JP7065980B2 - Laminate - Google Patents

Description

The present disclosure relates to laminates.

Equipment, building materials, etc. that are installed indoors or outdoors and used for a long period of time are exposed to various environments, so dust, dust, gravel, etc. gradually accumulate, and they get wet with rainwater during wind and rain. As a result, the planned functions and performance may be impaired.

For example, in a vehicle lamp such as a head lamp of an automobile, high-humidity air may enter the lighting chamber, the lens may be cooled by outside air, rainfall, or the like, and moisture may condense on the inner surface to cause fogging. As a result, the brightness of the vehicle light is lowered, and the aesthetic appearance of the lens surface is impaired, which may cause discomfort to the user.

In order to prevent such fogging of the lens, a method of applying an antifogging paint to a portion where fogging occurs is known. The layer (anti-fog layer) formed by applying an anti-fog material is a hydrophilic type that changes water droplets into an aqueous layer by making the surface super-hydrophilic, and absorbs water droplets by using a water-absorbing material. The water absorption type is known.

As a technique related to the above, for example, in Patent Document 1, a nanopore property including a first thickness portion having a first hole and a second thickness portion having a second hole different from the first hole. The surface containing the coating is described.

In Patent Document 2, in an antifogging antireflection optical article in which a water-absorbent layer is formed on a transparent substrate and a porous inorganic layer is formed on the water-absorbent layer, the porous inorganic layer absorbs water. From the layer side, a hydrophilic inorganic layer for improving the adhesion to the water-absorbent layer, an inorganic layer for improving the adhesion with the hydrophilic inorganic layer, and an inorganic layer having a low refractive index for exhibiting an antireflection function. An anti-fog anti-reflection optical article configured in the order of an inorganic layer for increasing the surface hardness is described.

Patent Document 3 has a base material and an anti-fog layer provided on at least a part of the base material, and the anti-fog layer comprises a siloxane binder, silica particles, and a water-absorbent organic polymer. The anti-fog layer has a structure in which the silica particles are deposited, has an uneven structure due to the silica particles on the surface of the anti-fog layer, and has voids inside the anti-fog layer. A laminated body having a film density of 0.80 g / cm ³ or more and 1.40 g / cm ³ or less and a film thickness of the anti-fog layer of more than 1 μm and 10 μm or less is described.

Japanese Patent Publication No. 2011-524289 Japanese Unexamined Patent Publication No. 11-052104 International Publication No. 2018/02544

When the anti-fog layer is a water-absorbent type, the better the water absorption amount, the better the anti-fog performance. Therefore, conventionally, a water-absorbent type anti-fog material for the purpose of excellent water absorption has been provided.

However, the anti-fog material as described above is only applied to places that cannot be touched by human hands, such as the inside of an in-vehicle headlight cover and the inside of a rear light cover. If the above anti-fog material is applied to a place that can be touched by human hands such as a windshield, the anti-fog layer may lack the abrasion resistance, and the function of the anti-fog layer may be maintained. This is because it can be difficult.

Further, when hydroxyethyl cellulose (HEC) is used as in Patent Document 3, the compatibility between HEC and alkoxysilane tends to be low, which causes a decrease in transparency due to uneven distribution of HEC. obtain.

If an anti-fog layer is to be constructed without using HEC, when the anti-fog layer is thick, there is an increased possibility that the anti-fog layer will be cracked due to the compressive force generated when the alkoxysilane is dehydrated and condensed. Is a concern. Therefore, when the anti-fog layer is formed without using HEC, only a relatively thin layer can be formed, and when the layer is thin, the amount of water absorption tends to be small. The cloudiness may decrease.

The inventions described in Patent Document 1 and Patent Document 2 are likely to be inferior in anti-fog property because the thickness of the coating is thin and good water absorption cannot be expected. Further, Patent Document 1 and Patent Document 2 do not describe scratch resistance.

If the dehydration condensation is promoted too much by using a tetramethoxysilane (TMS) oligomer or the like as in the invention described in Patent Document 3, cracks may occur in the anti-fog layer due to the compressive force generated during the dehydration condensation. .. Therefore, dehydration condensation cannot be greatly promoted, and the number of binding sites of the binder due to condensation is reduced, which contributes to a decrease in abrasion resistance.

An object to be solved by one embodiment of the present disclosure is to provide a laminated body having excellent anti-fog property and scratch resistance.

The anti-fog property refers to a property indicating the degree of fogging of the laminated body, and the above-mentioned fogging includes not only the case where the surface is covered with water droplets or the like and fogging, but also haze.

The means for solving the above problems include the following aspects.

<1> A direction in which the base material has an anti-fog layer provided on at least a part of the base material, the anti-fog layer contains voids inside, and the base material is directed toward the anti-fog layer. The average void diameter of the voids contained in the anti-fog layer on the side half close to the substrate is 20 of the average void diameter of the voids contained in the anti-fog layer on the side half far from the substrate. % Or less, the thickness of the anti-fog layer is 1 μm or more and 30 μm or less, the anti-fog layer contains silica particles, and the anti-fog layer occupies the projected area of the exposed surface of the anti-fog layer from the normal direction. It is a laminated body having an area ratio of 55% to 95%.

<2> The antifogging layer contains an inorganic binder, and the inorganic binder is a dehydrated condensation product of a trifunctional siloxane having three alkoxysilyl groups in the molecule, or a bifunctional product having two alkoxysilyl groups in the molecule. The laminate according to <1>, which is a dehydration condensate of the siloxane of.

<3> The method according to <1> or <2>, wherein the anti-fog layer contains a water-absorbing polymer in an amount of 1% by mass or less based on the total mass of the anti-fog layer, or does not contain a water-absorbing polymer. It is a laminated body.

<4> The laminate according to any one of <1> to <3>, wherein the anti-fog layer has a water absorption of 1.0 mg / cm ² or more and 26.5 mg / cm ² or less.

<5> The laminate according to any one of <1> to <4>, wherein the water contact angle of the exposed surface of the anti-fog layer is 25 ° or less.

<6> The anti-fog layer is the laminate according to any one of <1> to <5>, which is composed of a plurality of layers.

<7> The laminate according to any one of <1> to <6>, wherein the base material contains glass, a polycarbonate resin, or an acrylic resin.

<8> The laminate according to any one of <1> to <7>, wherein the anti-fog layer is a coating layer.

<9> The laminate according to any one of <1> to <8>, which has an adhesive layer between the base material and the anti-fog layer.

According to one embodiment of the present disclosure, it is possible to provide a laminated body having excellent anti-fog property and scratch resistance.

The contents of the present disclosure will be described in detail below. The description of the constituents described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.

In the present disclosure, "-" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

Further, in the notation of a group (atomic group) in the present disclosure, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Further, in the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.

Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

Further, for the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) are used. It is a molecular weight converted by using a gel permeation chromatography (GPC) analyzer as a standard substance, which is detected by a solvent THF (tetrahydrofuran) and a differential refraction meter.

In the present disclosure, the "solvent" means water, an organic solvent, and a mixed solvent of water and an organic solvent.

The term "solid content" in the present disclosure means a component excluding a solvent, and a liquid component such as a low molecular weight component other than the solvent is also included in the "solid content" in the present disclosure.

In the present disclosure, "(meth) acrylic" is a concept that includes both acrylic and methacrylic.

Hereinafter, the present disclosure will be described in detail.

≪Laminated body≫

The laminate of the present disclosure has a base material and an anti-fog layer provided on at least a part of the base material, the anti-fog layer contains voids inside, and the above-mentioned anti-fog from the base material. The average void diameter of the voids contained in the anti-fog layer on the side half closer to the base material is the average of the voids contained in the anti-fog layer on the side half far from the base material with reference to the direction toward the layer. It is 20% or less of the void diameter, the thickness of the anti-fog layer is 1 μm or more and 30 μm or less, the anti-fog layer contains silica particles, and occupies the projected area of the exposed surface of the anti-fog layer from the normal direction. The area ratio of the silica particles is 55% to 95%.

As in the invention described in Patent Document 3, a 2 to 3 μm laminate containing silica particles, a TMOS (tetramethoxysilane) oligomer and HEC (hydroxyethyl cellulose) as a binder is known, and has good water absorption and antifogging. It is said to have excellent sex. In addition, since the surface of the layer has good hydrophilicity, even if the amount of water absorbed by the anti-fog layer is saturated and the surface overflows with water, a good water film is formed on the surface of the anti-fog layer to exhibit the anti-fog effect. be able to.

Although the above technique can be applied to parts that cannot be touched by humans, such as the inside of a car headlight or rear light cover, it can be applied to parts that can be touched by humans, such as the front, side, or rear glass of a car. To apply, it is necessary to consider abrasion resistance.

Further, when hydroxyethyl cellulose (HEC) is used as in Patent Document 3, the compatibility between HEC and alkoxysilane tends to be low, which may cause a decrease in transparency due to uneven distribution of HEC. ..

If an anti-fog layer is to be constructed without using HEC, when the anti-fog layer is thick, there is an increased possibility that the anti-fog layer will be cracked due to the compressive force generated when the alkoxysilane is dehydrated and condensed. Is a concern. Therefore, when the anti-fog layer is formed without using HEC, only a relatively thin layer can be formed, and when the layer is thin, the amount of water absorption tends to be small. The cloudiness may decrease.

On the other hand, in the present disclosure, by increasing the area ratio of the silica particles existing on the surface of the anti-fog layer, the hydrophilicity of the layer surface can be improved and the abrasion resistance can be improved. .. Further, the structure shall be such that the average void diameter of the voids contained in the anti-fog layer on the side half close to the substrate is 20% or less of the average void diameter of the voids contained in the anti-fog layer on the side half far from the substrate. Then, a gradient of the void diameter is provided in the anti-fog layer so that the void diameter contained in the anti-fog layer becomes smaller in the direction from the surface of the laminated body to the base material (thickness direction), and a capillary force is generated in the layer. Therefore, the water absorption can be improved. As a result, anti-fog performance can be improved.

<Anti-fog layer>

The anti-fog layer in the present disclosure contains voids inside, and the voids contained in the anti-fog layer on the side half close to the base material with reference to the direction (thickness direction) from the base material to the anti-fog layer. The average void diameter is 20% or less of the average void diameter of the voids contained in the anti-fog layer on the side half far from the base material, and the thickness of the anti-fog layer is 1 μm or more and 30 μm or less. The anti-fog layer contains silica particles, and the area ratio of the anti-fog layer to the projected area seen from the normal direction on the exposed surface of the anti-fog layer is 55% to 95%.

The anti-fog layer may be a layer composed of one layer or a layer composed of a plurality of layers.

The anti-fog layer preferably has an exposed surface that is at least partially exposed. Here, exposure means that the laminate is not covered with a substrate or other layers.

(Area ratio of silica particles)

The anti-fog layer can have a structure in which silica particles are deposited, and has an uneven structure due to silica particles on the surface. In the present disclosure, the area ratio of silica particles to the projected area seen from the normal direction on the exposed surface of the anti-fog layer is 55% to 95%.

When the area ratio is 55% or more, the hydrophilicity of the layer surface can be improved and the abrasion resistance can be improved.

When the area ratio is 95% or less, the water absorption into the anti-fog layer can be improved. Further, when the area ratio is 95% or less, the haze can be improved.

From the above viewpoint, the area ratio of the silica particles to the projected area of the exposed surface of the anti-fog layer when viewed from the normal direction is preferably 60% to 90%, more preferably 65% to 85%.

The area ratio of the silica particles to the projected area on the exposed surface of the antifogging layer when viewed from the normal direction is determined by using a scanning electron microscope (for example, JSM-7500F, manufactured by JEOL Ltd.) on the surface of the antifogging layer. By observing the projected image of the silica particles, the total area of the exposed surface of the silica particles can be obtained.

Then, it can be obtained by dividing the total area by the area of the observation area of the projected image to calculate the percentage.

Examples of the method of setting the area ratio within the above range include a method of reducing the particle size of the silica particles existing on the surface of the layer to increase the area ratio of the silica particles.

(Average void diameter)

The anti-fog layer in the present disclosure contains voids inside, and the average void diameter of the voids contained in the anti-fog layer on the side half close to the base material is the average void diameter with respect to the direction from the base material to the anti-fog layer. It is 20% or less of the average void diameter of the voids contained in the anti-fog layer on the side half far from the base material.

As a result, by forming a gradient that reduces the diameter of the voids contained in the layer in the direction from the surface of the laminate toward the base material, capillary force can be generated in the layer, and water absorption can be improved. can. As a result, anti-fog performance can be improved.

From the same viewpoint as above, the average void diameter of the voids contained in the anti-fog layer on the side half close to the substrate is the average void diameter of the voids contained in the anti-fog layer on the side half far from the substrate. The diameter is preferably 15% or less, more preferably 10% or less.

