WO2019221268A1

WO2019221268A1 - Anti-fogging laminate and method for producing same

Info

Publication number: WO2019221268A1
Application number: PCT/JP2019/019655
Authority: WO
Inventors: 渡辺　誠; 岡崎　光樹; 貴行塙
Original assignee: 三井化学株式会社
Priority date: 2018-05-18
Filing date: 2019-05-17
Publication date: 2019-11-21
Also published as: JPWO2019221268A1; JP6945069B2

Abstract

The present invention addresses the problem of providing a laminate which can keep a high anti-fogging property and can also secure high scratch resistance. The laminate according to the present invention comprises a base material, a storage layer (A) having a specified thickness and a buffer layer (B) in this order, where the ratio of the thickness of the storage layer (A) to the thickness of the buffer layer (B) falls within a specified range, the storage layer (A) comprises a cured product of a specific composition (A-1) comprising a polyfunctional monomer (a1) having two or more (meth)acryloyl groups, inorganic particles (a2) and a surfactant (a3), and the buffer layer (B) comprises a cured product of a specific composition (B-1) comprising a polyfunctional monomer (b1) having two or more (meth)acryloyl groups and inorganic particles (b2).

Description

Antifogging laminate and method for producing the same

The present invention relates to an anti-fogging laminate and a method for producing the same, and more particularly to an anti-fogging laminate having excellent scratch resistance and a method for producing the same.

In recent years, there has been an increasing demand for improvement of fogging of base materials formed from organic materials such as plastics and inorganic materials such as glass.
It is known that fogging generated in plastic, glass, and the like is caused by minute water droplets adhering or condensing on the surface of the base material, and the water droplets scattering light. Therefore, generation of water droplets can be prevented in order to prevent fogging.

As a method of developing anti-fogging properties,
(A) a method of reducing the contact angle between the substrate and water;
(B) a method of preventing the formation of water droplets by making the substrate surface water absorbent;
(C) A method of increasing the contact angle between the substrate and water and rolling it off without causing water droplets to remain on the substrate, and
(D) A method has been proposed in which the substrate is always kept at a temperature equal to or higher than the dew point and water droplets are not attached (for example, see Non-Patent Document 1).

Various attempts have been made as a method for solving the fogging problem. Among these methods, from the viewpoint of high antifogging effect, wide application range, and simplicity, (a) and ( Attempts by the method b) are mainly made. For example, Non-Patent Document 1 proposes a method for improving hydrophilicity and water absorption by using an anti-fogging paint containing a reactive surfactant and an acrylic oligomer.

Among these methods, the method (b) can be performed by forming a water-absorbing layer containing a hydrophilic material on the surface of the substrate. Here, when using a general water-absorbing anti-fogging layer as the anti-fogging material on the surface (the surface that comes into contact with the outside air), it is not fogged while absorbing moisture, but a large amount of water is used as in bathroom use. It is well known that in a situation where moisture is continuously supplied to the surface, the anti-fogging property is lost in a relatively short time because it becomes saturated immediately and cannot absorb water. In addition, when a general water-absorbing antifogging layer is applied to an optical product as an antifogging material, when a large amount of water droplets adhere, the image tends to be distorted and visibility tends to deteriorate. In addition, the hydrophilic surface tends to have increased blowing resistance and poor scratch resistance.

On the other hand, when the hydrophilic material previously proposed by the present inventors is used on the surface, the antifogging property can be imparted by suppressing light scattering because it spreads even if moisture adheres due to condensation or the like. Such hydrophilic materials can be used for various purposes (glasses, goggles, window glass, mirrors, displays, headlamps, etc.) for a long time. In some cases, the “antifogging property” was not sufficient. This initial antifogging problem has also been improved by the proposal of the present inventors (Patent Document 1).

However, it was sometimes difficult to maintain this initial antifogging property semipermanently. In addition, there are scenes where high scratch resistance is required as well as the hard coat applied to transparent materials, and both a strong surface (scratch resistance similar to hard coat) and high anti-fogging properties (initial and long time) are required. There are still points to be improved in application to the intended use.

On the other hand, the method (a) can be carried out by allowing a surfactant to be present on the surface of the substrate. One specific method is application or adhesion of a surfactant to the surface of the substrate. However, in this method, it is known that the anti-fogging property is difficult to maintain because the surfactant easily flows out due to moisture aggregated on the surface.

As another specific method, there is a method in which a substrate is surface-treated with a resin containing a surfactant, and the surfactant inside the resin is bleed out to the surface. However, in the prior art, it tends to be difficult to control the bleeding property. In addition, in order to facilitate bleeding out of the surfactant to the surface, the resin containing the surfactant is often given flexibility, but in this case, the scratch resistance is sacrificed. There is a tendency.

International Publication No. 2013/187311

As described above, when the antifogging property is to be ensured by reducing the contact angle between the base material and water, it is still difficult to maintain the high antifogging property in the prior art, which is high. In order to maintain the anti-fogging property, maintenance tends to be required. On the other hand, when trying to maintain high antifogging properties, there is a tendency that sufficient scratch resistance is not obtained this time, and it is also desired to ensure high scratch resistance. In this regard, although glasses glasses with hard coat films that do not require maintenance have been put on the market in the past, there has been a drawback that the film hardness is low and scratches are immediately introduced.
In view of the above-described problems of the prior art, it is an object of the present invention to provide a laminate that can maintain high anti-fogging properties and can ensure high scratch resistance.

