TW201617421A - Layered body with antifouling layer, protective material for security camera, and security camera - Google Patents

Abstract

The invention provides layered body with antifouling layer, protective material for security camera and security camera. The layered body with antifouling layer comprises substrate and stain proofing layer allocated on the substrate. The stain proofing layer at least containing siloxane adhesive, antistatic agent and silicon dioxide particles of which are made of compounds is indicated by the formula (1) and the stain proofing layer further representing that the content of the surface active components is more than 0.5 mass percentages relative to the total solid components of the layer. Furthermore, R1, R2, R3 and R4 of the formula (1) respectively indicated as organic groups of which are carbon atom numbers from one to six and n represented as integer from two to twenty.

Description

Anti-fouling layer laminate, protective material for surveillance cameras, and surveillance cameras

The present invention relates to a laminate with an antifouling layer, a protective material for a surveillance camera, and a surveillance camera.

The device or building materials that are installed indoors or outdoors for a long period of time are exposed to various environments, so that dust, dust, gravel, etc., or rain and rain during rain or rain may occur slowly, and the set function may be Performance is impaired.

For example, in recent years, surveillance cameras have been widely used as a defense for residential use, or as a commercial building or an outdoor security system. The surveillance camera is a fixed type device having an imaging device such as a charge coupled device (CCD) camera and a protective cover, and is usually used for a long time once it is set. The protective cover exhibits an effect of providing light transmission capable of imaging and protecting the imaging device from rain or gravel.

The protective cover of the surveillance camera protects the camera while always producing a stable image, which requires maintenance-free maintenance that does not require cleaning in the long run. However, in general, a device such as a surveillance camera that is installed outdoors is used for a long period of time, and water droplets, dust, dust, sand, and the like adhere to the surface of the device, and the light transmittance tends to be slowly impaired. In the case of a surveillance camera, dust, dust, sand, and the like are likely to accumulate on the surface of the protective cover, and depending on the size or amount of the deposit, not only the light transmittance is remarkably lowered, but also the desired image may not be recorded. .

Therefore, research has been conducted on a technique for preventing adhesion of water, dust, dust, sand, or the like to the surface of equipment exposed to an outdoor environment.

In this respect, in addition to monitoring cameras, building materials such as lighting, equipment, signs, and the like, such as roofs of garages for automobiles and bicycles, and soundproof walls for roads and the like, are used in the same place.

As a technique related to the above, for example, a method has been disclosed in which an aqueous hydrophilization treatment agent using a tetraalkoxysilane, a nonionic surfactant, or an acidic colloidal cerium oxide is applied to the surface of a substrate. A hydrophilic film is formed to impart stain resistance (for example, see Japanese Patent No. 4648667).

Further, a camera cover having a hydrophilic coating layer formed of an inorganic material mainly composed of a cerium compound and having a water contact angle of 5 degrees or more on the surface is disclosed (for example, see Japanese Patent Laid-Open No. 2014-92654 Bulletin).

[Problems to be solved by the invention]

A device, a member, a building material, etc., which are installed in an outdoor environment and exposed to various changes such as wind and rain, tend to have a desired function as the dirt adheres. Therefore, it is customary to perform cleaning or parts periodically at regular intervals. replace. If the workload of cleaning or component replacement is not required, or the cleaning time or replacement period is delayed, the work load that has been indispensable in the past can be greatly reduced.

However, in the technique described in the above-mentioned Japanese Patent No. 4,648, 667 and Japanese Patent Publication No. 2014-92654, the actual situation is that the ability to prevent adhesion of dust, dust, sand, or the like in the atmosphere as a cause of dirt is not necessarily required. It is always satisfactory and has not yet reached the level of performance that is close to maintenance-free antifouling.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an antifouling layer laminate, a monitoring camera protective material, and a surveillance camera that are less likely to cause dirt and can easily remove dirt in the presence of dirt.

[Means for solving the problem]

Specific means for solving the problem include the following methods.

<1> A laminate with an antifouling layer comprising a substrate and an antifouling layer, the antifouling layer being provided on a substrate and comprising at least a decane formed of a compound represented by the following formula (1) The binder, the antistatic agent, and the cerium oxide particles have a content of the surface active component of 0.5% by mass or more based on the total solid content of the layer.

[Chemical 1] General formula (1)

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

<2> The antifouling layer laminate according to <1>, wherein the substrate comprises glass.

<3> The antifouling layer laminate according to <1> or <2>, wherein the substrate comprises a resin material.

<4> The antifouling layer laminate according to <3>, wherein the resin material contains at least one of polycarbonate and polymethyl methacrylate.

The antifouling layer laminate according to any one of <1> to <4> wherein the antifouling layer further comprises a catalyst that promotes formation of a siloxane binder.

The antifouling layer laminate according to any one of <1> to <5> wherein the antistatic agent contains an ionic surfactant.

<7> The antifouling layer laminate according to <6>, wherein the content of the ionic surfactant is 50% by mass or less based on the total mass of the antifouling layer.

The antifouling layer laminate according to any one of <1> to <7> wherein the antifouling layer further contains a nonionic surfactant as a component exhibiting surface activity.

The antifouling layer laminate according to any one of <1> to <8> wherein the antistatic agent contains metal oxide particles.

<10> The antifouling layer laminate according to <9>, wherein the metal oxide particles have an average primary particle diameter of 100 nm or less.

The antifouling layer laminate according to any one of the above aspects, wherein the content of carbon is 3% by mass or less based on the total solid content of the antifouling layer.

The antifouling layer laminate according to any one of the above aspects, wherein the content of the organic compound having a weight average molecular weight of 1100 or more is 0.2 with respect to the total solid content of the antifouling layer. Below mass%.

The antifouling layer laminate according to any one of the above aspects, wherein the surface resistivity of the antifouling layer is 1 × 10 ¹² Ω/sq (that is, Ω/square) or less. .

The antifouling layer laminate according to any one of <1> to <13> wherein the surface of the antifouling layer has a water contact angle of 40 or less.

The antifouling layer laminate according to any one of <1> to <14> wherein the integral sphere transmittance of the antifouling layer is an integral sphere transmittance in a wavelength region of 300 nm to 1200 nm. The average value (average value of the integrated sphere transmittance of the wavelength (λ) = 300 nm to 1200 nm) was 95% or more.

<16> A protective material for a surveillance camera, comprising the antifouling layer laminate according to any one of <1> to <15>.

<17> The protective material for a surveillance camera according to <16>, wherein the substrate in the antifouling layer laminate has a hemispherical shape, a semi-ellipsoidal shape, a planar shape, a quadrangular prism shape or a cylindrical shape. .

<18> A protective material for a surveillance camera as described in <16> or <17>, which is used in an outdoor surveillance camera.

<19> A surveillance camera according to any one of <16> to <18>, wherein the protective material for a surveillance camera is provided.

[Effects of the Invention]

According to an embodiment of the present invention, it is possible to provide an antifouling layer laminate, a protective material for a surveillance camera, and a surveillance camera which are less likely to generate dirt and which can easily remove dirt in the presence of dirt.

Next, an antifouling layer laminate according to an embodiment of the present invention and a protective material for a surveillance camera and a surveillance camera using the same will be described in detail.

<with antifouling layer laminate>

An antifouling layer laminate according to an embodiment of the present invention has a substrate and an antifouling layer provided on the substrate, and the antifouling layer contains at least an oxygen formed by a compound represented by the following formula (1) The content of the surface active component of the alkane binder, the antistatic agent, and the cerium oxide particles is 0.5% by mass or more based on the total solid content of the layer.

Conventionally, in order to easily remove dirt on the surface of a material, it is known to impart a decane compound, a surfactant, or the like to the surface of the material, or to prevent charging of the surface of the material so that dust or the like is not close. However, the ability to prevent adhesion of dust, dust, and gravel in the atmosphere, which is a cause of dirt, has not yet reached an extent that the antifouling function can be maintained for a long period of time and exhibits an antifouling function close to maintenance-free, and the antifouling performance is still improved. room.

In one embodiment of the present invention, the antifouling layer provided on the substrate is formed by using a composition containing a specific siloxane binder, cerium oxide particles, and an antistatic agent, thereby exhibiting more effectively The hydrophilicity of the surface of the layer is improved, and the properties of dust, dust, gravel, and the like (hereinafter also referred to as "contaminants") are less likely to adhere. With the component composition in one embodiment of the present invention, the antifouling layer is less likely to generate dirt, and in the case of dirt, the dirt can be easily removed.

(anti-fouling layer)

The antifouling layer in one embodiment of the present invention contains at least a naphthenic binder formed of a compound represented by the general formula (1), an antistatic agent, and cerium oxide particles, and the layer contained in the layer exhibits surface activity. The content of the component (hereinafter also referred to as a surface active component) is 0.5% by mass or more based on the total solid content of the antifouling layer.

Regarding the surface active component in the present disclosure, when the antistatic agent exhibits surface activity, the surface active component includes an antistatic agent; and an antistatic agent that does not exhibit surface activity additionally includes a surfactant or the like. In the case of a surface-active compound, the surface active component includes, for example, a compound exhibiting surface activity such as a surfactant.

