JP2021137964A - Antifogging laminate and composition for forming antifogging laminate - Google Patents

Abstract

To provide an antifogging laminate and a composition for forming the antifogging laminate capable of holding antifogging property for a long period of time, excellent in scratch resistance and hardly causing a dry mark on a surface.SOLUTION: Provided are: the antifogging laminate having a water absorbing layer containing a water absorbing resin on a base material and a particle layer containing silica particles and the water absorbing resin on the water absorbing layer; and the composition for forming the antifogging laminate.SELECTED DRAWING: None

Description

The present disclosure relates to an anti-fog laminate and a composition for forming an anti-fog laminate.

Equipment and building materials that are installed indoors and outdoors and used for a long period of time are easily exposed to various environments. The function and performance of the period may not be maintained. As a technique for solving such a situation, for example, a technique for making the surface texture hydrophilic has been studied.

As a technique for making the surface texture hydrophilic, a method of imparting a hydrophilic layer to the target surface is known. Specifically, a material for making the surface hydrophilic (hydrophilic material) and a material for making the surface water absorbent are known. Materials to be given (water-absorbing type materials) have been widely studied.
Of these, the hydrophilic type material utilizes the super-hydrophilicity of the material, for example, by forming a water film instead of water droplets on the surface of the transparent base material to impart the property of not blurring the transmitted image (anti-fog property). Can be done.
In addition, the water-absorbent type material can store water inside the material, thereby imparting anti-fog property.

As a technique related to the above, silica particles, a condensate of tetraethylalkoxysilane, a vinyl monomer having an N-methylol group or an N-alkoxymethylol group, and a hydrophilic group (sulfonic acid, carboxylic acid, phosphoric acid) are used. An antifogging agent composition containing a hydrophilic copolymer containing a vinyl monomer having a vinyl monomer and a (meth) acrylate monomer, and a water-absorbing antifogging layer using the same have been proposed (for example, Patent Document 1). reference).
Further, by having a film containing a specific hydrophilic material and a resin material, and having a composition gradient film in which the composition of the hydrophilic material and the resin material is continuously changed so as to have a specific ratio in the film, it is hydrophilic. It is disclosed that both properties and substrate adhesion are compatible (see, for example, Patent Document 2).
Further, it is possible to obtain an antifogging film which has been subjected to a swelling treatment by coating a coating liquid obtained by adding a silane hydrolyzate or the like to polyvinyl alcohol in two layers and immersing it in hot water after heat curing. It is disclosed (see, for example, Patent Document 3).

Among the above, in the case of the hydrophilic type material, if the amount of attached water becomes too large and exceeds a certain amount, there is a problem that the thickness of the water film becomes large and drops drip. Further, due to the influence of the thick water film formed on the surface, the transmitted image seen through the transparent substrate fluctuates, and not only the transmitted image is blurred, but also the transparency is impaired. Therefore, the use of hydrophilic materials has been limited.

Further, in the case of a water-absorbing type material, the material that swells due to water absorption cannot increase the degree of cross-linking, so that the mechanical strength of the material itself is inferior. Therefore, there is a problem that it cannot be applied to applications where there are many physical contacts.

As a technique capable of improving problems in hydrophilic type and water absorbing type materials, a laminated structure having a hydrophilic type upper layer on a water absorbing type lower layer has been studied.
By adopting the above-mentioned laminated structure, it is possible to maintain anti-fog property (including having transparency with little origin of the transmission image derived from the water film) for a long period of time without impairing the scratch resistance. It is based on the knowledge of.

As a technique related to the above, by providing a first coating containing a water-absorbent organic polymer on a base material and a second coating containing a hydrophilic inorganic oxide and a carboxylic acid-containing compound on the first coating, A hydrophilic material having both anti-fog property and scratch resistance is disclosed (see, for example, Patent Document 4).
Further, the water absorbing layer and the hydrophilic layer are provided on the base material in this order, the hydrophilic layer is made of a crosslinked resin having a hydrophilic group, and the hydrophilic group strength in the hydrophilic layer is inclined in the depth direction to withstand the resistance. A technique for improving anti-fog property while maintaining scratch property is disclosed (see, for example, Patent Document 5).

JP-A-2018-2865 Japanese Unexamined Patent Publication No. 2013-107255 Japanese Unexamined Patent Publication No. 2-18048 Japanese Patent No. 4013242 International Publication No. 2018/038270

Of the above, in the invention described in Patent Document 4, since the upper layer is composed of only silica particles and a carboxylic-containing compound, it is not possible to secure a sufficient amount of water absorption, and when water having a water absorption capacity or more adheres. Had the problem of water film fluctuations.
Further, in the invention described in Patent Document 5, since the degree of cross-linking of the hydrophilic layer is not sufficient, the anti-fog layer itself swells due to water absorption and dissolution occurs, leaving traces of water dripping at the dissolved portion, and the anti-fog layer. There was a problem that the uniformity, appearance, etc. deteriorated.
The reality is that no technology has been established that can more effectively improve the problems in hydrophilic and water-absorbent materials.

The present disclosure has been made in view of the above problems. That is,
The problem to be solved by one embodiment of the present invention is that it can maintain anti-fog property for a long period of time, has excellent scratch resistance, and prevents drying marks (dripping marks on the surface after drying) from occurring on the surface. The purpose is to provide a cloudy laminate.
The problem to be solved by another embodiment of the present invention is the manufacture of an anti-fog laminate that can maintain anti-fog properties for a long period of time, has excellent scratch resistance, and is less likely to cause drying marks on the surface. It is an object of the present invention to provide a method for producing an anti-fog laminate.

In the present disclosure, by adopting a laminated structure in which a hydrophilic type upper layer is provided on a water absorption type lower layer, anti-fog property (transparency with less fluctuation of a transmission image derived from a water film) is maintained for a long period of time without impairing scratch resistance. It is based on the finding that it is possible to retain the property and to improve the dripping marks on the dry surface.
The "drying mark" refers to a mark (dripping mark) that remains as if water drips on the surface when it is dried after being wet with water. It is considered that the occurrence of dripping marks appears, for example, when the small molecule component in the water-absorbent resin is eluted and remains as spots on the dry surface during drying.
Specific means for solving the problem include the following aspects.

<1> An antifogging laminate having a water-absorbent layer containing a water-absorbent resin on a base material and a particle layer containing silica particles and a water-absorbent resin on the water-absorbent layer.
<2> The anti-fog laminate according to <1>, wherein the water-absorbent resin contained in the particle layer is the same as the water-absorbent resin contained in the water-absorbent layer.
<3> The water-absorbent resin is selected from the group consisting of a cellulose-based resin, a polyvinyl alcohol-based resin, a polyvinyl acetal-based resin, a polyvinylpyrrolidone-based resin, a polyvinyl acetate-based resin, a polyvinyl acetamide-based resin, and a polyacrylamide-based resin. The antifogging laminate according to <1> or <2>, which comprises at least one type.
<4> The water-absorbent resin comprises a vinyl monomer having an acrylamide structure and a hydrocarbon group having 2 or more and 20 or less carbon atoms, a sulfonic acid group, a carboxylic acid group and a phosphoric acid group, and salts thereof. The antifogging laminate according to any one of <1> to <3>, which is a copolymer having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group.
<5> A structural unit derived from a vinyl monomer having an acrylamide structure and a hydrocarbon group having 2 or more and 20 or less carbon atoms is a structural unit represented by the following general formula (1). <4>> The antifogging laminate according to.

In the general formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a methyl group, an alkyl group having 2 or more carbon atoms, or a substituent represented by the following general formula (2).

In the general formula (2), L represents an alkylene group having 1 to 6 carbon ^{atoms, and R 21} represents a hydrogen atom, a methyl group, an unsubstituted alkyl group having 2 or more carbon atoms, or an aromatic substituted alkyl group. n represents the average number of moles added of the polyether, and n is 1 to 4.
<6> The water-absorbent resin is a copolymer having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group consisting of an N-methylol group, an N-alkoxymethylol group and a hydroxyl group. The antifogging laminate according to any one of <1> to <5>.
<7> The anti-fog laminate according to any one of <1> to <6>, which further has a support layer under the water absorption layer.
<8> The anti-fog laminate according to any one of <1> to <7>, which further has an adhesive layer under the water absorption layer or the support layer.
<9> A composition for forming an anti-fog laminate according to any one of <1> to <5>, which is a water-absorbent layer containing at least a water-absorbent resin. A composition for forming an anti-fog laminate, comprising a composition for forming a particle layer containing at least silica particles and a water-absorbent resin.
<10> The composition for forming an anti-fog laminate according to <9>, wherein the water-absorbent resin contained in the composition for forming a particle layer is the same as the water-absorbent resin contained in the composition for forming a water-absorbent layer. ..
<11> The composition for forming an anti-fog laminate according to <9> or <10>, wherein the composition for forming a particle layer contains a binder for silica particles.
<12> The anti-fog laminate formation according to any one of <9> to <11>, wherein the water-absorbent layer forming composition and / or the particle layer-forming composition contains a cross-linking agent for a water-absorbent resin. Composition for.
<13> The anti-fog laminate formation according to any one of <9> to <12>, wherein the water-absorbent layer forming composition and / or the particle layer-forming composition contains a curing catalyst of a water-absorbent resin. Composition for.
<14> The water-absorbent resin contained in the water-absorbent layer forming composition and / or the particle layer-forming composition is a cellulose-based resin, a polyvinyl alcohol-based resin, a polyvinyl acetal-based resin, a polyvinylpyrrolidone-based resin, or polyvinyl acetate. The composition for forming an antifogging laminate according to any one of <9> to <13>, which contains at least one precursor selected from the group consisting of a based resin, a polyvinyl acetamide based resin, and a polyacrylamide based resin. thing.
<15> The water-absorbent resin contained in the water-absorbent layer forming composition and / or the particle layer-forming composition is a vinyl monomer having an acrylamide structure and having a hydrocarbon group having 2 or more and 20 or less carbon atoms. , A copolymer having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group and a phosphoric acid group, and salts thereof <9>. The composition for forming an antifogging laminate according to any one of <14>.
<16> The composition for forming an anti-fog laminate according to any one of <9> to <15>, wherein the water-absorbent resin has a structural unit represented by the following general formula (1).

In the general formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a methyl group, an alkyl group having 2 or more carbon atoms, or a substituent represented by the following general formula (2). ..

In the general formula (2), L represents an alkylene group having 1 to 6 carbon ^{atoms, and R 21} represents a hydrogen atom, a methyl group, an unsubstituted alkyl group having 4 or more carbon atoms, or an aromatic substituted alkyl group. n represents the average number of moles added of the polyether, and n is 1 to 4.
<17> The water-absorbent resin is a copolymer having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group consisting of an N-methylol group, an N-alkoxymethylol group and a hydroxyl group. The composition for forming an antifogging laminate according to any one of <9> to <16>.

According to one embodiment of the present invention, there is provided an anti-fog laminate that can maintain anti-fog properties for a long period of time, has excellent scratch resistance, and is less likely to cause dry marks on the surface.
According to another embodiment of the present invention, anti-fog property is produced, which can maintain anti-fog property for a long period of time, has excellent scratch resistance, and hardly causes dry marks on the surface. A method for producing a laminate is provided.

It is sectional drawing which shows an example of the laminated structure of the anti-fog laminated body of the aspect which provided the particle layer on the water absorption layer.

Hereinafter, the anti-fog laminate of the present disclosure and a method for producing the same will be described in detail.

In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.