In the surface treatment of a base material with a material containing a surfactant, the present inventors have formed a combination of layers having a specific configuration on the surface of the base material, thereby causing the surface of the surfactant to bleed out. The inventors have found that a sufficiently high scratch resistance can be secured while appropriately controlling, and have completed the present invention.

That is, the present invention relates to the following [1] to [15].
[1]
Including a substrate, a storage layer (A), and a buffer layer (B) in this order;
The storage layer (A) and the buffer layer (B) are in direct contact with each other;
The ratio of the thickness of the storage layer (A) to the thickness of the buffer layer (B) is in the range of 1.3-15,
The storage layer (A) is
A polyfunctional monomer (a1) having two or more (meth) acryloyl groups,
Inorganic particles (a2), and surfactant (a3)
A cured product of the composition (A-1) comprising:
The buffer layer (B)
A polyfunctional monomer (b1) having two or more (meth) acryloyl groups, and inorganic particles (b2)
A cured product of the composition (B-1) comprising:
The composition (B-1) further contains or does not contain a surfactant (b3);
When the composition (B-1) further contains the surfactant (b3), the content of the surfactant (b3) relative to the total dry weight of the composition (B-1) Less than the content of the surfactant (a3) relative to the total dry weight of A-1); and
The inorganic particles (a2) include inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group, or
The inorganic particles (a2) are inorganic particles (a2-0) not modified with a functional group containing a (meth) acryloyl group, and the inorganic particles (b2) are modified with a functional group containing a (meth) acryloyl group Inorganic particles (b2-0) that are not
Laminated body.

[2]
The inorganic particles (a2) include inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group;
The laminate according to [1], wherein the inorganic particles (b2) include inorganic particles (b2-1) modified with a functional group containing a (meth) acryloyl group.

[3]
The inorganic particles (a2-1) and the inorganic particles (b2-1) are independently modified with a silica particle modified with a functional group containing a (meth) acryloyl group and a functional group containing a (meth) acryloyl group. The laminate according to [2], which is at least one selected from the group consisting of zirconia particles formed.

[4]
The inorganic particles (b2) include inorganic particles (b2-0) not modified with a functional group containing a (meth) acryloyl group, and
The weight of the inorganic particles (b2-1) modified with the functional group containing the (meth) acryloyl group in the composition (B-1) is modified with the functional group containing the (meth) acryloyl group. The laminate according to the above [2] or [3], which is larger than the content of the inorganic particles (b2-0) that are not present.

[5]
The content of the polyfunctional monomer (b1) relative to the total dry weight of the composition (B-1) is greater than the content of the polyfunctional monomer (a1) relative to the total dry weight of the composition (A-1). The laminate according to any one of [1] to [4], wherein the laminate is small.

[6]
The laminate according to any one of [1] to [5], wherein the polyfunctional monomer (a1) and the polyfunctional monomer (b1) include a polyfunctional monomer represented by the following formula (1).

(In the above formula (1), n represents an integer of 1 to 30.)

[7]
The laminate according to any one of [1] to [6], wherein the surfactant (a3) and the surfactant (b3) have a polyoxyalkylene structure.
[8]
The surfactant (a3) and the surfactant (b3) are any one or more selected from the group consisting of polyoxyethylene lauryl ether sulfate, polyoxyethylene oleyl cetyl ether sulfate, and polyoxyalkylene lauryl ether The laminate according to any one of [1] to [7], comprising:

[9]
The laminate according to any one of [1] to [8], wherein the content of the inorganic particles (b2) is 40 to 70% by weight relative to the total dry weight of the composition (B-1).

[10]
The laminate according to any one of [1] to [9], wherein the content of the surfactant (a3) with respect to the total dry weight of the composition (A-1) is 1.0 to 5.0% by weight. body.

[11]
The laminate according to any one of [1] to [10], wherein the composition (B-1) further comprises a compound having a (meth) acryloyl group and an anionic hydrophilic group.

[12]
The laminate according to any one of [1] to [11], wherein the buffer layer (B) contains a light stabilizer in an amount of 3% by weight or more based on the total dry weight of the composition (B-1).
[13]
The laminate according to any one of [1] to [12], wherein the storage layer (A) has a thickness of 4.0 μm or more.

