JP6702814B2 - Antifogging layer forming composition, laminate, and method for producing laminate - Google Patents

Description

The present disclosure relates to a composition for forming an antifogging layer, a laminate, and a method for producing a laminate.

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

For this reason, various measures have been taken to protect the surfaces of devices, building materials, etc., to further improve the durability of the devices, etc. Examples of the protective means include disposing a protective member such as a cover or a protective sheet on the surface of the device or the like, and coating the surface of the device or the like with a protective film.
Even if the surface has protective means such as a protective film, due to factors such as dust, dust or mud stains gradually accumulating on the surface over a long period of time or getting wet with rainwater during wind and rain. The desired function or performance of the protection means may not be exhibited.

Protective means for protecting the surface of surveillance camera protective covers, headlight protective covers, reflecting mirrors, traffic signs, etc. are usually used for a long time once the member or device to be protected is installed. Is. Therefore, the protection means is required to have a light-transmitting property, a protection performance for a member, a device, etc., which is necessary for a long period of time, and a self-cleaning property which does not require cleaning. Also, if water drops adhere to the protective cover, the surface will be fogged and the light transmission will be reduced, so it is especially necessary to protect the surface of the protective cover of the surveillance camera, the protective cover of the headlight, the reflection mirror, the traffic sign, etc. In addition to antifouling property, maintenance of antifogging property is important.
Usually, by making the surface of the protective member hydrophilic, it is possible to suppress the deterioration of the light transmission due to the cloudiness of the surface and to make it difficult for water-based stains to adhere.

As a means for forming a hydrophilic film on the surface of a member, for example, metal oxide particles, a vinyl monomer having an N-methylol group or an N-alkoxymethylol group, a hydrophilic group (sulfonic acid, carboxylic acid, phosphoric acid Has been proposed, and an antifog composition containing the hydrophilic copolymer containing a (meth)acrylate monomer and an antifog layer using the same have been proposed (see, for example, Patent Document 1). ).

Further, silica fine particles, a water-soluble polymer obtained by hydrolyzing and condensing a silane compound in a water solvent, an antistatic agent, an aqueous antifouling coating agent containing water and a hydrophilic film using the same, An antifogging film has been proposed (for example, see Patent Document 2).

JP-A-09-194828 JP, 2005-025030, A

In the water-absorption type antifogging layer formed using the antifogging agent composition containing the hydrophilic copolymer described in Patent Document 1, an attempt is made to improve hydrophilicity by treating the metal oxide particles with a silane coupling agent. However, since the antifogging layer itself swells and dissolves due to water absorption, traces of water dripping may remain at the dissolved location, which may deteriorate the uniformity and appearance of the antifogging layer. There was a problem in the durability and durability of the antifogging function.
The water-based antifouling coating agent described in Patent Document 2 can exhibit antifogging property due to the surface hydrophilicity of the silica particles, and the obtained antifogging layer is less likely to be eluted by water, resulting in water dripping. Even in the case, traces of water dripping were less likely to remain, and the durability of the antifogging layer was better.
However, in recent years, when a light emitting diode (hereinafter, also referred to as an LED) is used as a light source of a headlight instead of a conventional lamp, heat is not generated, so that dew condensation occurs more on the headlight cover. Especially, in a cold region, the amount of condensed water adsorbed may increase due to the headlight cover itself being cooled. Therefore, it has been desired to form an antifogging layer in which the amount of water absorption is further increased and the trace of water dripping is less likely to remain than before.

An object of one embodiment of the present invention is to provide a laminate having an anti-fogging layer which has good anti-fogging property and durability of anti-fogging effect, and hardly leaves traces of water dripping even after absorbing water.
An object of another embodiment of the present invention is to provide a laminate as described above, which has a low incidence of defective products and can be produced with high productivity, and a laminate using the same. It is to provide a method.

Specific means for solving the problems include the following aspects.
<1> At least one cross-link selected from the group consisting of silica particles having an average primary particle size of 2 nm or more and 100 nm or less, N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group. A structural unit derived from a vinyl-based monomer having a functional group, a structural unit derived from a vinyl-based monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and an alkyl (meth)acrylate-based monomer A composition for forming an antifogging layer, which comprises a copolymer containing at least a structural unit derived from the copolymer, and a hydrolyzate of a compound represented by the following general formula (1).

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

<2> The copolymer is derived from a vinyl monomer having at least one crosslinking functional group selected from the group consisting of N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group. Structural unit, a hydrophilic polymer portion containing a structural unit derived from a hydrophilic vinyl monomer, and, a sulfonic acid group, a structural unit derived from a vinyl monomer having a carboxyl group or a phosphoric acid group, The composition for forming an antifogging layer according to <1>, which is a copolymer composed of a hydrophobic polymer part containing a structural unit derived from alkyl (meth)acrylate.
<3> Base material, silica particles having an average primary particle diameter of 2 nm or more and 100 nm or less, N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group provided on the base material A structural unit derived from a vinyl monomer having at least one cross-linking functional group selected from the group consisting of, and a structural unit derived from a vinyl-based monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, A copolymer containing at least a structural unit derived from an alkyl (meth)acrylate-based monomer, and an antifogging layer containing a hydrolyzed condensate of a compound represented by the following general formula (1). Laminate.

In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 20.
<4> The laminate according to <3>, wherein the antifogging layer has a thickness of 1 μm or more and 10 μm or less.
<5> The laminate according to <3> or <4>, wherein the surface of the antifogging layer has an average surface roughness Ra of 10 nm or more and 100 nm or less.

<6> Any one of <3> to <5> in which the ratio of the area occupied by the silica particles to the total area of the antifogging layer is 60% or more when the surface of the antifogging layer is viewed in a plan view. The laminate according to item 1.

<7> Any one of <3> to <6>, in which the ratio of the area occupied by the silica particles to the total area of the antifogging layer is 80% or more when the surface of the antifogging layer is viewed in a plan view. The laminate according to item 1.
<8> The content of silica particles with respect to the total mass of the antifogging layer is 50% by mass or more and 99% by mass or less, and the content of the copolymer with respect to the total mass of the antifogging layer is 0.5% by mass or more and 49.5% or more. % Or less, and the content of the hydrolysis-condensation product of the compound represented by the general formula (1) is 0.5% by mass or more and 49.5% by mass or less based on the total mass of the antifogging layer <3> to The laminated body according to any one of <7>.

<9> The anti-fog layer is an anti-fog layer having a multilayer structure of two or more layers having at least a first anti-fog layer and a second anti-fog layer, and the first anti-fog layer has the general formula (1 ) The total content of the hydrolyzed condensate of the compound represented by the formula (1) and the silica particles is 50% by mass or more based on the total amount of the first antifogging layer, and the second antifogging layer is a copolymer. The laminate according to any one of <3> to <8>, in which the content of is 50% by mass or more based on the total amount of the second antifogging layer.

<10> A method for producing a laminate, which comprises a step of forming the antifogging layer by applying the composition for forming an antifogging layer according to <1> or <2> on a substrate.

<11> The method for producing a laminate according to <10>, wherein the step of forming the antifogging layer includes a step of spray-coating the composition for forming an antifogging layer on a substrate.
<12> The step of forming the anti-fogging layer is a step of forming an anti-fogging layer having a multi-layered structure of two or more layers having at least a first anti-fogging layer and a second anti-fogging layer, and is on the substrate. A silica gel, a copolymer, and a hydrolyzate of the compound represented by the general formula (1), wherein the content of the copolymer is 50% by mass or more with respect to the total amount of the composition. A step of applying a composition for forming a cloudy layer to form a second antifogging layer, and forming silica particles, a copolymer, and the general formula (1) on the formed second antifogging layer. A first hydrolyzate of the compound represented, wherein the total content of the hydrolyzate of the compound represented by the general formula (1) and the silica particles is 50% by mass or more based on the total amount of the composition. The method for producing a laminate according to <10> or <11>, including the step of applying a composition for forming an antifogging layer to form a first antifogging layer.

According to one embodiment of the present invention, there is provided a laminate having an anti-fogging layer which has good anti-fogging property and durability of the anti-fogging effect, and is hard to leave traces of water dripping even when the anti-fogging layer absorbs water. It
According to another embodiment of the present invention, the laminate described above, the composition for forming an anti-fog layer which has a low defective product rate and can be produced with high productivity, and a laminate using the same. A method is provided.

Hereinafter, the composition for forming an antifogging layer, the laminate and the method for producing the laminate of the present embodiment will be described in detail.
In the present specification, the numerical range indicated by using "to" means a range including the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the present specification, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, a plurality of components present in the composition unless otherwise specified. Means the total amount of.
In the numerical ranges described stepwise in the present specification, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. Good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
The term "solid content" in the present specification means a component excluding the solvent, and liquid components such as low molecular weight components other than the solvent are also included in the "solid content" in the present specification.
In the present specification, the “solvent” means water, an organic solvent, and a mixed solvent of water and an organic solvent.
Further, in the present specification, both or either of acrylic and methacrylic may be referred to as “(meth)acrylic”.
In the present specification, the term “process” is included in this term as long as the intended purpose of the process is achieved, not only when it is an independent process but also when it cannot be clearly distinguished from other processes. Be done.

<Composition for forming antifogging layer>
The composition for forming an antifogging layer of the present embodiment comprises silica particles having an average primary particle diameter of 2 nm or more and 100 nm or less, N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group. A structural unit derived from a vinyl-based monomer having at least one cross-linking functional group selected from the group consisting of, and a structural unit derived from a vinyl-based monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, A copolymer containing at least a structural unit derived from an alkyl (meth)acrylate-based monomer and a hydrolyzate of a compound represented by the following general formula (1) are included.

In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 20.
The composition for forming an antifogging layer of the present embodiment is preferably used for forming an antifogging layer of a laminate, which will be described in detail below.

In the following description, "silica particles having an average primary particle size of 2 nm or more and 100 nm or less" are referred to as "specific silica particles" and "N-methylol group, N-alkoxymethylol group, N-methylol". A vinyl-based monomer having a structural unit derived from a vinyl-based monomer having at least one crosslinking functional group selected from the group consisting of an ether group and a hydroxyl group and a sulfonic acid group, a carboxyl group or a phosphoric acid group. A "copolymer containing at least a structural unit derived from a structural unit derived from an alkyl (meth)acrylate-based monomer" is a "specific copolymer" and a "compound represented by the general formula (1)" "Specific siloxane compound", "specific siloxane compound hydrolyzate", "specific siloxane hydrolyzate", "condensation product of specific siloxane compound", "specific siloxane hydrolysis condensate" ," respectively.

The composition for forming an antifogging layer of the present embodiment contains a hydrolyzate of the specific siloxane compound described above.
At least part of the specific siloxane compound is hydrolyzed when it coexists with water. Therefore, the composition for forming an antifogging layer according to the present embodiment contains a hydrolyzate of a specific siloxane compound.
In the hydrolyzate of the specific siloxane compound, at least a part of OR ¹ , OR ² , OR ³ , and OR ⁴ bonded to the silicon atom of the specific siloxane compound becomes a hydroxy group by the reaction of the specific siloxane compound and water. It is presumed that the anti-fogging layer formed by, for example, coating and drying, which is a substituted compound and has a hydrophilic hydroxy group, has good surface hydrophilicity.

The specific copolymer has a structure derived from a vinyl monomer having at least one crosslinking functional group selected from the group consisting of N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group. Unit, a structural unit derived from a hydrophilic vinyl monomer, and a hydrophilic polymer part containing, and, a sulfonic acid group, a structural unit derived from a vinyl monomer having a carboxyl group or a phosphoric acid group, an alkyl It is preferably a copolymer composed of a hydrophobic polymer part containing a structural unit derived from (meth)acrylate.
Here, as the structural unit derived from an alkyl(meth)acrylate, for example, a structural unit derived from an alkyl(meth)acrylate having a lower alkyl group having 1 to 4 carbon atoms can be mentioned.