Therefore, in the antifouling layer of the present disclosure, the surface active component may contain only an antistatic agent, and may contain a compound exhibiting surface activity such as a surfactant other than the antistatic agent. In the former case, the antifouling layer comprises at least a siloxane binder, an antistatic agent exhibiting surface activity, and cerium oxide particles; in the latter case, the antifouling layer contains at least a siloxane binder, not displayed Surface-active antistatic agents, cerium oxide particles, and compounds exhibiting surface activity such as surfactants. Further, in the latter case, the antifouling layer may contain both an antistatic agent and a compound exhibiting surface activity such as a surfactant, regardless of whether or not the antistatic agent is surface active.

In addition, the antifouling layer may further contain other components as needed.

-Oxane binder -

The antifouling layer in one embodiment of the present invention contains at least one of a naphthenic binder formed of a compound represented by the formula (1) (hereinafter also referred to as "specific alkoxylate compound").

The specific oxane compound is a decane oligomer. The oxymethane binder in one embodiment of the present invention is a compound which is a condensation reaction product of a specific oxane compound (a siloxane oxide oligomer) represented by the following formula (1). By containing the naphthalene binder in the antifouling layer, the hydrophilicity of the antifouling layer can be improved.

[Chemical 2] General formula (1)

In the 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 2 to 20.

The organic group having 1 to 6 carbon atoms in R ¹ , R ² , R ³ and R ⁴ may be linear, may have a branch, or may have a ring shape. The monovalent organic group may, for example, be an alkyl group or an alkenyl group, and is preferably an alkyl group.

Examples of the alkyl group in the case where R ¹ , R ² , R ³ or R ⁴ represents an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group, and a n-pentyl group. , n-hexyl, cyclohexyl and so on.

When the organic group of R ¹ to R ⁴ in the specific alkoxyalkyl compound, preferably the alkyl group, has 1 to 6 carbon atoms, the hydrolyzability of the decane oxide oligomer is good. In addition, R ¹ to R ⁴ are each independently more preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms, from the viewpoint of more excellent hydrolyzability.

n in the formula (1) is an integer of 2 to 20. When n is in the range of 2 to 20, the preparation liquid for the antifouling layer containing the specific siloxane compound (for example, the coating liquid for forming an antifouling layer when the antifouling layer is formed by coating; the same applies hereinafter) The viscosity is in an appropriate range. Further, the reactivity of the siloxane oxide oligomer can be controlled to a preferred range. n is preferably from 3 to 12, more preferably from 5 to 10.

In the case where n is 20 or less, the viscosity of the preparation liquid is not excessively high, and the handleability and uniform coating property when the antifouling layer is formed by coating are good. On the other hand, when n is 2 or more, the reactivity of the siloxane compound can be easily controlled, and for example, an antifouling layer having excellent surface hydrophilicity can be applied.

Examples of the specific alkoxylate compound are described below by R ¹ to R ⁴ and n in the formula (1). However, embodiments of the invention are not limited to these exemplified compounds.

[Table 1〕

The weight average molecular weight (Mw) of the specific oxyalkylene compound (the siloxane oxide oligomer) is preferably in the range of 300 to 1,500, and more preferably in the range of 500 to 1200.

The specific oxane compound is at least partially hydrolyzed by coexistence with water. The hydrolyzate of the specific oxane compound is at least a part of OR ¹ , OR ² , OR ³ and OR ⁴ bonded to the ruthenium atom of the specific oxirane compound by reacting the oxirane oligomer with water. The compound substituted with a hydroxyl group is presumed to have good hydrophilicity on the surface of the antifouling layer formed by coating and drying, for example, by the action of a hydroxyl group as a hydrophilic group.

When the hydrolysis reaction is carried out, it is not necessary to react all of the alkoxy groups of the specific oxoxane compound, and the hydrophilicity of the coating film obtained by, for example, application and drying of the coating liquid for forming an antifouling layer is further improved. It is contemplated that more alkoxy groups are preferably hydrolyzed.

The amount of water required for the hydrolysis is a molar amount equivalent to that of the specific alkoxylate compound, and from the viewpoint of more efficiently performing the hydrolysis reaction, it is preferred to have a large excess of water.

The hydrolysis reaction of the specific oxane compound can be carried out at room temperature (25 ° C). In order to promote the reaction, after the specific oxoxane compound is brought into contact with water to prepare a mixture, the obtained mixture can be heated to 30 ° C to 50 ° C. about. If the reaction time of the hydrolysis reaction is long, the reaction proceeds further, which is preferable. Therefore, from the viewpoint of sufficiently carrying out the hydrolysis reaction, it is also preferred to carry out the reaction in a heated state for 1 hour to 36 hours. Further, by allowing the catalyst for promoting the hydrolysis reaction of the specific oxane compound to be coexisted in the mixture as described in detail below, the hydrolyzate of the specific oxane compound required for hydrophilicity can be obtained even in about half a day.

The hydrolysis reaction is a reversible reaction. Therefore, when water is removed from the mixture, the hydrolyzate of the siloxane oligomer starts a condensation reaction between the hydroxyl groups. Thus, in the case where a hydrolysis reaction is carried out in a mixture containing a specific oxoxane compound and preferably a large excess of water to obtain a hydrolyzate of a specific oxoxane compound, it is preferred to use the mixture (solution) directly without separation of the hydrolyzate. Preparation of a preparation liquid for forming an antifouling layer (for example, a coating liquid for forming an antifouling layer in the case of coating an antifouling layer).

A preparation liquid containing a specific oxoxane compound (a siloxane oxide oligomer) represented by the above formula (1) by preparing a oxoxane binder contained in the antifouling layer of one embodiment of the present invention ( For example, the coating liquid for forming an antifouling layer) is applied to a substrate and dried to bond at least a part of the hydroxyl groups of the hydrolyzate of the siloxane oxide oligomer to each other to obtain a low oxane-containing gas. An antifouling layer of a helium oxide binder obtained by condensation of a polymer.

The antifouling layer may contain only one type of siloxane binder or two or more types of siloxane binder.

The content of the naphthene binder in the antifouling layer is preferably 5% by mass to 95% by mass, and more preferably 10% by mass to 80% by mass based on the total solid content of the antifouling layer. When the content of the naphthalene binder is in the above range, the water contact angle of the surface of the antifouling layer is suppressed to be low, and dirt is less likely to be generated, and in the case where there is dirt, the scale can be easily removed.

In the case where the coating liquid for forming an antifouling layer is prepared, the content of the specific oxoxane compound (hydroxane oligomer) represented by the formula (1) in the coating liquid is relative to the coating liquid. The total mass is preferably from 3% by mass to 70% by mass, more preferably from 5% by mass to 60% by mass, even more preferably from 10% by mass to 50% by mass.

-Antistatic agent -

The antifouling layer in one embodiment of the present invention contains at least one antistatic agent. The anti-staining layer is provided with an antistatic property by containing an antistatic agent, and an antistatic agent is contained together with the oxoxane binder and the cerium oxide particles, thereby preventing the adhesion of the contaminant and having a large effect, and the antifouling property is drastically improve.

The antistatic agent may be any one of a compound exhibiting surface activity or a compound exhibiting no surface activity, and examples thereof include an ionic surfactant, metal oxide particles, and the like.

The ionic surfactant has a property of being easily segregated in the vicinity of the film surface of the coating film when the antifouling layer is formed by, for example, coating, and thus it is expected that the effect can be obtained by a small amount of addition. Further, since the metal oxide particles provide antistatic properties, a relatively large amount of addition is sometimes required, but since it is an inorganic substance, it is suitable for improving the durability of the antifouling layer.

Examples of the ionic surfactant include alkyl sulfates (for example, sodium lauryl sulfate, sodium lauryl sulfate, etc.) and alkylbenzenesulfonates (for example, sodium dodecylbenzenesulfonate, Anions such as sodium laurylbenzenesulfonate, etc., alkylsulfonated succinates (such as sodium bis(2-ethylhexyl)sulfonated succinate), alkylphosphates (such as sodium dodecyl phosphate) Surfactants; cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts; and amphoteric surfactants such as alkylcarboxy beets.

It should be noted that when the ionic surfactant is excessively added in the layer, the amount of the electrolyte in the system increases, causing aggregation of the cerium oxide particles, which is known, and thus the ionic surface has been avoided for a long time. The composition of the active agent in combination with the cerium oxide particles. However, the present inventors have obtained a technical idea that an ionic surfactant exhibits an antifouling function against a contaminant, and an embodiment of the present invention is based on the technical idea of containing an ionic surfactant as an anti-fouling layer. An electrostatic agent is the preferred mode. By containing an ionic surfactant, the antifouling property and the water repellency of the antifouling layer are effectively improved.

The metal oxide particles are not particularly limited, and examples thereof include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, and zinc oxide particles.

In addition, the metal oxide particles may be used in combination of particles having different sizes, shapes or materials. The shape of the particles is not particularly limited, and may be a spherical shape, a plate shape, or a needle shape.

The metal oxide particles have a large refractive index, and when the particle diameter is large, the transmitted light is easily lost due to excessive scattering. Therefore, the average primary particle diameter is preferably 100 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less.