[14]
(S1): For at least one surface of the layer containing the substrate,
The polyfunctional monomer (a1),
The inorganic particles (a2),
The surfactant (a3) and the solvent (a4)
Providing a coated layer (A2) of the composition (A-1a) containing:
(S2): A step of removing the solvent (a4) from the coated layer (A2) obtained in the step (S1),
(S3): After the step (S2), the coating layer (A2) is cured, and the coating layer (A2) is converted into a cured layer (A2 ′).
(S4): After the step (S3), on the cured product layer (A2 ′),
The polyfunctional monomer (b1),
The inorganic particles (b2), and the solvent (b4)
Providing a coated layer (B2) of the composition (B-1a) containing:
(S5): a step of removing the solvent (b4) from the coating layer (B2) obtained in the step (S4), and (S6): after the step (S5), the coating layer (B2) Curing, converting the coated layer (B2) into a cured layer (B2 ′),
Including:
The total dry weight of the composition (A-1a) per 100 parts by weight of the composition (A-1a) is 46 parts by weight or more and less than 100 parts by weight;
The composition (B-1a) further contains or does not contain the surfactant (b3);
When the composition (B-1) further contains the surfactant (b3), the content of the surfactant (b3) relative to the total dry weight of the composition (B-1) Less than the content of the surfactant (a3) relative to the total dry weight of A-1); and
The inorganic particles (a2) include inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group, or
The inorganic particles (a2) are inorganic particles (a2-0) not modified with a functional group containing a (meth) acryloyl group, and the inorganic particles (b2) are modified with a functional group containing a (meth) acryloyl group Inorganic particles (b2-0) that are not
The manufacturing method of the laminated body as described in said [1].

[15]
The production method according to [14], wherein the step (S5) is performed under heating at 50 to 90 ° C.

According to the present invention, it is possible to provide a laminate that can maintain high antifogging properties and also has excellent scratch resistance.

[Laminate]
The laminated body which concerns on this invention contains the base material, the storage layer (A), and the buffer layer (B) in this order. Here, in the laminate according to the present invention, the storage layer (A) and the buffer layer (B) are in direct contact with each other.

Here, in this specification, the term “(meth) acryloyl group” is used to collectively represent an acryloyl group and a methacryloyl group, and the term “(meth) acrylic acid” is acrylic acid. And the term “(meth) acrylate” are used to collectively represent acrylate and methacrylate, and the term “(meth) acrylamide”. Is used to collectively represent acrylamide and methacrylamide, and the term “(meth) acrylic” is used to collectively represent acrylic and methacrylic.

In addition, “total dry weight” for a composition means the total weight of components excluding the solvent component among the components constituting the composition, unless otherwise specified.
Hereinafter, each layer which comprises the laminated body of this invention is demonstrated.

<Storage layer (A)>
In the laminate of the present invention, the storage layer (A) is:
A polyfunctional monomer (a1) having two or more (meth) acryloyl groups,
Inorganic particles (a2), and surfactant (a3)
A cured product of the composition (A-1) containing

The storage layer (A) stores the surfactant (a3) therein, and constantly supplies the surfactant (a3) to the surface of the laminate of the present invention through the buffer layer (B) described later. Fulfill. Thereby, the laminated body of this invention exhibits high anti-fogging property.

The specific structure of the “surfactant (a3)” used in the present invention will be described in detail in the “surfactant (a3)” section below.
In the present specification, the “polyfunctional monomer (a1) having two or more (meth) acryloyl groups” may be simply referred to as “polyfunctional monomer (a1)”.

Multifunctional monomer (a1)
In the present invention, the polyfunctional monomer (a1) having two or more (meth) acryloyl groups is stored in the storage layer (A) through a network structure formed by bonding to each other through the curing of the composition (A-1). And a space for storing the surfactant (a3) in the storage layer (A). That is, the polyfunctional monomer (a1) is converted into a corresponding polymer through the curing of the composition (A-1), and constitutes a polymer component in the storage layer (A).

The polyfunctional monomer (a1) used in the present invention comprises two or more (meth) acryloyl groups and a linker moiety that fixes these (meth) acryloyl groups in one molecule. However, the polyfunctional monomer (a1) used in the present invention does not contain an anionic group or a cationic group. In this respect, it differs from the “anionic hydrophilic group-containing monomer” described later in the section “Buffer Layer (B)”.

In one embodiment of the present invention, the polyfunctional monomer (a1) is an ester of (meth) acrylic acid and a polyhydric alcohol having two or more hydroxyl groups. Here, the “polyhydric alcohol having two or more hydroxyl groups” may be an alkane polyol such as alkanediol or alkanetriol, or a polyoxyalkylene glycol such as polyethylene glycol or a polyoxyalkylene added to the alkane polyol. A compound having a polyoxyalkylene structure, such as a compound formed by adding The “polyhydric alcohol having two or more hydroxyl groups” may further contain an aromatic ring or may correspond to an alicyclic compound. In the present invention, the above “polyhydric alcohol having two or more hydroxyl groups” preferably contains a polyoxyalkylene structure, for example, a diol containing a polyoxyethylene structure. Examples of “polyhydric alcohol having two or more hydroxyl groups” containing an aromatic ring include ethylene oxide adducts of bisphenol.

Specific examples of the polyfunctional monomer (a1) suitably used in the present invention include compounds having a structure represented by the following formulas (1) and (2). Among these, the compound represented by the following formula (1) is used. A compound having a structure is preferably mentioned.

(In formula (1), n represents an integer of 1 to 30)

(In the formula (2), l and m each represent an integer of 1 to 40 with l + m.)

That is, specific examples of the polyfunctional monomer (a1) suitably used in the present invention include polyethylene glycol diacrylate and 2,2-bis- [4- (acryloxy-polyethoxy) phenyl] -propane. Examples of the polyethylene glycol di (meth) acrylate include tetradecaethylene glycol di (meth) acrylate and tricosaethylene glycol di (meth) acrylate.