Details of each component contained in the composition for forming an antifogging layer and a method for producing a laminate using the composition for forming an antifogging layer will be described later, and therefore description thereof is omitted here.

<Laminate>
The laminated body of the present embodiment is provided with a base material and silica particles having an average primary particle diameter of 2 nm or more and 100 nm or less, a N-methylol group, an N-alkoxymethylol group, and an N-methylol. A vinyl-based monomer having a structural unit derived from a vinyl-based monomer having at least one crosslinking functional group selected from the group consisting of an ether group and a hydroxyl group and a sulfonic acid group, a carboxyl group or a phosphoric acid group. Anti-fog containing a copolymer containing at least a structural unit derived from an alkyl (meth)acrylate-based monomer and a hydrolyzed condensate of a compound represented by the following general formula (1). And a layer.

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

〔Base material〕
The base material used for the laminate of the present embodiment is not particularly limited. For example, a base material containing at least one selected from various materials such as glass, resin materials (plastic materials), metals, and ceramics can be appropriately selected and used according to the purpose of use of the laminate.

Glass is widely used as a base material and is suitable as a base material for forming the laminate of the present invention. When glass is used as the base material, condensation of hydroxy groups on silicon in the specific siloxane compound also occurs with the hydroxy groups on the glass surface, thereby forming an antifogging layer having excellent adhesion to the base material. ..
A resin material is also suitable as the base material, and for example, a resin material is often used for the base material such as the protective cover of the surveillance camera and the protective cover of the headlight. Among the resin materials, polycarbonate and polymethylmethacrylate are preferable because of their excellent durability against light and heat.
The substrate may be a composite material. The base material that is a composite material includes, for example, a composite material that includes glass and a resin material, and is a composite material in which glass and a resin material are mixed, or a resin composite material in which a plurality of types of resin materials are kneaded or bonded. Any of

The thickness, shape, and size of the base material are not particularly limited and may be appropriately selected depending on the application of the laminate, the purpose of use, and the like.
The thickness of the base material can be, for example, 0.05 mm to 10 mm.
The antifogging layer is not particularly limited as long as it is provided on the substrate. When the substrate has a plate-like shape and has two surfaces, it may be provided on at least one of the two surfaces. For example, the protective cover for the surveillance camera described above can be provided at least on the outer side, that is, on the surface that is in contact with the outside air. Further, in the case of a headlight cover, it can be provided at least on the inner side, that is, on the surface having the light source.

[Anti-fog layer]
The antifogging layer in the laminate of the present embodiment contains specific silica particles, a specific copolymer, and a specific siloxane hydrolyzed condensate.

Although the mechanism of action of the antifogging layer in the laminate of the present embodiment is not clear, it is estimated as follows.
Since the antifogging layer in the present embodiment has the above-described structure, the uneven structure is formed on the surface of the antifogging layer due to the shape of the specific silica particles, so that the antistatic effect of the antifogging layer surface is further improved, Since the function of preventing the adhesion of dirt such as dust is improved, it is possible to suppress the adhesion of fine dust in the manufacturing environment during the formation of the anti-fog layer during the production of the laminated body, and the incidence of defective products due to the adhesion of dust can be reduced. It is possible to manufacture with extremely low productivity and good productivity.
The specific copolymer in the present embodiment includes a hydrophilic polymer portion and a hydrophobic polymer portion, as described in detail below.
Specific silica particles having excellent surface hydrophilicity, a specific copolymer containing a hydrophilic polymer part and a hydrophobic polymer part, and a function of a hydrolysis-condensation product of a specific siloxane compound are combined to form an antifogging layer. The water absorption amount of is further improved, and water dripping is less likely to occur. Furthermore, since fine voids are formed between the specific silica particles in the antifogging layer and the voids between the specific silica particles have an effect of retaining water when wet, the hydrophilic cohesion as described in Patent Document 1 The moisture retention effect is remarkably enhanced as compared with the antifogging layer formed using the antifogging composition containing a polymer.
Further, the antifogging layer, the crosslinked structure in the specific copolymer, and the strong film property in the hydrolysis-condensation product of the specific siloxane compound, the retention of the specific silica particles is good, even when absorbing water, It is presumed that peeling due to water swelling is suppressed, and even if dripping occurs, traces of dripping are less likely to remain.
In the present specification, the property that the traces of water drooping are unlikely to remain even if water drooling occurs may be referred to as good water droop resistance.

Hereinafter, each component that may be contained in the antifogging layer in the present embodiment will be described.

<Specific silica particles>
The antifogging layer of the present embodiment contains at least one kind of specific silica particles.
The specific silica particles have a function of enhancing scratch resistance of the antifogging layer and exhibiting hydrophilicity. That is, the specific silica particles play a role as a hard filler, and the hydroxy groups on the particle surface act to contribute to the improvement of hydrophilicity of the antifogging layer.

The specific silica particles in the present embodiment have an average particle size of primary particles (hereinafter, may be referred to as an average primary particle size) of 2 nm or more and 100 nm or less.
When the average primary particle diameter of the specific silica particles is 100 nm or less, the film property of the antifogging layer becomes good, and it becomes easy to form preferable voids between the specific silica particles in the antifogging layer.
The average primary particle diameter of the specific silica particles is preferably 90 nm or less, more preferably 80 nm or less, and further preferably 50 nm or less.
The lower limit of the average primary particle diameter of the specific silica particles is 2 nm from the same viewpoint as above. The average primary particle size of the specific silica particles is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more.

The average primary particle size of the specific silica particles, when the shape of the silica particles is spherical or elliptical in cross section, the dispersed silica particles are observed by 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 determined from the projected area, and the obtained equivalent circle diameter is defined as the average primary particle diameter of the specific silica particles. When the shape of the specific silica particles is not spherical or elliptical, another method such as the dynamic light scattering method is used to determine the average primary particle diameter of the specific silica particles.

Specific silica particles include, for example, fumed silica, colloidal silica and the like, and particles having an average primary particle diameter within the above-specified range.
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 (eg, 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 alkoxy silicon (eg, tetraethoxysilane), halogenated silane compound (eg, diphenyldichlorosilane), and the like.

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, or a shape in which two or more kinds of these are combined. In addition, the term “spherical shape” here includes not only a true spherical shape but also a shape such as a spheroid and an oval shape.

Silica particles are also available as commercial products. Examples of commercially available silica particles include AEROSIL (registered trademark) series manufactured by Evonik Japan, Snowtex (registered trademark) series manufactured by Nissan Chemical Industries (for example, Snowtex O), and Nalco (Nalco) manufactured by Nalco Chemical. (Registered trademark) series (eg Nalco8699 etc.), Fuso chemist's Quartlon PL series [eg PL-1], and the like. These are commercially available products, and particles having the above-mentioned average primary particle diameter range are appropriately selected. Can be used.

The antifogging layer in the present embodiment may include only one type of specific silica particles or may include two or more types of specific silica particles. When two or more specific silica particles are contained, particles having at least one of size and shape different from each other may be contained as long as they are within the range of the average primary particle diameter.

The content of the specific silica particles in the antifogging layer is preferably 30% by mass to 99.5% by mass, more preferably 40% by mass to 99% by mass, and 50% by mass with respect to the total solid content of the antifogging layer. ˜99% by mass is more preferred. When the content of the specific silica particles is within the above range, the hydrophilicity of the antifogging layer becomes good, the hardness and the scratch resistance are excellent, and the moisture can be retained between the specific silica particles in the antifogging layer. It becomes easier to form suitable voids.

[Specific copolymer]
The specific copolymer contained in the antifogging layer in the present embodiment has at least one cross-linking functional group selected from the group consisting of N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group. A structural unit (A) derived from a vinyl-based monomer, a structural unit (C) derived from a vinyl-based monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group), and an alkyl (meth)acrylate-based monomer It is a copolymer containing at least the structural unit (D) derived from a monomer.
N- methylol group, N- alkoxymethylolmelamine group, at least one functional group selected from the group consisting of N- methylol ether groups and hydroxyl groups is a functional group having a crosslinking (i.e., cross-linking officer functional group), When the specific copolymer contains the structural unit derived from the vinyl monomer having these functional groups, the film property of the antifogging layer becomes better.
The content of the structural unit (A) in the specific copolymer is preferably 3 to 20 parts by mass, more preferably 5 parts by mass in the total 100 parts by mass of the structural units (A), (C) and (D). ˜16 parts by mass.
The content of the structural unit (C) in the specific copolymer is preferably 3 to 20 parts by mass, more preferably 4 parts by mass in the total 100 parts by mass of the structural units (A), (C) and (D). ˜16 parts by mass.
The content of the structural unit (D) in the specific copolymer is preferably 60 to 94 parts by mass, more preferably 70 parts by mass in the total 100 parts by mass of the structural units (A), (C) and (D). ˜91 parts by mass.

The specific copolymer is preferably a polymer having a hydrophilic portion and a hydrophobic portion, and more preferably, N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group. A hydrophilic polymer part containing a structural unit derived from a vinyl monomer having at least one cross-linking functional group selected from the group consisting of groups, and a structural unit derived from a hydrophilic vinyl monomer, and a sulfone. A copolymer comprising a hydrophobic polymer part containing a structural unit derived from a vinyl monomer having an acid group, a carboxyl group or a phosphoric acid group, and a structural unit derived from an alkyl (meth)acrylate. ..

First, the hydrophilic polymer part will be described. The hydrophilic polymer part is a vinyl monomer having at least one cross-linking functional group selected from the group consisting of N-methylol group, N-alkoxymethylol group, N-methyl ether group and hydroxyl group. (A) and the structural unit (B) derived from the hydrophilic vinyl monomer, and (A) and (B) are copolymer portions having a block structure.

Examples of the vinyl monomer having an N-methylol group, an N-alkoxymethylol group and an N-methylol ether group include N-methylol (meth)acrylamide, N-methoxymethylol (meth)acrylamide, N- Examples thereof include ethoxymethyl (meth)acrylamide, N-butoxymethylol (meth)acrylamide, and N-methylol (meth)acrylamide is particularly preferably used because of its high crosslinking 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-hydroxy. Praxel FA-1, Praxel FM-1, Praxel FM-4 [above, manufactured by Daicel Chemical Industries, Ltd., trade name] etc. in which 1 to 4 mol of ε-caprolactone is added to 1 mol of ethyl (meth)acrylate In particular, 2-hydroxyethyl (meth)acrylate is preferably used because of its high crosslinking reactivity.

Examples of the hydrophilic vinyl monomer include (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, 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)acryloylpiperidine, N-(meth)acryloylmorpholine, methoxyethylene glycol (meth)acrylate (where the number of ethylene oxide is preferably an integer of 1 to 10), methoxypropyleneglycol- (Meth)acrylic acid (wherein 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 them is used. used. In particular, from the viewpoint of copolymerization reactivity and solubility of the resulting 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 specific copolymer preferably has a structural unit represented by the following general formula (2).

In the general formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following general formula (3). Represents a substituent represented.

In the general formula (3), L represents an alkylene group having 1 to 6 carbon atoms, R ³¹ represents a hydrogen atom, a methyl group, an unsubstituted alkyl group having 4 to 20 carbon atoms, or an aromatic substituent having 6 carbon atoms. Represents an alkyl group of 20. n represents the average number of moles of added polyether, and is 1 or more and 4 or less.

R ²¹ is a hydrogen atom or a methyl group.
Examples of the alkyl group having 1 to 6 carbon atoms in R ²² and R ²³ include a methyl group, an ethyl group, a propyl group and an isopropyl group. The alkyl groups in R ²² and R ²³ may be the same or different from each other.

Examples of the unsubstituted alkyl group having 4 to 20 carbon atoms in R ³¹ 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. Groups are preferred.
The alkyl group having 6 to 20 carbon atoms having an aromatic substituent in R ³¹ is preferably an alkyl group having a phenyl group, a naphthyl group, a benzyl group or the like as an aromatic substituent, and the alkyl group is a methyl group or ethyl. Groups and the like. 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.
Examples of the alkylene group represented by L in the general formula (3) include a methylene group, an ethylene group, a propylene group and the like, and an ethylene group is preferable from the viewpoint that hydrophilicity in antifogging property, antifogging property and the like are more improved. , N is preferably 2 or more and 4 or less.

