organic compound (B), a solvent (C), and an organometallic compound (D) is hard but hard. Although it has a drawback of being brittle (poor in impact resistance), by adding the organic compound (A) to the antifogging surface coating composition, the resulting antifogging surface coating has flexibility and flexibility. Properties can be imparted. The organic compound (A) does not participate in the hydrolysis-condensation reaction, but the antifogging surface coating obtained by reacting with the organic compound (B) by the functional group of the organic compound (A). It is incorporated into the constituting polymer chains to form a so-called soft segment portion in the polymer chains constituting the membrane. For this reason, the impact resistance of the anti-fogging surface coating can be improved without lowering the hardness, strength, and denseness.

The antifogging surface coating composition of the present invention is coated on the substrate surface by a coating operation such as coating (spin coating, spray coating, dip coating, etc.) to obtain a desired antifogging surface coating. The organic compound (A) has a nitrogen atom-containing component such as an amino group, or the organic compound (B) or the organometallic compound (D) has a nitrogen atom such as an amino group. It is necessary to have a contained component. When the organic compound (B) or the organometallic compound (D) has, for example, an amino group or the like, the organic compound (A) does not necessarily have to have an amino group or the like. Hereinafter, for convenience, the nitrogen-containing component is described as an amino group, and the amino-containing organic compound (A) is referred to as an organic compound (A-1), and the organic compound (A) having no amino group is referred to as an organic compound (A-2). ).

In a preferred embodiment of the antifogging surface coating composition of the present invention, the organic compound (A) is an organic compound (A-1) having an amino group. Among them, organic high molecular compounds having a number average molecular weight of 200 or more, preferably 250 to 100,000, more preferably 300 to 10,000.
When the number average molecular weight of the organic compound (A-1)) is 200 or more, it is preferable from the viewpoint that excellent flexibility can be imparted to the obtained antifogging surface coating. However, the organic compound having an amino group (A-1) of the present invention is not limited to such an organic polymer compound at all.
It is a low molecular compound having a number average molecular weight of less than 200, and can be sufficiently used as a composition for surface coating for antifogging.
However, the number average molecular weight of the organic compound (A-1) is 20
When it is less than 0, the flexibility of the obtained antifogging surface coating is poor, or the composition for forming the antifogging surface coating by coating the antifogging surface coating composition on a substrate. Since the film properties may be inferior, it is necessary to pay close attention to its use. On the other hand, the organic compound (A-1)) has a number average molecular weight of 2
If it exceeds 10,000, the formed antifogging surface coating may be inferior in transparency and the flexibility of the antifogging surface coating may be inferior, so that its use is limited. May be affected.

The organic compound having an amino group of the present invention (A
More preferred as -1) are polyalkylene imines, among which polyethylene imines. This is because the high molecular weight organic compound (A-1) is extremely effective and effective from the viewpoint of imparting flexibility to the anti-fogging surface coating and adhesion to the substrate (substrate). . in this case,
The organic compound (B) is an organic compound having a functional group capable of reacting with an amino group, which is a functional group of the organic compound (A), together with the Si (OR ¹ ) group. An organic compound having an epoxy group as a functional group capable of reacting with an amino group which is a group is preferable.

In the case where the organic compound (A) is an organic compound (A-2) having no amino group, it can be suitably used as a composition for surface coating for anti-fog. This organic compound (A
-2) is preferably an organic compound having at least one functional group selected from the group consisting of an epoxy group, an isocyanate group, a carboxyl group or an anhydride thereof, an oxazolinyl group, an alkyl halide group and a hydroxyl group. It is. Among them, it is preferable to have an epoxy group. In this case, it is preferable to use an organic compound (B) having an alkoxysilyl group and an amino group.