In addition, "half" is a cutting position when the anti-fog layer is cut in a direction perpendicular to the thickness direction from a position of half the thickness of the anti-fog layer with reference to the thickness direction of the anti-fog layer. To say.

In the present disclosure, the average void diameter can be measured by the following method.

The void diameter is measured by cutting an arbitrary point in a direction orthogonal to the surface of the antifogging layer and observing the cut surface with a scanning electron microscope (SEM).

In the SEM image of the cut surface (magnification 50,000 times), the equivalent circle diameter is calculated for each of 200 arbitrarily selected voids, and the average value thereof is used as the void diameter.

With the direction from the base material toward the anti-fog layer as a reference, the average void diameter of the voids contained in the anti-fog layer on the side half close to the base material becomes the anti-fog layer on the side half far from the base material. Examples of the method for producing the anti-fog layer having an average void diameter of 20% or less of the contained voids include the following methods.

When the anti-fog layer is produced by one layer, the anti-fog layer may be produced so that the average void diameter gradually decreases in the direction from the surface of the anti-fog layer toward the substrate. For example, particles having a multimodal particle size distribution are used for the secondary particle size (aggregate of primary particles), and the difference in sedimentation property depending on the particle size (the larger the particle size, the lower the effect of sedimentation) is used. , Can be made. However, in terms of easily providing a gradient of the average void diameter, a method of stacking two or more anti-fog layers is preferable. When two or more layers are stacked to form an anti-fog layer, a plurality of layers having different average void diameters are prepared, and the average void diameter becomes smaller toward the substrate from a position far from the substrate on the substrate. The layers may be stacked in such a manner (so that the average void diameter increases sequentially from the base material side).

(Thickness)

The thickness of the anti-fog layer in the present disclosure is 1 μm or more and 30 μm or less. This makes it possible to improve the water absorption of the anti-fog layer, the ability to suppress water dripping marks, and the transparency.

From the viewpoint of water absorption of the anti-fog layer, suppression of water dripping marks, and transparency, it is preferably 1.2 μm or more and 25 μm or less, more preferably 1.3 μm or more and 20 μm or less, and 1.5 μm or more 4 It is particularly preferable that it is 0.0 μm or less.

When the thickness is 1 μm or more, the accumulated amount of voids in the anti-fog layer is increased and the amount of water absorption is increased, so that it is considered that the stain resistance of the anti-fog layer is improved. It is considered that when the thickness is less than 30 μm, the amount of swelling and dissolution of the anti-fog layer can be suppressed, and the occurrence of water dripping marks can be suppressed. Further, the anti-fog layer having excellent transparency can be obtained.

When the anti-fog layer has a plurality of layers, the thickness of the anti-fog layer refers to the total thickness of each layer.

The method for measuring the thickness of the anti-fog layer is as follows.

The cross section of the laminate in the direction perpendicular to the antifogging layer is observed with a transmission electron microscope, the thickness of the antifogging layer is measured at 10 random points in the plane, and the average value is taken as the thickness of the antifogging layer.

-Silica particles-

The anti-fog layer contains silica particles.

The silica particles contribute to the improvement of the physical resistance and hydrophilicity of the anti-fog layer. That is, the silica particles function as a hard filler in the anti-fog layer, and the hydrophilicity of the anti-fog layer can be improved by the action of hydroxy groups on the particle surface. Examples of the silica particles include solid silica particles (silica particles having no hollow portion), hollow silica particles, and the like, and it is preferable to use solid silica particles from the viewpoint of physical resistance.

Examples of the solid silica particles include fumed silica and colloidal silica.

Humed silica can be obtained by reacting a compound containing a silicon atom with oxygen and hydrogen in the gas phase. Examples of the silicon compound as a raw material include silicon halide (for example, silicon chloride).

Colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed. Examples of the raw material compound of colloidal silica include alkoxysilicon (for example, tetraethoxysilane) and halogenated silane compound (for example, diphenyldichlorosilane).

The shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a plate shape, a needle shape, a chain shape, a necklace shape (bead shape), and the like. The term "spherical" as used herein includes not only a true spherical shape but also a spheroid, an oval shape, and the like.

Among these, from the viewpoint of water absorption, a shape selected from the group consisting of a spherical shape, a chain shape, and a necklace shape is preferable, and a chain shape or a necklace shape is more preferable, and a chain shape is preferable. It is particularly preferable to have.

The size of the silica particles is not particularly limited. For example, the average primary particle diameter of the silica particles is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less, from the viewpoint of water dripping trace suppression property, stain resistance and substrate adhesion. It is particularly preferably 10 nm or more and 20 nm or less.

When the shape of the silica particles is spherical or substantially spherical such as an elliptical cross section, the average primary particle diameter of the silica particles is 300 or more from the obtained photographs obtained by observing the dispersed silica particles with a transmission electron microscope. The projected area of the silica particles is measured, the equivalent circle diameter is obtained from the projected area, and the obtained equivalent circle diameter is defined as the average primary particle diameter of the silica particles. When the shape of the silica particles is not spherical or substantially spherical, another method, for example, a dynamic light scattering method, is used to determine the average primary particle diameter of the silica particles.

Commercially available products can be used as the silica particles.

Examples of commercially available silica particles include Snowtex® series manufactured by Nissan Chemical Industries, Ltd. [for example, Snowtex OXS, Snowtex O, Snowtex O-40, Snowtex OL, Snowtex PS- SO, Snowtex OUP], AEROSIL® series manufactured by Evonik Industries, Nalco® series (registered trademark) series manufactured by Narco Chemical Co., Ltd. [for example, Nalco® 8649], Quartron PL manufactured by Fuso Chemical Industry Co., Ltd. A series (for example, PL-1) and the like can be mentioned.

The anti-fog layer may contain only one type of silica particles, or may contain two or more types of silica particles. When the anti-fog layer contains two or more types of silica particles, silica particles having different shapes, average primary particle diameters, and the like may be used in combination.

The content of silica particles in the anti-fog layer is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 70% by mass or less with respect to the total mass of the anti-fog layer. , 40% by mass or more and 65% by mass or less is more preferable. Within the above range, an anti-fog layer having excellent hardness, scratch resistance and impact resistance and having desired hydrophilicity can be formed.

(Super absorbent polymer)

It is preferable that the anti-fog layer in the present disclosure contains 1% by mass or less of the water-absorbing polymer with respect to the total mass of the anti-fog layer, or does not contain the water-absorbing polymer. The content of the water-absorbent polymer is preferably 0% by mass to 1% by mass with respect to the total mass of the anti-fog layer.

This causes a problem when a large amount of water-absorbing polymer (particularly hydroxyethyl cellulose (HEC)) is used, which is caused by insufficient compatibility between the water-absorbing polymer and alkoxysilane. It is possible to avoid deterioration of transparency due to uneven distribution of water-absorbent polymer and deterioration of solvent resistance due to elution of water-absorbing polymer.

From the above viewpoint, it is more preferable that the water-absorbent polymer is contained or not contained in the anti-fog layer in an amount of 1% by mass or less based on the total mass of the anti-fog layer, and more preferably not.

The "water-absorbent polymer" in the present disclosure is a polymer having a solubility parameter value (SP value) of 19 MPa ^1/2 or more.

Further, the SP value of the water-absorbent polymer is preferably 20 MPa ^1/2 or more, more preferably 25 MPa ^1/2 or more, and 30 MPa ^1/2 from the viewpoint of anti-fog property and stain resistance. The above is particularly preferable. The upper limit is preferably 40 MPa ^1/2 or less.

The SP value in the present disclosure represents the value of the solubility parameter measured by the Hoy method. The Hoy method is described in POLYMER HANDBOOK FOURTH EDITION (Wiley).

The weight average molecular weight of the water-absorbent polymer is preferably 1,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 2 million or less.

Specific examples of the water-absorbent polymer include hydroxyethyl cellulose, hydroxypropyl cellulose, poly (meth) acrylamide, polyvinylpyrrolidone, polyvinylacetate, polyvinyl alcohol, polyvinyl butyral, polyethylene glycol and the like.

Among these, at least one organic polymer selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, poly (meth) acrylamide, polyvinylpyrrolidone, and polyethylene glycol from the viewpoint of antifogging property and stain resistance. It is preferably at least one polymer selected from the group consisting of hydroxyethyl cellulose and polyvinylpyrrolidone.

When the anti-fog layer contains a water-absorbing polymer, it may contain only one type of water-absorbing polymer, or may contain two or more types of water-absorbing polymer.

(Inorganic binder)

The anti-fog layer in the present disclosure can contain an inorganic binder.

Thereby, good anti-fog resistance can be imparted to the anti-fog layer.

Examples of the inorganic binder include a siloxane binder, an alumina hydrate binder, a phosphoric acid metal salt binder and the like.

Of these, a siloxane binder is preferable from the viewpoint of abrasion resistance.

-Siloxane binder-

The anti-fog layer can contain a siloxane binder.

The siloxane binder preferably contains at least one compound obtained by subjecting the siloxane oligomer to a condensation reaction.

As the siloxane oligomer in the present disclosure, a partially hydrolyzed condensate obtained by using one kind of silane compound and a partially hydrolyzed condensate obtained by using two or more kinds of silane compounds can be used. Hereinafter, these compounds may be referred to as "partial (co) hydrolysis condensate".

The silane compound is a compound having a hydrolyzable silyl group and / or a silanol group. The silyl group is hydrolyzed to a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond.

In this case, the partial (co) hydrolysis condensate may be a dimer to a 100-mer, preferably a dimer to a 50-mer, and more preferably a dimer to a 20-mer of the silane compound as described above. Can be preferably used, and it is also possible to use a partial (co) hydrolysis condensate made from two or more kinds of silane compounds. The dimer of the silane compound is a compound in which 2 mol of water is allowed to act on 2 mol of the silane compound to desorb 2 mol of alcohol to form a disiloxane unit.

As such a partial (co) hydrolyzed condensate, a commercially available compound as a silicone alkoxy oligomer may be used, or hydrolyzed water having an amount less than the equivalent with respect to the hydrolyzable silane compound based on a conventional method. After reacting with the above, the compound produced by removing by-products such as alcohol and hydrochloric acid may be used. The silicone alkoxy oligomer is commercially available, for example, from Shin-Etsu Chemical Co., Ltd.

In the present disclosure, the siloxane oligomer preferably has an alkoxysilyl group at the molecular end. As the siloxane oligomer having an alkoxysilyl group at the end of the molecule, a trifunctional or bifunctional siloxane oligomer can be used, including a tetrafunctional siloxane oligomer having four alkoxysilyl groups in the molecule. Among the above, a trifunctional or bifunctional siloxane oligomer is preferable from the viewpoint of abrasion resistance and antifog property.

In the present disclosure, the functional number of the siloxane oligomer refers to the number of alkoxysilyl groups.

Further, among the above, it is preferable that the inorganic binder is a dehydrated condensate of a trifunctional or bifunctional siloxane having at least three or two alkoxysilyl groups in the molecule.

The reason for this is that, as described above, the anti-fog layer in the present disclosure contains a water-absorbing polymer in an amount of 1% by mass or less based on the total mass of the anti-fog layer (“substantially free of the water-absorbing polymer”). If the anti-fog layer is thick, dehydration condensation using a tetrafunctional alkoxysilane causes cracks in the anti-fog layer due to the compressive force generated during the dehydration condensation. Tends to be more likely to occur.

Then, if the water-absorbent polymer is contained in an amount of 1% by mass or less based on the total mass of the anti-fog layer, or if it is not contained, only a relatively thin layer can be formed, so that the amount of water absorption is small when the layer is thin. There is a tendency, and there is concern about deterioration of water absorption.

As a result of diligent studies on the above problems, the present inventor further promotes the dehydration condensation reaction by using a trifunctional or bifunctional alkoxysilane instead of a tetrafunctional alkoxysilane such as TMOS (tetramethoxysilane). Therefore, we thought that better scratch resistance could be achieved. Further, the present inventor has relatively few reaction sites when dehydrating and condensing trifunctional alkoxysilane as compared with the case where tetrafunctional alkoxysilane is condensed, and even if the dehydration condensation reaction is promoted, the anti-fog layer It was found that the force of compressing silane can be relatively suppressed. As a result, for example, even when the water-absorbent polymer is contained or not contained in an amount of 1% by mass or less based on the total mass of the anti-fog layer, the compressive force generated when the dehydration condensation of the tetrafunctional alkoxysilane is promoted. It is possible to easily maintain the voids in the layer while suppressing the generation of cracks due to the above. As a result, water absorption can be further enhanced.