The hydrophilic polymer part may further contain a structural unit derived from an alkyl(meth)acrylate.
When the specific copolymer contains an alkyl (meth)acrylate, the film strength under high temperature environment, the adhesion to the substrate and the heat resistance are further improved.
Examples of the alkyl(meth)acrylate include alkyl(meth)acrylates having a lower alkyl group having 1 to 4 carbon atoms. 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 (Meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, tert-butyl (meth)acrylate and the like can be mentioned. Among them, a structural unit derived from methyl methacrylate is used. It is preferable to include it from the viewpoint of improving the film property.

The structure of the hydrophilic polymer portion in the specific copolymer, the structural unit derived from a vinyl monomer having a cross-linking officers functional group is, relative to the total structural units contained in the hydrophilic polymer portion, 1% by weight It is preferable that the structural unit derived from the hydrophilic vinyl monomer is in the range of 70% by mass to 99% by mass.
Structural units derived from a vinyl monomer having a cross-linking officers functional group is at least 1 wt%, by structural units derived from a hydrophilic vinyl monomer is not more than 99 wt%, cross-linking of the anti-fog layer The density is high, the permeability of water to the formed anti-fogging layer is suppressed, and the film strength is improved. It structural units derived from a vinyl monomer containing a cross-linking officers functional group is not more than 30 wt%, and that structural units derived from a hydrophilic vinyl monomer is 70 mass% or more, proof The crosslink density in the cloudy layer does not become too high, and good antifog property and good adhesion to the substrate are obtained.
Antifogging property, adhesiveness, in terms of balance, such as film strength, Oite hydrophilic polymer portion of the specific copolymer, N - methylol group, N- alkoxymethylolmelamine group, N- methylol ether group and a hydroxyl group at least one structural unit derived from a vinyl monomer having a crosslinking functional group selected from the group consisting of is 5% to 20% by weight relative to the total structural units contained in the hydrophilic polymer portion, a hydrophilic The structural unit derived from the vinyl monomer is particularly preferably in the range of 80% by mass to 95% by mass based on the total structural units contained in the hydrophilic polymer part.

Next, the hydrophobic polymer part will be described.
The hydrophobic polymer part has a structural unit (C) derived from a vinyl monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and a structural unit (D) derived from an alkyl (meth)acrylate. (C) and (D) are copolymer portions having a block structure. The structural unit derived from the 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 part described above.

Examples of the vinyl monomer having a sulfonic acid group include 2-sulfoethyl (meth)acrylate, 3-sulfopropyl (meth)acrylate, and 2-acrylamido-2-methylpropanesulfonic acid.
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 salts of sulfonic acid groups, carboxylic acid groups and phosphoric acid groups include alkali metal salts, alkaline earth metal salts, magnesium salts, aluminum salts and the like.

As the hydrophobic polymer part in the specific copolymer, a structural unit derived from an alkyl (meth)acrylate is contained in an amount of 70% by mass to 99% by mass based on all structural units contained in the hydrophobic polymer part, and a sulfonic acid group. A structural unit derived from a vinyl monomer having at least one functional group selected from the group consisting of a carboxyl group, a phosphoric acid group, or a salt thereof, with respect to all structural units contained in the hydrophobic polymer part. % To 30% by mass is preferable.
The content of the structural unit derived from alkyl (meth)acrylate is 70% by mass or more based on the total structural units contained in the hydrophobic polymer part, or from a sulfonic acid group, a carboxyl group, a phosphoric acid group, and salts thereof. When the content of the structural unit derived from the vinyl monomer having at least one functional group selected from the group is 30% by mass or less based on the total structural units contained in the hydrophobic polymer part, the antifogging layer And the adhesiveness to the base material become better. Further, the content of the structural unit derived from an alkyl (meth)acrylate is 99% by mass or less based on all structural units contained in the hydrophobic polymer portion, or a sulfonic acid group, a carboxyl group or a phosphoric acid group, Alternatively, the content of structural units derived from a vinyl monomer having at least one functional group selected from the group consisting of these salts is 1% by mass or more based on all structural units contained in the hydrophobic polymer portion. As a result, the transparency of the antifogging layer becomes better. Furthermore, from the viewpoint that the adhesion between the antifogging layer and the substrate, the balance of transparency, etc. are better, all structural units derived from the alkyl (meth)acrylate are contained in the hydrophobic polymer part. To 80% by mass to 95% by mass, and a structural unit derived from a vinyl monomer having at least one functional group selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphoric acid group, and salts thereof. It is more preferable to contain 5 to 20 mass% with respect to all structural units contained in the hydrophobic polymer part.

The specific copolymer has a hydrophilic polymer portion and a hydrophobic polymer portion, and the hydrophilic polymer portion contains a structural unit having a cross-linking functional group , whereby the anti-fogging property of the anti-fogging layer formed. Is further improved, and by further heat-curing the antifogging layer, the durability of water resistance and antifogging property of the antifogging layer can be further enhanced. Further, since the hydrophilic polymer part contains a structural unit derived from an alkyl (meth)acrylate, the film strength of the antifogging layer in a high temperature environment can be further increased.

When the specific copolymer has a hydrophobic polymer portion, the adhesion between the anti-fogging layer and the substrate becomes better, and the hydrophobic polymer portion has a sulfonic acid group, a carboxyl group, a phosphoric acid group, and these By including a structural unit derived from a vinyl monomer having at least one functional group selected from the group consisting of salts, the transparency of the antifogging layer can be further enhanced.

The content ratio of the hydrophilic polymer part and the hydrophobic polymer part in the specific copolymer is 5% by mass to 95% by mass of the hydrophilic polymer part with respect to the total amount of the specific copolymer, and the hydrophobic polymer part is The combined portion is preferably 5% by mass to 95% by mass.
When the hydrophilic polymer portion is 5% by mass or more or the hydrophobic polymer portion is 95% by mass or less, the hydrophilicity of the antifogging layer becomes better, and the antifogging property and the durability of the antifogging property are more improved. improves.
Further, when the hydrophilic polymer portion is 95% by mass or less or the hydrophobic polymer portion is 5% by mass or more, the adhesion between the antifogging layer and the base material becomes better. From the balance of anti-fogging property, durability of anti-fogging property, adhesion to the base material of anti-fogging layer, etc., the hydrophilic polymer part and the hydrophobic polymer part are hydrophilic with respect to the total amount of the copolymer. It is more preferable that the polymer portion is in the range of 50% by mass to 95% by mass and the hydrophobic polymer portion is in the range of 5% by mass to 50% by mass.

The specific copolymer is preferably a copolymer having a hydrophilic polymer portion and a hydrophobic polymer portion as described above, but each of the hydrophilic polymer portion and the hydrophobic polymer portion is preferable. From the viewpoint of easily exhibiting the characteristics, a block copolymer or a graft copolymer of a hydrophilic polymer portion and a hydrophobic polymer portion is more preferable.
The specific copolymer that can be used in this embodiment can be synthesized, for example, by the method described in JP-A-9-194282.

The antifogging layer in the present embodiment may include only one type of the specific copolymer or may include two or more types thereof.
The content of the specific copolymer with respect to the total solid content of the antifogging layer is preferably 0.5% by mass or more and 49.5% by mass or less, more preferably 1% by mass or more and 45% by mass or less, It is more preferable that the content is 5% by mass or more and 40% by mass or less.

[Hydrolysis condensate of specific siloxane compound]
The antifogging layer in the present embodiment contains at least one hydrolyzed condensate of the following specific siloxane compound.
When the antifogging layer contains the hydrolysis-condensation product of the specific siloxane compound, the retention of the specific silica particles in the antifogging layer becomes good, and the scratch resistance and hydrophilicity of the antifogging layer become good.

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

The monovalent organic group having 1 to 6 carbon atoms in R ¹ , R ² , R ³ , and R ⁴ may be linear, branched, or 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, an n-2-propenyl group, 1,2-dimethyl-vinyl group, 1-methyl-propenyl group, 2-methyl-propenyl group, n-1-butenyl group, n-2-butenyl group, n-3-butenyl group and the like can be mentioned.
In the specific siloxane compound, the monovalent organic group in R ^{1 to} R ⁴ preferably has 1 to 6 carbon atoms in the alkyl group, whereby the specific siloxane compound has good hydrolyzability. From the viewpoint of better hydrolyzability, it is more preferable that R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 or 2 carbon atoms. Is more preferable.

N in General formula (1) represents the integer of 1-20. 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 composition for forming an antifogging layer does not become too high, and the handling property and uniform coating property become good. n is preferably 3 to 12, and more preferably 5 to 10.
In Table 1 below, examples of specific siloxane compounds are described by R ¹ , R ² , R ³ , and R ⁴ in the general formula (1) and n. However, the specific siloxane compound in the present embodiment is not limited to the exemplified compounds shown in Table 1.

The antifogging layer of the present embodiment contains the hydrolysis-condensation product of the specific siloxane compound described above.
At least part of the specific siloxane compound is hydrolyzed when it coexists with water. In the hydrolyzate of the specific siloxane compound, at least a part of OR ¹ , OR ² , OR ³ , and OR ⁴ bonded to the silicon atom of the specific siloxane compound becomes a hydroxy group by the reaction of the specific siloxane compound and water. It is presumed that the anti-fogging layer formed by, for example, coating and drying, which is a substituted compound and has a hydrophilic hydroxy group, has good surface hydrophilicity.
In the hydrolysis reaction, not necessarily the end groups of the particular siloxane compound ^{(i.e., -OR 1, -OR 2, -OR} 3, or -OR ⁴⁾ but is not necessary to react all, for example, the anti-fog layer coating solution From the viewpoint of improving the hydrophilicity of the coating film obtained by coating and drying, it is preferable that more end groups are hydrolyzed.

When forming the antifogging layer of the present embodiment, at least some of the hydroxy groups of the specific siloxane compound are bonded to each other, and the specific siloxane compound is condensed. Therefore, the antifogging layer contains at least one hydrolysis-condensation product of the specific siloxane compound.
The composition for forming an antifogging layer used for forming the antifogging layer may contain only one type of hydrolyzate of the specific siloxane compound, or may contain two or more types thereof.

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

In addition, in this specification, a weight average molecular weight is measured by gel permeation chromatography (GPC). Specifically, HLC-8120GPC and SC-8020 (manufactured by Tosoh Corporation) are used, TSKgel and SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID×15 cm) are used as a column, and tetrahydrofuran is used as an eluent. It can be measured using (THF). As conditions, a sample concentration of 0.5 mass%, a flow rate of 0.6 ml/min, a sample injection amount of 10 μl (microliter), a measurement temperature of 40° C., and a differential refractometer (RI) detector were used. Can be done. The calibration curve is "polystyrene standard sample TSK standard" manufactured by Tosoh Corporation: "A-500", "F-1", "F-10", "F-80", "F-380", "A-2500". , "F-4", "F-40", "F-128", and "F-700" can be used.

The antifogging layer of the present embodiment can further contain a condensate of a partial cohydrolyzate obtained by using two or more kinds of silane compounds. The two or more kinds of silane compounds may be two or more kinds of specific siloxane compounds having different structures from each other, or may be a combination of the specific siloxane compound and another siloxane compound having a structure different from that of the specific siloxane compound. The hydrolyzate obtained from two or more siloxane compounds may be referred to as "(co)hydrolyzate", and the compound obtained by condensing these may be referred to as "(co)hydrolyzate condensate".
In addition, the silane compound in the present specification refers to a compound having at least one selected from a hydrolyzable silyl group and a silanol group, the silyl group is hydrolyzed to a silanol group, and the silanol group is dehydrated and condensed to form a siloxane. A bond is created.