Specific examples of the organic compound (A-1) include:
For example, allylamine, diallylamine, isopropylamine, diisopropylamine, iminobispropylamine, ethylamine, diethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3-diethylaminopropylamine, di-2
-Ethylhexylamine, dibutylaminopropylamine, propylamine, dimethylaminopropylamine,
One amino group such as methyliminobispropylamine, 3-methoxypropylamine, ethylenediamine, 1,4-diaminobutane, 1,2-diaminopropane, 1,3-diaminopropane, hexamethylenediamine, ethanolamine, diethanolamine, etc. Low molecular weight organic compounds having the above; polyalkylimines such as polyethyleneimines, for example, Epomin series manufactured by Nippon Shokubai Co., Ltd. (Epomin SP-003, Epomin SP-006, Epomin SP-012, Epomin SP-018, Epomin SP -103, Epomin SP-110, Epomin SP-
200, Epomin SP-300, Epomin SP-100
0, Epomin SP-1020, etc .; all are trade names),
Polyallylamines (for example, PA manufactured by Nitto Boseki Co., Ltd.
AL, PAA-H, etc .; all are trade names), homopolymers of amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like; ) Acrylates and copolymers of other (meth) acrylates and (meth) acrylic acid, and amino group-containing high molecular organic compounds such as polyoxyethylene alkylamines. These organic compounds (A-1)
One type may be used alone, or two or more types may be used in combination.

Further, among the organic compounds (A-2),
Specific examples of the epoxy group-containing compound include, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6
Aliphatic diglycidyl ethers such as hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether;
Glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-
(Hydroxyethyl) isocyanurate, polyglycidyl ethers such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; aliphatic and aromatic diglycidyl esters such as adipic acid diglycidyl ester and o-phthalic acid diglycidyl ester; Bisphenol A diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl ether,
And compounds represented by the following formula,

[0020]

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Glycidyls having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative); or oligomers having a glycidyl group as a functional group (for example, in the case of bisphenol A diglycidyl ether oligomer, Can be expressed);

[0022]

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And the like.

As the organic compound (A-2), in addition to the epoxy group-containing compound, for example, hexamethylene diisocyanate, tolylene diisocyanate, 1,4-diphenylmethane diisocyanate,
Isocyanates such as 5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate; dicarboxylic acids such as tartaric acid and adipic acid; carboxyl-containing polymers such as polyacrylic acid; Coalescence or the like can be used.

These organic compounds (A-2) may be used alone or in combination of two or more.
Further, the organic compound (A-1) and the organic compound (A-
Either one of 2) may be used, or both may be used in combination. In addition, the organic compound (A-
Among the organic compounds having an aromatic ring or a hydrogenated ring thereof (including a nuclear-substituted derivative), the organic compound having an aromatic ring or a hydrogenated ring thereof may be used as the water-resistant antifogging surface coating obtained by coating the substrate with the antifogging surface coating composition. This is advantageous in that it has the effect of improving the properties.

Next, the organic compound (B), which is one of the main components of the antifogging surface coating composition of the present invention, has a functional group capable of reacting with the functional group of the organic compound (A). And an organic compound having a SiOR ¹ group (R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described above), and together with an organic metal compound (D) described later, Is a compound serving as a Si source. When the organic compound (A) does not have an amino group, it is necessary to use an organic compound (B) having an amino group, and the organic compound (B) may be used in accordance with the functional group of the organic compound (A). ) May be determined.

R ¹ in the above SiOR ¹ group may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Here, the alkyl group having 1 to 4 carbon atoms is not particularly limited, and is a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a branched chain alkyl group such as an isopropyl group, and a cyclopropyl group. And a cyclic (alicyclic) alkyl group of a cyclobutyl group.

Specific examples of the organic compound (B) include, for example, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β ( Aminoethyl) γ-
Aminopropyltriisopropoxysilane, N-β (aminoethyl) γ-aminopropyltributoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl)
γ-aminopropylmethyldiisopropoxysilane, N
-Β (aminoethyl) γ-aminopropylmethyldibutoxysilane, N-β (aminoethyl) γ-aminopropylethyldimethoxysilane, N-β (aminoethyl) γ
-Aminopropylethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylethyldibutoxysilane, γ-aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane,
γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldisilane Butoxysilane, γ-aminopropylethyldimethoxysilane, γ
-Aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ-aminopropylethyldibutoxysilane, γ-aminopropyltriacetoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ Amino-containing compounds such as-(2-ureidoethyl) aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane,
β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ- Epoxy group-containing compounds such as glycidoxypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane; or γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane, γ-isocyanopropylmethyl Isocyanate group-containing compounds such as dimethoxysilane and γ-isocyanopropylmethyldiethoxysilane; and mercapto group-containing compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. These may be used alone or in combination of two or more.