In the present specification, the numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in a certain 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 present specification, the amount of each component in the composition is the sum of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means quantity.
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 a solvent is also included in the "solid content" in the present disclosure.

<Anti-fog laminate>
The antifogging laminate of the present disclosure has a water-absorbent layer containing a water-absorbent resin and a particle layer arranged on the water-absorbent layer and containing inorganic particles and a water-absorbent resin.
The anti-fog laminate of the present disclosure may have a non-absorbent support in addition to the water-absorbing layer and the particle layer, and may further have another layer such as an adhesive layer, if necessary. ..

Although anti-fog materials have been proposed conventionally, there are problems in hydrophilic materials and water-absorbing materials, in particular, anti-fog (fluctuation of transmission image derived from water film) without impairing scratch resistance. It was possible to retain (including having less transparency), and there was room for improvement in the dripping marks on the dry surface. As a technique for imparting anti-fog property, for example, the inventions described in the above-mentioned Patent Documents 1 to 5 have been proposed.

The present disclosure focuses on the structure in order to improve the problem of anti-fog performance.
Specifically, a water absorption layer containing inorganic particles is attached on the water absorption layer. This makes it possible to maintain the anti-fog property for a long period of time while maintaining a structure that does not impair the mechanical strength, which is a problem of absorbent materials, and even after getting wet with water, there are dry marks on the surface. It is said that the property that is less likely to occur can be obtained.

A specific embodiment of the anti-fog laminate of the present disclosure will be described with reference to FIG.
In the anti-fog laminate 10 shown in FIG. 1, the pressure-sensitive adhesive layer 18 is arranged on the non-water-absorbent support 16 on the side opposite to the side having the water-absorbing layer 14 and the water-absorbing layer 12 containing silica particles. It has a structure with and.

(Water absorption layer)
The water absorption layer is not particularly limited as long as it contains at least a resin and has water absorption. The water-absorbent layer may be a single layer containing a water-absorbent resin (water-absorbent resin), or may be two or more layers having a layer containing the water-absorbent resin and another water-absorbent layer. Further, if necessary, other components may be further contained.

The term "water absorption" as used in the present disclosure refers to a property in which the water absorption rate measured in accordance with Japanese Industrial Standards (JIS) K 7209: 2000 (Method A) is 1% or more.
Therefore, the water-absorbent resin in the present disclosure refers to a resin having a water absorption rate of 1% or more, and a resin having a water absorption rate of less than 1% is distinguished from the water-absorbent resin in the present disclosure as a non-water-absorbent resin.
The absorption rate is preferably 3% or more, more preferably 5% or more. The upper limit of the absorption rate is preferably 100% from the viewpoint of reducing the change in film thickness due to swelling.
The water-absorbent layer may contain either one type of water-absorbent resin or two or more types of resin.

(Particle layer)
The particle layer in the present disclosure contains silica particles and a water-absorbent resin, and may further contain other components if necessary.

The particle layer of the present disclosure has a structure in which a particle layer containing silica particles and a water-absorbent resin is laminated on the water-absorbing layer described above, so that the particle layer is first derived from silica particles and is hydrophilic. Is obtained, and an appropriate water film is formed instead of water droplets to ensure antifogging properties, and when the amount of water adhering to the antifogging layer increases, the water permeates to the lower layer side and is stored in the water absorption layer. Therefore, it becomes possible to maintain the antifogging property for a long period of time. In this structure, since the surface of the water-absorbent layer is covered with the silica particle layer, it is difficult for low-molecular-weight components derived from the water-absorbent resin to elute, and as a result, drying marks are unlikely to occur even after the surface is dried after wetting with water.

The particle layer may be provided on a part of the water absorption layer, or may be provided on the entire surface of the water absorption layer. Further, the particle layer may be provided in a state of being in direct contact with the water absorbing layer, or may be provided on the water absorbing layer via another layer.

It is desirable that the water-absorbent resin contained in the particle layer is the same as that contained in the water-absorbent layer. This is because the same water-absorbent resin is used to impart adhesion between the particle layer and the water-absorbent layer. By imparting adhesiveness, even when the water absorption layer absorbs and swells, peeling or cracking does not occur at the interface with the particle layer, and a good appearance can be maintained.

<Each component of anti-fog laminate>
Hereinafter, each component that can be contained in the anti-fog laminate of the present disclosure will be described.

(Water-absorbent resin)
Here, the "water-absorbent resin" means the entire water-absorbent resin contained in the water-absorbent layer and the particle layer according to the present disclosure.
Examples of the water-absorbent resin include cellulose-based resin, polyvinyl alcohol-based resin, polyvinyl acetal-based resin, polyvinylpyrrolidone-based resin, polyvinyl acetate-based resin, and polyvinylacetamide-based resin.

Examples of the cellulosic resin include triacetyl cellulose (TAC), nitrocellulose, hydroxypropyl cellulose, hydroxyethyl cellulose and the like, and commercially available products on the market may be used. Examples of commercially available products include tochisen's sanitized triacetyl cellulose (thickness of sanitized layer: 0.5 μm, water absorption: 5%) and Sumitomo Seika's "HEC AL-15 (hydroxyethyl cellulose)". ) ”And so on.
Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, and the like, and commercially available products on the market may be used. Examples of commercially available products include "Poval (polyvinyl alcohol)" manufactured by Kuraray.
Examples of the polyvinyl acetal-based resin include polyvinyl acetal, polyvinyl butyral, and the like, and commercially available products on the market may be used. Examples of commercially available products include "Eslek (polyvinyl acetal)" manufactured by Sekisui Chemical Co., Ltd.
Examples of the polyvinylpyrrolidone-based resin include polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, and the like, and commercially available products on the market may be used. Examples of commercially available products include "Pittscol (polyvinylpyrrolidone)" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
Examples of the polyvinyl acetate-based resin include polyvinyl acetate, vinylpyrrolidone-vinyl acetate copolymer, and the like, and commercially available products on the market may be used. Examples of commercially available products include "S-630 (vinylpyrrolidone-vinyl acetate copolymer)" manufactured by Ashland Japan.
Examples of the polyvinylacetamide-based resin include poly-N-vinylacetamide, and commercially available products on the market may be used. Examples of commercially available products include [GE191 (poly-N-vinylacetamide)] manufactured by Showa Denko KK.

As the water-absorbent resin, a specific copolymer may be used. Specifically, a structural unit derived from a vinyl-based monomer having at least one cross-linking functional group selected from the group consisting of an N-methylol group, an N-methylol ether group and a hydroxyl group, a sulfonic acid group and a carboxyl group. A copolymer containing at least a structural unit derived from a vinyl-based monomer having a group or a phosphate group and a structural unit derived from an alkyl (meth) acrylate-based monomer.
At least one functional group selected from the group consisting of an N-methylol group, an N-alkoxymethylol group and a hydroxyl group is a functional group having crosslinkability (hereinafter, may be referred to as a crosslinkable functional group), and is a specific common. When the polymer contains a structural unit derived from a vinyl monomer having these functional groups, the film property of the antifogging layer becomes better.
Preferably, it is derived from a structural unit derived from a vinyl monomer having at least one cross-linking functional group selected from the group consisting of an N-polymer group, an N-methylol ether group and a hydroxyl group, and a hydrophilic vinyl monomer. Hydrophobicity containing a hydrophilic polymer portion containing the structural unit of, a structural unit derived from a vinyl monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and a structural unit derived from a lower alkyl (meth) acrylate. It is a copolymer composed of a polymer portion.

First, the hydrophilic polymer portion will be described. The hydrophilic polymer portion comprises (A) a structural unit derived from a vinyl monomer having at least one crosslinked functional group selected from the group consisting of an N-methylol group, an N-methylol ether group and a hydroxyl group, and ( B) A copolymer moiety containing a structural unit derived from a hydrophilic vinyl monomer, and (A) and (B) having a block-type structure.

Examples of the vinyl monomer having an N-methylol group and an N-methylol ether group include N-methylol (meth) acrylamide, N-methoxymethylol (meth) acrylamide, N-butoxymethylol (meth) acrylamide and the like. In particular, N-methylol (meth) acrylamide is preferably used because it has a high cross-linking reactivity. Examples of the vinyl monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate 1. Examples thereof include Praxel FA-1, Praxel FM-1, and Praxel FM-4 [above, manufactured by Daicel Chemical Industry Co., Ltd., trade name] in which 1 to 4 mol of ε-caprolactone is added to the molars, and in particular, 2-hydroxyl. Ethyl (meth) acrylate is preferably used because it has a high cross-linking reactivity.

Examples of the hydrophilic vinyl monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide. , N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylamide, diacetone (meth) acrylamide , N- (meth) acryloyl piperidine, N- (meth) acryloylmorpholine, methoxyethylene glycol (meth) acrylate (where the number of ethylene oxide is preferably an integer of 1 to 10), methoxypropylene glycol (meth) acrylate ( Here, the number of propylene oxide is preferably an integer of 1 to 10), (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and the like, and at least one of these is used. In particular, from the viewpoint of copolymerizability and solubility of the obtained copolymer, those having an acrylamide structure are preferable, and those having an acrylamide structure having a hydrocarbon group having 2 to 20 carbon atoms are preferable. , More preferably used.
The anti-fog layer in the present embodiment preferably has a structural unit represented by the following general formula (1).

In the general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following general formula (2). Represents the represented substituent.

In the general formula (2), L represents an alkylene group having 1 to 6 carbon ^{atoms, and R 21} has a hydrogen atom, a methyl group, an unsubstituted alkyl group having 4 to 20 carbon atoms, or an aromatic substituent and has 6 carbon atoms. Represents ~ 20 alkyl groups. n represents the average number of moles added of the polyether, which is 1 or more and 4 or less.

R ¹¹ is a hydrogen atom or a methyl group.
Examples of the alkyl group having 1 to 6 carbon atoms in R ¹² and R ¹³ include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like. The alkyl groups in R ¹² and R ¹³ may be the same or different from each other.

Examples of the unsubstituted alkyl group having 4 to 20 carbon atoms in R ²¹ include an n-butyl group, an i-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group and the like. It may be chain-like or have branches. Of these, the n-butyl group is preferable.
The alkyl group having 6 to 20 carbon atoms having an aromatic substituent in R ²¹ is preferably an alkyl group having a phenyl group, a naphthyl group, a benzyl group or the like as the aromatic substituent, and a methyl group or ethyl as the alkyl group. The group etc. can be mentioned. The alkyl group may have only one aromatic substituent as a substituent, or may have two or more aromatic substituents. When it has two or more aromatic substituents, they may be the same or different from each other.
Examples of the alkylene group in L of the general formula (2) include a methylene group, an ethylene group, a propylene group and the like, and an ethylene group is preferable from the viewpoint of improving hydrophilicity, antifogging property and the like in antifogging property. , N is preferably 2 or more and 4 or less.

The hydrophilic polymer portion can further contain a structural unit derived from an alkyl (meth) acrylate having a lower alkyl group having 1 to 4 carbon atoms.
When the specific copolymer contains an alkyl (meth) acrylate, the film strength, the adhesion to the substrate and the heat resistance in a high temperature environment are further improved.
As the alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms, an alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and specifically, for example, methyl. Examples thereof include (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, etc., among which structural units derived from methyl methacrylate are included. However, it is preferable from the viewpoint of improving the film property.