When the average primary particle diameter of the metal oxide particles is a substantially spherical shape such as a spherical shape or an elliptical cross section, the dispersed particles are observed by a transmission electron microscope, and 300 or more photographs are obtained from the obtained photographs. The particles were measured for the projected area of the particles, and the circle-equivalent diameter was obtained from the projected area to obtain the average primary particle diameter. In addition, in the case where the shape of the metal oxide particles is not spherical, it can be obtained by another method (for example, dynamic light scattering method).

When the ionic surfactant is used as the antistatic agent, the content of the ionic surfactant is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 20% by mass or less based on the total solid content of the antifouling layer. 10% by mass or less. When the content of the ionic surfactant is within the above range, aggregation of the cerium oxide particles can be avoided, and the antifouling property of the antifouling layer can be improved. In addition, the content of the ionic surfactant is preferably 0.05% by mass or more from the viewpoint of improving the antifouling property of the antifouling layer obtained by containing the ionic surfactant.

In the case where the coating liquid for forming an antifouling layer is prepared by using an ionic surfactant, the content of the ionic surfactant in the coating liquid is preferably 1.0% by mass or less based on the total mass of the coating liquid. It is preferably 0.8% by mass or less, and more preferably 0.5% by mass or less. When the proportion of the ionic surfactant in the coating liquid is within the above range, aggregation of the cerium oxide particles can be avoided and the antifouling property of the antifouling layer can be improved.

When the metal oxide particles are used as the antistatic agent, the content of the metal oxide particles is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass based on the total solid content of the antifouling layer. %the following. When the content of the metal oxide particles is within the above range, the antistatic property can be effectively imparted without impairing the film formability in the case where the antifouling layer is formed by coating. In addition, the content of the metal oxide particles is preferably 1% by mass or more from the viewpoint of improving the antifouling property of the antifouling layer obtained by containing the metal oxide particles.

In the case where the coating liquid for forming an antifouling layer is prepared using the metal oxide particles, the content of the metal oxide particles in the coating liquid is preferably 30% by mass or less based on the total mass of the coating liquid, and more preferably 20% by mass or less, and more preferably 10% by mass or less. When the proportion of the metal oxide particles in the coating liquid is within the above range, the dispersibility of the metal oxide particles in the liquid is increased, and it is advantageous from the viewpoint of preventing aggregation and the like.

～ shows the surface active ingredients~

In the antifouling layer according to the embodiment of the present invention, the component (surface active component) exhibiting surface activity with respect to the total solid content of the antifouling layer is contained in an amount of 0.5% by mass or more. In the antifouling layer, when the content of the "surface-active component" contained in the oxoxane binder and the cerium oxide particles is 0.5% by mass or more, the prevention of the contamination (especially gravel, etc.) is exhibited. Excellent adhesion and excellent antifouling properties.

As described above, the component exhibiting surface activity may be a compound exhibiting surface activity, and also includes the above antistatic agent. Therefore, if the antistatic agent is a compound exhibiting surface activity, it is not necessary to additionally contain a surface active component in addition to the antistatic agent. On the other hand, in the case where the antistatic agent does not exhibit surface activity, it contains a surface active component such as a surfactant. That is, the antifouling layer in one embodiment of the present invention contains at least one of an antistatic agent and a surface active component other than the antistatic agent as a surface active component.

When the antifouling layer contains a surface active component, not only the antifouling property of the antifouling layer is improved, but also the coating property in the case where the antifouling layer is formed by coating, for example, the surface tension of the coating liquid used for coating is also lowered, and the coating film is coated. The uniformity is further improved.

Examples of the surface active component include a nonionic surfactant, an ionic (anionic, cationic, amphoteric) surfactant, and the like. An example of the ionic surfactant may be a compound exemplified in the antistatic agent. In addition, when an ionic surfactant is used as an antistatic agent, the ionic surfactant added as an antistatic agent can contribute to the improvement of wettability.

As described above, when the ionic surfactant is excessively added in the layer, the amount of the electrolyte in the system is increased, and aggregation of the cerium oxide particles is easily caused, so that in the case where an ionic surfactant is used as the antistatic agent, it is preferred. A nonionic surfactant is used in combination. It is only necessary that the nonionic surfactant is used in combination with the ionic surfactant, and a nonionic surfactant may be contained alone as a surface active component.

Examples of the nonionic surfactant include a polyalkylene glycol monoalkyl ether, a polyalkylene glycol monoalkyl ester, a polyalkylene glycol monoalkyl ester, and a monoalkyl ether. Specific examples of the nonionic surfactant include polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monohexadecyl ether, and polyethylene glycol single laurel. Ester, polyethylene glycol monostearyl ester, and the like.

The content of the surface active component in the antifouling layer is 0.5% by mass or more based on the total solid content of the antifouling layer, and preferably 1.0% by mass or more.

In addition, the content of the surface active component is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and still more preferably 30.0% by mass or less based on the total solid content of the antifouling layer. When the content of the surface active component is 30.0% by mass or less, the phenomenon in which the surface active component is segregated on the film surface is suppressed, and the hardness of the film can be favorably maintained, which is advantageous from this point of view. In addition, as described above, in the case of using an ionic surfactant, the content of the ionic surfactant is more preferably 50.0% by mass or less based on the total solid content of the antifouling layer.

In the case of preparing a coating liquid for forming an antifouling layer containing a surface active component, the content of the surface active component in the coating liquid is preferably 0.01% by mass or more, and more preferably 0.02, based on the total mass of the coating liquid. The mass% or more is more preferably 0.03% by mass or more. When the content of the surface active component is within the above range, the wettability on the substrate is more excellent. In addition, the content of the surface active component is preferably 15% by mass or less, more preferably 10.0% by mass or less, and still more preferably 5% by mass or less based on the total solid content of the coating liquid.

- cerium oxide particles -

The antifouling layer in one embodiment of the present invention contains at least one of cerium oxide particles. The cerium oxide particles have a function of further improving the physical resistance of the antifouling layer while further exerting hydrophilicity. That is, the cerium oxide particles act as a hard filler, and the hydroxyl groups on the surface of the particles act to contribute to hydrophilicity.

The shape of the cerium oxide particles is not particularly limited, and examples thereof include a spherical shape, a plate shape, a needle shape, and a bead shape.

Examples of the cerium oxide particles include, for example, the Snowtex (registered trademark) series (for example, Snowtex O) manufactured by Nissan Chemical Industries, Ltd., and the Nalco (registered trademark) series (for example, Nalco 8699) manufactured by Nalco Chemical Co., Ltd., and the like.

When the particle diameter of the cerium oxide particles is too large, the transmitted light may be scattered. Therefore, the average primary particle diameter of the cerium oxide particles is preferably 100 nm or less, more preferably 50 nm or less, and still more preferably 30 nm or less. In addition, the cerium oxide particles may also be mixed with particles of different sizes or shapes.

The average primary particle diameter of the cerium oxide particles can be observed by a transmission electron microscope in the same manner as the average primary particle diameter of the metal oxide particles described above, and the projected area of the particles of 300 or more particles is obtained from the obtained photograph. For the measurement, the circle-equivalent diameter was obtained from the projected area, and the average primary particle diameter of the cerium oxide particles was determined.

The content of the cerium oxide particles is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, even more preferably 20% by mass to 80% by mass based on the total solid content of the antifouling layer. When the content of the cerium oxide particles is within the above range, the hardness, the scratch resistance, and the impact resistance are excellent, and at the same time, the hydrophilic antifouling layer can be formed.

In the case of preparing a coating liquid for forming an antifouling layer containing cerium oxide particles, the content of the cerium oxide particles in the coating liquid is preferably 30% by mass or less based on the total mass of the coating liquid, and more preferably It is 20% by mass or less, and more preferably 10% by mass or less. When the proportion of the cerium oxide particles in the coating liquid is within the above range, the dispersibility of the cerium oxide particles in the liquid is increased, and it is advantageous from the viewpoint of preventing aggregation and the like.

-catalyst-

The antifouling layer in one embodiment of the present invention preferably contains at least one of a catalyst (condensation promoting catalyst) which promotes condensation of a siloxane oxide oligomer. By containing a catalyst, the formation of a naphthenic binder can be promoted. Thereby, the durability of the antifouling layer is more excellent.

When the antifouling layer is formed by application of the coating liquid for forming an antifouling layer, the coating film formed by coating is dried to reduce moisture, and at least a part of the hydroxyl groups of the hydrolyzate of the siloxane oxide oligomer are bonded to each other. The formation of a stable film in which the siloxane oxide oligomer has condensed. At this time, if a catalyst which can promote condensation of a siloxane oxide oligomer is contained, formation of an antifouling layer can be performed more rapidly.

The catalyst is not particularly limited, and examples thereof include an acid catalyst, a rhodium catalyst, and an organometallic catalyst. 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 the ruthenium catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and the like. Examples of the organometallic catalyst include aluminum chelates such as bis(acetonitrile ethyl acetate) mono(acetonitrile acetonide) aluminum, tris(acetonitrile acetonide) aluminum, and ethyl acetonitrile diisopropoxy aluminum. a compound; a zirconium chelate compound such as tetrakis(acetonitrile acetonide) zirconium or bis(butoxy)bis(acetonitrile acetonide) zirconium; tetra(acetonitrile acetonide) titanium, bis(butoxy) bis (B) a titanium chelate compound such as ruthenium acetonate; titanium; an organotin compound such as dibutyltin diacetate, dibutyltin dilaurate or dibutyltin dioctanoate; and the like.