The antifogging layer of the present embodiment contains at least a part of the specific siloxane compound that is hydrolyzed and contains a hydrolyzed condensate, so that the surface has good hydrophilicity and practically no problem film strength is obtained. Be done.
The siloxane compound represented by the general formula (1) is also available as a commercial product, for example, MKC (registered trademark) silicate MS51 (Mitsubishi Chemical Co., Ltd.) [R ¹ , R ² , R ³ , and R ^4: methyl radical, n average: 5], silicate MS56 ^{[R 1,} R 2, ^{R 3,} and ^{R 4:} methyl, the average of n: 11], silicate MS57 ^{[R 1,} R 2, ^{R 3} , And R ⁴ : methyl group, n average: 13], silicate MS56S [R ¹ , R ² , R ³ and R ⁴ : methyl group, n average: 16], methyl silicate 53A [R ¹ , R ² , R ³ , and R ⁴ : methyl group, average of n: 7], ethyl silicate 40 [R ¹ , R ² , R ³ , and R ⁴ : ethyl group, average of n: 5], ethyl silicate 48 [R ¹ , R ² , R ³ , and R ⁴ : ethyl group, average of n: 10] and the like.

The content of the hydrolysis-condensation product of the specific siloxane compound in the antifogging layer is preferably 0.5% by mass to 49.5% by mass, and more preferably 1% by mass to 45% by mass, based on the total solid content of the antifogging layer. Preferably, 5% by mass to 40% by mass is more preferable. When the content of the hydrolyzed condensate of the specific siloxane compound is in the above range, the surface hydrophilicity of the antifogging layer becomes good and the antifogging layer excellent in antifogging property is obtained.

That is, in the antifogging layer in the present embodiment, the content of the specific silica particles in the antifogging layer is 50% by mass or more and 99% by mass or less, and the content of the specific copolymer in the antifogging layer is 0.5% by mass. It is preferably 70% by mass or more and the content of the hydrolyzed condensate of the specific siloxane compound is 0.5% by mass or more and 60% by mass or less.

The anti-fogging layer of the present embodiment may contain any additive other than the above components as long as the effects of the present embodiment are not impaired. The optional additives will be described in the manufacturing method.

(Film thickness)
The thickness of the antifogging layer is preferably 1 μm or more. When the film thickness is 1 μm or more, the antifogging layer is more excellent in scratch resistance. The upper limit of the film thickness of the antifogging layer is not particularly limited, but is preferably 10 μm or less from the viewpoint of transparency and water dripping resistance.
The film thickness of the antifogging layer is more preferably 2 μm or more and 8 μm or less, and further preferably 3.5 μm or more and 8 μm or less.
The film thickness of the anti-fog layer is determined by cutting the formed laminate with a microtome in a direction perpendicular to the base material surface of the laminate, that is, in the thickness direction of the laminate to obtain a cross section of the laminate and performing field emission scanning. The film thickness can be measured by observing the cut cross section with a scanning electron microscope (FE-SEM) at a magnification of 50,000 times.

(Structure of anti-fog layer)
The antifogging layer may have a single layer structure or a multilayer structure of two or more layers.
When the antifogging layer has a multi-layer structure, each antifogging layer of the multi-layer structure contains specific silica particles, a specific copolymer, and a hydrolyzed condensate of a specific siloxane compound.
The anti-fog layer is an anti-fog layer having a multi-layer structure of two or more layers having at least a first anti-fog layer and a second anti-fog layer, and the first anti-fog layer is a hydrolytic condensation of a specific siloxane compound. The total content of the product and the specific silica particles is 50% by mass or more with respect to the total amount of the first antifogging layer, and the second antifogging layer has a specific copolymer content of the second It is also one of the preferable embodiments that the antifogging layer has a multilayer structure in which the content of the antifogging layer is 50% by mass or more based on the total amount.
In the first anti-fogging layer, that is, in the outermost anti-fogging layer, the total amount of the hydrolysis-condensation product of the specific siloxane compound and the specific silica particles is 50% by mass or more based on the total amount of the first anti-fogging layer. By including it, surface hydrophilicity, water dripping resistance, and dust adhesion prevention are further improved. Further, the second antifogging layer located on the base material side of the laminate is a layer containing the specific copolymer in an amount of 50% by mass or more of the total amount of the second antifogging layer, whereby the antifogging layer and the base material. The adhesiveness with and is further improved, and the content of the hydrophilic copolymer in the first antifogging layer is lower, so that the water dripping resistance is also better.
The total content of the specific silica particles, the specific copolymer and the hydrolysis-condensation product of the specific siloxane compound contained in the first anti-fogging layer and the second anti-fogging layer is the same as in the above-mentioned single anti-fogging layer. It is similar to the preferred range.

The thickness of the first antifogging layer is preferably 0.02 μm or more and 3 μm or less, and more preferably 0.1 μm or more and 2.5 μm or less.
The film thickness of the second antifogging layer is preferably 0.1 μm or more and 7 μm or less, and more preferably 1 μm or more and 5 μm or less.
The total thickness of the first antifogging layer and the second antifogging layer is preferably 1 μm or more and 10 μm or less as described above.
The film thickness of the anti-fogging layer having a multilayer structure can be measured by the same method as described above.

<Physical properties of anti-fog layer>
Hereinafter, preferred aspects of the antifogging layer in the present embodiment will be described.

(Average surface roughness Ra)
The average surface roughness Ra of the surface of the antifogging layer is preferably 10 nm or more and 100 nm or less, more preferably 15 nm or more and 80 nm or less, and further preferably 20 nm or more and 50 nm or less.
Here, the surface of the antifogging layer refers to the outermost surface on the side opposite to the side having the base material. For example, when the antifogging layer has a multi-layer structure, it means the average surface roughness of the antifogging layer located on the outermost surface.
When the average surface roughness Ra of the surface of the antifogging layer is within the above-described range, hydrophilicity is exhibited, and dust adhesion due to static electricity is effectively suppressed.
Since the average primary particle diameter and content of the silica particles used for forming the antifogging layer are in the above-described ranges, the average surface roughness Ra of the antifogging layer in the present embodiment is easily adjusted to the above range.
The average surface roughness Ra of the antifogging layer can be measured as follows.
First, using an atomic force microscope (AFM), a cantilever with a probe diameter of 10 nm is used to measure the surface shape, and three-dimensional data is obtained. Here, cut the laminated body into a size of 1 cm square, set it on a horizontal sample stand on the piezo scanner, approach the sample surface with a cantilever, and scan in the XY directions when the area where atomic force acts is reached. At that time, the unevenness of the sample is detected by the displacement of the piezo in the Z direction, and at the time of measurement, 512×512 points are measured in a range of 5 μm×5 μm on the surface.
Using the three-dimensional data (f(x,y)) obtained above, the average roughness Ra can be obtained.

(Ratio of silica particle area on antifogging layer surface)
The ratio of the area of silica particles to the total area of the surface of the antifogging layer in the present embodiment in plan view is preferably 60% or more, and more preferably 80% or more in terms of area ratio.
When the ratio of the area of the specific silica particles on the surface of the antifogging layer is in the above range, the effect of suppressing the adhesion of dust during the production of the laminate is further improved, the productivity is improved, and the presence of the specific silica particles The water dripping resistance becomes better.

The ratio of the area of silica particles to the total area of the antifogging layer surface can be measured by the following method.
The outermost surface of the antifogging layer in the laminate is cut by a microtome in a direction parallel to the surface of the base material, and is cut to a region where there is no unevenness due to silica particles on the surface to produce a smooth surface. Then, the obtained surface is observed with FE-SEM at a magnification of 100,000.
By observing the surface in a plan view, a region where the specific silica particles are present and a region where only the so-called binder where the specific silica particles are not present can be distinguished, so the total area of the observation region is measured, and the specific silica particles are The area of the existing area is measured, and the ratio (area ratio) of the area of the specific silica particles to the total area of the observation area on the surface of the antifogging layer is calculated.
Since the specific silica particles are uniformly dispersed in the antifogging layer, the measured area ratio is close to the constituent ratio of the specific silica particles in the antifogging layer.

(Uses of laminate)
The laminated body of the present embodiment is a protective material (so-called protective cover) for protecting surveillance cameras, lighting, sensor lighting, etc., motorcycles such as automobiles and motorcycles, mirrors for vehicles such as bicycles, and transparent headlights. It is suitable for use as a protective material.
Among them, the present invention can be preferably applied to headlights of vehicles such as automobiles, motorcycles such as motorcycles and bicycles, which have a large temperature difference in use environment, and particularly headlights using an LED light source that does not generate heat.

<Method for manufacturing laminated body>
The method for producing a laminated body of the present embodiment includes silica particles having an average primary particle size of 2 nm or more and 100 nm or less, N-methylol groups, N-alkoxymethylol groups, N-methylol ether groups, and Structural unit derived from vinyl monomer having at least one cross-linking functional group selected from the group consisting of hydroxyl group, and structure derived from vinyl monomer having sulfonic acid group, carboxyl group or phosphoric acid group A copolymer (specific copolymer) containing at least a unit and a structural unit derived from an alkyl (meth)acrylate-based monomer, and a compound (specific siloxane compound) represented by the following general formula (1) The method includes the step of forming an antifogging layer by applying a composition for forming an antifogging layer containing a decomposed product.

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

(Anti-fog layer forming composition)
The composition for forming an antifogging layer used in the production method of the present embodiment is the composition for forming an antifogging layer of the present embodiment described above. The specific silica particles and the specific copolymer in the composition for forming an antifogging layer of the present embodiment are the same as those described in the description of the laminate.
The hydrolyzate of the specific siloxane compound is a reaction product of the specific siloxane compound described above and water.

Here, the composition for forming an antifogging layer contains specific silica particles, a specific copolymer, a specific siloxane compound and a solvent, and the solvent contains water necessary for the hydrolysis of the specific siloxane compound.

(water)
The composition for forming an antifogging layer contains water.
As described above, water contributes to the hydrolytic condensation reaction of the specific siloxane compound.
The water that can be used in the composition for forming an antifogging layer of the present embodiment is preferably ion-exchanged water, pure water, distilled water or the like from the viewpoint of less impurities.
The content of water is appropriately determined as needed. Water may be contained in an amount of, for example, 1% by mass to 20% by mass, preferably 5% by mass to 15% by mass, and preferably 6% by mass to the total amount of the solvent contained in the composition for forming an antifogging layer. It is more preferable to contain 12% by mass.

[Other ingredients]
The composition for forming an anti-fogging layer may contain, in addition to the specific silica particles, the specific copolymer, and the specific siloxane hydrolyzate, other known components as long as the effects of the present embodiment are not impaired. Examples of other components include solvents other than water, antistatic agents, surfactants, catalysts that accelerate the condensation reaction of the specific siloxane compound, and the like, but are not limited to the components described above.

(Solvents other than water)
The composition for forming an antifogging layer of the present embodiment can contain a solvent other than water as a solvent.
Examples of the solvent other than water include a ketone solvent, a glycol solvent, an alcohol solvent, a glycol ether solvent, an ether solvent, and the like.

-Ketone solvent-
The ketone solvent in the composition for forming an antifogging layer of the present embodiment contributes to the adhesiveness between the antifogging layer formed of the composition and the substrate.
The ketone solvent is not particularly limited, and examples thereof include acetone, diacetone alcohol, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone and the like.

The ketone-based solvent is preferably a ketone-based solvent having an SP value (solubility parameter) of 10.0 MPa ^1/2 or more from the viewpoint that a film having more excellent transparency can be formed. The upper limit of the SP value of the ketone-based solvent is not particularly limited and is, for example, 13.0 MPa ^1/2 or less from the viewpoint of coating properties on the base material, for example, surface failure such as cissing is less likely to occur. Preferably.

Specific examples of the ketone-based solvent having an SP value of 10.0 MPa ^1/2 or more are shown below. However, this embodiment is not limited to the following specific examples. Numerical values in parentheses after the following specific examples indicate SP values (unit: MPa ^1/2 ).
Acetone (10.0), diacetone alcohol (10.2), acetylacetone (10.3), cyclopentanone (10.4).