The organic compound (B) reacts with the organic compound (A) and has a hydrolyzable SiOR ¹ group, so that it can be hydrolyzed before or after reacting with the organic compound (A). Decomposition condensation progresses, and co-hydrolysis condensation occurs with a hydrolyzable condensation group of the organometallic compound (D) described later, and polycondensation proceeds. Therefore, in the antifogging surface coating composition of the present invention, the organic compound (B) and / or its hydrolyzed condensate are used as its constituent components. In addition, the organic compound (A) and the organic compound (B) may react depending on the molar ratio, and the organic compound (A) or the organic compound (B) may not remain. The product is obtained by mixing or reacting the organic compound (A), the organic compound (B), the solvent (C), and the organic metal compound (D). In the present invention, a fine antifogging surface coating composition having excellent hard coat properties is rapidly obtained by the progress of polycondensation of the organic compound (B) and furthermore the organometallic compound (D) by (co) hydrolytic condensation. To form an anti-fogging surface coating having a coating layer obtained by coating. In addition, the organic compound (B)
It also has the effect of increasing the adhesion between the coating material (substrate) of the obtained antifogging surface coating and the coating layer obtained by coating the antifogging surface coating composition.

As described above, in the antifogging surface coating composition of the present invention, the organic compound (B) is used alone or in advance as a component of the composition or (co) hydrolyzed with the organometallic compound (D). The polymerization may be performed. Thereby, volatilization of the organic compound (B) and the organometallic compound (D) during the coating operation of the antifogging surface coating composition can be prevented, and the antifogging surface coating can be formed more quickly. This is advantageous in that it can be performed. When a low molecular weight compound is used as the organic compound (A), it is preferable to carry out hydrolytic condensation in advance.

Next, as the solvent (C) which is one of the main components of the antifogging surface coating composition of the present invention, the components other than the solvent of the antifogging surface coating composition are dissolved. Anything that can be used can be used. Specific examples of the solvent (C) include, for example, methanol, ethanol, 2-propanol, butanol, pentanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether and the like. Alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, toluene,
Aromatic hydrocarbons such as benzene and xylene, hexane,
Hydrocarbons such as heptane and octane; acetates such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; and others, ethyl phenol ether, tetrahydrofuran, propyl ether, water and the like. These can be used alone or in combination of two or more. Among them, methanol and methanol are excellent in stability and storage stability during hydrolysis reaction.
Alcohols such as ethanol are preferred.

Next, as the organometallic compound (D) which is a suitable value-added component of the antifogging surface coating composition of the present invention, the following general formula (I): R ² _mM (OR ³ ) _n (I) (wherein, M is a metal element, and R ² has 1 carbon atom)
Is an alkyl group having 1 to 4 carbon atoms having a functional group that does not react with an alkyl group or an amino group, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or more. And m + n matches the valence of the metal element M. ) Are not particularly limited. By adding the organometallic compound (D), the productivity in forming the anti-fogging surface coating is improved, and also in an environment where minute water droplets easily adhere (for example, in a high humidity / wet state).
In this case, it is possible to maintain a sufficiently high antifogging property. The organometallic compound (D) can be distinguished from the organic compound (B) in that it does not have a functional group capable of reacting with the functional group of the organic compound (A).

The organometallic compound (D) enhances the adhesion to the substrate (substrate) and, together with the organic compound (B), coats a dense antifogging surface coating composition having a polysiloxane skeleton. Since the antifogging surface coating having the coating layer obtained by this method can be formed, it is advantageous in that an antifogging surface coating having excellent hard coat properties and heat resistance can be formed.

M in the above formula is not particularly limited as long as it is a metal element, but from the viewpoint of easy handling during the coating operation, Si, Ti, Zr,
One type selected from Al, and particularly preferably Si.

R ² in the above formula may be an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a functional group which does not react with an amino group. Here, the functional group that does not react with the amino group is not particularly limited, and examples thereof include an amino group and a vinyl group. The alkyl group having 1 to 4 carbon atoms is the same as the alkyl group having 1 to 4 carbon atoms described for R ¹ . R ² is preferably a vinyl group from the viewpoint of heat resistance.