Among them, as the catalyst, an organometallic catalyst is preferred, and an aluminum chelate compound or a zirconium chelate compound is more preferred.

The content of the catalyst in the antifouling layer is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 15% by mass, even more preferably 0.3% by mass to 10% by mass based on the total solid content of the antifouling layer. When the content of the catalyst is within the above range, it is easy to form an antifouling layer having moderate hardness and durability. Further, the formability of the antifouling layer is also excellent.

In the case of preparing a coating liquid for forming an antifouling layer containing a catalyst, the content of the catalyst in the coating liquid is preferably 0.1% by mass to 20% by mass, and more preferably 0.2% based on the total solid content of the coating liquid. The mass% to 15% by mass, and more preferably 0.3% by mass to 10% by mass.

It is to be noted that a catalyst which promotes condensation of a siloxane oxide oligomer is also useful for hydrolysis of a siloxane oxide oligomer. Here, the hydrolysis reaction of the alkoxy group bonded to the oxime of the siloxane oligomer is in equilibrium with the condensation reaction. If there is much water in the system, the reaction proceeds in the direction of hydrolysis; if the water in the system is small Then, the reaction proceeds in the direction of condensation. Since the catalyst which promotes the condensation reaction of the alkoxy group can promote the reaction in two directions, the hydrolysis reaction can be promoted in a state where the moisture in the system is large. Hydrolysis of the oxirane oligomer can be carried out more reliably under more stable conditions due to the presence of the catalyst.

In this case, the catalyst used in the hydrolysis reaction of the siloxane oxide oligomer is directly used as a component of the coating liquid for forming an antifouling layer in the system, and is directly used as a catalyst for condensation of a decane oligomer. It is efficient.

-Other ingredients -

In addition to the above components, the antifouling layer according to the embodiment of the present invention may further contain an additive such as a binder component other than a decane binder or a preservative as another component.

Examples of the binder component other than the siloxane binder include a polyurethane, an acrylic resin, a polyphosphate, a methyl phosphate or the like having a polar group at the terminal (for example, a hydroxyl group, a carboxyl group, a phosphoric acid group, or a sulfonic acid group). A binder component of a base, an amino group, or the like.

By including the above-described binder component in the antifouling layer, the adhesion between the antifouling layer and the substrate (especially the polycarbonate substrate) is improved.

Among the above-mentioned binder components, a binder component having a hydroxyl group, a carboxyl group, or a phosphoric acid group at the terminal is preferable from the viewpoint of adhesion between the antifouling layer and the substrate, and more preferably a polyurethane, an acrylic resin, or a polyphosphoric acid. salt.

The polyurethane is not particularly limited, and examples thereof include a polyurethane having a soft segment/hard segment structure composed of a polyol skeleton and a polyisocyanate skeleton.

Commercially available products, for example, Takelac (registered trademark) W series manufactured by Mitsui Chemicals, Inc., WS series, WD series, PERMARIN (registered trademark) series manufactured by Sanyo Chemical Industries, Ltd., UCOAT (registered trademark) Series, UPRENE (registered trademark) series, etc.

Examples of the acrylic resin include an acrylic acid homopolymer (polyacrylic acid), an acrylic acid derivative such as acrylic acid or an ester thereof, and a methacrylic acid derivative such as methyl methacrylate.

Among these acrylic resins, polyacrylic acid is preferable, and polyacrylic acid having a weight average molecular weight of 2,000 to 5,000,000 is preferable, polyacrylic acid having a weight average molecular weight of 10,000 to 2,000,000 is more preferable, and a weight average molecular weight is more preferably 250,000 to 1,000,000. Polyacrylic acid.

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

It should be noted that the weight average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, HLC-8120GPC and SC-8020 (manufactured by Tosoh Corporation) can be used, and two TSKgels and SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15 cm) can be used as the column, and tetrahydrofuran can be used as an eluent. (THF), for measurement. Further, as a condition, a sample concentration of 0.5% by mass, a flow rate of 0.6 ml/min, a sample injection amount of 10 μl, and a measurement temperature of 40° C. can be used, and a differential refractive index (RI) detector can be used. The calibration curve can use the "polystyrene standard sample TSK standard" manufactured by Tosoh Corporation: "A-500", "F-1", "F-10", "F-80", "F-380" Calibration curves prepared from 10 samples of "A-2500", "F-4", "F-40", "F-128", and "F-700".

The content of the binder component other than the naphthene binder in the antifouling layer is preferably 0.001% by mass to 0.1% by mass, more preferably 0.001% by mass to 0.01% by mass, based on the total solid content of the antifouling layer, and further It is preferably 0.002% by mass to 0.008% by mass. When the content of the binder component other than the siloxane binder is within the above range, it is easy to form an antifouling layer having excellent adhesion to the substrate.

In the case of preparing a coating liquid for forming an antifouling layer containing a binder additive component, the content of the binder additive component in the coating liquid is preferably 0.001% by mass based on the total solid content of the coating liquid. 0.1% by mass, more preferably 0.001% by mass to 0.01% by mass, still more preferably 0.002% by mass to 0.008% by mass.

The antifouling layer in one embodiment of the present invention preferably does not contain a photopolymerization initiator and a thermal polymerization initiator. When the photopolymerization initiator and the thermal polymerization initiator are not contained, light irradiation or heat treatment can be omitted when the antifouling layer is formed. In addition, in the case of preparing the coating liquid for forming an antifouling layer, it is preferable that the photopolymerization initiator and the thermal polymerization initiator are not contained from the viewpoint of storage stability of the coating liquid for forming an antifouling layer.

The antifouling layer in one embodiment of the present invention contains cerium and oxygen as main components of a solid component, and the fact that the content of carbon is small is also a feature. By reducing the carbon content, for example, using a coating liquid for forming an antifouling layer to form a coating film and drying it to form an antifouling layer, the antifouling layer thus formed is formed in various environments exposed to wind and rain even when it is installed outdoors. It is also possible to minimize the influence of light and heat on the layer.

In the antifouling layer according to the embodiment of the present invention, the proportion of carbon in the total solid content is preferably 3% by mass or less, more preferably 2.5% by mass or less, and still more preferably 2% by mass or less.

Further, when the antifouling layer according to an embodiment of the present invention contains an organic compound containing carbon, the organic compound containing carbon is preferably a compound having a low weight average molecular weight. Specifically, in the antifouling layer, the content of the organic compound having a weight average molecular weight of 1100 or more is preferably 0.2% by mass or less, more preferably 0% by mass, that is, in addition to unavoidable impurities, with respect to the total solid content of the antifouling layer. This compound is not contained outside.

When the content of the organic compound having a weight average molecular weight of 1100 or more is in the above range, the compatibility of the solid component in the antifouling layer is further improved, and when the coating film is formed using the coating liquid for forming an antifouling layer, film formation can be further improved. Sex.

In addition, the above-mentioned "oxygenane binder" is not contained in the "organic compound having a weight average molecular weight of 1100 or more".

Further, the weight average molecular weight can be measured by the aforementioned method.

The thickness of the antifouling layer in one embodiment of the present invention is preferably in the range of 20 nm to 600 nm, and more preferably in the range of 50 nm to 350 nm.

~Formation method of antifouling coating~

The antifouling layer in one embodiment of the present invention can be formed by preparing a preparation liquid for forming an antifouling layer and imparting a preparation liquid to a desired substrate. The antifouling layer can be formed, for example, by preparing a coating liquid for forming an antifouling layer as a preparation liquid, applying a coating liquid for forming an antifouling layer to a substrate by a coating method to form a coating film, and drying the coating film to form an anti-staining layer. Stained layer.

The coating method for applying the coating liquid to the substrate is not particularly limited, and for example, a known method such as spray coating, brush coating, roll coating, bar coating, or dip coating (dip coating) can be applied.

The thickness of the coating film formed by coating is preferably in the range of 50 nm to 350 nm in terms of dry thickness.

The drying of the coating film after the application of the coating liquid can be carried out at room temperature (25 ° C) or at 40 ° C to 120 ° C. Further, in the case of heating, the drying time may be from about 1 minute to 30 minutes.

-Preparation method of coating liquid for forming antifouling layer~

The coating liquid for forming an antifouling layer used when the antifouling layer is formed by coating will be described.

The coating liquid for forming an antifouling layer can be prepared by mixing at least a siloxane oxide oligomer (a compound represented by the formula (1)), an antistatic agent, cerium oxide particles, and a water component. Preferably, the siloxane oligomer is first mixed with a water component to obtain a hydrolyzate of a siloxane oxide oligomer, followed by mixing other components. In this case, it is preferred to add a catalyst which promotes condensation of the siloxane oxide oligomer.