As the tetrafunctional siloxane oligomer, a commercially available product containing a compound represented by the following formula 1 can be used.

Examples of commercially available tetrafunctional siloxane oligomers include MKC® Silicate MS51 [ ^R1 , ^R2 , R3 ^, and ^R4 : Methyl group, average of n: 5] of Mitsubishi Chemical Corporation. MKC® Silicate MS56 [R ¹ , R ² , R ³ , and R ⁴ : Methyl group, mean of n: 11], MKC® Silicate MS 57 [R ¹ , R ² , R ³ , and R. ⁴ : Methyl group, average of n: 13], MKC® silicate MS56S [R ¹ , R ² , R ³ , and R ⁴ : methyl group, average of n: 16], MKC® methyl silicate 53A [R ¹ , R ² , R ³ , and R ⁴ : Methyl group, average of n: 7], MKC® ethyl silicate 40 [R ¹ , R ² , R ³ , and R ⁴ : Ethyl group, Average of n: 5], MKC® ethyl silicate 48 [R ¹ , R ² , R ³ , and R ⁴ : Ethyl group, average of n: 10], MKC® EMS485 [R ¹ , R ² , R ³ , and R ⁴ : 50% each of methyl group and ethyl group, average of n: 10] and the like.

Commercially available products of the trifunctional siloxane oligomer include, for example, KBE-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.), KBM-403 (3-glycidoxypropyltrimethoxysilane, Shinetsu). Silicone Co., Ltd.), KBE-503 (3-methacryloxypropyltriethoxysilane, Shinetsu Silicone Co., Ltd.), KBM-503 (3-methacryloxypropyltrimethoxysilane, Shinetsu Silicone Co., Ltd.), KBM -603 (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.), KBM-803 (3-mercaptopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.), KBM- 903 (3-aminopropyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.), KBE-903 (3-aminopropyltriethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.), KBM-1003 (vinyltrimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.) (Co., Ltd.), KBE-1003 (vinyltriethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.), KBM-1403 (p-styryltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.) and the like.

Examples of commercially available bifunctional siloxane oligomers include KBE-402 (3-glycidoxypropylmethyldiethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.), KBM-402 (3-glycidoxypropylmethyldimethoxysilane, etc.). Shin-Etsu Silicone Co., Ltd.), KBE-502 (3-methacryloxypropylmethyldiethoxysilane, Shin-Etsu Silicone Co., Ltd.), KBM-502 (3-methacryloxypropylmethyldimethoxysilane, Shin-Etsu Silicone Co., Ltd.) , KBM-602 (N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.), KBM-802 (3-mercaptopropylmethyldimethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.), etc. Can be mentioned.

The anti-fog layer may contain only one type of condensate of the hydrolyzate of the siloxane oligomer, or may contain two or more types.

Further, as the siloxane oligomer, only one type may be used, or two or more types may be used in combination.

The content of the inorganic binder in the anti-fog layer is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more with respect to the total mass of the anti-fog layer. Is more preferable.

The content of the inorganic binder in the anti-fog layer is preferably 80% by mass or less, more preferably 60% by mass or less, and 40% by mass or less with respect to the total mass of the anti-fog layer. It is more preferable to have.

When the content of the inorganic binder in the anti-fog layer is 1% by mass or more with respect to the total mass of the anti-fog layer, an anti-fog layer having excellent adhesion to the substrate and stain resistance can be formed. can. Further, when the content of the inorganic binder in the anti-fog layer is 1% by mass or more and 80% by mass or less with respect to the total mass of the anti-fog layer, the water contact angle of the surface is suppressed to a low level, and thus stain resistance. Can form a good anti-fog layer.

-Other ingredients-

The anti-fog layer may contain other components other than the components described above, if necessary. Examples of other components include adhesion aids and antistatic agents that contribute to the improvement of adhesion to the substrate, components other than the above used in the anti-fog coating composition described later, and the like.

<< Antistatic agent >>

The anti-fog layer preferably contains an antistatic agent.

In the anti-fog layer, the antistatic agent is used for the purpose of suppressing the adhesion of contaminants and further improving the stain resistance by imparting antistatic properties to the anti-fog layer.

The antistatic agent is not particularly limited and may be appropriately selected from compounds having an antistatic function. It may be either a compound showing surface activity or a compound showing no surface activity. Examples of the antistatic agent include an ionic surfactant, metal oxide particles and the like.

The metal oxide particles referred to here do not include the silica particles described above.

The ionic surfactant has a property of easily segregating in the vicinity of the film surface when the anti-fog layer is formed by coating, for example, and therefore an effect can be expected with a small amount. Further, the metal oxide particles may be required in a relatively large amount in order to impart antistatic properties to the film, but since they are inorganic substances, they are suitable in terms of improving the scratch resistance of the film.

Examples of the ionic surfactant include alkyl sulfates [sodium dodecyl sulphate, sodium lauryl sulphate, etc.], alkylbenzene sulfonates [sodium dodecylbenzene sulfonate, sodium laurylbenzene sulfonate, etc.], alkyl sulfosuccinates [di (2). -Ethylhexyl) sodium sulfosuccinate, etc.], and other anionic surfactants; examples thereof include cationic surfactants such as alkyltrimethylammonium salt and dialkyldimethylammonium salt.

Examples of the metal oxide particles include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, zinc oxide particles and the like.

The shape of the metal oxide particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.

When the metal oxide particles have a large refractive index and a large average primary particle diameter, loss due to excessive scattering of transmitted light is likely to occur. Therefore, the average primary particle diameter is preferably 100 nm or less, preferably 50 nm or less. More preferably, it is more preferably 30 nm or less.

The measurement of the average primary particle size of the metal oxide particles is the same as the method of measuring the average primary particle size of the silica particles. The projected area of the oxide particles is measured, the equivalent circle diameter is obtained from the projected area, and the obtained equivalent circle diameter is taken as the average primary particle diameter of the metal oxide particles. For the metal oxide particles existing in the antifogging layer, observe the cross section in the direction perpendicular to the antifogging layer and calculate the average primary particle size. For the metal oxide particles in the anti-fog coat composition described later, 5 μL of the composition is dropped on a slide glass, air-dried, and then the glass surface is observed to calculate the average primary particle size.

When the anti-fog layer contains an antistatic agent, it may contain only one type of antistatic agent, or may contain two or more types of antistatic agent.

When the anti-fog layer contains an ionic surfactant, the content of the ionic surfactant in the anti-fog layer is 5% by mass or less with respect to the total solid content of the anti-fog coating composition. It is preferably 1% by mass or less, more preferably 0.5% by mass or less.

Further, the content of the ionic surfactant in the anti-fog layer is based on the total mass of the anti-fog layer from the viewpoint of the effect of improving the stain resistance by containing the ionic surfactant. It is preferably 0.01% by mass or more.

When the content of the ionic surfactant in the anti-fog layer is 0.01% by mass or more and 5% by mass or less with respect to the total mass of the anti-fog layer, aggregation of silica particles is suppressed. At the same time, it is possible to form an anti-fog layer having excellent antifouling properties.

When the antifogging layer contains metal oxide particles as an antistatic agent, the content of the metal oxide particles in the antifogging layer shall be 40% by mass or less with respect to the total mass of the antifogging layer. Is more preferable, and it is more preferably 20% by mass or less, and further preferably 10% by mass or less.

Further, the content of the metal oxide particles in the anti-fog layer is 1% by mass with respect to the total mass of the anti-fog layer from the viewpoint of the effect of improving the antifouling property of the film by containing the metal oxide particles. The above is preferable.

When the content of the metal oxide particles in the anti-fog layer is 1% by mass or more and 40% by mass or less with respect to the total mass of the anti-fog layer, the anti-fog layer may be formed by coating. The anti-fog property can be effectively imparted to the anti-fog layer without impairing the film-forming property.

(Adhesion aid)

The anti-fog layer may contain an adhesion aid.

The adhesion aid contributes to improving the adhesion between the anti-fog layer and the base material (particularly, a polycarbonate base material or a polymethylmethacrylate base material).

Further, the adhesion aid in the present disclosure may function as the water-absorbent organic polymer.

Examples of the adhesion aid include film-forming components that do not have a siloxane structure in the molecule, for example, film-forming polymer compounds, and more specifically, urethane-based resins, (meth) acrylic resins, and polyphosphorus. Examples thereof include compounds having a polar group (hydroxyl group, carboxy group, phosphate group, sulfonic acid group, amino group, etc.) at the terminal, such as acid salt and metaphosphate.

Among these, as the adhesion aid, at least one selected from the group consisting of a hydroxyl group, a carboxy group, and a phosphoric acid group at the terminal from the viewpoint of better adhesion between the antifogging layer and the substrate. A compound having a functional group is preferable, and at least one selected from the group consisting of a urethane resin, a (meth) acrylic resin, and a polyphosphate is more preferable, and a compound consisting of a urethane resin and a (meth) acrylic resin is more preferable. At least one resin selected is further preferred.

The urethane-based resin is not particularly limited, and examples thereof include polyurethane having a soft segment / hard segment structure formed by a polyol skeleton and a polyisocyanate skeleton.

As the urethane resin, a commercially available product can be used.

Examples of commercially available urethane-based resins include Takelac (registered trademark) W series, WS series, WD series of Mitsui Chemicals, Inc., Permarin (registered trademark) series of Sanyo Chemical Industries, Ltd., and U-coat (registered trademark). Examples include the series, the Eupren (registered trademark) series, and the like.

In the present disclosure, the "(meth) acrylic resin" is defined as a structural unit derived from acrylic acid, a structural unit derived from methacrylic acid, a structural unit derived from an acrylic acid ester, and a structural unit derived from a methacrylic acid ester. A polymer containing at least one selected from the group.

Examples of the (meth) acrylic resin include a homopolymer of acrylic acid (that is, polyacrylic acid), a homopolymer of methacrylic acid (that is, polymethacrylic acid), acrylic acid, methacrylic acid, an acrylic acid ester, and methacrylic acid. Examples thereof include a copolymer containing at least one monomer selected from the group consisting of esters and the like.

Among these, polyacrylic acid is preferable as the (meth) acrylic resin. The weight average molecular weight of polyacrylic acid is preferably 25,000 or more and 5,000,000 or less, more preferably 50,000 or more and 2,000,000 or less, and 150,000 or more and 1,000, It is more preferably 000 or less.

The weight average molecular weight of polyacrylic acid can be measured by gel permeation chromatography (GPC).

For the measurement by gel permeation chromatography (GPC), HLC-8120GPC and SC-8020 (both from Tosoh Corporation) were used as measuring devices, and TSKgel (registered trademark) Super HM-H (6.0 mm ID ×) was used as a column. It can be measured by using two 15 cm, Tosoh Corporation, and using THF (tetrachloride) as the eluent. The measurement conditions are a sample concentration of 0.5% by mass, a flow velocity of 0.6 mL / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C., using a suggestion refractometer (RI) detector. be able to.

The calibration curve is "Standard sample TSK standard, polystyrene": "A-500", "F-1", "F-10", "F-80", "F-380", "A" of Tosoh Corporation. Those prepared from 10 samples of "-2500", "F-4", "F-40", "F-128", and "F-700" can be used.

Examples of the polyphosphate include sodium polyphosphate, potassium polyphosphate and the like.

The adhesive layer may contain only one type of adhesion aid, or may contain two or more types.

The content of the adhesion aid is preferably 0.001% by mass or more and 5% by mass or less with respect to the total mass of the antifogging layer from the viewpoint of adhesion between the base material and the antifogging layer. It is more preferably 01% by mass or more and 1% by mass or less, and further preferably 0.05% by mass or more and 0.5% by mass or less.

(Water absorption of anti-fog layer)

The water absorption of the anti-fog layer is preferably 1.0 mg / cm ² or more and 26.5 mg / cm ² or less. This makes it possible to maintain good anti-fog properties.

From the above viewpoint, the water absorption of the anti-fog layer is more preferably 2.0 mg / cm ² or more and 22.0 mg / cm ² or less, and 3.5 mg / cm ² or more and 20.0 mg / cm ² or less. Is even more preferable.

In the present disclosure, the amount of water absorption can be measured by, for example, the following method.

Prepare a hot water bath at 60 ° C., apply steam from the hot bath only to the predetermined 5 cm × 5 cm area of the antifogging layer of the obtained laminate, apply steam, and then in an environment of 25 ° C. and 50% RH. The laminated body is erected vertically and the amount of mass increase under the upper limit condition where water dripping does not occur is measured, and the amount of mass increase per unit area to which steam is applied is defined as the amount of water absorption (mg / cm ² ).

(Water contact angle of the exposed surface of the anti-fog layer)

From the viewpoint of the hydrophilicity of the exposed surface of the anti-fog layer, the water contact angle of the exposed surface of the anti-fog layer is preferably 25 ° or less.