R ³ in the above formula is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ is preferably a methyl group or an ethyl group from the viewpoint of the reactivity of hydrolytic condensation. When n is 2 or more, R ³ may be the same or different.

In the above formula, n is an integer of 1 or more, m is an integer of 0 or more, and m + n coincides with the valence of the metal element M. For example, when the metal element M is Si, m + n = 4, and from the viewpoint of heat resistance of a coating layer obtained by coating the antifogging surface coating composition, m = n.
It is preferably 0 and n = 4.

Specific examples of the organometallic compound (D) represented by the general formula (I) include, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane. Silane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
Ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacrylic Alkoxysilanes such as roxypropyltriethoxysilane, titanium tetraethoxide, titanium tetraisopropoxide,
Titanium alkoxides such as titanium tetrabutoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium alkoxides such as zirconium tetrabutoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum alkoxides such as aluminum tributoxide, or These complex compounds, methyltriacetoxysilane, trimethylsilanol, and the like, and high-molecular-weight organic compounds containing these compounds are exemplified.
Species or two or more can be used. Among them, tetramethoxysilane and tetraethoxysilane are preferred from the viewpoints of reactivity and improvement in moisture resistance and water resistance of the obtained antifogging surface coating.

It is preferable that the organic compound (B) and the organic metal compound (D) are previously subjected to hydrolysis and condensation in order to prevent drying when forming an antifogging surface coating. In other words, those which can be present in the form of these hydrolyzed condensates in the antifogging surface coating composition are preferable. These (co) hydrolytic condensation reactions proceed with moisture in the air, but can be performed efficiently using a known catalyst such as an acid or a base. The hydrolysis reaction is preferably performed in a solvent (C), and the composition for surface coating for anti-fog of the present invention containing the solvent (C) also facilitates the coating treatment.

The composition for surface coating for anti-fogging of the present invention may further comprise, if necessary, various inorganic or organic compounds such as a curing catalyst, a wettability improver, a plasticizer, a defoamer and a thickener. An appropriate amount of an additive can be added.

Next, the compounding amount of the organic compound (A) is
Since it differs depending on whether or not the organometallic compound (D) as an optional component is used, it cannot be uniquely defined, but the total of the antifogging surface coating composition (excluding the solvent (C)) When the amount is 100% by mass, usually 5 to
The range is 90% by mass, preferably 7 to 80% by mass, more preferably 10 to 60% by mass. When the compounding amount of the organic compound (A) is less than 5% by mass, the antifogging effect of the antifogging surface coating obtained by coating is insufficient, and the flexibility and the like become insufficient. The effect of improving the impact resistance may not be exhibited. On the other hand, when the compounding amount of the organic compound (A) is more than 90% by mass, the moisture resistance of the antifogging surface coating may be inferior, or the obtained antifogging surface coating may have a substrate (coating). In addition to reducing the adhesion of the coating layer obtained by coating the antifogging surface coating composition to the coating material), the composition of other components such as the organic compound (B) and the organometallic compound (D) Since the amount is relatively small, an antifogging surface coating having excellent hard coat properties cannot be obtained.

The amount of the organic compound (B) is as follows:
Since it differs depending on whether or not the organometallic compound (D) as an optional component is used, it cannot be uniquely defined, but the total of the antifogging surface coating composition (excluding the solvent (C)) When the amount is 100% by mass, usually 5 to
The range is 90% by mass, preferably 7 to 75% by mass, more preferably 10 to 60% by mass. When the compounding amount of the organic compound (B) is less than 5% by mass, the moisture resistance of the antifogging surface coating may be inferior, and the antifogging effect of the obtained antifogging surface coating may be reduced. In addition, the resulting anti-fogging surface coating has poor adhesion of the coating layer obtained by coating the anti-fogging surface coating composition to a substrate (substrate). On the other hand, when the compounding amount of the organic compound (B) exceeds 90% by mass, the compounding amount of (A) is relatively small, so that the flexibility of the anti-fogging surface coating may decrease. .