Specifically, after preparing a solution containing a hydrolyzate of a siloxane oxide oligomer, an antistatic agent and cerium oxide particles are added to the solution, and further, a condensation of a surfactant and a siloxane oligomer is added as needed. Promote the catalyst. The surfactant functions as a wettability improver.

In the above, in the case where an antistatic agent and a surfactant are added, a part or all of the antistatic agent and the surfactant may be added in the step of obtaining a hydrolyzate of the siloxane oxide oligomer.

The preparation conditions of the coating liquid for forming an antifouling layer are not particularly limited, and from the viewpoint of preventing aggregation of the ceria particles due to the concentration of the pH or the coexisting component, it is preferred to add in the latter half of the process of preparing the coating liquid, preferably at the end. Ceria particles. Here, in the case where the cerium oxide particles are used in the form of a dispersion (specifically, a dispersion obtained by dispersing cerium oxide particles in an aqueous solvent in advance, or a commercially available cerium oxide particle dispersion) Preferably, the pH of the dispersion and the pH of the solvent used in the coating liquid are both acidic or alkaline, and the dispersion of the cerium oxide particles and the pH of the solvent of the coating liquid are prepared to have the same or similar values.

~ Physical properties of antifouling layer ~

The antifouling layer in the present disclosure is excellent in light transmittance, and has excellent antistatic properties and hydrophilicity on the surface, so that the antifouling layer has excellent antifouling properties on the surface. Therefore, the antifouling layer is suitable as a protective material for a device or building material installed outdoors (for example, a surveillance camera, a protective material for protecting the lighting, a roofing material for a garage, a protective material for a sign, a wall material, etc.) The dirt layer and the adhesion of pollutants are suppressed. Further, since the antifouling layer has good hydrophilicity, when a contaminant is adhered to the surface, the contaminant can be easily removed by washing (for example, water washing), and a small amount of contaminant can be exhibited, for example, when it is rainy. The effect of rinsing off the rain.

Preferred physical properties of the film in one embodiment of the present invention are listed below.

[surface resistance]

The surface resistance value of the antifouling layer is preferably 1 × 10 ¹² Ω/sq (Ω/square; the same applies hereinafter), more preferably 1 × 10 ¹¹ Ω/sq or less, further preferably 1 × 10 ¹⁰ Ω/sq. the following. When the surface resistance of the antifouling layer is within the above range, the antifouling property of the antifouling layer is more excellent.

The surface resistance value was measured using a high-impedance analyzer MCP-HT450 (manufactured by Mitsubishi Chemical Analysis Co., Ltd.).

[water contact angle]

The water contact angle of the antifouling layer is preferably 40 or less, more preferably 30 or less, further preferably 25 or less, and particularly preferably 15 or less. When the water contact angle is in the above range, the surface of the antifouling layer is more excellent in hydrophilicity.

For the water contact angle, a contact angle meter M553G-XM (manufactured by Shiro Co., Ltd.) was used, and 1 μl of pure water was dropped on the surface of the antifouling layer by the θ/2 method, and the average value of the measurement was measured five times. The value is taken as the contact angle value.

[integral sphere transmittance]

The antifouling layer in one embodiment of the present invention is preferably excellent in light transmittance. From this point of view, it is preferable that the integrated sphere transmittance of the antifouling layer (the average value of the integrated sphere transmittance of the wavelength (λ) = 300 nm to 1200 nm) is above 95.

The integrating sphere transmittance here is obtained by measuring the integrating sphere transmittance at a wavelength of 5 nm in a wavelength range of 300 nm to 1200 nm, averaging the measured values, and obtaining an average value (wavelength (λ) = 300 nm to 1200 nm. The average value of the integrated sphere transmittance is the integrated sphere transmittance.

The integrating sphere transmittance is more preferably 95.5% or more.

Regarding the integrated sphere transmittance of the antifouling layer, the barium sulfate white plate is used as a reference to measure the integrating sphere transmittance of the substrate on which the antifouling layer is not formed and the substrate on which the antifouling layer is formed, from the substrate on which the antifouling layer is formed The integrating sphere transmittance is subtracted from the integrating sphere transmittance of the substrate on which the antifouling layer is not formed, thereby calculating the degree of improvement in light transmittance with respect to the substrate.

The integrating sphere transmittance was measured using a transmission type spectrophotometer with an integrating sphere. Specifically, for example, a device obtained by connecting an integrating sphere attachment device (ISR-2200, manufactured by Shimadzu Corporation) to an ultraviolet-visible infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation) or in ultraviolet In the infrared spectrophotometer (UV-3600, manufactured by Shimadzu Corporation), a device obtained by connecting a multi-purpose large sample chamber (MPC-3100, manufactured by Shimadzu Corporation) and the like is used, and light having a wavelength of 300 nm to 1400 nm is used. Determination.

The higher the degree of improvement in transmittance by measurement, the more excellent the transparency (low reflectance), and the degree of improvement in light transmittance (wavelength (λ) = 400 nm to 1400 nm) is preferably 1% or more, and more preferably 1.5% or more. It is particularly preferably 1.8% or more.

In addition, the degree of improvement of light transmittance is obtained as the average value of the wavelength region of 400 nm - 1400 nm.

[Transmittance]

The transmittance of the antifouling layer (the average value of λ = 300 nm to 1200 nm) is preferably 70% or more, and more preferably 80% or more. The transmittance of the antifouling layer can be determined by measuring the integrating sphere transmittance of the substrate on which the antifouling layer is formed by using the integrating sphere transmittance of the substrate on which the antifouling layer is not formed.

The transmittance is a value measured by a self-recording spectrophotometer (UV2400-PC, manufactured by Shimadzu Corporation).

(substrate)

The substrate on which the antifouling layer laminate is formed according to one embodiment of the present invention is not particularly limited, and may be appropriately selected from various materials such as glass, resin materials (plastic materials), metals, and ceramics.

Glass is widely used as a substrate, and it is suitable as a substrate which forms the antifouling layer laminate which forms one embodiment of this invention. When glass is used as a base material, condensation of a hydroxyl group on a crucible is also generated between the hydroxyl groups on the surface of the glass, and a film which is more excellent in adhesion to the base material can be formed.

Further, as the substrate, a resin material is also suitable. For example, a resin material is often used for a substrate such as a protective material for a surveillance camera. Among the resin materials, polycarbonate and polymethyl methacrylate are preferred from the viewpoint of excellent durability against light and heat.

The substrate can be a composite material. The base material may be, for example, a composite material containing glass and a resin material, and a composite material obtained by mixing and combining glass and a resin material, or a resin composite material obtained by kneading or bonding two or more resin materials. Any one.

The thickness of the substrate is not particularly limited and may be appropriately selected depending on the use, the purpose of use, and the like, and may be, for example, 0.05 mm to 10 mm.

The antifouling layer laminate according to one embodiment of the present invention is suitably used for a surveillance camera, a protective material for protecting lighting (so-called protective cover), a roofing material for a garage for a vehicle such as a car or a bicycle, and a road sign. It is used for protective materials such as signs, for the installation of highway roads, and for soundproof walls such as railways.

Among them, it can be suitably applied to the use of a protective material for a surveillance camera (a so-called camera cover) that protects an imaging device.

<Monitor Camera>

A monitoring camera according to an embodiment of the present invention includes an anti-fouling layer laminate according to an embodiment of the present invention for protecting an imaging device. The surveillance camera usually includes an imaging device for imaging, a fixing member, and the like.

The antifouling layer laminate according to one embodiment of the present invention has an antifouling property excellent in light transmissivity and antifouling property on a substrate, particularly a plastic substrate (preferably polycarbonate and polymethyl methacrylate). Floor. Therefore, the antifouling layer laminate according to the embodiment of the present invention is, for example, an imaging device of a surveillance camera that is required to be exposed to a harsh environment for a long period of time and which is required to maintain excellent light transmittance, transparency, and long-term durability. It is useful to protect the protective surface of the camera.

In the use of the surveillance camera, the shape of the substrate is preferably a hemispherical shape, a semi-ellipsoidal shape (including a so-called dome shape), a planar shape, a quadrangular prism shape, or a cylindrical shape.

Here, the ellipsoid is a shape in which the ellipse is three-dimensionally expanded so as to be symmetrical with respect to the xy plane, the yz plane, and the zx plane.

In addition, the size of the substrate is not particularly limited, and may be appropriately selected depending on the use, the purpose of use, and the like. For example, in the case of a hemispherical shape, the diameter of the circle of the opening surface may be, for example, in the range of 10 mm to 1000 mm.

As the kind of the substrate for the surveillance camera, a plastic substrate is suitably used, and for example, polycarbonate and polymethyl methacrylate are preferable. The antifouling layer in one embodiment of the present invention is in close contact with these plastic substrates, and exhibits excellent antifouling properties.

[Examples]

One embodiment of the present invention will now be described more specifically by way of examples. However, the present embodiment is not limited to the following embodiments as long as the gist of the invention is not exceeded.

(Example 1)

- Preparation of aqueous antifouling coating agent -

The rhodium oxide oligomer (the compound represented by the formula (1) (R ¹ to R ⁴ : ethyl group, n=5)) was added with respect to 81.07 g of ethanol, 3.06 g and bis(acetic acid ethyl acetate) mono ( 0.94 g of a 1% by mass isopropanol solution (a condensation promoting catalyst for a siloxane oxide) of acetamidine acetone was mixed and mixed.