As for the constitution of the hydrophilic polymer portion in the specific copolymer, the structural unit derived from the vinyl monomer having a crosslinkable functional group is 1% by mass or more based on the total structural unit contained in the hydrophilic polymer portion. It is preferable that the structural unit derived from 30% by mass and the hydrophilic vinyl monomer is in the range of 70% by mass to 99% by mass.
The crosslink density of the antifogging layer is such that the structural unit derived from the vinyl monomer having a crosslinkable functional group is 1% by mass or more and the structural unit derived from the hydrophilic vinyl monomer is 99% by mass or less. Is high, the permeability of water to the formed anti-fog layer is suppressed, and the film strength is improved. Further, the structural unit derived from the vinyl monomer containing a crosslinkable functional group is 30% by mass or less, and the structural unit derived from the hydrophilic vinyl monomer is 70% by mass or more to prevent fogging. The crosslink density in the layer does not become too high, and good antifogging property and good adhesion to the substrate are obtained.
From the viewpoint of the balance of antifogging property, adhesion, film strength, etc., it is selected from the group consisting of N-methylol group, N-methylol ether group and hydroxyl group having crosslinkable functional groups in the hydrophilic part of the specific copolymer. The structural unit derived from the vinyl monomer having at least one crosslinked functional group is derived from the hydrophilic vinyl monomer in an amount of 5% by mass to 20% by mass based on the total structural unit contained in the specific copolymer. The structural unit is particularly preferably in the range of 80% by mass to 95% by mass with respect to all the structural units contained in the specific copolymer.

Next, the hydrophobic polymer part will be described. The hydrophobic polymer portion contains (C) a structural unit derived from a vinyl monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and (D) a structural unit derived from a lower alkyl (meth) acrylate. , (C) and (D) are copolymer portions having a block type structure. The structural unit derived from the lower alkyl (meth) acrylate is a structural unit derived from the same monomer as the alkyl (meth) acrylate that can be contained in the hydrophilic polymer portion described above.

Examples of the vinyl monomer having a sulfonic acid group include 2-sulfoethyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-acrylamide-2-methylpropanesulfonic acid and the like.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and the like.
Examples of the vinyl monomer having a phosphoric acid group include mono (2- (meth) acryloyloxyethyl) acid phosphate and the like.
Of these, acrylic acid is particularly preferably used in terms of copolymerizability.
Examples of the sulfonic acid group, carboxylic acid group and phosphoric acid group salt include alkali metal salts, alkaline earth metal salts, magnesium salts and aluminum salts.

The hydrophobic polymer portion of the specific copolymer comprises a structural unit derived from an alkyl (meth) acrylate of 70% by mass to 99% by mass, a sulfonic acid group, a carboxyl group or a phosphoric acid group, or a salt thereof. It is preferable to contain 1% by mass to 30% by mass of the structural unit derived from the vinyl monomer having at least one functional group selected from the group.
A vinyl monopoly having a content of a structural unit derived from an alkyl (meth) acrylate of 70% by mass or more, or having at least one functional group selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a salt thereof. When the content of the structural unit derived from the weight is 30% by mass or less, the adhesion between the antifogging layer and the base material becomes better. Further, the content of the structural unit derived from the alkyl (meth) acrylate is 99% by mass or less, or at least one functional group selected from the group consisting of a sulfonic acid group, a carboxyl group or a phosphoric acid group, or a salt thereof. When the content of the structural unit derived from the vinyl monomer having a group is 1% by mass or more, the transparency of the antifogging layer becomes better. Further, from the viewpoint of improving the balance between the antifogging layer and the base material such as adhesion and transparency, the structural unit derived from alkyl (meth) acrylate is 80% by mass to 95% by mass, and sulfonic acid. It may contain 5% by mass to 20% by mass of a structural unit derived from a vinyl monomer having at least one functional group selected from the group consisting of a group, a carboxyl group, a phosphoric acid group, and a salt thereof. preferable.

The specific copolymer. By having a hydrophilic portion and a hydrophobic portion and the hydrophilic portion containing a structural unit having a crosslinkable group, the anti-fog property of the formed anti-fog layer becomes better, and further, the anti-fog layer is heated. By curing, the water resistance and anti-fog property of the anti-fog layer can be further enhanced. Further, since the hydrophilic portion contains a structural unit derived from an alkyl (meth) acrylate, the film strength of the anti-fog layer in a high temperature environment can be further increased.

When the specific copolymer has a hydrophobic portion, the adhesion between the antifogging layer and the base material becomes better, and the hydrophobic portion is a group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, and salts thereof. By including a structural unit having at least one functional group selected from the above, the transparency of the antifogging layer can be further enhanced.

The content ratio of the hydrophilic portion and the hydrophobic portion in the specific copolymer is 5% by mass to 95% by mass of the hydrophilic portion and 5% by mass to 5% by mass of the hydrophobic portion with respect to the total amount of the specific copolymer. It is preferably 95% by mass.
When the hydrophilic portion is 5% by mass or more or the hydrophobic portion is 95% by mass or less, the hydrophilicity of the anti-fog layer becomes better, and the anti-fog property and the sustainability of the anti-fog property are further improved.
Further, when the hydrophilic portion is 95% by mass or less or the hydrophobic portion is 5% by mass or more, the adhesion between the anti-fog layer and the base material becomes better. From the balance of anti-fog property, long-lasting anti-fog property, adhesion of the anti-fog layer to the base material, etc., the composition of the hydrophilic part and the hydrophobic part is 50 mass by mass of the hydrophilic part with respect to the total amount of the copolymer. It is more preferably in the range of% to 95% by mass and the hydrophobic portion in the range of 5% by mass to 50% by mass.

As described above, the specific copolymer is preferably a copolymer having a hydrophilic portion and a hydrophobic portion, but from the viewpoint that the characteristics of the hydrophilic portion and the hydrophobic portion are likely to be exhibited. Is more preferably a block copolymer of a hydrophilic portion and a hydrophobic portion, or a graft copolymer.
The specific copolymer that can be used in this embodiment can be synthesized, for example, by the method described in JP-A-9-194282.

(Silica particles)
The particle layer in the present disclosure preferably contains at least one type of silica particles.
Here, the "silica particles" mean silica particles contained in the particle layer according to the present disclosure.
Silica particles have a function of increasing the scratch resistance of the particle layer and further developing hydrophilicity. That is, the silica particles play a role as a hard filler, and the hydroxy groups on the particle surface act to contribute to the improvement of the hydrophilicity of the hydrophilic film. In addition, irregularities of silica particles are formed on the surface of the particle layer, which contributes to anti-fog property.

Examples of the silica particles include fumed silica and colloidal silica.
Fumed 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) and the like.
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 bead shape, and a shape in which two or more of these are combined. The term “spherical” as used herein includes not only a true spherical shape but also a spheroid, an oval shape, and the like.

Silica particles are also available as commercial products.
Commercially available silica particles include EVONIC's AEROSIL® series, Nissan Chemical Industry's Snowtex® series (for example, Snowtex O, Snowtex O-33, etc.), and Narco Chemical's. Examples include the Nalco (registered trademark) series (for example, Nalco8699) and the Quartron PL series (for example, PL-1) manufactured by Fuso Chemistry.

The average primary particle size of the silica particles is preferably 100 nm or less, more preferably 50 nm or less, and more preferably 30 nm or less from the viewpoint that the film property of the formed particle layer is good and the haze is lowered. Is more preferable, and 20 nm or less is particularly preferable. The lower limit of the average primary particle size of the silica particles is not particularly limited, but is preferably 2 nm or more from the viewpoint of handleability, and more preferably 10 nm or more from the viewpoint of easily exhibiting anti-fog performance.
In particular, the average primary particle size of the silica particles is preferably 10 nm to 20 nm from the viewpoint of improving anti-fog property and stain resistance.

The average primary particle size of the silica particles is such that when the shape of the silica particles is spherical or substantially spherical with an elliptical cross section, the dispersed silica particles are observed with a transmission electron microscope, and 300 or more particles are obtained from the obtained photograph. The projected area of the 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 size of the silica particles.

The particle layer in the present disclosure may contain only one type of silica particles, or may contain two or more types of silica particles. When two or more kinds of silica particles are contained, particles having at least one of different sizes and shapes may be contained.

The content of silica particles in the particle layer is 10% by mass or more with respect to the total solid content of the anti-fog layer from the viewpoint that the hydrophilicity of the particle layer is good and the anti-fog layer is excellent in hardness and scratch resistance. Preferably, 20% by mass or more is more preferable, and 30% by mass or more is further preferable.
Further, the upper limit of the content of the silica particles is preferably 60% by mass or less with respect to the total solid content mass of the particle layer from the viewpoint of maintaining the antifog performance of the particle layer.

<Other additives>
The water absorption layer and / or the particle layer in the present disclosure may contain, if necessary, other additives in addition to the above-mentioned components as long as the effects according to the present disclosure are not impaired.
Other additives include, for example, in the particle layer, a binder for silica particles, a resin having an acid group that contributes as a dispersant for silica particles, a curing catalyst for a water-absorbent resin, a high-boiling solvent, and a high-boiling solvent. Antistatic agents, surfactants, adhesion aids used to improve the film properties of antifogging layers and adhesion to substrates, etc. to improve the adhesion prevention effect of solvents and contaminants, deterioration by light Examples include an ultraviolet absorber that prevents the particles, an antioxidant that prevents deterioration due to heat, and the like.
Other additives include, for example, in the water-absorbing layer, a curing catalyst of a water-absorbent resin, a high boiling point solvent, a solvent other than the high boiling point solvent, an antistatic agent for improving the effect of preventing the adhesion of pollutants, and an antifogging layer. Examples thereof include adhesion aids used for the purpose of improving film properties and adhesion to a substrate, ultraviolet absorbers that prevent deterioration due to light, antioxidants that prevent deterioration due to heat, and the like.

(Silica particle binder)
The composition for forming a particle layer in the present disclosure preferably contains a binder for silica particles. Specifically, it preferably contains an organometallic compound. By containing the organometallic compound in the composition for forming the particle layer, it can be contained in the particle layer. By including the organometallic compound in the composition for forming the particle layer, the bonding between the silica particles is promoted, and the film-forming property of the coating liquid is enhanced.

Examples of organic metal compounds include metal chelate compounds (aluminum bis (ethyl acetoacetate) mono (acetyl acetonate), aluminum tris (acetyl acetonate), aluminum chelate compounds such as aluminum ethyl acetoacetate diisopropylate, zirconium tetrakis (zinc. (Acetylacetonate), zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate), titanium chelate compounds such as titaniumtetrakis (acetylacetonate), titaniumbis (butoxy) bis (acetylacetonate); Organic tin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, aluminum alkoxides such as aluminum ethylate, aluminum isopropylate, aluminum sec-butyrate, titanium (IV) ethoxydo, titanium isopropoxide, titanium (IV) n -Titanium alkoxides such as butoxide, zirconium (IV) ethoxyoxides, zirconium (IV) n-propoxides, zirconium alkoxides such as zirconium (IV) n-butoxide; and the like.
Among them, as the organic metal compound, a metal chelate compound such as an aluminum chelate compound, a titanium chelate compound, or a zirconium chelate compound is preferable, and an aluminum chelate compound is more preferable.

When the particle layer (or the composition for forming the particle layer) contains an organic metal compound, the content of the organic metal compound is preferably 0.1% by mass to 40% by mass with respect to the total solid content mass, and is 1% by mass. ~ 30% by mass is more preferable, and 5% by mass to 20% by mass is further preferable.
When the content of the organometallic compound is within the above range, a particle layer having scratch resistance is likely to be formed. Moreover, it is also excellent in the formability of the particle layer.