The amount of the organometallic compound (D) is preferably 90% by mass or less, when the total amount of the antifogging surface coating composition (excluding the solvent (C)) is 100% by mass. Is in the range of 10 to 80% by mass, more preferably 20 to 75% by mass, particularly preferably 30 to 70% by mass.
Since the organometallic compound (D) is an optional component, the lower limit of the amount of the organometallic compound is not particularly limited. However, when the amount of the organometallic compound (D) is less than 10% by mass, In some cases, the effect of improving the anti-fogging property due to the incorporation of the organometallic compound (D) may not be sufficiently exhibited, and the moisture resistance of the anti-fogging surface coating may be insufficient. On the other hand, when the compounding amount of the organometallic compound (D) is more than 90% by weight, the compounding amount of the organic compound (A) is relatively small, so that the flexibility of the antifogging surface coating decreases. It is not preferable because there is a fear.

Further, other than the above-mentioned organic compounds (A), organic compounds (B) and organometallic compounds (D), other hardening catalysts, wetting improvers, plasticizers, defoamers, thickeners and other inorganic or inorganic compounds. With the compounding amounts of the various organic additives, various properties possessed by the additives can be sufficiently exhibited, and anti-fogging by the organic compound (A), the organic compound (B) and the organic metal compound (D) can be achieved. There is no particular limitation as long as it does not affect the sexual expression effect.

The composition of the antifogging surface coating composition containing the organic compound (A), the organic compound (B), the organometallic compound (D) and other additives (excluding the solvent (C)) was used. Total amount is always 1 for any combination
00% by mass.

The blending amount of the solvent (C) is not particularly limited. When the total mass of the antifogging surface coating composition (here, including the solvent (C)) is 100% by mass,
Usually 30 to 95% by mass, preferably 50 to 90% by mass,
More preferably, it is in the range of 70 to 85% by mass. When the amount of the solvent (C) is less than 30% by mass, the reaction stability of the antifogging surface coating composition is poor, which is not preferable.
During coating, there is a possibility that the viscosity of the antifogging surface coating composition increases and uniform coating cannot be performed. On the other hand, the solvent (C)
If the compounding amount exceeds 95% by mass, the productivity in forming the anti-fogging surface coating is poor, which is not preferable. In addition, the concentration of the active ingredient is too low, so that the necessary anti-fogging surface coating is required. In some cases, the film thickness cannot be secured.

The method for preparing the antifogging surface coating composition is not particularly limited, and for example, (1)
A method of simply mixing an organic compound (A), an organic compound (B) and / or a hydrolytic condensate thereof, a solvent (C), and an organic metal compound (D) and / or a hydrolytic condensate thereof. (2) in the presence of the solvent (C) in advance,
A method of conducting a functional group reaction between the organic compound (A) and the organic compound (B) and then adding the organometallic compound (D) and / or a hydrolyzed condensate thereof; (3) an organic compound (A) and a solvent (C) (4) a method of (co) hydrolytic condensation of the organic compound (B) and the organometallic compound (D) in the presence of)
In the presence of the solvent (C), the organic compound (B) and the organometallic compound (D) are cohydrolyzed and condensed, and then the organic compound (A)
And the like, but are not limited to these. In addition, the said solvent (C)
It is desirable to replenish or add appropriate ones according to the preparation stage and method as needed.

Next, the antifogging surface coating of the present invention is obtained by coating a substrate with the above antifogging surface coating composition. Such an antifogging surface coating has excellent antifogging properties (see Examples), has sufficient strength and hardness,
Transparency, durability, weather resistance, impact resistance, heat resistance, flexibility,
Since it is excellent in moisture resistance, solvent resistance, light resistance, water resistance, flexibility, gas barrier properties, and the like, it can be applied to many fields requiring antifogging properties.

The substrate (substrate to be coated) which can be coated with the antifogging surface coating composition of the present invention is not particularly limited, and any substrate having a surface which requires antifogging property can be used. Examples include, but are not limited to, glass, ceramics, plastics, and metals. When a plastic substrate or the like is used as the substrate (substrate), for example, its surface is subjected to plasma treatment or corona discharge treatment in advance, or the substrate (substrate) surface contains oxygen. 200-40 in
It is preferable to apply the antifogging surface coating composition after irradiating ultraviolet rays having a wavelength of about 0 nm.