To the obtained solution, an aqueous solution 114.80 in which 0.057 g of polyethylene glycol monolauryl ether (repeated number 15 of the ethylene oxide moiety; nonionic surfactant which is a component exhibiting surface activity) was slowly added was added. g, stir at room temperature for more than 12 hours. Thus, the siloxane oxide oligomer was hydrolyzed to prepare a coating mother liquid S-1.

Next, 7.36 g of ethanol, 12.58 g of water, and polyethylene glycol monolauryl ether (repeated number 15 of the ethylene oxide moiety) were added to 19.99 g of the coating mother liquid S-1 as a component exhibiting surface activity. Nonionic surfactant) 0.0056 g. Thereafter, 0.0011 g of sodium bis(2-ethylhexyl)sulfonated succinate (an ionic surfactant as an antistatic agent) was further added for dilution. To the solution, a 1% by mass isopropyl alcohol solution (a condensation promoting catalyst for a siloxane oxide oligomer) of bis(acetonitrile ethyl acetate) mono(acetonitrile acetonate) aluminum was further added to 0.85 g and cerium oxide particles ( An aqueous antifouling coating agent AS-1 was prepared by using 1.70 g of a 33% by mass dispersion liquid of Snowtex (registered trademark) O, an average primary particle diameter: 10 nm to 15 nm, manufactured by Nissan Chemical Industries, Ltd.).

In addition, the "surface-active component" contained in the aqueous antifouling coating agent AS-1 contains polyethylene glycol monolauryl ether and di(2-ethylhexyl)sulfonated sodium succinate. .

-The production of the camera cover -

Next, the prepared aqueous antifouling coating agent AS-1 was spray-coated to a polymethyl methacrylate molding having a semi-ellipsoidal shape (dome shape) [maximum outer diameter: 150 mm, maximum height: 130 mm, thickness: 3 mm]. A coating film was formed on the entire outer peripheral curved surface of the component (monitoring camera cover K type (transparent), manufactured by Ebara Co., Ltd.; substrate). The coating film was dried at 25 ° C for 1 hour to form an antifouling layer having a thickness of 130 nm (0.13 μm). A sprayer spray device (Preval, manufactured by Precision Valve Co., Ltd.) was used for spray coating. Here, the siloxane oligomer contained in the coating film is condensed, and the oxyalkylene binder is contained in the antifouling layer.

A camera cover (with an antifouling layer laminate) for a surveillance camera having a semi-ellipsoidal shape (dome shape) having an antifouling layer was produced as described above.

-Evaluation-

The following measurement or evaluation was performed with the camera cover using the prepared surveillance camera. The evaluation results are shown in Table 2 and Table 3 below.

(1) Water contact angle

Using a contact angle meter M553G-XM (manufactured by Shiro Co., Ltd.), 1 μl of pure water was dropped on the surface of the antifouling layer, and the contact angle [°] was measured by the θ/2 method, and the average value of the measurement was measured five times. As a water contact angle.

The water contact angle is allowed to be 40 or less.

(2) Antifouling

After the natural loess pigment (manufactured by Holbein Co., Ltd.) was uniformly spread on the surface of the antifouling layer of the camera cover and adhered, the back surface of the camera cover was hit, and the adhered natural loess pigment was dropped, and the operation was repeated five times. Thereafter, the adhesion area of the natural loess pigment was determined, and the degree of the scale was evaluated in accordance with the following evaluation criteria. Among the evaluation criteria A to E, A and B are allowable ranges.

<Evaluation criteria>

A: The natural loess pigment is not attached to the surface of the antifouling layer and is colorless and transparent.

B: A natural loess pigment adhered to the surface of the antifouling layer, and the adhesion area is 10% or less of the total area.

C: A natural loess pigment adhered to the surface of the antifouling layer, and the adhesion area is more than 10% of the total area and 50% or less.

D: A natural loess pigment is adhered to the surface of the antifouling layer, and although the antifouling layer maintains transparency, the adhesion area is more than 50% of the total area.

E: A natural loess pigment is attached to the entire surface of the antifouling layer, and is partially or completely opaque.

(3) Surface resistance

The surface resistance of the produced antifouling layer with the antifouling layer laminate was measured and found to be 1.7 × 10 ⁹ Ω/sq (Ω/square). In addition, the surface resistance was measured by the high-impedance analyzer MCP-HT450 (manufactured by Mitsubishi Chemical Analysis Co., Ltd.).

(4) Integrating sphere transmittance

Moreover, the integral sphere transmittance of the antifouling layer of the produced antifouling layer laminate was measured and found to be 95% or more in terms of an average value of a wavelength band of 300 nm to 1200 nm.

In addition, as for the transmittance of the integrating sphere, a semi-ellipsoidal polymethyl methacrylate molding material used as a substrate is used as a reference, and it is used in an ultraviolet-visible infrared spectrophotometer (UV-3600, Shimadzu Corporation). A device in which a multi-purpose large sample chamber (MPC-3100, manufactured by Shimadzu Corporation) is connected and manufactured by a light source having a wavelength of 300 nm to 1400 nm is used for measurement.

(5) Adhesion

The anti-fouling layer of the camera cover obtained by the above-mentioned camera was cut into a size of 3 cm × 3 cm, and was wiped with a load of ¹ mN/cm ² by using a nonwoven fabric (Bemcoat manufactured by Asahi Kasei Co., Ltd.) infiltrated with 3 ml of pure water. 5,000 times, the adhesion between the substrate of the camera cover for the surveillance camera and the antifouling layer was evaluated according to the following evaluation criteria.

<evaluation standard>

A: No blemishes and flaking were observed in the antifouling layer.

B: Helium was observed in the antifouling layer, but no peeling was observed and retained.

C: Part of the antifouling layer peeled off.

D: The antifouling layer is completely peeled off.

(Example 2)

An aqueous antifouling coating agent AS-2 was prepared in the same manner as in Example 1 except that the amount of sodium bis(2-ethylhexyl)sulfonated succinate was changed from 0.0011 g to 0.011 g in Example 1. Further, a camera cover (with an antifouling layer laminate) for the surveillance camera was produced and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Example 3)

An aqueous antifouling coating agent AS-3 was prepared in the same manner as in Example 1 except that the amount of sodium bis(2-ethylhexyl)sulfonated succinate was changed from 0.0011 g to 0.11 g. Further, a camera cover (with an antifouling layer laminate) for the surveillance camera was produced and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Example 4)

An aqueous antifouling coating agent AS-4 was prepared in the same manner as in Example 1 except that the amount of sodium bis(2-ethylhexyl)sulfonated succinate was changed from 0.0011 g to 1.1 g in Example 1. Further, a camera cover (with an antifouling layer laminate) for the surveillance camera was produced and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Example 5)

In the first embodiment, the amount of the polyethylene glycol monolauryl ether used in the preparation of the coating mother liquid S-1 was changed from 0.057 g to 0 g, and the polyb was additionally added after the preparation of the coating mother liquid S-1. An aqueous antifouling coating agent AS-5 was prepared in the same manner as in Example 1 except that the amount of the diol monolauryl ether was changed from 0.0056 g to 0.0033 g, and a camera cover for a surveillance camera (with antifouling layer lamination) was further prepared. (body), and conduct measurements and evaluation. The results of the measurement and evaluation are shown in Table 2.

(Example 6)

In Example 1, 0.001 g of sodium di(2-ethylhexyl)sulfonated succinate was used, and 1.20 g of a 50% by mass dispersion of tin oxide particles (average primary particle diameter: 15 nm to 25 nm) was used. An aqueous antifouling coating agent AS-6 was prepared in the same manner as in Example 1, and a camera cover for a surveillance camera (with an antifouling layer laminate) was further prepared and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Example 7)

In Example 6, zinc oxide and cerium oxide composite oxide particles (average primary particle diameter: 15 nm to 25 nm) were used without using 1.20 g of a 50% by mass dispersion liquid of tin oxide particles (average primary particle diameter: 15 nm to 25 nm). An aqueous antifouling coating agent AS-7 was prepared in the same manner as in Example 6 except that the amount of the dispersion was 30% by mass, and a camera cover for a surveillance camera (with an antifouling layer laminate) was prepared and measured. Evaluation. The results of the measurement and evaluation are shown in Table 2.

(Example 8)

In Example 6, 30 mass% of a 50 mass% dispersion liquid of tin oxide particles (average primary particle diameter: 15 nm to 25 nm) was used, and 30 mass of gallium-doped zinc oxide particles (average primary particle diameter: 20 nm to 40 nm) was used. An aqueous antifouling coating agent AS-8 was prepared in the same manner as in Example 6 except that the dispersion liquid was used in the same manner as in Example 6, and a camera cover (with an antifouling layer laminate) for a surveillance camera was further prepared and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Example 9)

In Example 6, a dispersion of 1.20 g of a 50% by mass dispersion of tin oxide particles (average primary particle diameter: 15 nm to 25 nm) and 20% by mass of a dispersion of tin oxide particles (average primary particle diameter: 150 nm) was used. In the same manner as in Example 6, an aqueous antifouling coating agent AS-9 was prepared, and a camera cover for a surveillance camera (with an antifouling layer laminate) was further prepared and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Embodiment 10)

In Example 1, in the preparation of the coating mother liquid S-1 and the subsequent preparation of the aqueous antifouling coating agent AS-1, no bis(acetonitrile ethyl acetate) mono(acetonitrile) aluminum was added. An aqueous antifouling coating agent AS-10 was prepared in the same manner as in Example 1 except that the isopropyl alcohol solution was used in the same manner as in Example 1, and a camera cover for a surveillance camera (with an antifouling layer laminate) was prepared and measured and evaluated. . The results of the measurement and evaluation are shown in Table 2.