The polyfunctional monomer (a1) used in the present invention may be a single type or a combination of two or more types.
The specific amount of the polyfunctional monomer (a1) constituting the storage layer (A) is usually 30 to 70% by weight, preferably 45 to 45% by weight based on the total dry weight of the composition (A-1). 60% by weight.
In relation to the storage layer (A) used in the present invention, as will be described later in the section of “Buffer layer (B)”, the composition (B-1) that gives the buffer layer (B) by curing has many In addition to the functional monomer (b1), an anionic hydrophilic group-containing monomer can be further included. As long as the object of the present invention can be achieved, the composition (A-1) includes an anionic hydrophilic group-containing monomer similar to the anionic hydrophilic group-containing monomer that can be contained in the composition (B-1) described later. This does not necessarily exclude the possibility of being However, in a typical embodiment of the present invention, the composition (A-1) usually does not contain such an anionic hydrophilic group-containing monomer.

Inorganic particles (a2)
The inorganic particles (a2) are particles of an inorganic substance. In the present invention, the inorganic particles (a2) are incorporated in the storage layer (A) in the form of being incorporated into a network structure formed by the bonding of the polyfunctional monomers (a1) having two or more (meth) acryloyl groups. It is encapsulated and plays a role of imparting appropriate hardness and strength to the storage layer (A).

The inorganic particles (a2) used in the present invention may be called inorganic particles (a2-0) not modified with a functional group containing a (meth) acryloyl group (hereinafter simply referred to as “inorganic particles (a2-0)”). Or the inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group (hereinafter, simply referred to as “inorganic particles (a2-1)”). ).

Here, in a typical embodiment of the present invention, the inorganic particles (a2-0) are unmodified inorganic particles, that is, particles substantially composed of an inorganic substance. However, this does not mean that the content of the organic substance in the inorganic particles (a2-0) should be strictly zero. An organic substance that does not exhibit reactivity may be contained in a trace amount that does not affect the physical properties of the inorganic substance constituting the inorganic particles (a2-0). For example, the inorganic particles (a2-0) are inevitably mixed in due to the manufacturing process, and a small amount of organic substances that are unavoidably adsorbed on the surface by standing in the atmosphere. The trace amount of organic substance may be contained. Examples of the inorganic substance constituting the inorganic particles (a2-0) include metal oxides such as silica, zirconia, alumina, tin oxide, antimony oxide, and titania, and nanodiamond particles. Among these, silica and zirconia are particularly preferable from the viewpoints of dispersibility in resin, hardness, and light resistance.

The particle size of the inorganic particles (a2-0) is preferably 5 to 50 nm, more preferably 10 to 30 nm. It is preferable that the particle size of the inorganic particles (a2-0) is not less than the lower limit because hardness is easily obtained and the dispersibility of the particles in the composition (A-1) is improved. On the other hand, it is preferable that the particle size of the inorganic particles (a2-0) is not more than the above upper limit value because the transparency is improved when the composition (A-1) is a cured product such as a cured film. Here, the particle diameter of the inorganic particles (a2-0) can be determined by a dynamic scattering method using laser light.

The inorganic particles (a2-0) as described above may be used alone or in combination of two or more.
On the other hand, in a preferred embodiment of the present invention, the inorganic particles (a2) are inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group. The inorganic particles (a2-1) have the inorganic particles (a2-0) as basic particles and have functional groups containing (meth) acryloyl groups on the surface of the basic particles. In this embodiment, when the composition (A-1) is cured, the (meth) acryloyl group constituting the inorganic particles (a2-1) and the (meth) acryloyl group constituting the polyfunctional monomer (a1) A covalent bond will be formed between the two. Therefore, in the storage layer (A) obtained, the inorganic particles (a2-1) are integrated with the network structure formed by the bond between the polyfunctional monomers (a1) through the covalent bond. Preferable examples of such inorganic particles (a2-1) include silica particles modified with a functional group containing (meth) acryloyl groups and zirconia particles modified with a functional group containing (meth) acryloyl groups. .

The “functional group containing a (meth) acryloyl group” constituting the inorganic particle (a2-1) has a (meth) acryloyl group at the terminal, and further connects the (meth) acryloyl group and the base particle. And a linking group.

Such inorganic particles (a2-1) are commercially available, and examples of such commercially available products include organosilica sol PGM-AC-2140Y manufactured by Nissan Chemical Industries.

The inorganic particles (a2-1) may be used alone or in combination of two or more.
The specific amount of the inorganic particles (a2) in the storage layer (A) is usually 30 to 60% by weight, preferably 35 to 50% by weight, based on the total dry weight of the composition (A-1). Here, when the inorganic particles (a2) include both inorganic particles (a2-0) and inorganic particles (a2-1), the ratio of the inorganic particles (a2-0) to the inorganic particles (a2-1) is: When the total dry weight of the inorganic particles (a2-0) and the inorganic particles (a2-1) is 100% by weight, the amount of the inorganic particles (a2-0) is usually more than 0% by weight and 30% by weight or less. The amount of the inorganic particles (a2-1) is usually less than 100% by weight and 70% by weight or more.