Further, as the binder for the silica particles, a hydrolyzed condensate of the following siloxane compound can also be preferably used. By containing the hydrolyzed condensate of the siloxane compound, the retention of the silica particles is improved, and the scratch resistance and hydrophilicity of the antifog layer are improved.

In the general formula (3), R ¹ , R ² , R ³ and R ⁴ independently represent monovalent organic groups having 1 to 6 carbon atoms. n represents an integer of 1 to 20.

The ^{monovalent organic groups having 1 to 6 carbon atoms in R 1} , R ² , R ³ , and R ⁴ may be linear, may have a branch, or may be cyclic. .. Examples of the monovalent organic group include an alkyl group and an alkenyl group, and an alkyl group is preferable.
When R ¹ , R ² , R ³ or R ⁴ represents an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group and an n-. Examples thereof include a pentyl group, an n-hexyl group and a cyclohexyl group.
When R ¹ , R ² , R ³ , or R ⁴ represents an alkenyl group, examples of the alkenyl group include a vinyl group, a 1-methyl-vinyl group, a 2-methyl-vinyl group, and an n-2-propenyl group. Examples thereof include 1,2-dimethyl-vinyl group, 1-methyl-propenyl group, 2-methyl-propenyl group, n-1-butenyl group, n-2-butenyl group and n-3-butenyl group.
By setting the number of carbon atoms of the monovalent organic group, preferably the alkyl group in R ^{1 to} R ^{4 of the siloxane compound to 1 to 6, the siloxane compound has good hydrolyzability.} From the viewpoint of better hydrolyzability ^{, it is more preferable that R 1 to} R ⁴ are independently alkyl groups having 1 to 4 carbon atoms, and are alkyl groups having 1 or 2 carbon atoms. Is even more preferable.

N in the general formula (3) represents an integer of 1 to 20. When n is 1 or more, the reactivity of the siloxane compound can be easily controlled, and for example, a film having excellent surface hydrophilicity can be formed. When n is 20 or less, the viscosity of the anti-fog layer forming composition does not become too high, and the handleability and uniform coating property become good. n is preferably 3 to 12, more preferably 5 to 10.

The siloxane compound is hydrolyzed at least in part by coexisting with water. ^{In the hydrolyzate of the siloxane compound, at least a part of OR 1} , OR ² , OR ³ , and OR ⁴ bonded to the silicon atom of the siloxane compound was replaced with a hydroxy group by the reaction of the siloxane compound with water. It is presumed that the antifogging layer formed through, for example, coating and drying has good surface hydrophilicity due to the hydroxy group which is a compound and is a hydrophilic group.
In the hydrolysis reaction, not all end groups of the siloxane compound (that is, -OR ¹ , -OR ² , -OR ³ or -OR ⁴ ) need to react, but for example, application of an anti-fog layer forming coating solution. From the viewpoint of improving the hydrophilicity of the coating film obtained by drying, it is preferable that more terminal groups are hydrolyzed.

When forming the anti-fog layer of the present embodiment, at least a part of the hydroxy groups of the siloxane compound are bonded to each other, and the siloxane compound is condensed. Therefore, the anti-fog layer contains at least one hydrolyzed condensate of the siloxane compound.
The anti-fog layer forming composition used for forming the anti-fog layer may contain only one type of hydrolyzate of the siloxane compound, or may contain two or more types.

The weight average molecular weight of the siloxane compound is preferably in the range of 300 to 1500, more preferably in the range of 500 to 1200.

When the particle layer (or the composition for forming the particle layer) contains a siloxane compound, the content of the siloxane compound is preferably 0.1% by mass to 40% by mass and 1% by mass to 30% by mass with respect to the total solid content mass. The mass% is more preferable, and 5% by mass to 20% by mass is further preferable.
When the content of the siloxane compound is within the above range, a particle layer having scratch resistance is likely to be formed. Moreover, it is also excellent in the formability of the particle layer.

(Resin having an acid group)
The composition for forming a particle layer in the present disclosure may contain a resin having an acid group. The acid group in the resin having an acid group is not limited as long as it has an acid group having an adsorption performance for silica particles, and examples thereof include a carboxy group, a sulfonic acid group, and a phosphoric acid group.

The acid value of the resin having an acid group is preferably 180 mgKOH / g or less, preferably 100 mgKOH / g, from the viewpoints of exhibiting adsorption performance on silica particles, improving the dispersibility of silica particles, and making the void size between silica particles uniform. More preferably, it is / g or less.
The lower limit of the acid value is not particularly limited, but is preferably 3 mgKOH / g or more.
The acid value of the resin having an acid group can be measured by titration of an indicator. Specifically, the acid component in 1 g of the solid content of the resin having an acid group is neutralized according to the method described in JIS K 0070. It can be calculated by measuring the number of mg of potassium hydroxide.

The weight average molecular weight (Mw) of the resin having an acid group is 1000 to 200,000 from the viewpoints of exhibiting adsorption performance for silica particles, improving dispersibility of silica particles, making the void size between silica particles uniform, and the like. , More preferably 1,000 to 50,000, and even more preferably 5,000 to 30,000.

Resins having an acid group are also available as commercial products.
Examples of commercially available products of the resin having an acid group that can be used for the antifogging layer in the present disclosure include DISPERBYK (registered trademark) -2015 (acid group: carboxy group, acid value: 10 mgKOH / g) and DISPERBYK (registered trademark) of Big Chemie. Registered trademark) -2010 (acid group: carboxy group, acid value: 20 mgKOH / g), DISPERBYK (registered trademark) -194 ((acid group: carboxy group, acid value: 70 mgKOH / g), Aron of Toa Synthetic Co., Ltd. (Registered trademark) A-6012 (acid group: sulfonic acid group, weight average molecular weight: 10000), Aron (registered trademark) A-6001 (acid group: carboxy group, pH: 7-9 (aqueous concentration), weight average molecular weight : 8000), Aron® SD-10 (acid group: carboxy group, pH: 2-5 (aqueous concentration), weight average molecular weight: 10000), Ebonic's TEGO® Dispers 651 (acid group: phosphorus) Acid group, acid value: 30 mgKOH / g) and the like can be mentioned.

The particle layer in the present disclosure may contain only one type of resin having an acid group, or may contain two or more types of resin.

The content of the resin having an acid group in the particle layer (or the composition for forming the particle layer) is preferably in the range of 20% by mass to 60% by mass, preferably 25% by mass to 60% by mass, based on the content of the silica particles. The range of 50% by mass is preferable, and the range of 30% by mass to 45% by mass is more preferable.

(Crosslinking agent)
The composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate according to the present disclosure preferably contains a cross-linking agent. By forming a cross-linked structure in the anti-fog layer including a cross-linking agent, cross-linking of the water-absorbent resin is formed. As a result, it is possible to form an anti-fog laminate having a cross-linked structure and whose water absorption and water dripping resistance can be controlled by the cross-linking density.

It is more preferable that the cross-linking agent contains at least one selected from the group consisting of a compound having an epoxy group, a compound having an oxetanyl group, a blocked isocyanate compound, an ethylenically unsaturated compound, and a polyfunctional mercapto compound.
By using a cross-linking agent, the scratch resistance becomes more excellent.

(1) Compound having an epoxy group The compound having an epoxy group is a compound having at least one epoxy group in the molecule, and the number of epoxy groups in the molecule is preferably two or more.
Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like. Can be done.
As the compound having an epoxy group, a commercially available product on the market may be used. Examples of commercially available products include the following epoxy resins. In particular,
Examples of the bisphenol A type epoxy resin include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (all manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051 and EPICLON1051. (Made by Co., Ltd.).
Examples of the bisphenol F type epoxy resin include JER806, JER807, JER4004, JER4005, JER4007, JER4010 (all manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (all manufactured by DIC Corporation), LCE-21, RE- 602S (all manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned.
Examples of the phenol novolac type epoxy resin include JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC). (Manufactured by Co., Ltd.) and the like.
Examples of the cresol novolac type epoxy resin include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, and EPICLON N-695 (all manufactured by DIC Corporation). ), EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of the aliphatic epoxy resin include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (all manufactured by ADEKA Corporation), seroxide 2021P, seroxide 2081, seroxide 2083, seroxide 2085, EHPE3150, EPOLEAD PB 3600, Examples thereof include PB 4700 (all manufactured by Daicel Chemical Industries, Ltd.).
In addition to the above, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA CORPORATION) and the like can be mentioned.

Further, urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, or Japanese Patent Publication No. 62-39418 are also preferably mentioned. ..

When the composition for forming a water-absorbent layer and / or the composition for forming an antifogging laminate contains a compound having an epoxy group, the content of the compound having an epoxy group is 0.1 mass by mass with respect to the total solid content mass. % To 20% by mass is preferable, 0.5% by mass to 10% by mass is more preferable, and 1% by mass to 5% by mass is further preferable.
The composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate may contain one kind of compound having an epoxy group alone, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount of the two or more kinds of compounds is within the above range.

(2) Compound Having Oxetanyl Group The compound having an oxetanyl group is a compound having at least one oxetanyl group in the molecule, and the number of oxetanyl groups in the molecule is preferably two or more.
Specific examples of the compound having an oxetanyl group include Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (all manufactured by Toagosei Co., Ltd.).
Further, the compound containing an oxetanyl group is preferably used alone or in combination with a compound containing an epoxy group.

When the composition for forming a water-absorbent layer and / or the composition for forming an antifogging laminate contains a compound having an oxetanyl group, the content of the compound having an oxetanyl group is 0.1 mass by mass with respect to the total solid content mass. % To 20% by mass is preferable, 0.5% by mass to 10% by mass is more preferable, and 1% by mass to 5% by mass is further preferable.
The composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate may contain one kind of compound having an oxetanyl group alone, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount of the two or more kinds of compounds is within the above range.

(3) Blocked Isocyanate Compound The blocked isocyanate compound is not limited as long as it has a blocked isocyanate group in the molecule, and from the viewpoint of curability, a compound having two or more blocked isocyanate groups in the molecule is preferable. The upper limit of the number of blocked isocyanate groups is not particularly limited, but is preferably 6 or less.
The blocked isocyanate compound is not particularly limited in its skeleton, and may be appropriately selected from compounds having two or more isocyanate groups in the molecule, and is any of aliphatic, alicyclic or aromatic polyisocyanates. good.
Examples of the blocked isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, and 1,4-tetramethylene diisocyanate. , 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexanediisocyanate, 2,2' -Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-ximethylene diisocyanate, m-xamethylene diisocyanate, p-xamethylene diisocyanate, methylene bis (cyclohexamethylene diisocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4 -Dimethylene diisocyanate, 1,5-naphthalenedisocyanate, p-phenylenediocyanate, 3,3'-methylene ditrilen-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylenediisocyanate, norbornan diisocyanate, hydrogen Isocyanate compounds such as chemical 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate and prepolymer-type skeleton compounds derived from these compounds can be preferably used.
Of these, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are more preferable.

Examples of the mother structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, bifunctional prepolymer type and the like.
Examples of the blocking agent forming the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. Can be done. Among them, a blocking agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.
As the blocked isocyanate compound, a commercially available product on the market may be used. Examples of commercially available products include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B. -820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60P, 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (all manufactured by Asahi Kasei Chemicals Co., Ltd.), Death Module BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumijour BL3175 (all manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are suitable.

The composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate may contain one type of blocked isocyanate compound alone, or may contain two or more types. When two or more kinds are included, it is preferable that the total amount of the two or more kinds of compounds is within the above range.
When the composition for forming a water-absorbent layer and / or the composition for forming an antifogging laminate contains a blocked isocyanate compound, the content of the blocked isocyanate compound is 0.1% by mass to 20% by mass with respect to the total solid content mass. % Is preferable, 0.5% by mass to 10% by mass is more preferable, and 1% by mass to 5% by mass is further preferable.

(4) Polyfunctional mercapto compound The polyfunctional mercapto compound is not particularly limited as long as it is a compound having two or more mercapto groups in the molecule, and a compound having two to six mercapto groups in the molecule is preferable. Compounds having 2 to 4 groups are more preferable.
As the polyfunctional mercapto compound, an aliphatic polyfunctional mercapto compound is preferable. A preferred example of the aliphatic polyfunctional mercapto compound is a compound consisting of a combination of an aliphatic hydrocarbon group and −O−, −C (= O) −, and at least 2 hydrogen atoms of the aliphatic hydrocarbon group. Examples are compounds in which one is substituted with a mercapto group.
Examples of the aliphatic polyfunctional mercapto compound include pentaerythritol tetrakis (3-mercaptobutyrate) and 1,4-bis (3-mercaptobutyryloxy) butane. Commercially available products on the market may be used, and examples of the commercially available products include Karenz MT-PE-1, Karenz MT-BD-1, and Lens MT-NR-1 (manufactured by Showa Denko KK). Be done.

When the composition for forming a water-absorbent layer and / or the composition for forming an antifogging laminate contains a polyfunctional mercapto compound, the content of the polyfunctional mercapto compound is 0.1% by mass or more based on the total solid content mass. 20% by mass is preferable, 0.5% by mass to 10% by mass is more preferable, and 1% by mass to 5% by mass is further preferable.
The composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate may contain one type of polyfunctional mercapto compound alone, or may contain two or more types. When two or more kinds are included, it is preferable that the total amount of the two or more kinds of compounds is within the above range.

(5) Ethylene Unsaturated Compounds Specific examples of the ethylenically unsaturated compound include (meth) acrylate monomers and vinyl monomers described in JP-A-2010-34513.
When the composition for forming a water-absorbent layer and / or the composition for forming an antifogging laminate contains an ethylenically unsaturated compound, the content of the ethylenically unsaturated compound is 0.1 mass by mass with respect to the total solid content mass. % To 20% by mass is preferable, 0.5% by mass to 10% by mass is more preferable, and 1% by mass to 5% by mass is further preferable.
The composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate may contain one kind of ethylenically unsaturated compound alone, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total amount of the two or more kinds of compounds is within the above range.

(Curing catalyst)
The composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate according to the present disclosure preferably contains a curing catalyst. The cross-linking reaction can be promoted by containing a curing catalyst in the composition for forming a water-absorbent layer and / or the composition for forming an anti-fog laminate.

Examples of the curing catalyst include a photoacid generator, a thermoacid generator, a photobase generator, a thermobase generator, and a photopolymerization initiator.
Examples of the photoacid generator include diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate. Preferred photosensitizers include imide sulfonate, oxime sulfonate, and o-nitrobenzyl sulfonate, which are compounds that generate sulfonic acid.
Examples of the thermoacid generator include K-PURE TAG series and K-PURE CXC series manufactured by Kusumoto Kasei Co., Ltd.

Examples of photobase generators include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane , N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6 -Dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2', 4'-dinitrophenyl)- 1,4-Dihydropyridine and the like can be mentioned.
As an example of the thermobase generator, the compound described in International Publication No. 2015/199219 can be used.

Examples of photopolymerization initiators are Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure®. 184 (1-Hydroxycyclohexylphenylketone), Irgacure® 500 (1-hydroxycyclohexylphenylketone, benzophenone), Irgacure® 651 (2,2-dimethoxy-1,2-diphenylethane-1-) On), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl-1 [4-methylthiophenyl) ] -2-morpholinopropan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6-dimethoxy) Benzoyl) -2,4,4-trimethyl-pentylphosphenyl oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethyl-pentylphosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propane-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio)) Phenyl] -2- (O-benzoyloxime), Darocur® 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur® 1116, 1398, 1174 And 1020, CGI242 (Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), Lucirin TPO (available from BASF). 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide), Lucirin TPO-L (2,4,6-trimethylbenzoylphenylethoxyphosphenyl oxide), ESACUR 1001M (1- [4-benzoylphenyl) available from Sibel Hegner, Japan. Sulfanyl] Phenyl] -2-Methyl-2- (4-Methylphenylsulfonyl) Pro Pan-1-one, N-1414 Adecaoptomer (registered trademark) N-1414 (carbazole / phenone type), Adekaoptomer (registered trademark) N-1717 (aclysin type), Adekaopter available from Asahi Denka Co., Ltd. Mar (registered trademark) N-1606 (triazine type), TFE-triazine manufactured by Sanwa Chemical (2- [2- (fran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3 , 5-Triazine), TME-Triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-Triazine) manufactured by Sanwa Chemical Co., Ltd. ), MP-triazine manufactured by Sanwa Chemical (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-113 manufactured by Midori Chemical Co., Ltd. (2- [2] -(3,4-dimethoxyphenyl) ether] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3,4-dimethoxyphenyl) -4, manufactured by Midori Chemical Co., Ltd.) , 6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-phenylbenzophenone , Ethylmichillers ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxanthone ammonium salt , Benzoyl, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosberone, o- Methyl benzoyl benzoate, 2-benzoyl naphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoyl benzene, benzyl, 10-butyl-2-chloroacrydone, [4- (methylphenylthio) phenyl] phenyl Methane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4', 5'-tetrakis (3,4,5-trimethoxyphenyl) 1,2'-bi Midazole, 2,2-bis (o-chlorophenyl) 4,5,4', 5'-tetraphenyl-1,2'-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl-4- (dimethylamino) ) Benzoate, 2- (dimethylamino) ethylbenzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.

(High boiling point solvent)
The composition for forming a water absorption layer and / or the composition for forming a particle layer in the present disclosure preferably contains a high boiling point solvent, and more preferably contains a high boiling point solvent having a boiling point of 120 ° C. or higher.
When the anti-fog layer contains a high boiling point solvent, the leveling property of the applied coating film is improved, and an anti-fog layer having low haze and high surface smoothness can be obtained.
The boiling point of the high boiling point solvent is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 150 ° C. or higher, from the viewpoint of further enhancing the leveling property of the coating film and obtaining an anti-fog layer having a lower haze. The upper limit of the boiling point of the high boiling point solvent is preferably 230 ° C. from the viewpoint of suppressing poor drying of the coating film formed by the anti-fog layer forming coating liquid.

Examples of the high boiling point solvent include those shown below. In addition, the numerical value in parentheses described side by side with the name of the high boiling point solvent shown below indicates a boiling point.
Specific examples of the high boiling point solvent include alcohol solvents such as 1,3-butanediol (207 ° C.), 1,4-butanediol (228 ° C.), benzyl alcohol (205 ° C.), and terpioner (217 ° C.);
Glycol solvents such as ethylene glycol (197 ° C), diethylene glycol (244 ° C), triethylene glycol (287 ° C), propylene glycol (187 ° C), dipropylene glycol (230 ° C);
Diethylene glycol monomethyl ether (194 ° C), diethylene glycol monoethyl ether (202 ° C), diethylene glycol monobutyl ether (231 ° C), triethylene glycol monomethyl ether (249 ° C), propylene glycol monomethyl ether (121 ° C), propylene glycol monobutyl ether (170 ° C). ℃), Propylene Glycol Monopropyl Ether (150 ℃), 3-methoxy-3-methyl-1-butanol (174 ℃), Diethylene Glycol Monohexyl Ether (261 ℃ or higher), Propylene Glycol Monomethyl Ether Propionate (160 ℃) ), Methyl cellosolve (ethylene glycol monomethyl ether, 125 ° C), ethyl cellosolve (ethylene glycol monoethyl ether, 135 ° C), butyl cellosolve (ethylene glycol monobutyl ether, 171 ° C), ethylene glycol-mono-tert-butyl ether (153 ° C). , Tripropylene glycol monomethyl ether (243 ° C), dipropylene glycol monomethyl ether (188 ° C) and other glycol ether-based solvents;
Ether-based solvents such as diethylene glycol dimethyl ether (162 ° C), diethylene glycol ethyl methyl ether (176 ° C), diethylene glycol isopropylmethyl ether (179 ° C), and triethylene glycol dimethyl ether (216 ° C);
Ester solvents such as ethylene glycol monomethyl ether acetate (145 ° C), diethylene glycol monoethyl ether acetate (217 ° C), ethyl acetate (154 ° C), ethyl lactate (154 ° C), 3-methoxybutyl acetate (172 ° C);
Ketone-based solvents such as diacetone alcohol (169 ° C.), cyclohexanone (156 ° C.), cyclopentanone (131 ° C.); and the like can be mentioned.

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.
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.
The glycol ether solvent refers to a solvent having a structure having one hydroxy group and at least one ether group in one molecule.
The ether solvent refers to a solvent having a structure that does not have a hydroxy group or an ester group in one molecule and has at least one ether group.
The ester solvent refers to a solvent having a structure having at least one ester group in one molecule.
The ketone solvent refers to a solvent having a structure having at least one ketone group in one molecule.

As the high boiling point solvent, it is preferable to use a glycol ether solvent because the surface energy is low and the leveling property of the coating film by the composition for forming a water absorbing layer and / or the composition for forming a particle layer is enhanced.
For the same reason, it is preferable to use a solvent having a branched alkyl group as the high boiling point solvent contained in the composition for forming a water absorption layer and / or the composition for forming a particle layer.

The composition for forming a water absorption layer and / or the composition for forming a particle layer may contain only one type of high boiling point solvent, or may contain two or more types.
When two or more kinds of high boiling point solvents are contained, it is preferable to contain a glycol ether solvent as one of them. By containing the glycol ether solvent, the flatness of the coating film by the anti-fog layer forming coating liquid is improved.
The content of the glycol ether solvent is preferably in the range of 10% by mass to 50% by mass, more preferably in the range of 15% by mass to 40% by mass, based on the total solvent.
When two or more kinds of high boiling point solvents are contained, it is preferable to contain a ketone solvent as one of them. By containing the ketone solvent, the adhesion between the water absorbing layer and the particle layer formed by the composition for forming the water absorbing layer and / or the composition for forming the particle layer is improved.
When a ketone solvent is contained, the content of the ketone solvent is preferably in the range of 5% by mass to 40% by mass, more preferably in the range of 5% by mass to 15% by mass, based on the total solvent. When the anti-fog layer contains two or more kinds of high boiling point solvents, it is also preferable that the anti-fog layer contains both a glycol ether solvent and a ketone solvent.

^{The ketone solvent as a high boiling point solvent has an SP value (solubility parameter) of 10.0 MPa 1/2} or more from the viewpoint of being able to form a water absorption layer and / or a particle layer having more excellent transparency. Is preferable. The upper limit of the SP value of the ketone solvent is not particularly limited, and is ^{13.0 MPa 1/2} or less, for example, from the viewpoint of applicability to a base material, for example, surface failure such as repellent is unlikely to occur. Is preferable.
Specific examples of the ketone solvent which is a high boiling point solvent and has an SP value of 10.0 MPa ^{1/2 or more are shown below.} However, the present disclosure is not limited to these. The numerical values in parentheses shown in the specific example indicate the SP value (unit: MPa ^1/2 ).
Diacetone alcohol (10.2)
Cyclopentanone (10.4)

The SP value is a value represented by the square root of the molecular aggregation energy, and R.I. F. It is a value calculated by the method described in Fedors, Polymer Engineering Science, 14, p147 to p154 (1974).