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

-Glycol solvent-
The composition for forming an antifogging layer of the present embodiment can contain a glycol solvent.
When the composition for forming an antifogging layer of the present embodiment contains a glycol solvent, coating suitability becomes better. Specifically, the composition for forming an antifogging layer of the present embodiment further contains a glycol solvent, whereby the viscosity of the composition is increased, and it is difficult for the composition for forming an antifogging layer to drip during coating. Become.

Examples of the grill coal type solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and the like.
Among these, as the glycol solvent, at least one selected from propylene glycol and dipropylene glycol is preferable from the viewpoint of improving the coatability on the base material, for example, improving the surface state such as leveling.

-Alcohol solvent-
Examples of alcohol solvents include methanol, ethanol, butanol, 2-methyl-1-butanol, n-propanol, 2-propanol, tert-butanol, 2-butanol, 1,3-butanediol, 1,4-butanediol, Examples thereof include benzyl alcohol and 2-methyl-2-butanol.

-Glycol ether solvent-
As the glycol ether solvent, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol monomethyl ether. Hexyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve and the like can be mentioned.

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

The solvent that may be contained in the composition for forming an antifogging layer of the present embodiment is not limited to the above exemplified solvents.
The composition for forming an antifogging layer may contain only one kind of solvent other than water, or may contain two kinds or more.
The content of the solvent other than water is preferably in the range of 5% by mass to 80% by mass, more preferably in the range of 10% by mass to 70% by mass, based on the total amount of the composition for forming an antifogging layer.

(Antistatic agent)
The composition for forming an antifogging layer of the present embodiment preferably contains at least one kind of antistatic agent.
By including the antistatic agent, the resulting anti-fogging layer is provided with antistatic properties, the effect of preventing contaminants from adhering is improved, and the antifouling properties are improved.

The antistatic agent can be appropriately selected from compounds having an antistatic function, and may be either a compound having surface activity or a compound having no surface activity. Examples of the antistatic agent include ionic surfactants and metal oxide particles. The above-mentioned silica particles are not included in the metal oxide particles as the antistatic agent.
The ionic surfactant as an antistatic agent has, for example, a property of easily segregating near the film surface of the coating film when the composition for forming an antifogging layer is applied to a substrate to form an antifogging layer. Yes, the effect can be expected with a small amount of addition.
Further, the metal oxide particles as the antistatic agent may need to be added in a relatively large amount in order to impart antistatic properties to the antifogging layer, but since it is an inorganic substance, it has scratch resistance of the antifogging layer. Suitable for increasing the

Examples of other ionic surfactants include alkylsulfates (eg, sodium dodecylsulfate, sodium laurylsulfate, etc.), alkylbenzenesulfonates (eg, sodium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, etc.), Anionic surfactants such as alkyl sulfosuccinates (eg sodium di(2-ethylhexyl)sulfosuccinate), alkyl phosphates (eg sodium dodecyl phosphate); alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, etc. Mention may be made of cationic surfactants; and amphoteric surfactants such as alkylcarboxybetaines.

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 antifogging layer forming composition. It is preferably 5% by mass, more preferably 1% by mass or less. When the content of the other ionic surfactant is within the above range, the antifogging property of the antifogging layer can be enhanced while suppressing the aggregation of silica particles. The content of the other ionic surfactant is preferably 0.05% by mass or more from the viewpoint of the effect of improving the antifouling property of the antifogging layer by including the ionic surfactant. ..

The metal oxide particles used as the antistatic agent are not particularly limited. Examples thereof include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, and zinc oxide particles.
As the metal oxide particles, two or more kinds of particles having different sizes, shapes or materials may be used. The particle shape of the metal oxide particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.
When the metal oxide particles have a large refractive index and a large particle diameter, loss due to excessive scattering of transmitted light is likely to occur. Therefore, the average primary particle diameter is preferably 100 nm or less, and 50 nm or less. It is more preferable that the thickness is 30 nm or less.
The average primary particle diameter of the metal oxide particles, when the particle shape is an ellipse such as a spherical shape or an elliptical cross section, the dispersed particles are observed with a transmission electron microscope, and 300 or more particles are obtained from the obtained photograph. It can be obtained by measuring the projected area of particles and determining the equivalent circle diameter from the projected area. When the shape of the metal oxide particles is not spherical, it can be determined by using another method, for example, the dynamic light scattering method.

When using metal oxide particles as the antistatic agent, the content of the metal oxide particles is preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the composition for forming an antifogging layer. It is preferably 5% by mass or less, and more preferably 5% by mass or less. When the content of the metal oxide particles is within the above range, the antistatic property can be effectively imparted without impairing the film forming property when the antifogging layer is formed by coating. The content of the metal oxide particles is preferably 1% by mass or more from the viewpoint of the effect of improving the antifouling property of the antifogging layer by including the metal oxide particles.

[Surfactant]
The composition for forming an anti-fogging layer in the present embodiment may further contain a surfactant.
By containing a surfactant in the antifogging layer, the ability to prevent adherence of contaminants is further improved.
It should be noted that the surfactant mentioned here does not include the compounds having an antistatic function mentioned above as the antistatic agent (for example, an ionic surfactant).

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

By containing a surfactant in the antifogging layer, not only the antifouling property of the antifogging layer can be enhanced, but also the coating property when the antifogging layer is formed by coating, for example, can be enhanced, and a coating liquid used for coating. The surface tension of is also reduced and the uniformity of the coating film is further enhanced.

Examples of the surfactant include nonionic surfactants and the like.
When an ionic surfactant is used as the above-mentioned antistatic agent, if the ionic surfactant is excessively added to the film as described above, the electrolytic mass in the system increases and the silica particles are aggregated. Since it is easily invited, it is preferable to use a nonionic surfactant together. However, the nonionic surfactant does not necessarily have to be used in combination with the ionic surfactant, and may contain the nonionic surfactant alone as the surfactant.

Examples of the nonionic surfactant include polyalkylene glycol monoalkyl ether, polyalkylene glycol monoalkyl ester, polyalkylene glycol monoalkyl ester/monoalkyl ether, and the like. 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 composition for forming an antifogging layer, the content thereof is preferably 0.5% by mass or more and 1.0% by mass or more based on the total solid content of the composition for forming an antifogging layer. Is more preferable.
The content of the surfactant is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and 30.0% by mass or less with respect to the total solid content of the composition for forming an antifogging layer. Is more preferable.

(Catalyst that accelerates condensation reaction of specific siloxane compound)
The composition for forming an antifogging layer in the present embodiment may contain at least one catalyst that accelerates the condensation reaction of the specific siloxane compound (condensation acceleration catalyst). The effect of the condensation promoting catalyst will be described later.

The condensation accelerating catalyst is not particularly limited, and examples thereof include acid catalysts, alkali catalysts, and organometallic catalysts.
Examples of the acid catalyst include nitric acid, hydrochloric acid, sulfuric acid, acetic acid, chloroacetic acid, formic acid, oxalic acid, toluenesulfonic acid and the like.
Examples of alkali catalysts include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like.
Examples of organometallic catalysts include aluminum bis(ethylacetoacetate) mono(acetylacetonate), aluminum tris(acetylacetonate), aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate; zirconium tetrakis(acetylacetonate). , Zirconium chelate compounds such as zirconium bis(butoxy)bis(acetylacetonate); titanium chelate compounds such as titanium tetrakis(acetylacetonate) and titanium bis(butoxy)bis(acetylacetonate); and dibutyltin diacetate, dibutyltin dilaurate. , An organic tin compound such as dibutyltin dioctiate; and the like.
Among these catalysts, nitric acid is preferable as the acid catalyst, sodium hydroxide is preferable as the alkali catalyst, and an aluminum chelate compound or a zirconium chelate compound is preferable as the organic metal catalyst. Among these catalysts, an organometallic catalyst is more preferable, and an aluminum chelate compound is particularly preferable.

The content of the condensation promoting catalyst in the total solid content of the composition for forming an antifogging layer is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 15% by mass, and 0.3% by mass. % To 10% by mass is more preferable. When the content of the condensation accelerating catalyst is within the above range, it is easy to form an antifogging layer having scratch resistance. Further, it is also excellent in the formability of the antifogging layer.

(Other additives)
The composition for forming an antifogging layer of the present embodiment may further contain other additives, if necessary, in addition to the components described above. As the other additive, for example, the specific siloxane hydrolyzate described above is used for the purpose of improving the film property of the antifogging layer formed by the composition for forming an antifogging layer, improving the adhesion to a substrate, and the like. Other examples include film-forming components other than adhesion promoters.

Examples of the adhesion aid include a film-forming component having no siloxane structure in the molecule, for example, a film-forming polymer compound, and more specifically, for example, polyurethane, acrylic resin, polyphosphate, and metaline. Examples thereof include compounds having a polar group (for example, a hydroxyl group, a carboxy group, a phosphoric acid group, a sulfonic acid group, an amino group, etc.) at the terminal such as an acid salt.
When the composition for forming an antifogging layer contains an adhesion aid, the adhesion between the antifogging layer obtained by the composition for forming an antifogging layer and a substrate, especially a polycarbonate substrate is further improved.
Among the adhesion aids, from the viewpoint that the adhesion between the antifogging layer and the substrate is better, a compound having a hydroxyl group, a carboxy group, or a phosphoric acid group at the terminal is preferable, and a polyurethane, an acrylic resin, and a polyphosphoric acid are used. Salts are more preferred.

The polyurethane is not particularly limited, and examples thereof include polyurethane having a soft segment/hard segment structure composed of a polyol skeleton and a polyisocyanate skeleton.
As the polyurethane, commercially available products may be used, for example, Takelac (registered trademark) W series, WS series, WD series manufactured by Mitsui Chemicals, Inc., Permarin (registered trademark) series manufactured by Sanyo Kasei Co., Ltd., and U-coat ( The registered trademark) series, the Euprene (registered trademark) series and the like can be mentioned.
Examples of the acrylic resin include homopolymers of acrylic acid (polyacrylic acid), acrylic acid derivatives such as acrylic acid and its esters, and methacrylic acid derivatives such as methyl methacrylate.
Among acrylic resins, polyacrylic acid is preferred, polyacrylic acid having a weight average molecular weight of 2,000 to 5,000,000 is preferred, polyacrylic acid of 10,000 to 2,000,000 is more preferred, and polyacrylic acid of 250,000 to 1,000,000 is further preferred. preferable.
Examples of the polyphosphate include sodium polyphosphate, potassium polyphosphate, and the like. The weight average molecular weight of the polyphosphate is preferably 500 to 100,000, more preferably 1000 to 50,000.
The weight average molecular weight can be measured by the method described above.

When the composition for forming an antifogging layer contains an adhesion aid, the content of the adhesion aid is 0.001% by mass to 0.1% by mass based on the total solid content of the composition for forming an antifogging layer. Is preferable, 0.001 mass% to 0.01 mass% is more preferable, and 0.002 mass% to 0.008 mass% is further preferable. When the content of the adhesion aid is within the above range, it is easy to form an antifogging layer having excellent adhesion to the substrate.

(Applying the composition for forming an antifogging layer on a substrate)
A method for forming an antifogging layer by applying a composition for forming an antifogging layer containing a specific silica particle, a specific copolymer, and a hydrolyzate of a specific siloxane compound onto a substrate.
Furthermore, it is preferable to prepare the composition for forming an antifogging layer of the present embodiment, and to dry the composition for forming an antifogging layer applied to a substrate at a temperature of 20° C. or higher and 150° C. or lower. ..

Preparation of the anti-fogging layer forming composition in the production method of the present embodiment will be described.
The composition for forming an antifogging layer in the present embodiment can be prepared by mixing silica particles, a specific copolymer, a specific siloxane hydrolyzate, and other components optionally contained.
Further, when preparing the composition for forming an antifogging layer, it is preferable to further mix a catalyst (condensation acceleration catalyst) that accelerates the condensation reaction of the specific siloxane compound.