Further, depending on the adhesion of dirt on the substrate (substrate to be coated), if the above-mentioned antifogging surface coating composition cannot be uniformly applied by, for example, repelling, the surface of the substrate is washed or modified. Quality can be improved. As a method of cleaning and surface modification, alcohol, acetone, degreasing cleaning with an organic solvent such as hexane, cleaning with an alkali or acid, a method of polishing the surface with an abrasive, a cleaning method such as ultrasonic cleaning,
Surface modification methods such as ultraviolet irradiation treatment, ultraviolet ozone treatment, plasma treatment, corona discharge treatment, and heat treatment can be given.

The method for coating (coating) the surface of the substrate with the antifogging surface coating composition is not particularly limited, and any conventionally known technique can be appropriately used. For example, roll coating, dip coating, bar coating, nozzle coating, die coating, spray coating, spin coating, curtain coating, flow coating, screen printing, gravure printing, curved surface printing, etc. Or a combination of these methods. Among them, the die coating method is preferable from the viewpoint of increasing the stability of the antifogging surface coating composition.

After coating (coating), the antifogging surface coating is cured and dried. In such curing and drying, heating or heating and humidification is preferable because an antifogging surface coating having a dense coating layer having excellent hard coat properties can be quickly formed. When heating here, it is preferable to heat at a temperature lower than the heat resistant temperature of the substrate. In addition, in order to prevent the evaporation of the organometallic compound (D) during drying, it is preferable that the organometallic compound (D) is subjected to hydrolysis and condensation in advance. For this hydrolysis-condensation reaction, a known catalyst can be used, and the solvent (C)
The reaction is advantageously carried out in water. In particular, it is preferable to carry out cohydrolysis condensation with the organic compound (B) in advance. The organometallic compound (D) also has the effect of improving the moisture resistance of the formed antifogging surface coating.

Further, reducing the unreacted SiOR ¹ group of the organic compound (B) and the MOR ³ group of the organometallic compound (D) in the coating layer of the antifogging surface coating can be achieved even in a high-temperature and high-humidity environment. Since it is desirable to maintain sufficient antifogging properties, the above antifogging surface coating composition is coated (coated) on a substrate surface by a suitable coating method, and then the antifogging surface coating is cured and dried. Do
After that, it is preferable to perform an aging treatment for reacting (condensing) the unreacted SiOR ¹ group of the organic compound (B) and the MOR ³ group of the organometallic compound (D) in the coating layer of the antifogging surface coating, For example, after the composition for surface coating for antifogging is applied and dried on a substrate, heat treatment effective for reducing unreacted groups (for example, heat treatment at a temperature between 40 and 60 ° C. for 1 to 7 days) Or a method of performing corona treatment. Here, the heat-resistant temperature of the substrate is substantially the upper limit temperature at which the properties of the substrate can be maintained. For a glass substrate, for example, the softening point or the devitrification temperature (normally 600
-700 ° C.), for example, if it is a plastic substrate,
Examples include a glass transition point, a crystallization temperature, and a decomposition point.
Prior to the application of the antifogging surface coating composition, a known anchor coat layer such as a urethane resin may be provided on the surface of the substrate.

By the above curing, drying and heat treatment, an antifogging surface coating having a coating layer obtained by coating the substrate with the above antifogging surface coating composition can be formed. In the antifogging surface coating obtained in this way, the thickness of the coating layer obtained by coating the substrate with the antifogging surface coating composition after drying differs depending on the intended use, so that it is not specified uniquely. I can't,
Any material that can at least effectively exhibit antifogging properties may be used, and is usually 0.01 to 20 μm, preferably 0.1.
10 μm, more preferably 0.5 to 5 μm. The thickness of the coating layer after drying is 0.01 μm.
If it is less than m, the coating will not be uniform and sufficient anti-fogging properties will not be easily exhibited. On the other hand, if the thickness of the coating layer after drying exceeds 20 μm, cracks tend to occur in the coating.

In the antifogging surface-coated body of the present invention, the same type (composition) of the antifogging surface coating composition may be applied to the substrate several times or may be applied separately. By separately applying antifogging surface coating compositions having different (compositions), antifogging surface coatings having a multilayer structure having different compositions and thicknesses for each layer may be formed.