The content of the high boiling point solvent in the water absorbing layer and / or the particle layer (or the composition for forming the water absorbing layer and / or the composition for forming the particle layer) is the composition for forming the water absorbing layer and / or the composition for forming the particle layer. It is preferably 15% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and further preferably 20% by mass or more and 40% by mass or less, based on the total solid content mass of the product.

(Solvents other than high boiling point solvents)
The composition for forming a particle layer in the present disclosure preferably contains a solvent other than water and a high boiling point solvent in addition to the other additives described above.
Further, the composition for forming a water absorption layer in the present disclosure preferably contains a solvent other than the high boiling point solvent in addition to the other additives described above.

(water)
Water contributes as a dispersion medium for silica particles in the composition for forming a particle layer.

The water content of the particle layer forming composition is preferably in the range of 5% by mass to 60% by mass, more preferably in the range of 10% by mass to 55% by mass, based on the total mass of the particle layer forming composition. The range of 10% by mass to 35% by mass is more preferable.

(Organic solvent with boiling point less than 120 ° C)
The composition for forming a water absorption layer and / or the composition for forming a particle layer in the present disclosure preferably contains an organic solvent having a boiling point of less than 120 ° C.
Examples of the organic solvent having a boiling point of less than 120 ° C. include methanol, ethanol, butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, n-propanol, 2-propanol, tert-butanol, 2-butanol and the like. Alcoholic solvent;
Glycol ether solvent such as dipropylene glycol methyl ether;
Ether-based solvents such as isopropyl ether, 1,4-dioxane, tert-butyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, diethyl ether;
Ketone-based solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone; and the like.
As the organic solvent having a boiling point of less than 120 ° C., an alcohol solvent is preferable from the viewpoint that the surface energy is low and the spreadability of the composition for forming a water absorption layer and / or the composition for forming a particle layer can be enhanced.

With respect to the composition for forming a water absorption layer and / or the composition for forming a particle layer in the present disclosure, only one kind of organic solvent having a boiling point of less than 120 ° C. may be used, or two or more kinds may be used.
When two or more organic solvents having a boiling point of less than 120 ° C. are contained, a ketone solvent is used as one of them to improve the adhesion between the anti-fog layer formed by the anti-fog layer forming coating liquid and the water-absorbing layer. It may be improved. As the ketone solvent used here, acetone (10.0) and acetylacetone (10.3) having ^{an SP value of 10.0 MPa 1/2 or more are preferable.} The numerical value in parentheses is the SP value.
Regardless of the boiling point, the ketone solvent is preferably used in the range of 1% by mass to 15% by mass, and more preferably in the range of 3% by mass to 10% by mass in the total solvent.

When the water-absorbent layer forming composition and / or the particle layer forming composition in the present disclosure contains an organic solvent having a boiling point of less than 120 ° C., the content of the organic solvent having a boiling point of less than 120 ° C. is the antifogging layer forming coating. The range of 20% by mass to 70% by mass is preferable, and the range of 25% by mass to 65% by mass is more preferable with respect to the total mass of the liquid.

(Antistatic agent)
The composition for forming a water absorption layer and / or the composition for forming a particle layer of the present embodiment preferably contains at least one antistatic agent.
By including the antistatic agent, the obtained antifog layer is imparted with antistatic properties, the effect of preventing the adhesion of pollutants is improved, and the antifouling properties are further improved.

The antistatic agent can be appropriately selected from compounds having an antistatic function, and may be either a compound exhibiting surface activity or a compound exhibiting no surface activity. Examples of the antistatic agent include an ionic surfactant and metal oxide particles. The metal oxide particles as an antistatic agent do not include the silica particles described above.
An ionic surfactant as an antistatic agent has a property of easily segregating near the film surface of a coating film when, for example, a composition for forming an anti-fog layer is applied to a base material to form an anti-fog layer. Yes, the effect can be expected with a small amount of addition.
Further, the metal oxide particles as an antistatic agent may need to be added in a relatively large amount in order to impart antistatic properties to the particle layer, but since they are inorganic substances, they are water-absorbent layers and / or particle layers. It is suitable for improving the scratch resistance of the particles.

Examples of other ionic surfactants include alkyl sulfates (eg sodium dodecyl sulfate, sodium lauryl sulfate, etc.), alkylbenzene sulfonates (eg sodium dodecylbenzene sulfonate, sodium laurylbenzene sulfonate, etc.), Anionic surfactants such as alkyl sulfosuccinates (eg, di (2-ethylhexyl) sodium sulfosuccinate, etc.), alkyl phosphates (eg, sodium dodecyl phosphate, etc.); alkyltrimethylammonium salts, dialkyldimethylammonium salts, etc. Cationic surfactants; and amphoteric surfactants such as alkylcarboxybetaine can be mentioned.

When another ionic surfactant is used as the antistatic agent, the content of the other ionic surfactant is 10% by mass or less based on the total solid content of the anti-fog layer forming composition. Preferably, 5% by mass is more preferable, and 1% by mass or less is further preferable. When the content of the other ionic surfactant is within the above range, the antifouling property of the antifog layer can be enhanced while suppressing the aggregation of silica particles. Further, the content of the other ionic surfactant is 0.05% by mass or more from the viewpoint of the effect of improving the antifouling property of the water absorption layer and / or the particle layer by including the ionic surfactant. It is preferable to have.

(Surfactant)
The composition for forming a water-absorbent layer and / or the composition for forming a particle layer in the present embodiment may further contain a surfactant. By containing the surfactant in the water absorption layer and / or the particle layer, the ability to prevent the adhesion of pollutants is further improved.

As the surfactant, the antistatic agent and the surfactant may be used in combination regardless of whether the antistatic agent has a surfactant or not. When the antistatic agent is a compound that does not exhibit surface activity, it is preferable to contain the surface active agent from the viewpoint of water detergency. When the antistatic agent is a compound exhibiting surface activity, it is preferable to contain the surfactant separately from the antistatic agent from the viewpoint of further improving the antifouling property.

When the composition for forming a water absorbing layer and / or the composition for forming a particle layer contains a surfactant, not only the antifouling property of the water absorbing layer and / or the particle layer type is enhanced, but also the water absorbing layer and / or the particle layer is enhanced. For example, the coatability can be improved when the coating film is formed by coating, and the surface tension of the coating liquid used for coating is also reduced to further enhance the uniformity of the coating film.

Examples of the surfactant include nonionic surfactants and the like.
When an ionic surfactant is used as the antistatic agent as described above, when the ionic surfactant is excessively added to the membrane as described above, the electrolytic mass in the system increases and the silica particles are aggregated. It is preferable to use a nonionic surfactant in combination because it is easy to invite. 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 ethers, polyalkylene glycol monoalkyl esters, polyalkylene glycol monoalkyl esters and monoalkyl ethers. 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 surfactant is contained in the water absorbing layer forming composition and / or the particle layer forming composition, the content thereof is based on the total solid content of the water absorbing layer forming composition and / or the particle layer forming composition. , 0.5% by mass or more, more preferably 1.0% by mass or more.
The content of the surfactant is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, based on the total solid content of the water-absorbent layer forming composition and / or the particle layer forming composition. It is preferable, and 30.0% by mass or less is more preferable.

<Thickness of anti-fog laminate>
The thickness of the water-absorbing layer constituting the anti-fog laminate is preferably in the range of several μm to several tens of μm, more preferably 5 μm to 30 μm, from the viewpoint of ensuring water absorption capacity. When the thickness of the anti-fog layer is within the above range, a sufficient amount of water absorption can be secured.
The thickness of the particle layer constituting the anti-fog laminate may be appropriately selected depending on the application, purpose, etc., and is preferably in the range of several hundred nm to several μm. When the thickness of the anti-fog layer is within the above range, the anti-fog layer has excellent crack resistance while ensuring transparency.

<Non-absorbent support>
It is preferable that a non-water-absorbent support is arranged on the side opposite to the side having the anti-fog laminate. When the anti-fog laminate has an adhesive layer, it is preferable to have a non-water-absorbing support between the water-absorbing layer and the pressure-sensitive adhesive layer.
The material of the non-water-absorbent support can be appropriately selected from various materials such as glass, resin (including plastic), metal, and ceramics, and is preferably resin.
When the anti-fog laminate of the present disclosure is applied to, for example, a protective material for an automobile light or a protective material for a surveillance camera, it is preferable to use a resin base material in terms of light weight and excellent strength.

When the material of the non-water-absorbent support is a resin, a laminated body having excellent durability against light and heat, maintaining the transparency of the support itself with the antifogging layer, and having excellent adhesion can be obtained. From the viewpoint of being able to form, the non-water-absorbent support is preferably a support using acrylic resin, polycarbonate, polyolefin or polyethylene terephthalate, and from the viewpoint of being able to form a laminated body having better adhesion, acrylic resin or polycarbonate. The support using the above is more preferable, and the support using polycarbonate or polymethylmethacrylate is further preferable.

As the material of the non-water-absorbent support, a composite material formed from a plurality of materials may be used. For example, the material of the non-water-absorbent support includes glass and a resin material, and the glass and the resin material are mixed. The composite material may be a composite material obtained by kneading or laminating a plurality of types of resin materials.

The thickness and shape of the non-water-absorbent support are not particularly limited and can be appropriately selected depending on the application target. The thickness of the non-water-absorbent support can be several tens of μm to several hundreds of μm.

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 such as corona discharge treatment can be used.

<Adhesive layer>
The anti-fog laminated body of the present disclosure may have a laminated structure in which an adhesive layer is provided on the side opposite to the side having the particle layer, depending on the intended use or purpose. The pressure-sensitive adhesive layer is preferably provided as the outermost layer on the side opposite to the side having the particle layer, and when the non-water-absorbing support is provided on the side opposite to the side having the particle layer, the non-water-absorbing support on the particle layer is provided. It is preferable that an adhesive layer is further provided on the support.
By attaching the pressure-sensitive adhesive layer, the anti-fog laminate can be installed at a desired position.

The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyvinyl butyral (PVB) resin, acrylic resin, styrene / acrylic resin, urethane resin, polyester resin, etc. Examples include silicone resin. These may be used alone or in combination of two or more. The adhesive layer made of these materials can be formed by coating. Further, an antistatic agent, a lubricant, an antiblocking agent and the like may be added to the adhesive layer. Examples include Panaclean PD-S1 manufactured by Panac Co., Ltd.

The thickness of the pressure-sensitive adhesive layer is preferably several tens of μm, more preferably 10 μm to 50 μm.

<Manufacturing method of anti-fog laminate>

The method for producing the anti-fog laminate of the present disclosure includes, for example, a step of applying the above-mentioned coating liquid for forming a water-absorbing layer according to the present disclosure on a non-water-absorbing support (hereinafter, referred to as a water-absorbing layer coating step). , The coating liquid for forming a particle layer is applied onto the water absorbing layer obtained through the step of drying the coating film formed by coating (hereinafter referred to as the water absorbing layer drying step), and further through the water absorbing layer coating step and the water absorbing layer drying step. It is preferable to have a step of performing (hereinafter, referred to as a particle layer coating step) and a step of drying the coating film formed by coating (hereinafter, referred to as a particle layer drying step).