From the same viewpoint, the water contact angle of the exposed surface of the anti-fog layer is more preferably 20 ° or less, and further preferably 15 ° or less.

The water contact angle of the exposed surface of the anti-fog layer is measured by DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd. as the contact angle of water droplets on the surface at 25 ° C. (after 0.2 seconds).

(Membrane density)

The film density of the anti-fog layer can be 0.80 g / cm ³ or more and 1.40 g / cm ³ or less. The film density of the antifogging layer is preferably 0.80 g / cm ³ or more and 1.40 g / cm ³ or less, preferably 0.90 g / cm, from the viewpoint of antifogging property, stain resistance and water dripping trace suppressing property. It is more preferably cm ³ or more and 1.35 g / cm ³ or less, and particularly preferably 1.05 g / cm ³ or more and 1.30 g / cm ³ or less.

The film density of the anti-fog layer is measured by the following method.

Prepare a laminated body to be measured for 100 cm and ² minutes, and measure the mass. In addition, the film thickness of the antifogging layer is measured from a transmission electron microscope (SEM) image of the cross section of the laminated body. The film thickness measured by SEM is the average of 10 random points in the plane in the above laminated body. Next, the anti-fog layer is scraped off, and the mass of the base material after scraping is measured.

The mass per unit area of the base material after scraping off the antifogging layer is xg / cm ² , the mass per unit area of the first measured laminate is yg / cm ² , and the film of the laminate measured from SEM. When the thickness is zcm, the film density of the antifogging layer is calculated by the following method.

Film density of anti-fog layer [g / cm ³ ] = (y-x) [g / cm ² ] / z [cm]

The film density of the anti-fog layer can also be referred to as the bulk density of the anti-fog layer.

When the solid mass of the silica particles is B and the solid mass of the inorganic binder is C in the anti-fog layer, it is preferable to satisfy the following relational expression (B).

0.15 ≤ C / B ≤ 2.00 Relational expression (B)

By satisfying the above relational expression (B), an anti-fog layer having a preferable film density is formed.

Further, when the solid mass of the silica particles is B and the solid mass of the inorganic binder is C in the anti-fog layer from the viewpoints of stain resistance, water dripping trace suppressing property, and substrate adhesion. It is preferable to satisfy the following relational expression (B1), and it is more preferable to satisfy the following relational expression (B2).

0.15 ≤ C / B ≤ 1.50 Relational expression (B1)

0.20 ≤ C / B ≤ 1.30 Relational expression (B2)

When the C / B is 0.15 or more, the amount of the inorganic binder fixing the silica particles in the anti-fog layer becomes a preferable ratio, and the adhesion to the substrate becomes good. In addition, it is considered that the generation of water dripping marks due to the swelling and dissolution of the anti-fog layer can be suppressed. It is considered that when the C / B is 2.00 or less, voids are generated in the anti-fog layer, the amount of water that can be taken in is increased, and the anti-fog and stain resistance are improved.

When the solid mass of the water-absorbent organic polymer is A and the solid mass of the silica particles is B in the antifogging layer from the viewpoints of antifogging property, stain resistance, and water dripping trace suppressing property, It is preferable to satisfy the following relational expression (A), more preferably to satisfy (A1), and further preferably to satisfy the following relational expression (A2).

0.01 ≤ A / B ≤ 0.20 Relational expression (A)

0.02 ≤ A / B ≤ 0.15 Relational expression (A1)

0.04 ≤ A / B ≤ 0.10 Relational expression (A2)

When the A / B is 0.01 or more, the content ratio of the water-absorbing organic polymer in the anti-fog layer becomes large, so that voids are generated in the anti-fog layer and the amount of water absorption of the laminated body becomes large. It is considered that the stain resistance of the anti-fog layer is improved. When the A / B is 0.20 or less, it is considered that the hydrophilicity due to the silica particles in the anti-fog layer can be maintained, and the generation of water dripping marks due to the swelling and dissolution of the anti-fog layer can be suppressed.

<Base material>

The laminate according to the present disclosure has a base material.

In addition, the laminate according to the present disclosure has an anti-fog layer provided on at least a part of the base material. The anti-fog layer may be provided on a part of the base material or may be provided on the entire surface. Further, the anti-fog layer may or may not be in direct contact with the base material, but the laminate according to the present disclosure is in direct contact with the base material because the anti-fog layer has excellent adhesion to the base material. Is preferable.

The material of the base material is not particularly limited, and various materials such as glass, resin (that is, plastic), metal, and ceramics can be appropriately selected and used. Further, as the material of the base material, a composite material formed from a plurality of materials can also be used. For example, the material of the base material may be a composite material containing glass and a resin material, in which glass and the resin material are mixed and composited, a resin composite material in which a plurality of types of resin materials are kneaded or bonded, and the like. good.

Further, as the base material, a resin base material is preferably mentioned. For example, a resin base material is often used as a protective material for automobile lights and a protective material for surveillance cameras.

When the material of the base material is a resin material, the base material has excellent durability against light and heat, and has excellent adhesion to the antifogging layer while maintaining the transparency of the base material. An acrylic resin base material, a polycarbonate base material, or a polyethylene terephthalate base material is preferable from the viewpoint of being able to form a laminated body, and an acrylic resin base material or a polyethylene terephthalate base material is preferable from the viewpoint of being able to form a laminated body having better adhesion. A polycarbonate base material is more preferable, and a polycarbonate base material or a polymethylmethacrylate base material is particularly preferable.

From the viewpoint of being able to form a laminate having excellent adhesion, the base material is preferably glass or resin, and more preferably glass, polycarbonate resin or acrylic resin.

The thickness and shape of the base material are not particularly limited, and are appropriately set according to the application target.

Further, the surface of the base material may be surface-treated, if necessary. The surface treatment method is not particularly limited, and a known method can be used.

<Use of laminated body>

The laminate according to the present disclosure can be used for various purposes. Specifically, for example, protective materials for protecting surveillance cameras, lighting, sensor lamps, etc. (so-called protective covers); roofing materials for garages of vehicles such as automobiles and two-wheeled vehicles; signs such as road signs; highway road shoulders Soundproof walls for installation, railways, etc .; Vehicle bodies such as automobiles and two-wheeled vehicles; To impart functions such as antifogging to automobile window glass, mirrors, protective materials for lights (for example, lenses), etc. , Can be suitably used.

Among these, the laminate according to the present disclosure can be more preferably used as a protective material for automobile lights (headlights, tail lamps, door mirror winker lights, etc.) and a protective material for surveillance cameras.

In general, an automobile is equipped with a light unit that includes a light and a lens for protecting the light. The transparent base material such as glass and plastic used in this light unit is used when one surface becomes below the dew point due to the difference in temperature and humidity between the inner surface and the outer surface of the base material, or with respect to the base material. When a sudden change in temperature and humidity occurs (when boiling steam comes into contact with the base material, or when the environment moves from a low temperature part to a high temperature and high humidity environment, etc.), the moisture in the atmosphere adheres as water droplets, and the surface of the base material becomes Condensation. As a result, so-called "cloudiness", in which light is scattered by the condensed water droplets, may occur. When such "cloudiness" occurs in the headlights and rear lights, the appearance is significantly impaired. Such fogging also occurs in the protective cover of a surveillance camera having a protective cover (that is, a surveillance camera integrated with a housing), and in this case, visibility and safety are significantly impaired. Since the laminate according to the present disclosure is excellent in transparency, it does not impair the appearance, function and performance of automobile lights and surveillance cameras, and is excellent in stain resistance and substrate adhesion, so that it is excellent in anti-fog. Sex can be maintained for a long period of time.

Further, since the laminated body of the present disclosure has remarkably good scratch resistance, it is also suitable for the front, side, rear, roof, in-vehicle window and other parts of an automobile that come into contact with human hands. Can be used.

(Manufacturing method of laminated body)

The method for producing the laminate according to the present disclosure is not particularly limited as long as the laminate according to the present disclosure can be produced.

The method for producing the laminate according to the present disclosure is preferably a method of applying the anti-fog coating composition described later on the substrate and drying it. That is, it is preferable that the anti-fog layer is a coating layer formed by coating the anti-fog coating composition.

Further, the laminate according to the present disclosure can be suitably produced by, for example, a method including forming an anti-fog layer by applying an anti-fog coating composition on a base material.

Further, the anti-fog layer may be a layer composed of one layer or a layer composed of a plurality of layers.

The method for applying the anti-fog coating composition on the substrate is not particularly limited, and is preferably a coating method. The coating method for applying the anti-fog coating composition on the substrate is not particularly limited, and is a known coating method such as spray coating, brush coating, roller coating, bar coating, and dip coating (so-called dip coating). Can be applied. Among these, as a coating method, spray coating is preferable when coating on a three-dimensional structure having various surface shapes such as curved surfaces and irregularities.

When the anti-fog coating composition is applied to the base material by spray coating, the method of setting the base material is not particularly limited. Depending on the shape of the base material, the orientation of the base material can be appropriately changed such as in the horizontal direction and the vertical direction with respect to the coating direction. In order to make the coating film more uniform, it is preferable to arrange the spray nozzles at positions where the distance between the spray nozzle and the base material is equal and apply the spray nozzle to the base material. The distance is preferably 10 mm or more and 1,000 mm or less.

As a method of supplying the anti-fog coating composition to the coating device, any of a pressure feeding type, a suction type, and a gravity type can be used.

The nozzle diameter of the spray nozzle is preferably 0.1 mmφ or more and 1.8 mmφ or less, and the air pressure is preferably 0.02 MPa or more and 0.60 MPa or less. By applying under such conditions, the coating film thickness can be made more uniform. In order to form a more suitable coating film by spray coating, it is necessary to adjust the amount of air, the amount of the anti-fog coating composition ejected, the pattern opening, and the like.

When the anti-fog coating composition is applied to the substrate by spray coating, the amount of air is preferably 5 L (liter) / min or more and 600 L / min or less, and the paint ejection amount is 5 L / min or more and 600 L / min or less. The pattern opening is preferably 40 mm or more and 450 mm or less.

In spray application, the environment at the time of application also affects the formation of the coating film. The temperature condition is preferably 15 ° C. or higher and 35 ° C. or lower, and the humidity condition is preferably 80% RH or lower.

The cleanliness is not particularly limited, but for example, from the viewpoint of suppressing surface failure due to fine particles (that is, particles) in the coating environment, a cleanliness of class 10,000 or higher is preferable, and a cleanliness of class 1,000 or higher is preferable. Is more preferable.

The amount of the anti-fog coating composition applied is not particularly limited, and may be appropriately set in consideration of operability, etc., according to the concentration of the solid content in the anti-fog coating composition, the desired film thickness, and the like. can. For example, the coating amount of the anti-fog coating composition is preferably 1 mL / m ² or more and 400 mL / m ² or less, more preferably 2 mL / m ² or more and 100 mL / m ² or less, and 4 mL / m ² . It is more preferably 40 mL / m ² or more, and particularly preferably 6 mL / m ² or more and 20 mL / m ² or less. Within the above range, the coating accuracy is good.

In the present disclosure, when the anti-fog layer is formed, it is formed so as to have a gradient in which the average void diameter decreases in the direction from the surface of the anti-fog layer toward the substrate.

The anti-fog layer having the above gradient can be produced, for example, by the following method.

When the anti-fog layer is produced by one layer, the anti-fog layer may be produced so that the average void diameter gradually decreases in the direction from the surface of the anti-fog layer toward the substrate. For example, particles having a multimodal particle size distribution are used for the secondary particle size (aggregate of primary particles), and the difference in sedimentation property depending on the particle size (the larger the particle size, the lower the effect of sedimentation) is used. , Can be made. However, in terms of easily providing a gradient of the average void diameter, a method of stacking two or more anti-fog layers is preferable. When two or more layers are stacked to form an anti-fog layer, a plurality of layers having different average void diameters are prepared, and the average void diameter becomes smaller toward the substrate from a position far from the substrate on the substrate. The layers may be stacked in such a manner (so that the average void diameter increases sequentially from the base material side).

In the method for producing a laminate of the present disclosure, when the anti-fog layer includes a plurality of layers, the same method as above is further applied on the layer formed by the anti-fog coating composition applied to the base material. Allows the anti-fog coating composition to be applied.

As a result, layers having different average void diameters can be stacked. For example, the voids contained in the anti-fog layer on the side half close to the substrate with reference to the direction from the substrate to the anti-fog layer. It is possible to form an anti-fog layer having an average void diameter of 20% or less of the average void diameter of the voids contained in the anti-fog layer on the side half far from the base material.

The method for producing a laminate according to the present disclosure preferably includes drying the anti-fog coating composition applied on the substrate.