(Example 11)

In the first embodiment, the amount of polyethylene glycol monolauryl ether (the number of repetitions of the ethylene oxide portion 15) added after the preparation of the coating mother liquid S-1 is proportional to the amount of the coating mother liquid S-1. An aqueous antifouling coating agent AS-11 was prepared in the same manner as in Example 1 except that the amount was changed to 0.11 g, and a camera cover for a surveillance camera (with an antifouling layer laminate) was further prepared and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Embodiment 12)

In Example 1, 0.0056 g of polyethylene glycol monolauryl ether (repeated number 15 of the ethylene oxide moiety) additionally added after the preparation of the coating mother liquid S-1 was replaced with stearic acid polyoxyethylene hard. An aqueous antifouling coating agent AS-12 was prepared in the same manner as in Example 1 except that the aliphatic ether (the number of repetitions of the ethylene oxide portion was 15) was 0.11 g, and a camera cover for a surveillance camera (with an antifouling layer) was further prepared. Integral), and measurement and evaluation. The results of the measurement and evaluation are shown in Table 2.

(Example 13)

In the same manner as in Example 1, the aqueous antifouling coating agent AS-1 was prepared in the same manner as in Example 1 except that the spray coating was changed to the immersion (dip coating), and a camera cover for a surveillance camera (with an antifouling layer) was further prepared. Laminated body), and measured and evaluated. The dip coating is carried out by bringing the outer peripheral surface of the semi-ellipsoidal polymethyl methacrylate molded member into contact with the aqueous antifouling coating agent AS-1 stored in the container so that the aqueous antifouling coating agent adheres to the entire outer peripheral surface. The results of the measurement and evaluation are shown in Table 2.

(Example 14)

An aqueous antifouling coating agent was prepared in the same manner as in Example 1 except that 0.0011 g of sodium bis(2-ethylhexyl)sulfonated succinate was used instead of 0.0011 g of sodium lauryl sulfate. AS-14, a camera cover (with an antifouling layer laminate) for surveillance cameras was further produced and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Example 15)

In Example 1, in the preparation of the coating mother liquid S-1 and the subsequent preparation of the aqueous antifouling coating agent AS-1, polyethylene glycol monolauryl ether (the number of repetitions of the ethylene oxide portion) was not used. 15) In the same manner as in Example 1, except that polyethylene glycol monostearyl ether (repeated number 15 of the ethylene oxide moiety; nonionic surfactant which is a component which exhibits surface activity) was used. The aqueous antifouling coating agent AS-15 was prepared, and a camera cover (with an antifouling layer laminate) for a surveillance camera was further prepared and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Comparative Example 1)

In the same manner as in Example 1, except that 0.0011 g of sodium bis(2-ethylhexyl)sulfonated succinate was not added, the comparative aqueous antifouling coating agent AS-21 was prepared and further prepared for monitoring. The camera is covered with a camera cover and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Comparative Example 2)

In the first embodiment, the amount of the polyethylene glycol monolauryl ether used in the preparation of the coating mother liquid S-1 was changed from 0.057 g to 0 g, and the addition of the coating agent mother liquid S-1 was additionally added. A water-based antifouling coating agent AS-22 for comparison was prepared in the same manner as in Example 1 except that the amount of the ethylene glycol monolauryl ether was changed from 0.0056 g to 0.0024 g, and a camera cover for a surveillance camera was further produced and subjected to Determination and evaluation. The results of the measurement and evaluation are shown in Table 2.

(Comparative Example 3)

In Example 1, in the preparation of the coating mother liquid S-1 and the subsequent preparation of the aqueous antifouling coating agent AS-1, polyethylene glycol monolauryl ether was not added, and Example 1 was The aqueous antifouling coating agent AS-23 for comparison was prepared in the same manner, and a camera cover for a surveillance camera was further produced and measured and evaluated. The results of the measurement and evaluation are shown in Table 2.

(Reference example 1)

Further, as a reference example 1, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced by directly using a polymethyl methacrylate molded member having a semi-ellipsoidal shape in which an antifouling layer was not formed. The measurement and evaluation were carried out in the same manner as in Example 1, and the evaluation results were listed in Table 2 together with the evaluation results of the examples and the like.

(Embodiment 16)

In the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced in the same manner as in Example 1 except that the coating agent AS-1 was replaced with the coating agent AS-31 described below.

The coating agent AS-31 was prepared by weighing 100 g of the above-mentioned coating agent AS-1 and adding 0.01 g of "Takelac WS-5100" (urethane resin) manufactured by Mitsui Chemicals, Inc.

The measurement and evaluation of the camera cover for the surveillance camera produced in the same manner as in the first embodiment were carried out. The results of the measurement and evaluation are shown in Table 3.

(Example 17)

In the same manner as in the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced in the same manner as in the first embodiment except that the coating agent AS-1 was replaced with the coating agent AS-32 described below.

The coating agent AS-32 was prepared by weighing 100 g of the above-mentioned coating agent AS-1 and adding 0.01 g of "PERMARINUA-368" (urethane resin) manufactured by Sanyo Chemical Industries Co., Ltd..

The measurement and evaluation of the camera cover for the surveillance camera produced in the same manner as in the first embodiment were carried out. The results of the measurement and evaluation are shown in Table 3.

(Embodiment 18)

In the same manner as in the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced in the same manner as in the first embodiment except that the coating agent AS-1 was replaced with the coating agent AS-33 described below.

The coating agent AS-33 was prepared by weighing 100 g of the above-mentioned coating agent AS-1 and adding 0.01 g of "UCOATUWS-145" (urethane resin) manufactured by Sanyo Chemical Industries Co., Ltd..

The measurement and evaluation of the camera cover for the surveillance camera produced in the same manner as in the first embodiment were carried out. The results of the measurement and evaluation are shown in Table 3.

(Embodiment 19)

In the same manner as in the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced in the same manner as in the first embodiment except that the coating agent AS-1 was replaced with the coating agent AS-34 described below.

The coating agent AS-34 was prepared by weighing 100 g of the above-mentioned coating agent AS-1 and adding 0.01 g of "UPRENEUX A-307" (urethane resin) manufactured by Sanyo Chemical Industries Co., Ltd.

The measurement and evaluation of the camera cover for the surveillance camera produced in the same manner as in the first embodiment were carried out. The results of the measurement and evaluation are shown in Table 3.

(Embodiment 20)

In the same manner as in the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced in the same manner as in the first embodiment except that the coating agent AS-1 was replaced with the coating agent AS-35 described below.

The coating agent AS-35 was prepared by weighing 100 g of the above-mentioned coating agent AS-1 and adding 0.01 g of polyacrylic acid (weight average molecular weight: 250,000) manufactured by Wako Pure Chemical Industries, Ltd.

The measurement and evaluation of the camera cover for the surveillance camera produced in the same manner as in the first embodiment were carried out. The results of the measurement and evaluation are shown in Table 3.

In addition, the weight average molecular weight is measured by gel permeation chromatography (GPC). Specifically, HLC-8120GPC and SC-8020 (manufactured by Tosoh Corporation) were used, and two TSKgels and SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15 cm) were used as the column, and tetrahydrofuran was used as an eluent. THF) to carry out the measurement. Further, as a condition, a sample concentration of 0.5% by mass, a flow rate of 0.6 ml/min, a sample injection amount of 10 μl, and a measurement temperature of 40 ° C were used, and the measurement was carried out using a differential refractive index (RI) detector. The calibration curve is “polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “ Ten samples of A-2500", "F-4", "F-40", "F-128", and "F-700" were produced.

(Example 21)

In the same manner as in the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced in the same manner as in the first embodiment except that the coating agent AS-1 was replaced with the coating agent AS-36 described below.

The coating agent AS-36 was prepared by weighing 100 g of the above-mentioned coating agent AS-1 and adding 0.01 g of polyacrylic acid (weight average molecular weight of 1,000,000) manufactured by Wako Pure Chemical Industries, Ltd. It should be noted that the method for measuring the weight average molecular weight is as described above.

The measurement and evaluation of the camera cover for the surveillance camera produced in the same manner as in the first embodiment were carried out. The results of the measurement and evaluation are shown in Table 3.

(Example 22)

In the same manner as in the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced in the same manner as in the first embodiment except that the coating agent AS-1 was replaced with the coating agent AS-37 described below.

The coating agent AS-37 was prepared by weighing 100 g of the above-mentioned coating agent AS-1 and adding 0.01 g of sodium polyphosphate (weight average molecular weight: 1000) manufactured by Kanto Chemical Co., Ltd..