(Water absorption layer coating process)
In the water absorption layer coating step and, first, the composition for forming the water absorption layer is applied to the non-water absorption support which is the material to be coated. The non-water-absorbent support is as described above.

The coating method may be determined according to the shape and size of the water absorbing layer, the thickness of the coating film, and the like. For example, spray coating, brush coating, roller coating, bar coating, dip coating (so-called dip coating), etc. Known coating methods such as spin coating, slit coating, slit & spin coating can be applied.
Above all, as a coating method, bar coating is preferable from the viewpoint of film thickness uniformity.

When the composition for forming a water-absorbent layer is applied to the non-water-absorbent support by spray coating, the method for setting the non-water-absorbent support is not particularly limited.
Depending on the shape of the non-water-absorbent support, the water-absorbing layer can be applied while being appropriately changed in the horizontal direction, the vertical direction, or the like with respect to the application direction. In order to make the coating layer thickness more uniform, it is preferable to arrange the spray nozzles at positions where the distance between the spray nozzle and the water absorption layer is equal and apply the spray nozzle to the non-water absorption support. The distance from the water absorption layer is preferably 10 mm or more and 1,000 mm or less.

As a method of supplying the composition for forming a water absorption layer 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 layer thickness can be made more uniform. In addition, in order to form a more suitable coating layer by spray coating, it is necessary to adjust the amount of air, the amount of sprayed coating liquid, the pattern opening, and the like.

When the composition for forming a water absorption layer is applied to the water absorption layer by spray coating, the amount of air is preferably 5 L (liter) / min or more and 600 L / min or less, and the amount of the coating liquid ejected 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 coating, the environment at the time of coating 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 coating amount of the composition for forming a water-absorbing layer is not particularly limited, and may be appropriately set in consideration of operability, etc., according to the concentration of solid content in the coating liquid, the desired layer thickness of the anti-fog layer, and the like. can.
For example, the coating amount of the water-absorbing layer forming composition, more preferably is preferably 1 mL / ^{m 2} or more 400 mL / ^{m 2} or less, 2 mL / ^{m 2} or more 100 mL / ^{m 2} or less, 4 mL / ^{m 2} above 40 mL / ^m more preferably ² or less, particularly preferably 6 mL / ^{m 2} or more 20 mL / ^{m 2} or less. Within the above range, the coating accuracy is good.

(Water absorption layer drying process)
In the water absorption layer drying step, the coating liquid applied to the non-water absorption support is dried.
The composition for forming a water absorption layer may be dried using a heating device.
As the heating device, any known heating device can be used without particular limitation as long as it can be heated to a target temperature. 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.

The drying conditions of the composition for forming the water absorption layer are not particularly limited, and can be appropriately set in consideration of the curability of the coating layer.
The composition for forming a water absorption layer may be dried under constant temperature conditions in which a predetermined set temperature is kept constant, or the temperature conditions may be changed stepwise.
In the former case, the drying condition of the composition for forming a water absorbing layer is preferably a drying condition in which the coating liquid is heated at a surface temperature of 20 ° C. or higher and 150 ° C. or lower for 1 to 60 minutes, and the surface temperature is 40 ° C. or higher and 150 ° C. or higher. Drying conditions of heating at ° C. or lower for 1 minute to 60 minutes are more preferable, and drying conditions of heating at a surface temperature of 60 ° C. or higher and 150 ° C. or lower for 1 minute to 60 minutes are more preferable.
In the latter case, the drying of the composition for forming a water absorbing layer is preferably carried out separately for pre-drying and main drying. As the pre-drying condition, it is preferable to heat the surface temperature at 20 ° C. or higher and 60 ° C. or lower for 5 seconds to 10 minutes.
The surface temperature can be measured with an infrared thermometer or the like.

When the composition for forming a water absorption layer 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 water absorption layer. 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 water absorption layer is not directly exposed to the drying air.

The non-water-absorbent support coated with the water-absorbent layer forming composition may be placed directly on the pedestal (that is, placed flat) and dried depending on the shape of the non-water-absorbing support. It may be hung to dry, or it may be hung to dry.

A water-absorbent layer is formed on the non-water-absorbent support through the water-absorbent layer coating step and the water-absorbent layer drying step.

(Particle layer coating process)
The particle layer coating step can be carried out by changing the non-water-absorbing support in the water-absorbing layer coating step to a water-absorbing layer and changing the water-absorbing layer forming composition to a particle layer forming composition.

(Particle layer drying process)
The particle layer drying step can be carried out by changing the non-water-absorbing support in the water-absorbing layer drying step to a water-absorbing layer and changing the water-absorbing layer drying composition to a particle layer forming composition.

A particle layer is formed on the water absorbing layer through a particle layer coating step and a particle layer drying step. The formed water absorption layer and particle layer are collectively defined as an anti-fog laminate.

Hereinafter, embodiments of the present invention will be specifically described 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.

(Synthesis Example 1)
-Preparation of specific copolymer 1-
200 g of ethylene glycol monoethyl ether was charged in a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and the mixture was heated and stirred to 70 ° C. while blowing nitrogen gas.
Further, a mixture of monomers containing 4 g of polypeptide peroxide represented by the following formula (4), 50 g of N, N-dimethylacrylamide, 8 g of N-methylolacrylamide, 12 g of methyl methacrylate, and 40 g of ethylene glycol monoethyl ether. The mixture was prepared and added dropwise to 200 g of the above-mentioned ethylene glycol monoethyl ether over 2 hours, and the reaction was further carried out for 2 hours.
Then, a monomer mixture containing 28 g of methyl methacrylate and 2 g of acrylic acid was added dropwise over 30 minutes, and the reaction was carried out at 80 ° C. for 5 hours. After the reaction, the mixture was cooled to 25 ° C. to obtain a solution of the specific copolymer 1 having a solid content of 30%.

(Synthesis Example 2)
-Preparation of specific copolymer 2-
200 g of propylene glycol monomethyl ether was charged into the reactor used in Synthesis Example 1, and the mixture was heated and stirred to 85 ° C. while blowing nitrogen gas, and 6 g of t-butylperoxyoctanoate and 6 g of t-butylperoxymethacryloxyethyl carbonate. A monomer mixture containing 10 g of N-methylolacrylamide, 10 g of 2-hydroxyethyl methacrylate, 66 g of N, N-dimethylacrylamide, and 40 g of propylene glycol monomethyl ether was placed in a reactor charged with 200 g of propylene glycol monomethyl ether. The mixture was added dropwise over a minute, and the reaction was further carried out for 2 hours.
Then, the mixture was further heated to 110 ° C., and a monomer mixture containing 20 g of methyl methacrylate, 2 g of acrylic acid and 40 g of propylene glycol monomethyl ether was added dropwise over 30 minutes, and the reaction was further carried out for 4 hours.
After the reaction, the mixture was cooled to 25 ° C. to obtain a solution of the specific copolymer 2 having a solid content of 30%.

-Preparation of composition A for forming a water absorption layer-
The laminate of Example 1 was produced by the following method.
Anionic surfactant di (2-ethylhexyl) sodium sulfosuccinate (made by Kishida Chemical Co., Ltd. to a solid content concentration of 0.2% by mass) in a mixed solvent of 23.00 g of ethanol and 2.00 g of water. 2.30 g of a diluted aqueous solution) was added and stirred for 30 minutes. Further, 1.50 g of the solution of the specific copolymer 1 obtained in Synthesis Example 1 described above was added to obtain a water-absorbent layer forming composition A.

-Preparation of composition A for forming particle layer-
Add 1.90 g of silica particles (“Snowtex OYL” manufactured by Nissan Chemical Industry Co., Ltd. (solid content concentration 20%, primary particle size 50 to 80 nm): specific silica particles) to the composition A for forming a water absorption layer for 30 minutes. The mixture was stirred to obtain a particle layer forming composition A.

-Preparation of composition B for forming a water absorption layer-
Di (2-ethylhexyl) sodium sulfosuccinate (manufactured by Kishida Chemical Co., Ltd., solid content concentration 0.2 mass) in a mixed solvent containing 21.50 g of ethanol and 3.50 g of water. 2.30 g of the aqueous solution diluted to%)) was added and stirred for 30 minutes to obtain a mixed solution. To the obtained mixed solution, 1.50 g of the specific copolymer 2 solution obtained in Synthesis Example 2 was further added to obtain a composition B for forming an anti-fog layer.

-Preparation of composition B for forming particle layer-
3.40 g of silica particles (“Snowtex OUP” manufactured by Nissan Chemical Industries, Ltd. (solid content concentration 15%, primary particle size 40 nm to 100 nm): specific silica particles)) is added to composition B for forming a water absorbing layer 30. The mixture was stirred for a minute to obtain a composition B for forming a particle layer.

-Preparation of composition C for particle layer formation-
To 81.07 g of ethanol, 1.70 g of siloxane compound (manufactured by Mitsubishi Chemical Corporation) MKC silicate MS-57 and 1 mass% isopropanol solution of aluminum bis (ethylacetoacetate) mono (acetylacetonate) (compound Condensation accelerating catalyst) 0.94 g was added and mixed, and further silica particles (“Snowtex OUP” manufactured by Nissan Chemical Corporation (solid content concentration 15%, primary particle size 40 nm to 100 nm): specific silica particles)) 3.40 g was added and stirred for 30 minutes to obtain a particle layer forming composition B.

[Example 1]
The obtained composition A for forming a water-absorbing layer was coated on a transparent acrylic base material using an air spray gun W-101-101G manufactured by Anest Iwata Co., Ltd. so as to have a film thickness of 2 to 3 μm, and then 80 ° C. It was dried and cured for 40 minutes to obtain a water absorption layer A.
Subsequently, the composition A for forming a particle layer was coated on the water absorption layer A using an air spray gun W-101-101G manufactured by Anest Iwata Co., Ltd. so as to have a film thickness of 1 μm, and then dried and cured at 80 ° C. for 40 minutes. Was carried out to obtain a particle layer A. Then, it was left at 25 ° C. for 1 day to obtain a laminate of Example 1 having a water absorbing layer A and a particle layer A on a transparent acrylic base material.
The transparent acrylic base material used had a thickness of 5 mm and a haze of the base material alone was 0.4%.

[Example 2]
A laminate of Example 2 was obtained in the same manner as in Example 1 except that the film thickness of the water absorption layer A in Example 1 was changed from 2 to 3 μm to 10 to 20 μm.

[Example 3]
The obtained composition B for forming a water-absorbing layer was coated on a transparent polycarbonate substrate using an air spray gun W-101-101G manufactured by Anest Iwata Co., Ltd. so as to have a film thickness of 2 to 3 μm, and then at 40 ° C. After pre-drying for 5 minutes, it was dried and cured at 120 ° C. for 20 minutes to obtain a water absorption layer B.
Subsequently, the composition B for forming a particle layer was coated on the water absorption layer B with an air spray gun W-101-101G manufactured by Anest Iwata Co., Ltd. so as to have a film thickness of 1 μm, and then pre-dried at 40 ° C. for 5 minutes. After that, the particle layer B was obtained by drying and curing at 120 ° C. for 20 minutes. Then, it was left at 25 ° C. for 1 day to obtain a laminate of Example 3 having a water absorbing layer B and a particle layer B on a transparent polycarbonate base material.
The transparent polycarbonate base material used had a thickness of 5 mm and a haze of the base material alone was 0.4%.