The anti-fog coating composition may be dried using a heating device. As the heating device, any known heating device can be used as long as it can be heated to a target temperature without particular limitation. As the heating device, in addition to an oven, an electric furnace, etc., a heating device originally manufactured according to the production line can be used.

In the method for producing a laminate according to the present disclosure, when the anti-fog layer contains a plurality of layers, each layer may be formed with the anti-fog coating composition and then dried, and each layer is sequentially dried. May be good. In the method for producing a laminate according to the present disclosure, it is preferable that each layer is sequentially dried from the viewpoint of adhesion of each layer.

The drying conditions of the anti-fog coating composition are not particularly limited, and can be appropriately set in consideration of the curability of the coating film.

The anti-fog coating composition may be dried under constant temperature conditions in which a predetermined set temperature is kept constant, or the temperature conditions may be changed stepwise.

As the drying condition of the anti-fog coating composition in the former case, the drying condition in which the anti-fog coating composition is heated at a surface temperature of 20 ° C. or higher and 150 ° C. or lower for 1 to 60 minutes is preferable. The drying condition of heating at 40 ° C. or higher and 150 ° C. or lower for 1 minute to 60 minutes is more preferable, and the drying condition of heating at 60 ° C. or higher and 150 ° C. or lower for 1 minute to 60 minutes is further preferable.

In the latter case, the anti-fog coating composition is preferably dried separately as pre-drying and main drying. The conditions for pre-drying are preferably a condition in which the surface temperature is set to 20 ° C. or higher and 60 ° C. or lower and heated for 5 seconds to 10 minutes.

The surface temperature can be measured with an infrared thermometer or the like.

When the anti-fog coating composition is dried by blowing dry air, the air volume of the dry air can be appropriately set in consideration of the optimum temperature when the composition reaches the substrate. However, in consideration of uneven drying, it is preferable to suppress the air volume as much as possible, and it is more preferable to perform drying under the condition that there is no wind, that is, the substrate is not directly exposed to the drying air.

Depending on the shape of the base material, the base material coated with the anti-fog coating composition may be placed directly on the pedestal (that is, placed flat) and dried, or may be placed upright and dried. Alternatively, it may be hung and dried.

A solvent such as thinner, water, alcohol, a surfactant, or the like may be used for cleaning the parts of the spray gun, the coating device, and the like after being used for coating. Further, in order to effectively clean the stains to which scales and the like are attached, the residual antifogging coating composition and the like, it is preferable to wash with an acidic or alkaline aqueous solution, and the pH is 3.0 or less, or the pH is 8. It is more preferable to wash with an aqueous solution of .0 or more. The temperature of the cleaning liquid is preferably room temperature or higher, more preferably 50 ° C. or higher.

The storage container for the antifogging coating composition is not particularly limited, and may be a metal container such as an Ito can or a royal can, or a resin container such as polyethylene or polypropylene.

The storage temperature of the anti-fog coating composition is preferably 0 ° C. or higher and 50 ° C. or lower.

(Composition for anti-fog coat)

The anti-fog coating composition is not particularly limited as long as it is a composition capable of forming an anti-fog layer in the laminate according to the present disclosure, but preferably contains silica particles and an inorganic binder.

The preferred embodiments of the silica particles and the inorganic binder in the antifogging coating composition are the same as the preferred embodiments of the silica particles and the inorganic binder in the antifogging layer of the laminate according to the present disclosure described above, except for the following.

The content of the inorganic binder in the anti-fog coating composition is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass, based on the total solid content of the anti-fog coating composition. It is more preferably mass% or more.

The content of the inorganic binder in the anti-fog coating composition is preferably 80% by mass or less, more preferably 60% by mass or less, based on the total solid content of the anti-fog coating composition. , 40% by mass or less, more preferably.

When the content of the inorganic binder in the anti-fog coating composition is 1% by mass or more with respect to the total solid content of the anti-fog coating composition, the anti-fog excellent in adhesion to the substrate and stain resistance. Layers can be formed. Further, when the content of the inorganic binder in the anti-fog coating composition is 1% by mass or more and 80% by mass or less with respect to the total solid content of the anti-fog coating composition, the water contact angle of the surface is kept low. Therefore, it is possible to form an anti-fog layer having good stain resistance.

The content of silica particles in the antifogging coating composition is preferably 10% by mass or more and 90% by mass or less, and is 20% by mass or more and 70% by mass or less, based on the total solid content of the antifogging coating composition. It is more preferable that it is 40% by mass or more and 65% by mass or less. Within the above range, an anti-fog layer having excellent hardness, scratch resistance and impact resistance and having desired hydrophilicity can be formed.

<Ketone solvent>

The anti-fog coating composition preferably contains a ketone solvent.

In the anti-fog coating composition, the ketone solvent contributes to the improvement of the adhesion to the substrate.

The ketone solvent is not particularly limited, and examples thereof include acetone, diacetone alcohol, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and cyclopentanone.

The ketone solvent is preferably a ketone solvent having an SP value (solubility parameter) of 10.0 MPa ^1/2 or more from the viewpoint of being able to form a film having more excellent transparency. The upper limit of the SP value of the ketone solvent is not particularly limited, and is 13.0 MPa ^1/2 or less from the viewpoint of applicability to the substrate (for example, the property that surface failure such as repellent is unlikely to occur). It is preferable to have.

Specific examples of the ketone solvent having an SP value of 10.0 MPa ^1/2 or more are shown below. However, this embodiment is not limited to the following specific examples. Further, as the method for measuring the SP value, the above-mentioned method is used. The numerical value in parentheses after the specific example below indicates the SP value (unit: MPa ^1/2 ).

Acetone (10.0), diacetone alcohol (10.2), acetylacetone (10.3), cyclopentanone (10.4).

Among these, it is preferable to contain diacetone alcohol (4-hydroxy-4-methyl-2-pentanone).

The anti-fog coating composition may contain only one kind of ketone solvent, or may contain two or more kinds of ketone solvents.

The content of the ketone solvent in the antifogging coating composition is preferably 1% by mass or more and 95% by mass or less, and more preferably 2% by mass or more and 50% by mass or less from the viewpoint of transparency and substrate adhesion. 3% by mass or more and 10% by mass or less are particularly preferable. The content of the ketone solvent in the anti-fog coating composition can be appropriately set according to the type of the base material used, the solubility of the material contained in the anti-fog coating composition, and the like.

<Water>

The anti-fog coating composition preferably contains water from the viewpoint of transparency and substrate adhesion.

The content of water in the anti-fog coating composition is not particularly limited and can be appropriately set.

From the viewpoint of transparency and substrate adhesion, it is preferable to contain 1% by mass or more and 70% by mass or less of water with respect to the total mass of the solvent contained in the antifogging coating composition, and 10% by mass or more. It is more preferable to contain water in an amount of 65% by mass or less, and further preferably to contain water in an amount of 20% by mass or more and 60% by mass or less.

<Specific solvent>

The antifogging coating composition preferably further contains at least one solvent (hereinafter, also referred to as "specific solvent") selected from the group consisting of an alcohol solvent, a glycol ether solvent, and an ether solvent. ..

The anti-fog coating composition can form a film having better adhesion by further containing a specific solvent in addition to the above-mentioned ketone solvent.

In the present disclosure, the "alcohol-based solvent" refers to a solvent having a structure in which one hydroxy group is substituted for one carbon atom of a hydrocarbon.

In the present disclosure, the "glycol ether-based solvent" refers to a solvent having a structure having one hydroxy group and at least one ether group in one molecule.

In the present disclosure, the "ether-based solvent" refers to a solvent having a structure that does not have a hydroxy group in one molecule and has at least one ether group.

Examples of the alcohol solvent include methanol, ethanol, n-butanol, n-propanol, 2-propanol, tert-butanol, 2-butanol, benzyl alcohol, 2-methyl-1-butanol, 2-methyl-2-butanol and the like. Can be mentioned.

Glycol ether-based solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, and diethylene glycol mono. Examples thereof include hexyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, methyl cellosolve, ethyl cellosolve, and butyl cellosolve.

Examples of the ether solvent include isopropyl ether, 1,4-dioxane, tert-butylmethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2 dimethoxyethane, diethyl ether and the like.

When the anti-fog coating composition contains a specific solvent, it may contain only one type of the specific solvent, or may contain two or more types of the specific solvent.

When the anti-fog coating composition contains a specific solvent, the content of the specific solvent in the anti-fog coating composition is not particularly limited.

The content of the specific solvent in the anti-fog coating composition is the total amount of the solvent contained in the anti-fog coating composition from the viewpoint of applicability to the substrate (for example, surface failure such as repellent is unlikely to occur). With respect to the mass, 5% by mass or more is preferable, 10% by mass or more is more preferable, 20% by mass or more is further preferable, and 40% by mass or more is particularly preferable.

Further, the content of the specific solvent in the antifogging coating composition is preferably 75% by mass or less with respect to the total mass of the solvent contained in the antifogging coating composition from the viewpoint of adhesion to the substrate. , 65% by mass or less is more preferable, and 55% by mass or less is further preferable.

When the antifogging coating composition contains a specific solvent, the content of the specific solvent with respect to the content of the ketone solvent in the antifogging coating composition (that is, alcohol-based solvent, glycol ether-based solvent, and ether-based solvent). The ratio of (total content) is preferably 0.1 to 51.4 on a mass basis from the viewpoint of applicability to the base material and adhesion to the base material. The ratio of the content of the specific solvent to the content of the ketone solvent in the anti-fog coating composition depends on the type of the base material used, the solubility of the material contained in the anti-fog coating composition, and the like. , Can be set as appropriate.

The total content of the solvent in the anti-fog coating composition is 50% by mass or more with respect to the total mass of the anti-fog coating composition from the viewpoint of maintaining good stability of the anti-fog coating composition over time. It is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 90% by mass or more.

<Other ingredients>

The anti-fog coating composition may contain other components other than those described above, if necessary. Other components include a viscosity regulator that adjusts the viscosity of the anti-fog coating composition, a catalyst that promotes the condensation reaction of the hydrolyzate of the specific siloxane compound (hereinafter, also referred to as "condensation promoting catalyst"), and surfactant. Examples thereof include an agent, a pH adjuster, and other components (antistatic agent, etc.) that may be contained in the above-mentioned anti-fog layer.

-Viscosity adjuster-

The anti-fog coating composition may further contain a viscosity modifier.

When the anti-fog coating composition contains a viscosity modifier, the viscosity of the anti-fog coating composition increases, liquid dripping is less likely to occur during coating, and coating suitability is improved.

Further, the viscosity modifier in the present disclosure may function as the water-absorbent organic polymer.

The viscosity adjusting agent is not particularly limited, and examples thereof include known thickeners and highly viscous solvents. The viscosity modifier can be appropriately selected depending on the method of applying the anti-fog coating composition to the substrate.

The thickener is not particularly limited and is preferably selected as appropriate depending on the type of solvent contained in the anti-fog coating composition. As the thickener, a thickener having a weight average molecular weight of 3,000 or more and 10,000,000 or less is preferable from the viewpoint that a thickening effect can be obtained by using a relatively small amount.

The thickener referred to here does not include the urethane-based resin and the (meth) acrylic-based resin described above.

The weight average molecular weight of the thickener can be measured by the same method as the weight average molecular weight of the polyacrylic acid described above.

Specific examples of the thickener include SEPIGER 305 manufactured by Seiwa Kasei Co., Ltd. and DISPERBYK (registered trademark) 410, 411, 415, 420, 425, 428, 430, 431, 7410ET, 7411ES manufactured by Big Chemie. , 7420ES, Coscat GA468 manufactured by Osaka Organic Chemical Industry Co., Ltd., inorganic materials [silicate (water-soluble alkali silicate), montmorillonite, organic montmorillonite, colloidal alumina, etc.], fiber element derivative materials (carboxymethyl cellulose, Methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropylmethyl cellulose, etc.), protein-based materials (casein, sodium casenate, ammonium caseite, etc.), alginic acid-based materials (sodium alginate, etc.), polyvinyl System materials (polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl benzyl ether copolymer, etc.), polyether materials (pluronic polyether, polyether dialkyl ester, polyether dialkyl ether, polyether urethane modified product, polyether epoxy modified product, etc.) , Anhydrous maleic acid copolymer system material (vinyl ether-partial ester of maleic anhydride copolymer, dry oil fatty acid allyl alcohol ester-half ester of maleic anhydride, etc.) and the like. In addition to the above, examples of the thickener include polyamide wax salts, acetylene glycols, zentan gums, oligomers or polymers having a polar group at the molecular end or side chain, and the like.

When the anti-fog coating composition further contains a thickener as a viscosity modifier, it may contain only one thickener or two or more thickeners.