In the present invention, the ratio of the inorganic particles (a2) to the polyfunctional monomer (a1) constituting the storage layer (A) is the same as the content of the inorganic particles (a2) in the composition (A-1). The ratio with respect to the content of the polyfunctional monomer (a1) is usually in the range of 0.6 / 1 to 1/1.

Surfactant (a3)
In the present invention, the surfactant (a3) is stored inside the storage layer (A), and oozes out to the surface of the laminate of the present invention through the buffer layer (B) described later, whereby the laminate of the present invention. It plays a role of imparting antifogging properties to the water. As long as the surfactant (a3) can fulfill such a role, there is no particular limitation on the structure it should have. In a preferred embodiment of the present invention, the surfactant (a3) has a polyoxyalkylene structure.

Here, when the surfactant (a3) has a polyoxyalkylene structure, in a typical embodiment of the present invention, the surfactant (a3) preferably does not have an acrylic polymer structure or a methacrylic polymer structure. That is, the surfactant (a3) preferably does not have any of the structures represented by the following formulas (AC1) to (AC2):

(In the above formulas (AC1) and (AC2), R represents a hydrogen atom or a methyl group, and n represents an integer of 2 or more).

In this case, the surfactant (a3) used in the present invention is
The surfactant is not particularly limited as long as it satisfies the following conditions: (i) having a polyoxyalkylene structure, (ii) not having any of the structures represented by the above formulas (AC1) to (AC2) It can be. However, in the present invention, as the surfactant (a3), those having no polymerizability are used, particularly those not containing an unsaturated bond in the molecule.

In a typical embodiment of the present invention, the surfactant (a3) contains a hydrocarbon group and a polyoxyalkylene structure, and examples of the hydrocarbon group include an alkyl group and an alkenyl group. Further, examples of the repeating units constituting the polyoxyalkylene _{_{structure, -O-CH 2 CH 2 -}} , - O-CH 2 CH 2 CH 2 -, - O-CH 2 CH 2 CH 2 CH 2 - and the like include Among these, —O—CH ₂ CH ₂ — is preferable. The number of repeating units constituting the polyoxyalkylene structure is preferably 1-30.

Here, in a preferred embodiment of the present invention, the surfactant (a3) further has an anionic hydrophilic group. Examples of the anionic hydrophilic group include a sulfo group, a carboxyl group, a phosphate group, an O-sulfate group (—O—SO ₃ ⁻ ), an N-sulfate group (—NH—SO ₃ ⁻ ), and the like. Among these anionic hydrophilic groups, a phosphate group and an O-sulfate group (—O—SO ₃ ⁻ ) are preferable. These anionic hydrophilic groups may be in the form of a free acid or a salt with a suitable cation, but in many cases have the corresponding sodium, potassium or ammonium salt form.

One of the surfactants (a3) suitably used in the present invention includes, for example, one having a structure represented by the following formula (SS1):
R — [— O—R′—] _n —X (SS1)
In the above formula, R represents an alkyl group having 10 to 20 carbon atoms or an alkenyl group having 10 to 20 carbon atoms, R ′ represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 30 X represents a hydroxyl group or any anionic hydrophilic group selected from the group consisting of a sulfo group, a phosphono group, a carboxyl group, a phosphate group, an O-sulfate group and an N-sulfate group. Here, as an example of the _{R ', -O-CH 2 CH} 2 -, - O-CH 2 CH 2 CH 2 -, - O-CH 2 CH 2 CH 2 CH 2 - and the like, and among these , —O—CH ₂ CH ₂ — is preferred. Among the anionic hydrophilic groups that can be X, a phosphoric acid group and an O-sulfuric acid group are preferable. The anionic hydrophilic group exemplified as X may be in the form of a free acid or a salt with an appropriate cation, but in many cases, it has a corresponding sodium salt, potassium salt or ammonium salt form. doing. Among these salts, sodium salt is the most common, but it does not preclude having a salt form with other cations such as ammonium salt.

Examples of the surfactant (a3) having an anionic hydrophilic group include polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, and mixtures thereof. Specific examples thereof include polyoxyalkylene alkyl ether sulfates. Examples thereof include polyoxyethylene oleyl cetyl ether sulfate such as sodium oxyethylene oleyl cetyl ether sulfate, and polyoxyethylene lauryl ether sulfate such as sodium polyoxyethylene lauryl ether sulfate.

However, the surfactant (a3) used in the present invention may be a nonionic surfactant having a polyoxyalkylene structure. Examples of such surfactant (a3) include polyoxyalkylene alkyl ethers such as polyoxyalkylene monoalkyl ether, polyoxyalkylene alkenyl ethers such as polyoxyalkylene monoalkenyl ether, and mixtures thereof. . Here, examples of the polyoxyalkylene alkyl ether include polyoxyalkylene branched decyl ether, polyoxyalkylene dodecyl ether (polyoxyalkylene lauryl ether), polyoxyalkylene tridecyl ether, and polyoxyalkylene oleyl cetyl ether. Here, in an exemplary embodiment of the present invention, the polyoxyalkylene alkyl ether is a polyoxyethylene alkyl ether, and examples thereof include polyoxyethylene isodecyl ether and polyoxyethylene lauryl ether.