[Example 4]
A laminate of Example 4 was obtained in the same manner as in Example 3 except that the film thickness of the water absorption layer B in Example 3 was changed from 2 to 3 μm to 10 to 20 μm.

[Example 5]
A laminate of Example 5 was obtained in the same manner as in Example 3 except that the particle layer B in Example 3 was changed to the particle layer C.

[Comparative Example 1]
A laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except that the particle layer A in Example 1 was not provided.

[Comparative Example 2]
A laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except that the water absorption layer A in Example 1 was not provided.

[Comparative Example 3]
A laminate of Comparative Example 3 was obtained in the same manner as in Example 4 except that the particle layer B in Example 4 was not provided.

[Comparative Example 4]
A laminate of Comparative Example 3 was obtained in the same manner as in Example 4 except that the water absorption layer B in Example 4 was not provided.

(evaluation)
The following evaluation was performed on the anti-fog material prepared above. The evaluation results are shown in Table 1 below.

-Measurement of anti-fog layer film thickness-
The thickness of the particle layer and / or the water absorbing layer is determined by cutting the formed antifogging laminate with a microtome in the direction perpendicular to the substrate surface of the laminate, that is, in the thickness direction of the laminate, and forming a cross section of the laminate. Then, the cut cross section was observed and measured at a magnification of 50,000 times with an electric field radiation scanning electron microscope (FE-SEM).
When observed, the thickness of the layer in which the particles were observed in the anti-fog laminate was defined as the thickness of the particle layer, and the thickness of the layer in which the particles were not observed was defined as the thickness of the water absorbing layer.

-Initial anti-fog property-
A sample having a size of 10 cm × 10 cm was prepared as an anti-fog material, and ice water was brought into contact with the opposite side of the anti-fog surface of the sample in a laboratory at a temperature of 20 ° C. and a humidity of 50% RH to laminate the anti-fog property. The state of the surface holding the body was visually observed for 1 minute. The evaluation passed the standard "3".
<Evaluation criteria>
3: There is no cloudiness, and there is no fluctuation in which the transmitted image appears blurred.
2: There is no cloudiness, but there are fluctuations in which the transmitted image appears blurred.
1: Cloudy occurs and the transmitted image cannot be seen.

-Long-term anti-fog property-
A sample having a size of 10 cm × 10 cm was prepared as an anti-fog material, and ice water was brought into contact with the opposite side of the anti-fog surface of the sample in a laboratory at a temperature of 20 ° C. and a humidity of 50% RH to laminate the anti-fog property. The state of the surface holding the body was visually observed for 30 minutes. The evaluation passed the standard "3".
<Evaluation criteria>
3: There is no cloudiness, and there is no fluctuation in which the transmitted image appears blurred.
2: There is no cloudiness, but there are fluctuations in which the transmitted image appears blurred.
1: Cloudy occurs and the transmitted image cannot be seen (including the case of temporary cloudiness in the middle of 30 minutes).

-Measurement of water absorption-
Prepare a hot water bath at 60 ° C., apply steam from the hot bath only to a 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 was erected vertically and the amount of mass increase under the upper limit condition where water dripping did not occur was measured, and the amount of mass increase per unit area to which steam was applied was defined as the amount of water absorption (mg / cm ² ).

-Scratch resistance-
A sample having a size of 10 cm × 10 cm was prepared as an anti-fog material, the surface having the anti-fog laminate was rubbed under the following conditions, and the presence or absence of significant scratches in the rubbed area was visually evaluated to generate scratches. Those without the above were accepted.
<Conditions>
Load: 100 g / cm ²
Cotton canvas: Canvas cloth (JIS L 3120-1961-1206)
Stroke speed: 1 round trip / sec Number of strokes: 1000 round trips

-Dripping marks on the dry surface after water film formation (dry marks)-
A sample having a size of 10 cm × 10 cm was prepared as an anti-fog material, and 10 ml of water was sprayed on the surface having the anti-fog laminate to forcibly form a water film, and then the sample was hung vertically. It was allowed to stand in the state and dried.
<Evaluation criteria>
3: There is no dripping mark.
2: Slight dripping marks are visible.
1: The dripping mark is clearly visible.

As shown in Table 1, the anti-fog layer obtained in the examples can maintain good anti-fog performance for a long period of time, and is also excellent in scratch resistance and dripping trace suppressing property after drying. It was a table. Further, the amount of water absorption could be adjusted by adjusting the film thickness of the water absorption layer.
On the other hand, in Comparative Examples 1 and 3, since the water-absorbent material structure without the particle layer was adopted, the initial anti-fog property could be obtained, but the anti-fog performance could not be maintained for a long period of time. .. In addition, since the structure does not include a particle layer that covers the water absorption layer, the scratch resistance is inferior, and the occurrence of dripping marks after drying is remarkable.
Further, in Comparative Examples 2 and 4, since the hydrophilic type material structure without the water absorption layer was adopted, the initial anti-fog property could be obtained, but the anti-fog performance could not be maintained for a long period of time.

The antifogging laminate of the present disclosure can be used for various purposes, for example, a protective material for protecting a surveillance camera, lighting, a sensor lamp, etc. (so-called protective cover); a vehicle such as an automobile or a two-wheeled vehicle. Cargo roofing materials; signs such as road signs; soundproof walls for highway road shoulder installation, railways, etc .; vehicle bodies such as automobiles and motorcycles; automobile window glass, mirrors, light protective materials (for example, lenses) It is preferably used in terms of imparting functions such as anti-fog property.
Above all, it is more suitable for use as a protective material for automobile lights (headlights, tail lamps, door mirror winker lights, etc.) and a protective material for surveillance cameras.
Generally, an automobile includes a light unit including a light and a lens for protecting the light. The transparent base material such as glass and plastic used for the light unit has one surface below the dew point due to the difference in temperature and humidity between the inner surface and the outer surface across the base material, or suddenly with respect to the base material. Moisture in the atmosphere adheres as water droplets when a change in temperature and humidity occurs (when boiling steam comes into contact with the base material, when the environment moves from a low temperature part to a high temperature and high humidity environment, etc.), and the surface of the base material tends to condense. Become. As a result, so-called "cloudiness" may occur in which light is scattered by the condensed water droplets. When such "cloudiness" occurs in the headlights, rear lights, etc., the appearance is significantly impaired. Fogging is likely to occur even in the protective cover of a surveillance camera having a protective cover (that is, a surveillance camera with an integrated housing), and visibility and safety may be significantly impaired.
From the above viewpoints, the anti-fog laminate of the present disclosure does not impair the appearance, function and performance of automobile lights and surveillance cameras, and is excellent in anti-fog and stain resistance for a long period of time. Anti-fog property can be maintained throughout.

10 ... Anti-fog laminate 12 ... Anti-fog layer 14 ... Water absorption layer 16 ... Adhesive layer 18 ... Non-absorbent support

Claims (17)

An antifogging laminate having a water-absorbent layer containing a water-absorbent resin on a base material and a particle layer containing silica particles and a water-absorbent resin on the water-absorbent layer. The anti-fog laminate according to claim 1, wherein the water-absorbent resin contained in the particle layer is the same as the water-absorbent resin contained in the water-absorbent layer. The water-absorbent resin is at least one selected from the group consisting of cellulose-based resin, polyvinyl alcohol-based resin, polyvinyl acetal-based resin, polyvinylpyrrolidone-based resin, polyvinylacetate-based resin, polyvinylacetamide-based resin, and polyacrylamide-based resin. The antifogging laminate according to claim 1 or 2, which comprises. The water-absorbent resin has a structural unit derived from a vinyl monomer having an acrylamide structure and a hydrocarbon group having 2 or more and 20 or less carbon atoms, a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and salts thereof. The antifogging laminate according to any one of claims 1 to 3, which is a copolymer having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group consisting of. body. The anti-fog according to claim 4, wherein the structural unit derived from a vinyl monomer having an acrylamide structure and a hydrocarbon group having 2 or more and 20 or less carbon atoms is a structural unit represented by the following general formula (1). Sex laminate.

In the general formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a methyl group, an alkyl group having 2 or more carbon atoms, or a substituent represented by the following general formula (2). ..

In the general formula (2), L represents an alkylene group having 1 to 6 carbon ^{atoms, and R 21} represents a hydrogen atom, a methyl group, an unsubstituted alkyl group having 2 or more carbon atoms, or an aromatic substituted alkyl group. n represents the average number of moles added of the polyether, and n is 1 to 4. The water-absorbent resin is a copolymer having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group consisting of an N-methylol group, an N-alkoxymethylol group and a hydroxyl group. The antifogging laminate according to any one of items 1 to 5. The anti-fog laminate according to any one of claims 1 to 6, further comprising a support layer under the water absorption layer. The anti-fog laminate according to any one of claims 1 to 7, further comprising an adhesive layer under the water absorption layer or the support layer. A composition for forming an anti-fog laminate according to any one of claims 1 to 5.
A composition for forming a water-absorbent layer containing at least a water-absorbent resin,
A composition for forming an anti-fog laminate, comprising a composition for forming a particle layer containing at least silica particles and a water-absorbent resin. The composition for forming an anti-fog laminate according to claim 9, wherein the water-absorbent resin contained in the composition for forming a particle layer is the same as the water-absorbent resin contained in the composition for forming a water-absorbent layer. The composition for forming an anti-fog laminate according to claim 9 or 10, wherein the composition for forming a particle layer contains a binder for silica particles. The composition for forming an anti-fog laminate according to any one of claims 9 to 11, wherein the composition for forming a water-absorbent layer and / or the composition for forming a particle layer contains a cross-linking agent for a water-absorbent resin. .. The composition for forming an anti-fog laminate according to any one of claims 9 to 12, wherein the composition for forming a water-absorbent layer and / or the composition for forming a particle layer contains a curing catalyst of a water-absorbent resin. .. The water-absorbent resin contained in the water-absorbent layer forming composition and / or the particle layer-forming composition is a cellulose-based resin, a polyvinyl alcohol-based resin, a polyvinyl acetal-based resin, a polyvinylpyrrolidone-based resin, a polyvinyl acetate-based resin, and the like. The composition for forming an antifogging laminate according to any one of claims 9 to 13, which contains at least one precursor selected from the group consisting of a polyvinyl acetamide-based resin and a polyacrylamide-based resin. The water-absorbent resin contained in the water-absorbent layer forming composition and / or the particle layer forming composition is a vinyl monomer having an acrylamide structure and having a hydrocarbon group having 2 or more and 20 or less carbon atoms, and a sulfonic acid group. 9 to 14 of claims, which are copolymers having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group consisting of a carboxylic acid group and a phosphoric acid group, and salts thereof. The composition for forming an antifogging laminate according to any one of the above items. The composition for forming an anti-fog laminate according to any one of claims 9 to 15, wherein the water-absorbent resin has a structural unit represented by the following general formula (1).

In the general formula (1), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a methyl group, an alkyl group having 2 or more carbon atoms, or a substituent represented by the following general formula (2). ..

In the general formula (2), L represents an alkylene group having 1 to 6 carbon ^{atoms, and R 21} represents a hydrogen atom, a methyl group, an unsubstituted alkyl group having 2 or more carbon atoms, or an aromatic substituted alkyl group. n represents the average number of moles added of the polyether, and n is 1 to 4. The water-absorbent resin is a copolymer having a structural unit derived from a vinyl-based monomer having at least one functional group selected from the group consisting of an N-methylol group, an N-alkoxymethylol group and a hydroxyl group. The composition for forming an antifogging laminate according to any one of Items 9 to 16.

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