The measurement and evaluation of the camera cover for the surveillance camera produced in the same manner as in the first embodiment were carried out. The results of the measurement and evaluation are shown in Table 3.

(Reference example 2)

In the first embodiment, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced and measured in the same manner as in Example 1 except that the coating agent AS-1 was replaced with the AS-38 described below. And evaluation. The results of the measurement and evaluation are shown in Table 3.

<Coating agent AS-38>

・Colloidal cerium oxide dispersion 20% by mass aqueous solution (Snowtex C) 100g

・The following sol-gel preparation liquid 500g

・5 mass% aqueous solution of sodium bis(2-ethylhexyl)sulfonated succinate (ionic surfactant as antistatic agent) 30g

・Pure water 450g

<sol gel preparation liquid>

8 g of tetramethoxy decane (manufactured by Tokyo Chemical Industry Co., Ltd.) and the following hydrophilicity having a decane coupling group at the terminal were mixed with 200 g of ethanol, 10 g of acetonitrile, 10 g of tetraethyl titanate, and 100 g of purified water. The sol-gel preparation liquid was prepared by stirring 5 g of a polymer at room temperature for 2 hours.

<Synthesis of a hydrophilic polymer having a decane coupling group at the end>

To a 500 mL three-necked flask, 25 g of acrylamide, 3.5 g of 3-mercaptopropyltrimethoxydecane, and 51.3 g of dimethylformamide were added and mixed. The mixture was heated to a liquid temperature of 65 ° C under a nitrogen stream, and 0.25 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added to initiate a reaction. The mixture was stirred for 6 hours while maintaining the liquid temperature of the mixture at 65 ° C, and then the liquid temperature was cooled to room temperature. The mixture was poured into 1.5 L of ethyl acetate to give a solid. Thereafter, the precipitated solid was filtered off. The obtained solid was sufficiently washed with ethyl acetate, and then dried to obtain a hydrophilic polymer having a decane coupling group at the terminal. The quality of the dried polymer was 21 g. The weight average molecular weight of the obtained polymer was measured by GPC (polystyrene standard) and found to be 4,000. It should be noted that the method for measuring the weight average molecular weight is as described above.

(Reference Example 3)

In Reference Example 2, the hydrophilic polymer having a decane coupling group at the terminal in the coating agent AS-38 was used, and the following hydrophilic polymer having a decane coupling group in the side chain (coating agent AS) was used. In the same manner as in Reference Example 2, a camera cover for a surveillance camera (with an antifouling layer laminate) was produced and measured and evaluated. The results of the measurement and evaluation are shown in Table 3.

<Synthesis of a hydrophilic polymer having a decane coupling group in a side chain>

Into a 500 ml three-necked flask, 13.9 g of acrylamide, 11.6 g of acrylamide-3-(ethoxymethylmethane)propyl ester, and 280 g of 1-methoxy-2-propanol were added and mixed. The mixture was heated to a liquid temperature of 80 ° C under a nitrogen stream, and 1.8 g of 2,2'-azobis(2-methylpropionic acid) dimethyl ester was added to initiate a reaction. The mixture was stirred for 6 hours while maintaining the liquid temperature of the mixture at 80 ° C, and then the liquid temperature was cooled to room temperature. The mixture was poured into 2 L of acetone, and as a result, a solid was precipitated. Thereafter, the precipitated solid was filtered off. The obtained solid was sufficiently washed with acetone, and then dried to obtain a hydrophilic polymer having a decane coupling group in a side chain. The quality of the dried polymer was 23.3 g. The weight average molecular weight of the obtained polymer was measured by GPC (polystyrene standard) and found to be 15,000. It should be noted that the method for measuring the weight average molecular weight is as described above.

(Example 23)

In the first embodiment, a surveillance camera was produced in the same manner as in the first embodiment except that the type of the substrate was replaced by a polycarbonate (polycarbonate transparent dome manufactured by Shenzhen Yujinda Technology Co., Ltd.). A camera cover (with an antifouling layer laminate) was used for measurement and evaluation. The results of the measurement and evaluation are shown in Table 3.

(Example 24)

In the same manner as in Example 1, except that the type of the substrate was replaced with a polycarbonate (a polycarbonate transparent dome manufactured by Shenzhen Yujinda Technology Co., Ltd.). The camera is covered with a camera cover (with an antifouling layer laminate) and measured and evaluated. The results of the measurement and evaluation are shown in Table 3.

(Reference example 4)

In the same manner as in Example 1, except that the type of the substrate was replaced with a polycarbonate (a polycarbonate transparent dome manufactured by Shenzhen Yujinda Technology Co., Ltd.). The camera is covered with a camera cover (with an antifouling layer laminate) and measured and evaluated. The results of the measurement and evaluation are shown in Table 3.

[Table 2〕

*1: The concentration indicates the content [% by mass] relative to the total solid content in the antifouling layer.

*2: It is an antistatic agent which is also a component which shows surface activity.

[table 3〕

*1: The concentration indicates the content [% by mass] relative to the total solid content in the antifouling layer.

*2: It is an antistatic agent which is also a component which shows surface activity.

As shown in Tables 2 and 3, in the embodiment, the camera cover for any of the surveillance cameras is colorless and transparent, showing good antifouling properties.

On the other hand, in Comparative Example 1 to Comparative Example 3, although the surface of the camera cover for the surveillance camera has relatively good hydrophilicity, it is inferior in antifouling properties. Specifically, in Comparative Example 1 which does not contain an antistatic agent, the antifouling effect by the antifouling layer is inferior. Further, in Comparative Example 2 in which the concentration of the component exhibiting surface activity was low, the antifouling effect by the antifouling layer was also insufficient. Further, in Comparative Example 3 having a low concentration, the antifouling effect by the antifouling layer was remarkably lowered. .

Further, as shown in Table 3, in Reference Example 4, the adhesion to the polycarbonate substrate was inferior to those of Example 23 and Example 24.

The disclosures of Japanese Patent Application No. 2014-206480 and Japanese Application No. 2015-004370 are hereby incorporated by reference herein in its entirety.

All of the documents, patent applications, and technical standards described in the specification are incorporated in the specification to the extent that the respective documents, patent applications, and technical standards are incorporated by reference.

no

no

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Claims (19)

An antifouling layer laminate comprising: a substrate and an antifouling layer, wherein the antifouling layer is provided on the substrate and contains at least a siloxane having a compound represented by the following formula (1) The binder, the antistatic agent, and the cerium oxide particles, the content of the component exhibiting surface activity is 0.5% by mass or more based on the total solid content of the layer; In the formula (1), R ¹ , R ² , R ³ and R ⁴ each independently represent an organic group having 1 to 6 carbon atoms, and n represents an integer of 2 to 20. The antifouling layer laminate according to claim 1, wherein the substrate comprises glass. The antifouling layer laminate according to claim 1 or 2, wherein the substrate comprises a resin material. The antifouling layer laminate according to claim 3, wherein the resin material contains at least one of polycarbonate and polymethyl methacrylate. The antifouling layer laminate according to claim 1 or 2, wherein the antifouling layer further comprises a catalyst for promoting formation of the above-mentioned naphthalene binder. The antifouling layer laminate according to claim 1 or 2, wherein the antistatic agent contains an ionic surfactant. The antifouling layer laminate according to claim 6, wherein the content of the ionic surfactant is 50% by mass or less based on the total mass of the antifouling layer. The antifouling layer laminate according to claim 1 or 2, wherein the antifouling layer further comprises a nonionic surfactant as the component exhibiting surface activity. The antifouling layer laminate according to claim 1 or 2, wherein the antistatic agent contains metal oxide particles. The antifouling layer laminate according to claim 9, wherein the metal oxide particles have an average primary particle diameter of 100 nm or less. The antifouling layer laminate according to claim 1 or 2, wherein the content of carbon is 3% by mass or less based on the total solid content of the antifouling layer. The antifouling layer laminate according to claim 1 or 2, wherein the content of the organic compound having a weight average molecular weight of 1100 or more is 0.2% by mass or less based on the total solid content of the antifouling layer. The antifouling layer laminate according to claim 1 or 2, wherein the antifouling layer has a surface resistance value of 1 × 10 ¹² Ω/sq or less. The antifouling layer laminate according to claim 1 or 2, wherein a water contact angle of a surface of the antifouling layer is 40 or less. The antifouling layer laminate according to claim 1 or 2, wherein an integrating sphere transmittance of the antifouling layer is 95% of an average value of an integrating sphere transmittance in a wavelength region of 300 nm to 1200 nm. the above. A protective material for a surveillance camera, comprising the antifouling layer laminate according to any one of claims 1 to 15. The protective material for a surveillance camera according to claim 16, wherein the shape of the substrate in the antifouling layer laminate is a hemispherical shape, a semi-ellipsoidal shape, a planar shape, a quadrangular prism shape, or a cylindrical shape. A protective material for a surveillance camera according to claim 16 or claim 17, which is used for a surveillance camera that is installed outdoors. A surveillance camera comprising the protective material for a surveillance camera according to any one of claims 16 to 18.