The composition for forming the antifogging layer is prepared, for example, by bringing a specific siloxane compound into contact with water to prepare a mixed solution containing a hydrolyzate of the specific siloxane compound, and then adding an average primary particle diameter of 2 nm to the prepared mixed solution. A method of adding silica particles having a particle size of 100 nm or less can be mentioned. The specific copolymer is preferably contained in the obtained mixed liquid.
The hydrolysis reaction of the specific siloxane compound proceeds even at room temperature (25° C.), but in order to accelerate the reaction, the specific siloxane compound and water are brought into contact with each other to prepare a mixed liquid, and the obtained mixed liquid is then heated at 30° C. You may heat to about -50 degreeC. The longer the reaction time of the hydrolysis reaction, the better the reaction proceeds, which is preferable. Therefore, from the viewpoint of allowing the hydrolysis reaction to proceed sufficiently, it is also preferable to carry out the reaction for 1 hour to 36 hours in a heated state.
Further, by allowing a catalyst that accelerates the hydrolysis reaction of the specific siloxane compound to coexist in the mixed liquid, it is possible to obtain a hydrolyzate of the specific siloxane compound necessary for hydrophilicity even for about half a day.

The hydrolysis reaction of the specific siloxane compound is a reversible reaction. Therefore, when water is removed from the mixed solution, the hydrolyzate of the specific siloxane compound starts and progresses the condensation reaction between the hydroxy groups. Therefore, when a hydrolyzate of the specific siloxane compound is obtained by a hydrolysis reaction in a mixed liquid containing the specific siloxane compound and preferably a large excess of water, the mixed liquid is not isolated. As it is, it is preferable to add silica particles to prepare a composition for forming an antifogging layer.
When the composition for forming an antifogging layer is applied to a substrate, a condensation reaction of a hydrolyzate of a specific siloxane compound proceeds in the composition for forming an antifogging layer, so that the composition for forming an antifogging layer is formed. The antifogging layer contains a hydrolytic condensate of a specific siloxane compound.

From the viewpoint of suppressing the aggregation of silica particles, the specific silica particles are preferably contained in the composition for forming an antifogging layer as a dispersion liquid in which a dispersion agent has been previously dispersed.
As the dispersant, a known surfactant or the like may be used, and the dispersant may be used alone or in combination of two or more.

The composition for forming an antifogging layer may contain a viscosity modifier.
A thickener may be used as the viscosity modifier. By using a thickener as the viscosity modifier, the viscosity of the composition for forming an antifogging layer can be increased according to the coating method.
The thickener is not particularly limited, and a known thickener can be used. As the thickener, it is preferable to use appropriately according to the solvent of the composition for forming an antifogging layer, and the weight average molecular weight is 3,000 or more and 10,000 from the viewpoint that the effect of thickening can be obtained by adding a small amount. It is preferably a thickening agent of 1,000 or less.

Examples of the thickener include SEPIGEL 305, NS, EG, FL, SEPIPLUS 265, S, 400, SEPINOV EMT10, P88, SEPIMAX ZEN (manufactured by Seiwa Kasei), Aron A-10H, A-20P-X, A. -20L, A-30, A-7075, A-7100, A-7185, A-7195, A-7255, B-300K, B-500K, Jurimer (registered trademark) AC-10LHPK, AC-10SHP, Rheozic 260H. , 845H, Junron PW-120 (manufactured by Toagosei Co., Ltd.), DISPERBYK 410, 411, 415, 420, 425, 428, 430, 431, 7410ET, 7411ES, 7420ES, OPTIFLO-L1400 (manufactured by Big Chemie), Koskat GA468 (Osaka). Organic Chemicals Co., Ltd.), inorganic materials (silicate (water-soluble alkali silicate), montmorillonite, organic montmorillonite, colloidal alumina, etc.), fibrin derivative materials (carboxymethylcellulose, methylcellulose, hydroxycellulose, etc.), proteins Materials (casein, sodium caseinate, ammonium caseinate, etc.), Alginic acid materials (sodium alginate, etc.) Polyvinyl materials (polyvinyl alcohol, polyvinylpyrrolidone, polyvinylbenzyl ether copolymers, etc.), Polyacrylic acid materials (polyacrylic) Acid soda, polyacrylic acid-(meth)acrylic acid copolymer, etc.), polyether material (pluronic polyether, polyether dialkyl ester, polyether dialkyl ether, polyether urethane modified product, polyether epoxy modified product, etc.) , Maleic anhydride copolymer-based materials (vinyl ether-maleic anhydride copolymer partial ester, drying oil fatty acid allyl alcohol ester-maleic anhydride half ester, etc.). Other than the above, examples of the thickener include a polyamide wax salt, acetylene glycol, zentan gum, and an oligomer or polymer having a polar group at the molecular end or side chain.
The thickeners may be used alone or in combination of two or more.

As the viscosity modifier, a solvent having a high viscosity, for example, a solvent having a viscosity at 25° C. of 30 mPa/s or more may be used. It is preferable to use a solvent having a high viscosity as the viscosity modifier, since it has both a function as a solvent and a function as a viscosity modifier, and the viscosity modifier component does not remain in the formed film.
Examples of the high-viscosity solvent that can be used as the viscosity modifier include glycol-based solvents.
In the present specification, the "glycol solvent" has a structure in which two or more carbon atoms of hydrocarbon are each substituted by one hydroxy group.
Examples of glycol solvents include ethylene glycol, diethylene glycol, triethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, diethanolamine, triethanolamine and the like.
Among these, the glycol solvent is preferably at least one selected from propylene glycol and dipropylene glycol from the viewpoint that the dispersibility of the specific silica particles and the drying property when applied are better.

The viscosity of the composition for forming an antifogging layer can be appropriately selected according to the coating method.

The content of the viscosity adjusting agent, the thickener and the like in the antifogging layer forming composition is preferably 0.01% by mass to 10% by mass with respect to the total mass of the antifogging layer forming composition, and is preferably 0. 1% by mass to 5% by mass is more preferable, and 0.5% by mass to 2% by mass is further preferable.

When preparing the antifogging layer forming composition, as described above, other components such as a condensation accelerating catalyst, an antistatic agent, and an adhesion improving agent are added to the antifogging layer forming composition as necessary. be able to.

When the composition for forming an antifogging layer contains the specific siloxane compound and the condensation accelerating catalyst, the condensation reaction of the specific siloxane compound is promoted, and the formation of the hydrolyzed condensate of the specific siloxane compound is accelerated. Thereby, the antifogging layer becomes a film having more excellent scratch resistance.

The condensation accelerating catalyst is the same as the condensation accelerating catalyst in the antifogging layer described above, and the preferred embodiment is also the same.

The addition amount of the condensation accelerating catalyst to the antifogging layer forming composition is preferably 0.1% by mass to 20% by mass, and 0.2% by mass to the total solid content of the antifogging layer forming composition. 15% by mass is more preferable, and 0.3% by mass to 10% by mass is further preferable. When the content of the condensation accelerating catalyst is within the above range, it is easy to form an antifogging layer having scratch resistance. Further, it is also excellent in the formability of the antifogging layer.

The condensation promoting catalyst is also useful for hydrolysis of the specific siloxane compound. Here, there is an equilibrium relationship between the hydrolysis reaction and the condensation reaction in the reaction century, such as the alkoxy group bonded to the silicon atom of the specific siloxane compound, and when the water content in the system is large, the reaction proceeds in the direction of hydrolysis and If the water content is low, the reaction proceeds in the direction of condensation. A catalyst that promotes a condensation reaction in a reactive group such as an alkoxy group promotes a reaction in both directions, so that the hydrolysis reaction can be promoted when the system contains a large amount of water. The presence of the catalyst enables the hydrolysis of the specific siloxane compound to proceed more reliably under milder conditions.
At this time, it is efficient to use the catalyst used for the hydrolysis reaction of the specific siloxane compound as it is as a contained component of the composition for forming an antifogging layer, and use it as it is as a condensation catalyst for the specific siloxane compound.

In the above, when other components such as an antistatic agent and an adhesion improver are added, some or all of them may be added when obtaining the hydrolyzate of the specific siloxane compound.

The antifogging layer-forming composition prepared preferably does not contain a photopolymerization initiator or a thermal polymerization initiator. By omitting the photopolymerization initiator and the thermal polymerization initiator, light irradiation or heat treatment can be omitted when the antifogging layer is formed. Further, from the viewpoint of storage stability of the composition for forming an antifogging layer, it is preferable not to include a photopolymerization initiator and a thermal polymerization initiator.

The preparation conditions of the composition for forming an antifogging layer are not particularly limited, but from the viewpoint of suppressing aggregation of silica particles due to pH and the concentration of coexisting components, silica particles are used in the latter half of the process of preparing a coating liquid. Preferably it is added, more preferably last. Here, when the silica particles are used as a dispersion liquid (specifically, a dispersion liquid in which silica particles are previously dispersed in an aqueous solvent, or a commercially available silica particle dispersion liquid), the pH of the dispersion liquid and the solvent used for the coating liquid are It is preferable to adjust both the pH of the dispersion liquid of silica particles and the pH of the solvent of the coating liquid to the same or close value by making both pH acidic or both basic.

In the method for producing the laminate of the present embodiment, the method of applying the composition for forming an antifogging layer to the substrate is not particularly limited, and any of a coating method, a transfer method, a dipping method and the like may be used.
From the viewpoint that the uniformity and productivity of the formed film are good, the method of applying the composition for forming an antifogging layer is preferably a method of applying it to a substrate.
The coating method for coating the antifogging layer forming composition on the substrate is not particularly limited and, for example, a known method such as spray coating, brush coating, roller coating, bar coating, dip coating (immersion coating) is applied. be able to.
Above all, it is preferable that applying the composition for forming an anti-fogging layer on the substrate includes spray coating.
When applying to a three-dimensional structure having various shapes such as a curved line and unevenness such as a three-dimensional structure in the field where the production of the laminated body of the present embodiment is used, spray coating is suitable, and lamination is performed with high productivity. The body can be manufactured. The composition for forming an antifogging layer in the present embodiment is less likely to drip, and thus can be suitably applied to a spray coating method.
In the case of spray coating, the viscosity of the composition for forming an antifogging layer is preferably 2 mPa/s or more and 200 mPa/s or less, more preferably 3 mPa/s or more and 100 mPa/s or less, and 4 mPa/s or more. It is more preferably 50 mPa/s or less. The viscosity of the composition can be adjusted using, for example, the above-mentioned viscosity modifier.

When the composition for forming an antifogging layer of the present embodiment is applied to a substrate by spray coating, the method of setting the substrate is not particularly limited. Depending on the shape of the base material, the orientation of the base material can be applied while appropriately changing the direction of application, such as the horizontal direction or the vertical direction. In order to make the coating film thickness more uniform, it is preferable to dispose the spray nozzles at positions where the distance between the spray nozzle and the base material is equal, and to apply to the base material. Is preferably 10 mm or more and 1000 mm or less.

As a method of supplying the composition for forming an antifogging layer of the present embodiment to a coating apparatus, any of a pressure-feeding method, a wicking method, and a gravity method 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 coating under such conditions, the coating film thickness can be made more uniform. In order to form a more suitable coating film by spray coating, it is necessary to adjust the amount of air, the amount of paint sprayed, the amount of sprayed composition for film formation, pattern opening, and the like.

When the composition for forming an antifogging layer of the present embodiment is applied to a substrate by spray coating, the amount of air used (the amount of air) is preferably 5 L/min or more and 600 L/min or less, and the paint ejection amount is 5 L/min. It is preferable that the length is not less than minutes and not more than 600 L/min, and the pattern opening is not less than 40 mm and not more than 450 mm.

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 failures due to fine particles (that is, particles) in the coating environment, cleanliness of class 10,000 or higher is preferable, and cleanliness of class 1,000 or higher. Is more preferable.