The antifogging property of the antifogging surface coating of the present invention cannot be uniquely defined because it differs depending on its constituent components and the overall laminated structure, but at least the constituent requirements of the present invention are satisfied. By that, as shown in the examples described below, the type and thickness of the base material used, even when exposed to a high-temperature and high-humidity environment, is always the highest level in the fogging evaluation "no fogging at all" ”Can be achieved.

[0057]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples do not limit the present invention in any way, and can be changed and implemented without departing from the spirit of the preceding and the following. Everything is included in the technical scope of the present invention.

Synthesis Example 1 In a flask equipped with a stirrer, a thermometer and a condenser, methanol / solvent (C) / 200 g, toluene / solvent (C) / 6
0 g and γ-aminopropyltrimethoxysilane ｛organic compound (B)｝ 50 g were charged and heated to 65 ° C. under a nitrogen atmosphere. Then, a mixed solution of bisphenol A diglycidyl ether {organic compound (A-2)} 10 g and toluene {solvent (C)} 10 g was added, and the mixture was added under nitrogen atmosphere.
After stirring at 5 ° C. for 3 hours, the mixture was cooled to room temperature, and water / solvent (C) / 10 g for hydrolysis of alkoxysilyl groups was used.
A mixture of methanol and solvent (C) (40 g) was added, and the mixture was stirred at room temperature for 1 hour to obtain antifogging surface coating composition 1.

Synthesis Example 2 In a flask equipped with a stirrer, a thermometer, and a condenser, methanol / solvent (C) / 220 g, toluene / solvent (C) / 6
0 g and γ-aminopropyltrimethoxysilane ｛organic compound (B)｝ 50 g were charged and heated to 65 ° C. under a nitrogen atmosphere. Then, a mixed solution of bisphenol A diglycidyl ether {organic compound (A-2)} 10 g and toluene {solvent (C)} 10 g was added, and the mixture was added under nitrogen atmosphere.
After stirring at 5 ° C. for 3 hours, the mixture was cooled to room temperature, and 15 g of water / solvent (C) for hydrolysis of alkoxysilyl groups was used.
And a mixed solution of methanol ｛solvent (C)｝ 40 g,
Stirred at room temperature for 1 hour. Further, tetramethoxysilane oligomer [M silicate 51: trade name of Tama Chemical Co., Ltd.] ｛Organic metal compound (D)｝ 30 g, methanol ｛solvent (C)｝ 65 g, ethanol ｛solvent (C)｝ 25
g of the mixture was added and reacted at room temperature for 2 hours to obtain Antifogging Surface Coating Composition 2.

Synthesis Example 3 In a flask equipped with a stirrer, a thermometer, and a cooling tube, ethanol / solvent (C) / 75 g, Epomin SP-018 [polyethyleneimine: trade name of Nippon Shokubai Co., Ltd.] / Organic compound (A -1) 15 g of γ-glycidoxypropyltrimethoxysilane ｛organic compound (B)｝ 12 g were charged, stirred at 65 ° C. for 3 hours under a nitrogen atmosphere, cooled to room temperature, and hydrolyzed to an alkoxysilyl group. Water ｛Solvent (C)｝ 6 g and ethanol ｛Solvent (C)｝ 220
g of the mixed solution was added, and the mixture was stirred at room temperature for 1 hour to obtain Antifogging Surface Coating Composition 3.

Synthesis Example 4 In a flask equipped with a stirrer, a thermometer and a cooling tube, ethanol / solvent (C) / 75 g, Epomin SP-018 [polyethyleneimine: trade name of Nippon Shokubai Co., Ltd.] / Organic compound (A -1) 15 g of γ-glycidoxypropyltrimethoxysilane ｛organic compound (B)｝ 12 g were charged, stirred at 65 ° C. for 3 hours under a nitrogen atmosphere, cooled to room temperature, and hydrolyzed to an alkoxysilyl group. Water for use (solvent (C)) 6 g and ethanol (solvent (C)) 250
g of the mixture was added, and the mixture was stirred at room temperature for 1 hour. Furthermore, tetramethoxysilane oligomer [M silicate 51: trade name of Tama Chemical Co., Ltd.] {organometallic compound (D)} 6
A mixed solution of 0 g and ethanol / solvent (C) / 120 g was added and reacted at room temperature for 2 hours to obtain antifogging surface coating composition 4.