The surfactant (a3) used in the present invention may be a single type or a combination of two or more types.
The specific amount of the surfactant (a3) in the storage layer (A) is usually 1.0 to 5.0% by weight, preferably 1.5%, based on the total dry weight of the composition (A-1). ~ 3.0 wt%.

Other surfactants In the present invention, the composition (A-1) does not correspond to the surfactant (a3) in addition to the surfactant (a3), depending on the composition and use of the laminate of the present invention. Other surfactant (hereinafter referred to as “other surfactant”) may further be included.
The “other surfactant” is not particularly limited as long as it does not correspond to the surfactant (a3), and may be a conventionally known surfactant.

As "other surfactant" that can be used in the present invention,
(I) a surfactant having an acrylic polymer structure or a methacrylic polymer structure (hereinafter referred to as “surfactant (a3 ′)”);
(Ii) Surfactant having no polyoxyalkylene structure, acrylic polymer structure, or methacrylic polymer structure (hereinafter referred to as “surfactant (a3 ″)”)
Is mentioned.

Here, as one of the “surfactant (a3 ′)”, a surfactant having an acrylic polymer structure or a methacrylic polymer structure and a polyoxyalkylene structure (hereinafter referred to as “surfactant (a3′-1)”). ). The “surfactant (a3′-1)” typically has an acrylic polymer structure or a methacrylic polymer structure as a main chain, and has a polyoxyalkylene structure as a pendant group. As one of such “surfactant (a3′-1)”, a (meth) acrylic acid ester having a (poly) oxyalkylene group having a hydroxyl group at the terminal, as disclosed in Japanese Patent No. 3308581 And a surfactant having a structural unit corresponding to the alkyl ester of (meth) acrylic acid. Here, this surfactant may further have other structural units such as a structural unit corresponding to (meth) acrylate.

Such “surfactant (a3′-1)” may be a commercially available product, and examples thereof include Polyflow WS-314 manufactured by Kyoeisha Chemical Co., Ltd.
On the other hand, the “surfactant (a3 ′)” does not necessarily have a polyoxyalkylene structure. That is, the “surfactant (a3 ′)” is a surfactant having an acrylic polymer structure or a methacrylic polymer structure but not having a polyoxyalkylene structure (hereinafter referred to as “surfactant (a3′-2)”). It may be. This “surfactant (a3′-2)” has a hydrophilic group other than the polyoxyalkylene structure as the hydrophilic group. Examples of hydrophilic groups other than the polyoxyalkylene structure include anionic hydrophilic groups such as sulfo group, phosphono group, carboxyl group, phosphate group, O-sulfate group and N-sulfate group, amino group, and quaternary ammonium structure. And cationic hydrophilic groups such as As one of such “surfactant (a3′-2)”, an N-alkyl (meth) acrylamide polymer segment and a hydrophilic group-containing polymer as disclosed in JP 2012-177040 A, etc. (Meth) acrylic block copolymers having the following segments.

The “surfactant (a3 ′)” is a temperature-sensitive acrylic polymer-based surfactant, that is, an acrylic polymer-based interface that exhibits surface activity below a certain temperature and does not exhibit surface activity above a certain temperature. An activator may be used, and examples of the commercially available product include KL-850 manufactured by Kyoeisha Chemical Co., Ltd.

On the other hand, examples of the “surfactant (a3 ″)” include dialkylsulfosuccinate.
Here, the laminate of the present invention may have two or more storage layers (A). Among these storage layers (A), the storage layer closest to the substrate (hereinafter referred to as “storage layer”). (A0) ") and storage layers other than the" storage layer (A0) "(hereinafter," storage layer (A1) ") may have different roles. In particular, as will be described later in the section “Structure of Laminate”, the base material is polydiethylene glycol diallyl carbonate, polydiallyl carbonate, etc., and a primer layer is provided between the base material and the storage layer (A). When present, the “storage layer (A0)” may function as a protective layer (P) in order to prevent the surfactant (a3) contained in the storage layer (A) from entering the primer layer. is there. In such a case, the “storage layer (A0)” and the “storage layer (A1)” may be separately created by “other surfactant”.

In this case, as the “other surfactant” that can be contained in the storage layer (A0), a surfactant corresponding to the “surfactant (a3′-1)” such as Polyflow WS-314 manufactured by Kyoeisha Chemical Co., Ltd. is used. Can be mentioned. The specific amount of such “other surfactant” is usually more than 0% by weight and 0.2% by weight based on the total dry weight of the composition (A-1) for the storage layer (A0). Yes, preferably 0.03 to 0.1% by weight.

On the other hand, examples of “other surfactants” that can be contained in the storage layer (A1) include Polyflow KL-850 manufactured by Kyoeisha Chemical Co., Ltd. The specific amount of such “other surfactant” is usually more than 0% by weight and 0.05% by weight based on the total dry weight of the composition (A-1) for the storage layer (A1). Yes, preferably 0.25 to 0.35% by weight.
“Other surfactants” that may be contained in the composition (A-1) may be used alone or in combination of two or more.

Configuration of Storage Layer (A) In the present invention, the storage layer (A) comprises a composition (A-1) containing the polyfunctional monomer (a1), the inorganic particles (a2) and the surfactant (a3). It can be obtained by curing. That is, the storage layer (A) is a cured product of the composition (A-1).