When the antifogging coating composition contains a thickener as a viscosity modifier, the content of the thickener in the antifogging coating composition is 0.01 with respect to the total mass of the antifogging coating composition. It is preferably 0% by mass or more and 40% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, and further preferably 0.1% by mass or more and 10% by mass or less.

As the viscosity adjusting agent, a solvent having a high viscosity is preferable in that the viscosity adjusting agent component does not remain in the formed film.

In the present disclosure, the "solvent having a high viscosity" means, for example, a solvent having a viscosity of 30 mPa / s or more at 25 ° C.

The viscosity in the present disclosure is a value measured using a B-type viscometer (model: TVB-10) manufactured by Toki Sangyo Co., Ltd.

Examples of the highly viscous solvent include glycol-based solvents.

In the present disclosure, the "glycol-based solvent" refers to a solvent having a structure in which one hydroxy group is substituted for each of two or more carbon atoms of a hydrocarbon.

Glucol-based solvents include ethylene glycol, diethylene glycol, triethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1 , 4-Butandiol, Diethanolamine, Triethanolamine, Propylene Glycol, Dipropylene Glycol and the like.

Among these, as the glucol-based solvent, at least one selected from propylene glycol and dipropylene glycol is preferable from the viewpoint of dispersibility of silica particles and drying property when applied.

When the anti-fog coating composition further contains a glycol-based solvent as a viscosity modifier, it may contain only one type of glycol-based solvent, or may contain two or more types of glycol-based solvent.

When the antifogging coating composition contains a glycol-based solvent as a viscosity modifier, the content of the glycol-based solvent in the antifogging coating composition is based on the total mass of the solvent contained in the antifogging coating composition. , 40% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

When the content of the glycol-based solvent is 40% by mass or less with respect to the total mass of the solvent contained in the anti-fog coating composition, it is possible to prevent the anti-fog coating composition from dripping during coating. At the same time, it is possible to form a film having excellent adhesion.

Further, the content of the glycol-based solvent in the anti-fog coating composition is based on the total mass of the solvent contained in the anti-fog coating composition from the viewpoint of the effect of improving the coating suitability by further containing the glycol-based solvent. Therefore, it is preferably 0.1% by mass or more.

When the anti-fog coating composition further contains a viscosity modifier, the viscosity may be adjusted by using a thickener and a highly viscous solvent in combination. The optimum viscosity of the anti-fog coating composition varies depending on the coating method on the substrate. For example, in the case of spray coating, the viscosity of the anti-fog coating composition is 2 mPa / s or more and 200 mPa / s or less. It is preferably 3 mPa / s or more and 100 mPa / s or less, and further preferably 4 mPa / s or more and 50 mPa / s or less.

-Condensation catalyst-

The anti-fog coating composition preferably contains a catalyst (that is, a condensation catalyst) that promotes the condensation reaction of the hydrolyzate of the specific siloxane compound.

The anti-fog coating composition can form a more durable film by containing a condensation catalyst. In the present disclosure, after the anti-fog coating composition is applied onto the substrate, the applied anti-fog coating composition is dried to reduce the water content, and as a result, the specific siloxane in the anti-fog coating composition is used. At least a part of the hydroxy groups of the hydrolyzate of the compound are condensed with each other to form a condensate, whereby a stable film is formed. Further, the anti-fog coating composition can form a film more quickly by containing a condensation catalyst.

The condensation catalyst is not particularly limited, and examples thereof include catalysts such as acid catalysts, alkali catalysts, and organic metal catalysts.

Acid catalysts include nitrate, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, chloroacetic acid, formic acid, oxalic acid, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, dinonylnaphthalene monosulfonic acid, dinonylnaphthalenedisulfonic acid, dodecyl. Examples thereof include benzenesulfonic acid, polyphosphate, metaphosphate and the like.

Among these, as the acid catalyst, at least one selected from the group consisting of phosphoric acid, toluenesulfonic acid, polyphosphate, and metaphosphate is preferable.

Examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium hydrogencarbonate, urea and the like.

Among these, as the alkali catalyst, at least one selected from baking soda and urea is preferable.

Examples of the organic metal catalyst include aluminum chelate compounds such as aluminum bis (ethyl acetoacetate) mono (acetyl acetonate), aluminum tris (acetyl acetonate), and aluminum ethyl acetoacetate diisopropylate; zirconium tetrakis (acetyl acetonate) and zirconium. Zirconium chelating compounds such as bis (butoxy) bis (acetylacetonate); titanium chelating compounds such as titaniumtetrakis (acetylacetonate) and titanium bis (butoxy) bis (acetylacetonate); dibutyltin diacetate, dibutyltin dilaurate, dibutyltingeo Organic tin compounds such as cutietes, aluminum alkoxides such as aluminum ethylate, aluminum isopropylate, aluminum sec-butyrate; titanium alkoxides such as titanium (IV) ethoxydo, titanium isopropoxide, titanium (IV) n-butoxide; zirconium ( IV) Titanium alkoxides such as ethoxydo, zirconium (IV) n-propoxide, zirconium (IV) n-butoxide and the like can be mentioned.

Among these, as the organometallic catalyst, at least one selected from the group consisting of an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound is preferable.

Among the above, as the condensation catalyst, an organometallic catalyst is more preferable from the viewpoint of crack suppression of the obtained antifogging layer, and an aluminum chelate compound (for example, aluminum chelate D, manufactured by Kawaken Fine Chemical Co., Ltd., 1% by mass) is preferable. Ethanol diluted solution) is more preferable.

When the anti-fog coating composition contains a condensation catalyst, it may contain only one type of condensation catalyst, or may contain two or more types of condensation catalyst.

When the anti-fog coating composition contains a condensation catalyst, the content of the condensation catalyst in the anti-fog coating composition is 0.1% by mass or more and 40% by mass with respect to the total solid content of the anti-fog coating composition. % Or less, more preferably 1% by mass or more and 30% by mass or less, and further preferably 5% by mass or more and 20% by mass or less. Within the above range, an anti-fog layer having excellent transparency can be formed more quickly.

The content of the aluminum chelate compound in the antifogging coating composition is preferably 0.1% by mass or more and 40% by mass or less with respect to the total solid content of the antifogging coating composition by 1% by mass. It is more preferably% or more and 30% by mass or less, and further preferably 5% by mass or more and 20% by mass or less. Within the above range, an anti-fog layer having excellent crack suppression and transparency can be formed more quickly.

-Surfactant-

The anti-fog coating composition preferably contains a surfactant.

By containing a surfactant, the anti-fog coating composition can form a film having excellent antifouling property, that is, antifouling property.

The surfactant referred to here does not include the compound (that is, an ionic surfactant) that exhibits surface activity and has an antistatic function, which is mentioned as the above-mentioned antistatic agent.

In the anti-fog coating composition, the antistatic agent and the surfactant may be used in combination regardless of whether the antistatic agent exhibits surface activity or not.

When the antistatic agent is a compound that does not exhibit surface activity, the anti-fog coating composition preferably contains a surface active agent from the viewpoint of water detergency. When the antistatic agent is a compound exhibiting surface activity, it is preferable that the anti-fog coating composition contains a surface active agent in addition to the antistatic agent from the viewpoint of further improving the antifouling property.

By containing the surfactant, the anti-fog coating composition not only enhances the antifouling property of the film to be formed, but also enhances the coatability when the film is formed by coating, for example. Specifically, when the anti-fog coating composition contains a surfactant, the surface tension of the anti-fog coating composition is lowered, so that the uniformity of the film is further enhanced.

-Nonionic surfactant-

Examples of the surfactant include nonionic surfactants.

When an ionic surfactant is used as the antistatic agent, if the ionic surfactant is excessively present in the antifogging coating composition, the electrolytic mass in the system increases and the silica particles tend to aggregate. Therefore, it is preferable to use a non-ionic surfactant in combination. However, the nonionic surfactant does not necessarily have to be used in combination with the ionic surfactant, and the nonionic surfactant may be contained alone as the surfactant.

Examples of the nonionic surfactant include polyalkylene glycol monoalkyl ether, polyalkylene glycol monoalkyl ester, polyalkylene glycol monoalkyl ester and monoalkyl ether. Specific examples of the nonionic surfactant include polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, polyethylene glycol monostearyl ester and the like.

When the composition for antifogging coating contains a nonionic surfactant, the nonionic surfactant has an HLB value (hydrophilic lipophilic oil) from the viewpoint of forming an antifogging layer having better hydrophilicity and antifouling property. A nonionic surfactant having a balance) greater than 15 (hereinafter, also referred to as “specific nonionic surfactant”) is preferable.

When the anti-fog coating composition contains a specific nonionic surfactant, the hydrophilicity of the formed anti-fog layer is further improved, and the adhesion prevention property of a contaminant (for example, silicone) which is a hydrophobic component is good. Will be.

The HLB value of the specific nonionic surfactant is preferably 15.5 or more, more preferably 16 or more, further preferably 17 or more, and particularly preferably 18 or more.

The upper limit of the HLB value of the specific nonionic surfactant is not particularly limited, and is preferably 20 or less, for example.

The HLB value (Hydrophile-Lipophile Balance) of the surfactant is the hydrophilic lipophilic balance of the surfactant.

The HLB value of the surfactant in the present disclosure is defined by the following formula (I) by the Griffin method (completely revised edition, Introduction to Surfactants, p128), and is a value obtained by arithmetic.

HLB value of surfactant = (molecular weight of hydrophilic group portion / molecular weight of surfactant) × 20 ... (I)

Specific nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenol ether, polyoxyalkylene aryl ether, polyoxyalkylene alkyl aryl ether, sorbitan derivative, formalin condensate of polyoxyalkylene aryl ether, and polyoxy. Formalin condensates of alkylene alkyl aryl ether, polyethylene glycol and the like can be mentioned.

Among these, the polyoxyalkylene alkyl ether is particularly preferable as the specific nonionic surfactant.

Examples of the alkyl group of the polyoxyalkylene alkyl ether in the specific nonionic surfactant include a linear alkyl group having 1 to 36 carbon atoms and a branched alkyl group having 3 to 36 carbon atoms.

Further, the oxyalkylene portion of the polyoxyalkylene alkyl ether is preferably polyoxyethylene from the viewpoint of being able to form a film having particularly excellent hydrophilicity. Further, the number of polyoxyethylene structural units contained in the specific nonionic surfactant is preferably 6 or more, more preferably 10 or more, further preferably 15 or more, and further preferably 20 or more. Is particularly preferable. Further, the number of polyoxyethylene structural units can be, for example, 100 or less from the viewpoint of solubility.

When the specific nonionic surfactant is a polyoxyalkylene alkyl ether, the surfactant represented by the following formula (II) is preferable.

RO- (C ₂ H ₄₀ ) m-H ... (II)

In formula (II), m represents an integer of 6 to 100. R represents a linear alkyl group having 1 to 36 carbon atoms or a branched alkyl group having 3 to 36 carbon atoms.

As the specific nonionic surfactant, a commercially available product can be used. Examples of commercially available products of specific nonionic surfactants are EAMLEX 715 (HLB value: 15.6), EAMLEX 720 (HLB value: 16.5), and EAMLEX 730 (HLB value: 17) of Nippon Emulsion Co., Ltd. .5), EMALEX 750 (HLB value: 18.4) (trade name, polyoxyethylene lauryl ether), Leodor TW-P120 (trade name, polyoxyethylene sorbitan monopalmitate, HLB value) from Kao Co., Ltd. : 15.6), PEG2000 (trade name, HLB value: 19.9) of Sanyo Kasei Kogyo Co., Ltd. and the like.

When the anti-fog coating composition contains a nonionic surfactant, it may contain only one nonionic surfactant or two or more.

When the antifogging coating composition contains a nonionic surfactant (preferably a specific nonionic surfactant), the content of the nonionic surfactant in the antifogging coating composition is antifogging. It is preferably 0.01% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and 1% by mass or more and 10% by mass, based on the total solid content of the coating composition. It is more preferably mass% or less. Within the above range, the hydrophilicity of the formed anti-fog layer becomes good, and the adhesion-preventing property of a contaminant (for example, silicone) which is a hydrophobic component becomes good.

-Ionic surfactant-

Examples of the surfactant include an ionic surfactant.

As the ionic surfactant, an ionic surfactant having at least one of a phosphoric acid group and a carboxy group (hereinafter, also referred to as “specific ionic surfactant”) is preferable.

When the antifogging coating composition contains a specific ionic surfactant, at least one functional group of a phosphoric acid group and a carboxy group possessed by the specific ionic surfactant functions as an acid adsorptive group, and the above-mentioned silica Adsorbs to the surface of particles. This adsorption improves the dispersion stability of the silica particles. Further, since the adsorption of the hydrophobic component on the surface of the silica particles is suppressed by this adsorption, the good hydrophilicity caused by the silica particles is not impaired, and the good antifouling property is maintained.