The coating amount of the composition for forming an antifogging layer is not particularly limited, depending on the concentration of the solid content in the composition for forming an antifogging layer, the desired film thickness, etc., considering operability, etc., It can be set appropriately. The coating amount of the anti-fog layer forming composition ^is preferably ^{0.1mL / m 2 ~1000mL / m 2} , more preferably ^{0.5mL / m 2 ~500mL / m 2} , 1mL / m More preferably, it is ^{2 to} 200 mL/m ² . When the coating amount of the composition for forming an antifogging layer is within the above range, the coating accuracy tends to be good.

The method for producing a laminate of the present embodiment can include drying a coating film of the composition for forming an antifogging layer, which is applied onto a substrate by coating or the like, at a temperature of 20°C or higher and 150°C or lower.

The coating film formed by applying the composition for forming an antifogging layer is preferably heated to a temperature of 20° C. or higher and 150° C. and dried to form an antifogging layer on the substrate.

You may dry the coating film of the composition for forming an anti-fogging layer using a heating device. The heating device is not particularly limited as long as it can be heated to a target temperature, and any known heating device can be used. As the heating device, an oven, an electric furnace, or the like, as well as a heating device that is uniquely manufactured according to the production line can be used.

The coating film of the composition for forming an antifogging layer can be dried, for example, by using the above heating device under the condition that the surface temperature of the film is 20° C. or higher and 150° C. or lower. The drying time can be, for example, a heating time of about 1 minute to 60 minutes.
As a drying condition of the composition film for forming an antifogging layer, a drying condition of heating the film at a surface temperature of 20° C. or higher and 150° C. or lower for 1 to 60 minutes is preferable, and a surface temperature of 40° C. or higher and 150° C. or lower is set. Drying conditions of heating for 60 minutes to 60 minutes are more preferable, drying conditions of heating for 1 minute to 30 minutes at a surface temperature of 60° C. to 150° C. are more preferable, heating temperatures of 90° C. to 150° C. for 1 minute to 10 minutes. Drying conditions for heating are particularly preferable.
From the viewpoint of maintaining the surface shape of the coating film, it is preferable to dry the coating film at a high temperature for a short time.
The surface temperature of the film can be measured by a measuring means such as an infrared thermometer.

The dried coating film, that is, the formed anti-fogging layer preferably has a thickness of 1 μm or more and 10 μm or less. When the film thickness is 1 μm or more, the antifogging layer is excellent in scratch resistance.
The film thickness of the antifogging layer is more preferably 1.5 μm or more and 9 μm or less, and further preferably 2 μm or more and 8 μm or less.

As described above, the antifogging layer according to this embodiment may have a multilayer structure.
Each of the antifogging layer-forming compositions for forming each antifogging layer having a multilayer structure contains specific silica particles, a specific copolymer, and a hydrolyzate of a specific siloxane compound.
When forming an anti-fogging layer having a multilayer structure, the step of forming the anti-fogging layer includes the step of forming an anti-fogging layer having at least a first anti-fogging layer and a second anti-fogging layer on the substrate. It is a step of forming a cloudy layer, which contains a specific silica particle, a specific copolymer, and a hydrolyzate of a specific siloxane compound on a substrate, and the content of the copolymer is 50 mass with respect to the total amount of the composition. % Or more of the second antifogging layer-forming composition to form the second antifogging layer, and on the formed second antifogging layer, specific silica particles A first protective layer containing a polymer and a hydrolyzate of a specific siloxane compound, wherein the total content of the hydrolyzate of the specific siloxane compound and the specific silica particles is 50% by mass or more based on the total solid content of the composition. It is preferable to include a step of applying the composition for forming a cloudy layer to form a first anti-fog layer.

When forming an antifog layer having a multilayer structure, first, a second antifog layer is formed on the substrate as described above and dried to form a second antifog layer. It is preferable to form another antifogging layer to be laminated, for example, the first antifogging layer by the method described above. When the number of layers is three or more, these steps may be repeated.
The composition of each antifogging layer having a multilayer structure is appropriately selected according to the purpose.
The method for forming the anti-fogging layer having a multilayer structure is not limited to the above-mentioned sequential coating method, and for example, two or more layers may be coated in a multilayer manner.

According to the method for producing a laminate of the present embodiment, the anti-fog property and the durability of the anti-fog effect described above are good, and even if the anti-fog layer absorbs water, an anti-fog layer is unlikely to leave traces of water dripping. It is possible to manufacture the laminated body having the low defective rate and high productivity.

Hereinafter, the embodiments of the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

(Synthesis example 1)
-Preparation of Specific Copolymer 1-
200 g of ethylene glycol monoethyl ether was charged into 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.
Furthermore, a mixture of monomers containing 4 g of polymeric 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 was used. It was prepared and added dropwise to 200 g of the above-mentioned ethylene glycol monoethyl ether over 2 hours, and further reacted for 2 hours.
Thereafter, a monomer mixture containing 28 g of methyl methacrylate and 2 g of acrylic acid was further added dropwise over 30 minutes, and a reaction was performed at 80° C. for 5 hours. After the reaction, the solution was cooled to 25° C. to obtain a solution of specific copolymer 1 having a solid content of 30%.

(Synthesis example 2)
-Preparation of Specific Copolymer 2-
The reactor used in Synthesis Example 1 was charged with 200 g of propylene glycol monomethyl ether, heated and stirred to 85° C. while blowing nitrogen gas, 6 g of t-butylperoxyoctanoate and t-butylperoxymethacryloxyethylcarbohydrate. A monomer mixture containing 6 g of Nate, 10 g of N-methyl acrylamide, 10 g of 2-hydroxyethyl methacrylate, 66 g of N,N-dimethyl acrylamide and 40 g of propylene glycol monomethyl ether was added to propylene glycol. To the reactor charged with 200 g of monomethyl ether was added dropwise over 30 minutes, and the reaction was further performed for 2 hours.
Then, the mixture was further heated to 110° C., 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 performed for 4 hours.
After the reaction, the solution was cooled to 25° C. to obtain a solution of the specific copolymer 2 having a solid content of 30 mass %.

[Example 1]
The laminate of Example 1 was produced by the following method.
To ethanol 81.07 g, 3.06 g of a specific siloxane compound (compounds R ^{1 to} R ⁴ represented by the general formula (1): all are methyl groups (n=5)) and aluminum bis(ethylacetoacetate) mono 0.94 g of a 1 mass% isopropanol solution of (acetylacetonate) (condensation accelerating catalyst of the compound) was added and mixed to obtain a mixed solution.
114.80 g of an aqueous solution in which 0.057 g of polyethylene glycol monolauryl ether (the repeating number of ethylene oxide part: 15; a nonionic surfactant which is a component showing surface activity) was dissolved in the obtained mixed liquid was gradually added. In addition, the mixture was stirred at room temperature for 12 hours or more. Thereby, the coating agent mother liquor 1 was prepared by hydrolyzing the specific siloxane compound.

Sodium di(2-ethylhexyl)sulfosuccinate, which is an anionic surfactant, was added to 13.00 g of the coating agent mother liquor 1 obtained above, 10.00 g of ethanol, and 2.00 g of water in a mixed solvent. Manufactured by Nissan Chemical Industries, Ltd.) to have a solid content concentration of 0.2% by mass)) 2.30 g, silica particles (Nissan Chemical Co., Ltd. “Snowtex OYL” (solid content concentration 20% by mass, primary particle size 50- (80 nm): 1.90 g of specific silica particles) 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 composition 1 for forming an antifogging layer.
Next, the obtained composition A for forming an anti-fog layer was coated on a transparent acrylic substrate using an air spray gun W-101-101G manufactured by Anest Iwata. The coating amount was 60 mL/m ² .
After coating the composition A for forming an anti-fog layer, it was dried and cured at 80° C. for 40 minutes. Then, it was left for 1 day under the condition of 25° C. to obtain a laminate of Example 1 having an antifogging layer on a transparent acrylic substrate.
The transparent acrylic substrate used had a thickness of 5 mm, and the haze of the substrate alone was 0.4%.

[Example 2]
A laminate of Example 2 was obtained in the same manner as in Example 1 except that the amount of the specific silica particles added in Example 1 was changed from 1.90 g to 3.15 g.

[Example 3]
A laminate of Example 3 was obtained in the same manner as in Example 1 except that the amount of the specific silica particles added in Example 1 was changed from 1.90 g to 4.20 g.

[Example 4]
A laminate of Example 4 was obtained in the same manner as in Example 1 except that the amount of the specific copolymer 1 solution obtained in Synthesis Example 1 in Example 1 was changed from 1.50 g to 3.20 g. It was

[Example 5]
To the mixed solvent containing the coating agent mother liquor 1:13.00 g used in Example 1, ethanol 8.50 g, and water 3.50 g, anionic surfactant sodium di(2-ethylhexyl)sulfosuccinate was used. ((Aqueous solution of Kishida Chemical Co., Ltd. diluted to a solid content concentration of 0.2% by mass)) 2.30 g, silica particles (Nissan Chemical Co., Ltd. "Snowtex OUP" (solid content concentration 15% by mass, 3.40 g of primary particle size 40 nm to 100 nm): specific silica particles)) was added and stirred for 30 minutes to obtain a mixed solution.
1.50 g of the specific copolymer 2 solution obtained in Synthesis Example 2 was further added to the obtained mixed liquid to obtain a composition B for forming an antifogging layer.
The obtained composition B for forming an antifogging layer was coated on a transparent polycarbonate substrate using an air spray gun W-101-101G manufactured by Anest Iwata. The coating amount was 90 mL/m ² .
After coating the composition B for forming an antifogging layer, preliminary drying was performed at 40° C. for 5 minutes, and then dry curing was performed at 120° C. for 20 minutes. Then, it was left for 1 day under the condition of 25° C. to obtain a laminate of Example 5 having an antifogging layer on a transparent polycarbonate substrate.
The transparent polycarbonate substrate used had a thickness of 5 mm, and the haze of the substrate alone was 0.4%.

[Example 6]
Example 6 was repeated in the same manner as in Example 5 except that the amount of liquid discharged during spray coating of the composition B for forming an antifogging layer was 0.25 times (22.5 mL/m ² ) in Example 5 described above. A laminated body of was obtained.

[Example 7]
The laminate of Example 7 was prepared in the same manner as in Example 5 except that the liquid discharge amount of the composition B for forming an antifogging layer during spray coating was doubled (180 mL/m ² ). Got

[Example 8]
1.50 g of the specific copolymer 1 solution obtained in the above Synthesis Example 1 was diluted with 1-methoxy-2-propanol to obtain a final film thickness of 1 μm, and an air spray gun W-101-1 manufactured by Anest Iwata Co., Ltd. 101G was used to paint on the same transparent acrylic substrate as used in Example 1 and dried and cured at 80° C. for 40 minutes to form a second antifogging layer.
On the formed second anti-fogging layer, 13.00 g of the coating agent mother liquor 1 obtained in Example 1, 10.00 g of ethanol, 2.00 g of water, and di(2-ethylhexyl) which is an anionic surfactant. ) 2.30 g of sodium sulfosuccinate ((aqueous solution of Kishida Chemical Co., Ltd. diluted to a solid concentration of 0.2% by mass)) and specific silica particles (Nissan Chemical Co., Ltd. "Snowtex O-30") (Solid content concentration 30% by mass, primary particle size 10 nm to 15 nm): Specific silica particles) 1.90 g was added and stirred for 30 minutes using an air spray gun W-101-101G manufactured by Anest Iwata. Coating was performed so that the finished thickness would be 200 nm, and the coating was dried and cured at 120° C. for 20 minutes to form a first antifogging layer. Then, it was left to stand for 1 day under the condition of 25° C. to obtain a laminate of Example 8 having a second antifogging layer and a first antifogging layer in this order on a transparent acrylic substrate.