The shape of the storage layer (A) in the present invention may be a plate shape or a film shape. However, in the present invention, if the thickness of the storage layer (A) is too thin, sufficient antifogging properties may not be exhibited after the laminate is washed with water. Therefore, the thickness of the storage layer (A) is preferably 4.0 μm or more, and more preferably 5.3 μm or more so that the laminate can exhibit sufficient antifogging properties even after being washed with water. Thus, since the amount of surfactant contained in the storage layer (A) increases as the thickness of the storage layer (A) increases, high anti-fogging performance and anti-fogging durability tend to be improved. The upper limit of the thickness of the layer (A) is not particularly limited as long as the function of the laminate of the present invention is not impaired. However, the thickness of the storage layer (A) is usually 30 μm or less, and preferably 20 μm or less in terms of coating. Moreover, it is preferable also when it is set as the thickness below fixed in this way also when obtaining the suitable coating-film external appearance.
In addition, the specific conditions at the time of forming the storage layer (A) will be described later in the section “Manufacturing Method of Laminate”.

<Buffer layer (B)>
In the laminate of the present invention, the buffer layer (B) is
A polyfunctional monomer (b1) having two or more (meth) acryloyl groups, and inorganic particles (b2)
A cured product of the composition (B-1) containing

Here, unlike the composition (A-1), the composition (B-1) does not necessarily contain a surfactant. However, in a preferred embodiment of the present invention, the composition (B-1) further contains a surfactant (b3).

This buffer layer (B) has a higher hardness than the storage layer (A), and plays a role of imparting sufficient scratch resistance to the laminate of the present invention. Further, the laminate of the present invention exhibits high antifogging properties when the surfactant (a3) stored in the storage layer (A) exudes to the outside, and this buffer layer (B) Also, it plays a role of controlling the leaching rate of the surfactant (a3). Thereby, the laminated body of this invention not only has high anti-fogging property but can maintain high anti-fogging property even after repeating washing with water. Control of exudation speed is
The weight ratio (filler / matrix ratio) between the inorganic particles and the polymer component (especially the polymer component corresponding to the polyfunctional monomer) in the buffer layer (B) is sufficiently larger than that of the storage layer (A), or the buffer layer The solvent contained after the application of the composition (B-1) to give (B) is removed by heating or the like and then cured with ultraviolet rays or the like to crosslink the polymer components constituting the buffer layer (B). This can be done by raising the degree.

The specific structure of the “surfactant (b3)” used in the present invention will be described in detail in the section “surfactant (b3)” below.
In the present specification, the “polyfunctional monomer (b1) having two or more (meth) acryloyl groups” may be simply referred to as “polyfunctional monomer (b1)”.

Multifunctional monomer (b1)
In the present invention, the polyfunctional monomer (b1) having two or more (meth) acryloyl groups is bonded to the buffer layer (B) through a network structure formed by bonding to each other through the curing of the composition (B-1). In addition to providing the basic skeleton, the surfactant (a3) contained in the storage layer (A) plays a role of providing a space necessary for appropriately exuding outward. That is, the polyfunctional monomer (b1) is converted into a corresponding polymer through the curing of the composition (B-1), and constitutes a polymer component in the buffer layer (B).

The polyfunctional monomer (b1) used in the present invention comprises two or more (meth) acryloyl groups and a linker moiety for fixing these (meth) acryloyl groups in one molecule. However, the polyfunctional monomer (b1) used in the present invention does not contain an anionic group or a cationic group. In this respect, it differs from the “anionic hydrophilic group-containing monomer” described later.

Here, the specific configuration of the polyfunctional monomer (b1) used in the present invention can be the same as that described above in the section of the polyfunctional monomer (a1). For example, the formula (1), The compound which has a structure shown by (2) is mentioned, Among these, the compound which has a structure shown by the said Formula (1) is mentioned preferably.

The polyfunctional monomer (b1) used in the present invention may be a single type or a combination of two or more types. The polyfunctional monomer (b1) may be the same as the polyfunctional monomer (a1) or may be different from each other.

In the present invention, the content of the polyfunctional monomer (b1) relative to the total dry weight of the composition (B-1) is the content of the polyfunctional monomer (a1) relative to the total dry weight of the composition (A-1). Less than. The specific amount of the polyfunctional monomer (b1) constituting the buffer layer (B) is usually 20 to 50% by weight, preferably 25 to 25% by weight based on the total dry weight of the composition (B-1). 47.5% by weight.

Inorganic particles (b2)
The inorganic particles (b2) are particles of an inorganic substance, like the inorganic particles (a2). In the present invention, the inorganic particles (b2) are incorporated in the buffer layer (B) in a form incorporated into a network structure formed by the bonding of the polyfunctional monomers (b1) having two or more (meth) acryloyl groups. It is included and plays a role of imparting high hardness and sufficient scratch resistance to the buffer layer (B).

The inorganic particles (b2) used in the present invention may be called inorganic particles (b2-0) not modified with a functional group containing a (meth) acryloyl group (hereinafter simply referred to as “inorganic particles (b2-0)”). Or inorganic particles (b2-1) modified with a functional group containing a (meth) acryloyl group (hereinafter sometimes simply referred to as “inorganic particles (b2-1)”). It may be present or a combination thereof.