The specific ionic surfactant is preferably an anionic surfactant in consideration of its adsorptivity with silica particles, and the hydrophobic group includes a hydrocarbon group having 1 to 36 carbon atoms, a cyclohexyl group and a cyclobutyl. It has a hydrophobic group selected from an aliphatic cyclic hydrocarbon group such as a group and an aromatic hydrocarbon group such as a styryl group, a naphthyl group, a phenyl group and a phenylene ether group, and has phosphorus as an acid-adsorbing group. More preferably, it is a compound having at least one of an acid group and a carboxy group. The hydrophobic group described above may further have a substituent.

The specific ionic surfactant preferably has only at least one functional group selected from a phosphoric acid group and a carboxy group as an acid adsorbing group. That is, it is preferable that the specific ionic surfactant does not have an acid adsorbing group other than a phosphoric acid group such as a sulfonic acid group and a sulfate group and a carboxy group.

Examples of the specific ionic surfactant having a phosphoric acid group include an alkyl phosphate ester salt and a polyoxyethylene alkyl ether phosphate.

Specific ionic surfactants having a carboxy group include N-acylamino acids, polyoxyethylene alkyl ether carboxylates, aliphatic carboxylates, aliphatic dicarboxylates, and polycarboxylics having a weight average molecular weight of less than 25,000. Examples thereof include acid-based copolymers and maleic acid-based copolymers having a weight average molecular weight of less than 25,000.

The acid value of the specific ionic surfactant is preferably 180 mgKOH / g or less, and more preferably 100 mgKOH / g or less, from the viewpoint of dispersion stability of silica particles and adsorption inhibitory of hydrophobic components.

The lower limit of the acid value of the specific ionic surfactant is not particularly limited, and is preferably 3 mgKOH / g, for example.

The acid value of the specific ionic surfactant in the present disclosure can be measured by titration of an indicator. Specifically, the number of mg of potassium hydroxide that neutralizes the acid component in 1 g of the solid content of the specific ionic surfactant is measured and calculated according to the method described in JIS (Japanese Industrial Standards) K0070. It is a value obtained by.

As the specific ionic surfactant, a commercially available product can be used. Examples of commercially available specific ionic surfactants include DISPERBYK (registered trademark) -2015 (acid-adsorbing group: carboxy group, acid value: 10 mgKOH / g, solid content: 40% by mass) manufactured by BYK. (Registered trademark) -180 (acid-adsorbing group: phosphoric acid group, acid value: 94 mgKOH / g), Ebonic's TEGO (registered trademark) Dispers 660C (acid-adsorbing group: phosphoric acid group, acid value: 30 mgKOH / g) , BYK®-P104 (acid-adsorbing group: carboxy group, acid value: 180 mgKOH / g) and the like.

When the anti-fog coating composition contains an ionic surfactant, it may contain only one type of ionic surfactant or two or more types.

When the anti-fog coating composition contains an ionic surfactant (preferably a specific ionic surfactant), the content of the ionic surfactant in the anti-fog coating composition is the anti-fog coating composition. It is preferably 0.05% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and 1% by mass or more and 15% by mass or less with respect to the total solid content of the substance. Is more preferable. Within the above range, the effect of preventing the aggregation of silica particles and the effect of preventing the adsorption of hydrophobic components become better, and the effect of improving the antifouling property of the hydrophilic film by containing the ionic surfactant becomes easy to obtain.

<Preparation method of anti-fog coat composition>

The anti-fog coating composition is preferably prepared by mixing an inorganic binder, silica particles, a ketone solvent, water, and any of the above-mentioned components, if necessary.

For example, as a method for preparing a composition for an antifogging coat, first, an inorganic binder is mixed with a solvent containing water to form a hydrolyzate of the inorganic binder, and a hydrolyzed solution containing the hydrolyzate of the inorganic binder is prepared. It is preferable to prepare.

Next, a ketone solvent and silica particles are added to the obtained hydrolyzed solution. At this time, if desired, the above-mentioned optional components such as a specific solvent, polyacrylic acid, a glycol-based solvent, a surfactant, a condensation catalyst, and an antistatic agent can be added.

When a siloxane binder is used as the inorganic binder, the hydrolysis reaction of the siloxane binder proceeds even at room temperature (25 ° C.), but in order to promote the reaction, the siloxane binder and water are brought into contact with each other to prepare a mixed solution, and then obtained. The resulting mixed solution may be heated to about 30 ° C to 50 ° C. It is preferable that the reaction time of the hydrolysis reaction is longer because the reaction proceeds more. From the viewpoint of sufficiently advancing the hydrolysis reaction, it is also preferable to carry out the reaction in a heated state for 1 to 36 hours.

Further, by coexisting a catalyst that promotes the hydrolysis reaction of the siloxane binder in a mixed solution containing the siloxane binder and water, it is possible to obtain a hydrolyzate of the siloxane binder required for hydrophilicity even in about half a day. ..

Since the hydrolysis reaction of the siloxane binder is a reversible reaction, when water is removed from the mixed solution containing the hydrolyzate of the siloxane binder, the condensation reaction between the hydroxy groups of the hydrolyzate of the siloxane binder starts and proceeds. Therefore, when the hydrolysis reaction of the inorganic binder is allowed to proceed in a mixed solution containing a siloxane binder and water (preferably an excessive amount of water) to obtain a hydrolyzate of the siloxane binder, the obtained hydrolyzate is simply used. It is preferable to prepare a composition for an antifogging coating by mixing the mixed solution with silica particles or the like without separating the mixture.

If the amount of water in the anti-fog coating composition decreases due to storage or the like, the condensation reaction of the hydrolyzate of the siloxane binder may proceed. Therefore, the anti-fog coating composition includes hydrolysis of the siloxane binder. It may contain a condensation reaction product of the substance.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, "part" is based on mass.

<Preparation of binder mother liquor A1>

The following components were mixed to obtain a mixture. The mixture was stirred at 40 ° C. for 7 hours or longer. As a result, a trifunctional siloxane oligomer mother liquor A1 was prepared.

Ethanol (solvent): 22.90 parts by mass

KBE-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.): 25.10 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1% by mass ethanol diluted solution): 0.27 parts by mass

Water (solvent): 48.62 parts by weight

Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade): 3.09 parts by mass

<Preparation of binder mother liquor A2>

The following components were mixed to obtain a mixture. The mixture was stirred at 25 ° C. for 24 hours or longer.

As a result, a tetrafunctional siloxane oligomer mother liquor A2 was prepared.

Ethanol (solvent): 25.24 parts by mass

MKC (registered trademark) silicate MS51 (tetraethyl orsosilane oligomer, manufactured by Mitsubishi Chemical Corporation): 23.30 parts by mass

Water (solvent): 48.54 parts by weight

Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade): 2.91 parts by mass

<Preparation of binder mother liquor A3>

The following components were mixed to obtain a mixture. The mixture was stirred at 40 ° C. for 12 hours or longer.

As a result, a bifunctional siloxane oligomer mother liquor A3 was prepared.

Ethanol (solvent): 22.90 parts by mass

KBE-402 (3-glycidoxypropylmethyldiethoxysilane, manufactured by Shinetsu Silicone Co., Ltd.): 25.10 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1% by mass ethanol diluted solution): 0.27 parts by mass

Water (solvent): 48.62 parts by weight

Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., special grade): 3.09 parts by mass

<Preparation of silica dispersion B1>

Silica dispersion B1 was prepared by mixing each of the following components.

Ethanol (solvent): 21.93 parts by mass

Snowtex (registered trademark) OXS (spherical silica particle dispersion having an average primary particle diameter of 4-6 nm, manufactured by Nissan Chemical Co., Ltd., 10 mass% aqueous diluted solution): 20.40 parts by mass

<Preparation of silica dispersion B2>

Silica dispersion B2 was prepared by mixing each of the following components.

Ethanol (solvent): 21.93 parts by mass

Snowtex (registered trademark) O (spherical silica particle dispersion with an average primary particle diameter of 10-15 nm, manufactured by Nissan Chemical Co., Ltd., 10% by mass water diluted solution): 20.40 parts by mass

<Preparation of silica dispersion B3>

Silica dispersion B3 was prepared by mixing each of the following components.

Ethanol (solvent): 21.93 parts by mass

Snowtex (registered trademark) O-40 (spherical silica particle dispersion with an average primary particle diameter of 20-25 nm, manufactured by Nissan Chemical Co., Ltd., 10% by mass diluted with water): 20.40 parts by mass

<Preparation of silica dispersion B4>

Silica dispersion B4 was prepared by mixing each of the following components.

Ethanol (solvent): 21.93 parts by mass

Snowtex (registered trademark) OL (spherical silica particle dispersion with average primary particle diameter of 40-50 nm, manufactured by Nissan Chemical Co., Ltd., 10% by mass water diluted solution): 20.40 parts by mass

<Preparation of silica dispersion B5>

Silica dispersion B5 was prepared by mixing each of the following components.

Ethanol (solvent): 21.93 parts by mass

Snowtex (registered trademark) OUP (chain silica particle dispersion with average primary particle diameter of 40-100 nm, manufactured by Nissan Chemical Co., Ltd., 10% by mass water diluted solution): 20.40 parts by mass

<Preparation of silica dispersion B6>

Silica dispersion B6 was prepared by mixing each of the following components.

Ethanol (solvent): 21.93 parts by mass

Snowtex (registered trademark) PS-SO (pearl necklace-shaped silica particle dispersion with average primary particle diameter of 80-120 nm, manufactured by Nissan Chemical Co., Ltd., 10% by mass water diluted solution): 20.40 parts by mass

<Preparation of coating liquid 1>

By mixing each of the following components, a coating liquid 1 (trifunctional silanol, spherical silica having an average primary particle diameter of 4-6 nm) was prepared.

Binder mother liquor A1: 40.15 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B1: 195.55 parts by mass

<Preparation of coating liquid 2>

Coating liquid 2 (trifunctional silanol, spherical silica having an average primary particle diameter of 10-15 nm) was prepared by mixing each of the following components.

Binder mother liquor A1: 40.15 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B2: 195.55 parts by mass

<Preparation of coating liquid 3>

By mixing each of the following components, a coating liquid 3 (trifunctional silanol, spherical silica having an average primary particle diameter of 20-25 nm) was prepared.

Binder mother liquor A1: 40.15 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B3: 195.55 parts by mass

<Preparation of coating liquid 4>

By mixing each of the following components, a coating liquid 4 (trifunctional silanol, spherical silica having an average primary particle diameter of 40-50 nm) was prepared.

Binder mother liquor A1: 40.15 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B4: 195.55 parts by mass

<Preparation of coating liquid 5>

By mixing each of the following components, a coating liquid 5 (trifunctional silanol, average primary particle diameter 40-100 nm chain silica) was prepared.

Binder mother liquor A1: 40.15 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B5: 195.55 parts by mass

<Preparation of coating liquid 6>

By mixing each of the following components, a coating liquid 6 (trifunctional / tetrafunctional silanol (20/80; mass ratio), average primary particle diameter 4-6 nm spherical silica) was prepared.

Binder mother liquor A2: 32.12 parts by mass

Binder mother liquor A1: 8.03 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B1: 195.55 parts by mass

<Preparation of coating liquid 7>

By mixing each of the following components, a coating liquid 7 (trifunctional / tetrafunctional silanol (20/80; mass ratio), average primary particle diameter 20-25 nm spherical silica) was prepared.

Binder mother liquor A2: 32.12 parts by mass

Binder mother liquor A1: 8.03 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B3: 195.55 parts by mass

<Preparation of coating liquid 8>

By mixing each of the following components, a coating liquid 8 (trifunctional / tetrafunctional silanol (20/80; mass ratio), average primary particle diameter 40-100 nm chain silica) was prepared.

Binder mother liquor A2: 32.12 parts by mass

Binder mother liquor A1: 8.03 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B5: 195.55 parts by mass

<Preparation of coating liquid 9>

By mixing each of the following components, a coating liquid 9 (bifunctional silanol, spherical silica having an average primary particle diameter of 4-6 nm) was prepared.

Binder mother liquor A3: 40.15 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B1: 195.55 parts by mass

<Preparation of coating liquid 10>

By mixing each of the following components, a coating liquid 10 (trifunctional silanol, average primary particle diameter 80-120 nm pearl necklace-like silica) was prepared.

Binder mother liquor A1: 40.15 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B6: 195.55 parts by mass

<Preparation of coating liquid 11>

By mixing each of the following components, a coating liquid 11 (trifunctional silanol, spherical silica having an average primary particle diameter of 4-6 nm) was prepared.