[Example 9]
In the coating agent mother liquor 1 in Example 1 above, a specific siloxane compound (compounds R ^{1 to} R ⁴ represented by the general formula (1): all methyl groups (n=5)) was added to tetramethoxysilane (Tokyo Chemical Industry ( Co., Ltd. (n=1)), and a stirring time of 12 hours to 1 without adding a 1% by mass solution of aluminum bis(ethylacetoacetate)mono(acetylacetonate) in isopropanol (condensation accelerating catalyst). A laminate of Example 9 was obtained in the same manner as in Example 1 except that the time was changed.

[Comparative Example 1]
A laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except that 13.00 g of ethanol was added instead of the coating agent mother liquor 1 used in Example 1 above.

[Comparative Example 2]
A laminate of Comparative Example 2 was obtained in the same manner as in Example 1 except that the specific silica particles were not added to the composition 1 for forming an antifogging layer in Example 1 described above.

[Comparative Example 3]
A laminate of Comparative Example 3 was obtained in the same manner as in Example 1 except that the specific copolymer 1 solution obtained in Synthesis Example 1 was not added to the composition 1 for forming an antifogging layer in Example 1 above. It was

<Evaluation>
The physical properties and performance of the antifogging layer in the obtained laminates of Examples and Comparative Examples were evaluated as follows.
The results are shown in Table 2.

[Measurement of average surface roughness Ra]
First, the surface shape is measured using an atomic force microscope (AFM): NANONAVI STATION/SPA500 (manufactured by Hitachi High-Tech Co., Ltd.) and a cantilever: SI-DF20 (manufactured by Seiko Instruments Inc.) to obtain three-dimensional data. It was Here, cut the laminated body into a size of 1 cm square, set it on a horizontal sample stand on the piezo scanner, approach the sample surface with a cantilever, and scan in the XY directions when the area where atomic force acts is reached. At that time, the unevenness of the sample was grasped by the displacement of the piezo in the Z direction, and at the time of measurement, 512×512 points were measured in a range of 5 μm×5 μm on the surface.
Using the three-dimensional data (f(x,y)) obtained above, the average roughness Ra was obtained.

[Measurement of film thickness of anti-fog layer]
The film thickness of the anti-fog layer is determined by cutting the formed laminate with a microtome in a direction perpendicular to the base material surface of the laminate, that is, in the thickness direction of the laminate to obtain a cross section of the laminate and performing field emission scanning. The cross section was observed with a scanning electron microscope (FE-SEM) at a magnification of 50,000 and measured.

[Measurement of water absorption]
Prepare a water bath at 60°C, apply steam from the warm bath only to the predetermined 5 cm × 5 cm area of the antifogging layer of the obtained laminate, and after applying steam, in an environment of 25°C and 50% RH The vertical direction was used to stand the laminated body, and the amount of increase in mass was measured under the upper limit condition in which no water dripping occurred. The amount of increase in mass per unit area where steam was applied was taken as the water absorption amount (mg/cm ² ).

[Measurement of haze]
The haze of the obtained laminate was measured with a haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. in a wavelength range of 380 nm to 780 nm.

[Ratio of area of silica particles on antifogging layer surface]
The outermost surface of the antifogging layer in the laminate is cut by a microtome in a direction parallel to the surface of the base material, and is cut to a region where there is no unevenness due to silica particles on the surface to produce a smooth surface. Then, the obtained surface was observed with FE-SEM at a magnification of 100,000.
By observing the surface in a plan view, a region where the specific silica particles are present and a region where only the so-called binder where the specific silica particles are not present can be distinguished, so the total area of the observation region is measured, and the specific silica particles are The area of the existing area was measured, and the ratio (area ratio) of the area of the specific silica particles to the total area of the observation area on the surface of the antifogging layer was calculated.
In addition, in Table 2, the evaluation item is described as “silica particle occupancy ratio”.

..
[Evaluation of initial anti-fog property]
Prepare a hot water bath at 60°C, keep the steam on the predetermined 5 cm x 5 cm area of the antifogging layer of the obtained laminate for 1 minute, and then, under the environment of 25°C 50%RH, the surface of the antifogging layer. Was visually observed and evaluated according to the following criteria.
A: No cloudiness was visually observed in the anti-fog layer.
B: Haze that can be visually confirmed was observed in a part of the anti-fogging layer.
C: Fogging was observed in the entire area of the antifogging layer to which steam was applied.

[Persistence evaluation of anti-fog property]
A water bath at 60°C was prepared, and steam was continuously applied to a predetermined area of 5 cm x 5 cm of the antifogging layer of the obtained laminate for 5 hours, and thereafter, the surface of the antifogging layer was kept in an environment of 25°C and 50% RH. Was visually observed and evaluated according to the following criteria.
A: No cloudiness was visually observed in the anti-fog layer.
B: Haze that can be visually confirmed was observed in a part of the anti-fogging layer.
C: Fogging was observed in the entire area of the antifogging layer to which steam was applied.

[Evaluation of water dripping resistance]
A water bath at 60° C. was prepared, steam was continuously applied to a predetermined area of 5 cm×5 cm of the antifogging layer of the obtained laminate for 1 minute, and then the laminate was vertically inclined to cause water dripping. ..
This treatment was repeated 50 times, and the number of repetitions until the trace of water dripping due to the elution and peeling of the antifogging layer was recognized was measured. In Table 2, the number of occurrences of water dripping is described. It is evaluated that the greater the number of times, the more excellent the water dripping resistance.
That is, when the number of repetitions is small, it means that elution and peeling occurred a small number of times, and 50 times or more means that elution and peeling did not occur even after repeating 50 times.

[Evaluation of defective product rate]
100 sheets of each of the laminated bodies of Examples 1 to 9 and Comparative Examples 1 to 3 were produced under a clean environment of class 10,000 and a clean environment of class 1,000, respectively. That is, the antifogging layer was applied to the surface of the base material in a clean environment, the resulting laminate was confirmed, and the laminate with dust was regarded as a defective product, and the laminate without dust was produced. The body was regarded as a good product, and the defective product occurrence rate was evaluated.

As shown in Table 2, the laminate having the antifogging layer obtained in the example had a high water absorption of the antifogging layer and was excellent in the antifogging property and the durability of the antifogging property. Further, it can be seen that the rate of defective products in the painting temple of the anti-fog layer is low, and the product is manufactured with high productivity.
On the other hand, in the laminates of Comparative Example 1 using the composition for forming an antifogging layer containing no hydrolyzate of the specific siloxane compound and Comparative Example 2 using the composition for forming an antifogging layer containing no specific silica particles. The cloudy layer was inferior in anti-fog persistence and water dripping resistance. Furthermore, in Comparative Example 2, the defective product rate was high and the productivity was also poor.
The antifogging layer in the laminate of Comparative Example 3 using the composition for forming an antifogging layer that does not contain the specific copolymer has good antifogging property and antifogging property durability, but in terms of water dripping resistance, Note that there is room for improvement.

Claims (12)

At least one cross-linking functional group selected from the group consisting of silica particles having an average particle diameter of primary particles of 2 nm or more and 100 nm or less, N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group. Having a structural unit derived from a vinyl-based monomer, a structural unit derived from a vinyl-based monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and a structure derived from an alkyl (meth)acrylate-based monomer A block copolymer having at least a unit and having a hydrophilic polymer portion and a hydrophobic polymer portion, or a graft copolymer having a hydrophilic polymer portion and a hydrophobic polymer portion, wherein the hydrophilic polymer is a hydrophilic polymer. The part contains 1% by mass to 30% by mass of a structural unit derived from a vinyl monomer having a crosslinking functional group and 70% by mass to 99% by mass of a structural unit derived from a hydrophilic vinyl monomer, and is hydrophobic. The polymer portion is a structure derived from a vinyl-based monomer having 70% by mass to 99% by mass of a structural unit derived from an alkyl (meth)acrylate-based monomer and a sulfonic acid group, a carboxyl group or a phosphoric acid group. A composition for forming an antifogging layer, comprising a copolymer containing a unit of 1% by mass to 30% by mass, and a hydrolyzate of a compound represented by the following general formula (1).


In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 20. The copolymer is at least one selected from the group consisting of N-methylol group, N-alkoxymethylol group, N-methylol ether group and hydroxyl group as a structural unit derived from a vinyl monomer having a crosslinkable functional group. And a hydrophilic polymer part containing a structural unit derived from a hydrophilic vinyl monomer, and a structural unit derived from a vinyl monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and an alkyl ( The composition for forming an antifogging layer according to claim 1, which is a copolymer composed of a hydrophobic polymer part containing a structural unit derived from (meth)acrylate. Base material,
At least selected from the group consisting of silica particles having an average primary particle diameter of 2 nm or more and 100 nm or less, N-methylol group, N-alkoxymethylol group, N-methylol ether group, and hydroxyl group provided on a substrate. Structural unit derived from vinyl-based monomer having one kind of crosslinking functional group, structural unit derived from vinyl-based monomer having sulfonic acid group, carboxyl group or phosphoric acid group, and alkyl (meth)acrylate-based A block copolymer having at least a structural unit derived from a monomer and having a hydrophilic polymer portion and a hydrophobic polymer portion, or a graft copolymer having a hydrophilic polymer portion and a hydrophobic polymer portion. And a hydrolysis-condensation product of a compound represented by the following general formula (1), and an antifogging layer having a water absorption of 1.2 mg/cm ^{2 to} 8.0 mg/cm ^2. And a laminated body having.


In formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 20. The laminate according to claim 3, wherein the antifogging layer has a thickness of 1 μm or more and 10 μm or less. The laminate according to claim 3 or 4, wherein the average surface roughness Ra of the surface of the antifogging layer is 10 nm or more and 100 nm or less. The ratio of the area occupied by the silica particles to the total area of the anti-fogging layer when the surface of the anti-fogging layer is viewed in plan is 60% or more in terms of area ratio. The laminate described. The ratio of the area occupied by the silica particles to the total area of the anti-fogging layer in plan view of the surface of the anti-fogging layer is 80% or more in terms of area ratio, according to any one of claims 3 to 6. The laminate described. The content of the silica particles with respect to the total mass of the antifogging layer is 50% by mass or more and 99% by mass or less, and the content of the copolymer with respect to the total mass of the antifogging layer is 0.5% by mass or more 49. It is 5 mass% or less, and the content of the hydrolysis-condensation product of the compound represented by the general formula (1) is 0.5 mass% or more and 49.5 mass% or less with respect to the total mass of the antifogging layer. The laminated body according to any one of claims 3 to 7. The antifogging layer is an antifogging layer having a multi-layered structure of two or more layers having at least a first antifogging layer and a second antifogging layer,
The total content of the hydrolysis-condensation product of the compound represented by the general formula (1) and the silica particles in the first antifogging layer is 50 mass with respect to the total amount of the first antifogging layer. % Or more,
The said 2nd anti-fogging layer WHEREIN: The content of the said copolymer is 50 mass% or more with respect to the total amount of the said 2nd anti-fogging layer, The any one of Claims 3-8 characterized by the above-mentioned. Laminate. A method for producing a laminate, which comprises a step of applying the composition for forming an antifogging layer according to claim 1 or 2 onto a substrate to form an antifogging layer. The method for producing a laminate according to claim 10, wherein the step of forming the antifogging layer includes a step of spray-coating the composition for forming the antifogging layer onto the base material. The step of forming the anti-fogging layer is a step of forming an anti-fogging layer having a multilayer structure of two or more layers having at least a first anti-fogging layer and a second anti-fogging layer,
The silica particles, the copolymer, and a hydrolyzate of the compound represented by the general formula (1) are contained on the substrate, and the content of the copolymer is 50 with respect to the total amount of the composition. A step of forming a second anti-fogging layer by applying a second anti-fogging layer forming composition in an amount of at least mass%; and
The silica particles, the copolymer, and the hydrolyzate of the compound represented by the general formula (1) are contained on the formed second anti-fogging layer and are represented by the general formula (1). The total content of the hydrolyzate of the compound and the silica particles is 50% by mass or more based on the total solid content of the composition, and the first anti-fogging layer-forming composition is applied to give the first anti-fogging layer composition. Forming a cloudy layer,
The manufacturing method of the laminated body of Claim 10 or Claim 11 containing.