Examples 1 to 12 Antifogging surface coating composition 1 obtained in Synthesis Examples 1 to 4 above.
4 was coated on the transparent support (substrate) surface (only one surface) shown in Table 2 so that the thickness after drying was 1.2 μm, dried at 95 ° C. and 10% Rh for 10 seconds, and further dried at 60 ° C. Aging was performed at 7 ° C. for 7 days. The obtained anti-fogging surface coatings 1 to 4 were placed in a thermo-hygrostat at a temperature of 5 ° C. and a humidity of 10% Rh, and allowed to stand for 10 minutes.
Quickly transfer to a 0% Rh constant temperature and humidity chamber (here, about 3
The transfer was completed in seconds), and the degree of haze was visually observed from the lapse of 30 seconds to the lapse of 2 minutes.
"Fogging evaluation" was performed according to the four-level evaluation criteria shown in Table 1. Table 2 shows the results.

Comparative Examples 1 to 3 The same "Evaluation of fogging" as in Examples 1 to 12 was carried out without coating the transparent support (substrate) with the antifogging surface coating compositions 1 to 4. Table 2 shows the results.

[0064]

[Table 1]

[0065]

[Table 2]

In the above table, PET represents a polyethylene terephthalate film, and OPP represents a biaxially oriented polypropylene film.

[0067]

As described above, the antifogging surface coating composition and the antifogging surface coating obtained by coating the antifogging surface coating composition according to the present invention have minute water droplets on the surface even in a high-temperature and high-humidity environment. Can be effectively and effectively prevented from adhering, such as lenses, glass, transparent resin panels and films that require anti-fog properties because they can maintain a sufficiently high anti-fog property Cloudiness can be suppressed stably irrespective of environmental changes. Therefore, in the field of industry (including agriculture), which is required to have anti-fog properties, for example, construction and housing materials such as window glass of buildings, windshields and mirrors of automobiles, and transportation equipment such as window glass of trains. Field, electronic equipment-related fields such as liquid crystal display panels and cathode ray tubes of personal computers and mobile phones, optical equipment-related fields such as microscopes and cameras, eyeglass lenses, goggles,
Applicable to a wide range of applications including daily necessities such as mirrors, food and beverage containers and packaging materials such as PET bottles, commercial products such as show windows and showcases, and medical equipment such as endoscope lenses. You can do it.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 185/00 C09D 185/00 C09K 3/18 C09K 3/18 G02B 1/04 G02B 1/04 1/10 G02C 11 / 08 G02C 11/08 G02B 1/10 Z F term (reference) 2K009 BB24 CC42 CC45 DD02 EE02 4F100 AH06B AH06K AK52B AK52K AL05B AT00A BA02 GB07 GB31 GB71 GB90 JL07 4G059 AA01 AA11 AC21 FA22 FB05 AB02A04B07A02 CR071 CR072 DB001 DB002 DF041 DF042 DG021 DG022 DJ011 DJ012 DL021 DL022 DL031 DL032 DL051 DL052 DL081 DL082 DL091 DL092 DL111 DL112 DL121 DL122 DM022 GA06 GA09 JA01 JA19 JA20 JA25 JA33 JA39 JA56 JB02 KA06 NA14 NA03 NA03 NA04 NA03 PC03 PC08

Claims (3)

[Claims] 1. A functional group [however, SiOR ¹ group (R ¹ group represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)]
And an organic compound (B) having a functional group capable of reacting with a functional group of the organic compound (A) and a SiOR ¹ group (R ¹ is as defined above) and / or A composition for surface coating for antifogging, which is obtained from the hydrolysis condensate and a solvent (C). 2. A compound represented by the following general formula (I): R ² _mM (OR ³ ) _n (I) (wherein, M is a metal element and R ² is an alkyl or amino group having 1 to 4 carbon atoms) An alkyl group having 1 to 4 carbon atoms having a functional group that does not react with, R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 or more, and m + n is a valence of the metal element M. The composition for surface coating for antifogging according to claim 1, which is obtained by adding an organometallic compound (D) represented by the following formula: 3. An antifogging surface coating obtained by coating a substrate with the antifogging surface coating composition according to claim 1 or 2.