Binder mother liquor A1: 40.15 parts by mass

Ethylene grease mono-t-butyl ether (solvent): 18.00 parts by mass

Diethylene glycol (solvent): 10.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B1: 195.55 parts by mass

<Preparation of coating liquid 12>

By mixing each of the following components, a coating liquid 12 (trifunctional silanol, spherical silica having an average primary particle diameter of 20-25 nm) was prepared.

Binder mother liquor A1: 40.15 parts by mass

Ethylene grease mono-t-butyl ether (solvent): 18.00 parts by mass

Diethylene glycol (solvent): 10.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B3: 195.55 parts by mass

<Preparation of coating liquid 13>

By mixing each of the following components, a coating liquid 13 (tetrafunctional silanol, water-absorbent polymer, average primary particle diameter 40-100 nm chain silica) was prepared.

Binder mother liquor A2: 20.10 parts by mass

Hydroxyethyl cellulose SP200 (super absorbent polymer, manufactured by Tokyo Chemical Industry Co., Ltd., 25% by mass water / ethanol = 1/1 diluted solution): 20.05 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B2: 195.55 parts by mass

<Preparation of coating liquid 14>

In a reaction vessel equipped with a thermometer, agitator, nitrogen introduction tube and cooling tube, 50.00 parts by mass of isopropanol, 80 parts by mass of N, N-dimethylacrylamide, 5.00 parts by mass of methylmethacrylate, and N-methylol. 1.50 parts by mass of acrylamide was charged and heated to 65 ° C. while blowing nitrogen gas, and a hydrocarbon diluted product of 3,5,5-trimethylhexanoyl peroxide (Parloyl (registered trademark) 355 (S), Japanese oil and fat ( Manufactured by Co., Ltd .: 0.27 g was dissolved in 30 g of isopropanol) was added dropwise over 1 hour. At the same time, 15 g of methyl methacrylate was dissolved in 150 g of isopropanol and added dropwise over 3 hours. After further polymerizing for 6 hours, the temperature was raised to 80 ° C., and polymerization was carried out at that temperature for 1 hour to obtain an organic polymer solution 1.

Further, 32.30 parts by mass of the organic polymer solution 1, 27.70 parts by mass of isopropanol, 30.00 parts by mass of methyl ethyl ketone, and Solfit® (3-methoxy-3-methyl-1-butano-). 10.00 parts by mass of Le, Claret Co., Ltd. was added to adjust the solid content to 10% by mass, 0.2 parts by mass of p-toluenesulfonic acid, BYK (registered trademark) 302 (polyether-modified polydimethyl). Siloxane and (manufactured by Big Chemie Japan Co., Ltd.) were mixed in an amount of 0.1 part by mass to obtain a coating liquid 14 (without inorganic binder and silica particles, only water-absorbent polymer).

<Preparation of coating liquid 15>

Each of the following components was mixed to obtain a coating liquid 15 (tetrafunctional silanol, water-absorbent polymer, average primary particle diameter 10-15 nm, spherical silica).

Tetraethoxysilane: 0.06 parts by mass

Water: 0.19 parts by mass

Ethanol: 15.75 parts by mass

Snowtex (registered trademark) IPA-ST (spherical silica particle dispersion, manufactured by Nissan Chemical Co., Ltd., 30% by mass water diluted solution): 2.00 parts by mass

<Preparation of coating liquid 16>

By mixing each of the following components, a coating liquid 16 (trifunctional silanol, spherical silica having an average primary particle diameter of 10-15 nm) was prepared.

Binder mother liquor A1: 160.45 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1% by mass ethanol diluted solution): 2.22 parts by mass

Silica dispersion B2: 75.25 parts by mass

<Preparation of coating liquid 17>

A coating liquid 17 (trifunctional silanol, average primary particle diameter 40-100 nm, chain silica) was prepared by mixing each of the following components.

Binder mother liquor A1: 4.02 parts by mass

Diacetone alcohol (solvent): 28.90 parts by mass

Aluminum chelate D (condensation catalyst (aluminum chelate compound), manufactured by Kawaken Fine Chemical Co., Ltd., 1 mass% ethanol diluted solution): 2.22 parts by mass

Silica dispersion B5: 231.68 parts by mass

(Examples 1 to 14 and Comparative Examples 1 to 10)

<Manufacturing of laminated body>

In Examples 1 to 14 and Comparative Examples 1 to 10, the coating liquids shown in Tables 1 to 3 were sprayed onto the substrates shown in Tables 1 to 3 with a spray gun (type: W-). It was applied using 101-101G, Anest Iwata Co., Ltd. After coating, the substrate to which the coating liquid was applied was allowed to stand at 25 ° C. for 1 minute. After standing, the applied liquid is dried under the conditions shown in Tables 1 to 3, and the anti-fog layer having the film thickness shown in Tables 1 to 3 is provided on the substrate in each Example and Comparative Example. A laminate was produced.

When different anti-fog coat layers are formed in layers, they are placed at 25 ° C. for 1 minute, then applied and dried under the conditions shown in Tables 1 to 3 to be used in Examples and Comparative Examples. The laminated body in the above was prepared.

[evaluation]

The following performance evaluation was performed using the coating liquid (composition for anti-fog coating) prepared above and the prepared laminate. The results are shown in Tables 1 to 3.

The average void diameter, film thickness, water absorption amount and water contact angle were measured by the same method as described above.

(Breathing anti-fog, steam anti-fog)

Prepare a hot water bath at 40 ° C, and under the conditions of an atmospheric temperature of 25 ° C and a relative humidity of 50%, the hot water is kept at a distance of 5 cm from the water surface of the hot water bath only within a 5 cm square area of the laminated body film. The bath steam was applied for 1 minute. After that, the steam anti-fog property was evaluated by visually observing the appearance.

In addition, the anti-fog property of exhaled breath was evaluated by the same method as above except that the hot water bath at 40 ° C. was changed to exhaled breath.

In the following evaluation criteria, "A" and "B" are practically acceptable levels.

<Evaluation criteria>

A: No fogging is observed, and there is no distortion in the transmitted image that can be observed through the laminated body.

B: No fogging is observed, and the transmitted image observable through the laminate is slightly distorted.

C: No cloudiness is observed, and the transmitted image that can be observed through the laminated body is distorted.

D: Cloudy is observed.

(transparency)

A haze meter (model number: NDH 5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure the haze of the laminated body, and the obtained measured value was used as an index for evaluating transparency. In order to eliminate the difference depending on the base material, the haze value was calculated by subtracting the haze value of only the base material from the measured value of the laminated body. In the measurement, the base material surface of the laminated body, that is, the surface opposite to the surface on which the film of the laminated body was formed was measured toward the light source and used as an index of anti-fog property.

In this evaluation test, the lower the measured value of haze, the better the transparency of the laminated body. Further, the excellent transparency of the laminated body means that the transparency of the film is excellent.

In the following evaluation criteria, "A", "B", and "C" are practically acceptable levels.

<Evaluation criteria>

A: The haze was less than 0.8%.

B: The haze was 0.8% or more and less than 1.2%.

C: The haze was 1.2% or more and less than 2.1%.

D: The haze was 2.1% or more.

(Pencil hardness)

As an anti-fog material, a sample obtained by cutting the laminate produced in each Example and Comparative Example into a size of 10 cm × 10 cm was prepared, and the surface of the above sample having an anti-fog layer was designated as JIS K 5600 5-4 (1999). A pencil hardness test was conducted under the conditions of (H) or higher, and the result was H or higher.

(Water resistant)

A sample obtained by cutting the laminate prepared in each Example and Comparative Example into a size of 10 cm × 10 cm was prepared, and the surface of the sample having an anti-fog layer was rubbed with a cotton cloth moistened with water, and Nippon Denshoku Industries Co., Ltd. Co., Ltd. The scratch resistance was evaluated by measuring the difference in haze values before and after the scratch test with a spectroscopic haze meter SH7000 manufactured by the same company. The smaller the value, the better the scratch resistance. Of the following evaluation criteria, if it is B or higher, there is no practical problem.

<Evaluation criteria>

A: The difference in haze value before and after the scraping test is less than 1.0%.

B: The coating liquid is transferred to a slightly rubbed cotton cloth, and the difference in haze value before and after the rubbing test is 1.0% or more and less than 2.0%.

C: The coating liquid is transferred to a cotton cloth that has been heavily rubbed, and the difference in haze value before and after the rubbing test is 2.0% or more and less than 5.0%.

D: The peeling of the anti-fog layer at the rubbing portion can be visually confirmed, and the difference in haze value before and after the rubbing test is 5.0% or more.

(Solvent scratch resistance)

The solvent scratch resistance was evaluated by the same method as the above water scratch resistance and the same evaluation criteria except that the water was changed to gasoline (manufactured by Showa Shell Sekiyu Co., Ltd.).

Details of each base material shown in Tables 1 to 3 are shown below.

Comoglass (registered trademark): Polymethylmethacrylate substrate (PMMA, trade name: Comoglass CGP, thickness: 1 mm, size: 10 cm x 10 cm, manufactured by Kuraray Co., Ltd.)

Carboglass (registered trademark): Polycarbonate substrate (PC, trade name: Carboglass (registered trademark) C-110, thickness: 0.5 mm, size: 10 cm x 10 cm, manufactured by Asahi Glass Co., Ltd.)

OA-10: Glass substrate (non-alkali glass, trade name: OA-10, thickness: 1 mm, size: 10 cm x 10 cm, manufactured by Nippon Electric Glass Co., Ltd.)

In the prescription column in Tables 1 to 3, "-" means that there is no item corresponding to the item. In Comparative Example 3 and Comparative Example 4 in Table 3, since no void is generated, the column of B / A ratio is set to "-".

As shown in Tables 1 to 3, Examples 1 to 14 were excellent in anti-fog property and scratch resistance. Among them, Example 1 in which the inorganic binder is a dehydration condensate of a trifunctional or bifunctional siloxane was superior in abrasion resistance to Example 9 containing a dehydration condensate of a tetrafunctional siloxane as an inorganic binder.

Comparative Example 1 and Comparative Example 2 in which the average void diameter of the voids contained in the anti-fog layer on the side half close to the substrate exceeds 20% of the average void diameter of the voids contained in the anti-fog layer on the side half far from the substrate. Was inferior in anti-fog. Further, Comparative Example 3 and Comparative Example in which the average void diameter of the voids contained in the anti-fog layer on the side half close to the substrate is the same as the average void diameter of the voids contained in the anti-fog layer on the side half far from the substrate. 4 was also inferior in anti-fog property. Further, Comparative Example 3 and Comparative Example 4 containing more than 1% by mass of the water-absorbing polymer were inferior in solvent scratch resistance.

Comparative Example 7 having a film thickness of more than 30 μm was inferior in haze, and Comparative Example 8 having a film thickness of less than 1 μm was inferior in anti-fog property.

Claims (8)

With the base material
An anti-fog layer provided on at least a part of the substrate,
Have,
The anti-fog layer contains voids inside and
With the direction from the base material toward the anti-fog layer as a reference, the average void diameter of the voids contained in the anti-fog layer on the side half close to the base material is the anti-fog layer on the side half far from the base material. 20% or less of the average void diameter of the voids contained in
The thickness of the anti-fog layer is 1 μm or more and 30 μm or less.
The antifogging layer contains silica particles, and the area ratio of the silica particles to the projected area seen from the normal direction on the exposed surface of the antifogging layer is 55% to 95% .
The anti-fog layer contains an inorganic binder and
A laminate in which the inorganic binder is a dehydration condensate of a trifunctional siloxane having three alkoxysilyl groups in the molecule or a dehydration condensate of a bifunctional siloxane having two alkoxysilyl groups in the molecule . The laminate according to claim 1 , wherein the antifogging layer contains a water-absorbing polymer in an amount of 1% by mass or less based on the total mass of the antifogging layer, or does not contain a water-absorbing polymer. The laminate according to claim 1 or 2 , wherein the anti-fog layer has a water absorption of 1.0 mg / cm ² or more and 26.5 mg / cm ² or less. The laminate according to any one of claims 1 to 3 , wherein the water contact angle of the exposed surface of the anti-fog layer is 25 ° or less. The laminate according to any one of claims 1 to 4 , wherein the anti-fog layer is composed of a plurality of layers. The laminate according to any one of claims 1 to 5 , wherein the base material contains glass, a polycarbonate resin, or an acrylic resin. The laminate according to any one of claims 1 to 6 , wherein the anti-fog layer is a coating layer. The laminate according to any one of claims 1 to 7 , wherein the average primary particle diameter of the silica particles is 1 nm to 100 nm.