Here, the material and particle size of the inorganic substance constituting the inorganic particles (b2-0) can be the same as those of the inorganic substance constituting the inorganic particles (a2-0). The particle size of the inorganic particles (b2-0) can be determined by a dynamic scattering method using laser light. Preferable examples of the inorganic particles (b2-0) include silica and zirconia. The inorganic particles (b2-0) may be a single type or a combination of two or more types. The inorganic particles (b2-0) may be the same as the inorganic particles (a2-0) or may be different from each other.

On the other hand, in a preferred embodiment of the present invention, the inorganic particles (b2) are inorganic particles (b2-1) modified with a functional group containing a (meth) acryloyl group. The inorganic particles (b2-1) have the inorganic particles (b2-0) as basic particles and have a functional group containing a (meth) acryloyl group on the surface of the basic particles. In this embodiment, when the composition (B-1) is cured, the (meth) acryloyl group constituting the inorganic particle (b2-1) and the (meth) acryloyl group constituting the polyfunctional monomer (b1) A covalent bond will be formed between the two. Therefore, in the obtained buffer layer (B), the inorganic particles (b2-1) are integrated with the network structure formed by the bond between the polyfunctional monomers (b1) through the covalent bond.

The “functional group containing a (meth) acryloyl group” constituting the inorganic particle (b2-1) has a (meth) acryloyl group at the terminal, and further connects the (meth) acryloyl group and the base particle. And a linking group. The specific configuration can be the same as the “functional group containing a (meth) acryloyl group” constituting the inorganic particles (a2-1). The inorganic particles (b2-1) having a functional group containing a (meth) acryloyl group can be obtained by the same surface treatment as the inorganic particles (a2-1) having a functional group containing a (meth) acryloyl group. it can.

The inorganic particles (b2-1) as described above may be used alone or in combination of two or more. The inorganic particles (b2-1) may be the same as the inorganic particles (a2-1) or may be different from each other. In a preferred and exemplary embodiment of the present invention, the inorganic particles (a2-1) and the inorganic particles (b2-1) are each independently silica particles modified with a functional group containing a (meth) acryloyl group and (meta 1) One or more selected from the group consisting of zirconia particles modified with a functional group containing an acryloyl group.

As described above, the inorganic particles (b2) used in the present invention may be the inorganic particles (b2-0), the inorganic particles (b2-1), or a combination thereof. It may be.

Here, when the inorganic particles (a2) constituting the composition (A-1) are the inorganic particles (a2-0), the inorganic particles (b2-1) are employed as the inorganic particles (b2). Although the cause is unknown, there is a tendency that the adhesion between the storage layer (A) and the buffer layer (B) in the laminate is not sufficiently obtained, and the resulting laminate does not necessarily exhibit sufficiently high antifogging properties. There is a case.
Therefore, when the inorganic particle (a2) is the inorganic particle (a2-0), the inorganic particle (b2) is also an inorganic particle (b2−2) that is not modified with a functional group containing a (meth) acryloyl group. 0).

On the other hand, when the inorganic particles (a2) constituting the composition (A-1) include the inorganic particles (a2-1), particularly when the inorganic particles (a2) are inorganic particles (a2-1). The inorganic particles (b2) may be the inorganic particles (b2-0), the inorganic particles (b2-1), or a combination thereof. However, when the inorganic particles (b2) include both inorganic particles (b2-0) and inorganic particles (b2-1), the content weight of the inorganic particles (b2-1) in the composition (B-1) is: The content is preferably larger than the content of the inorganic particles (b2-0).

The specific amount of the inorganic particles (b2) in the buffer layer (B) is usually 40 to 70% by weight, preferably 41.5 to 65% by weight, based on the total dry weight of the composition (B-1). is there. Here, when the inorganic particles (b2) include both inorganic particles (b2-0) and inorganic particles (b2-1), the ratio of the inorganic particles (b2-0) to the inorganic particles (b2-1) is: When the total dry weight of the inorganic particles (b2-0) and the inorganic particles (b2-1) is 100% by weight, the amount of the inorganic particles (b2-0) is usually more than 0% by weight and 30% by weight or less. The amount of the inorganic particles (b2-1) is usually less than 100% by weight and 70% by weight or more.

In the present invention, the ratio of the inorganic particles (b2) to the polyfunctional monomer (b1) constituting the buffer layer (B) is the content of the inorganic particles (b2) in the composition (B-1). The ratio with respect to the weight of the polyfunctional monomer (b1) is usually 0.9 / 1 to 2.2 / 1, preferably 1.3 / 1 to 2.2 / 1.

Here, since high scratch resistance is obtained for the obtained laminate, the ratio between the content of the inorganic particles (b2) in the composition (B-1) and the content of the polyfunctional monomer (b1) is as follows. It is preferable that it is large to some extent. Also in the relationship with the composition (A-1), the ratio of the content weight of the inorganic particles (b2) to the content weight of the polyfunctional monomer (b1) in the composition (B-1) is The ratio of the content weight of the inorganic particles (a2) in the product (A-1) to the content weight of the polyfunctional monomer (a1) is preferably larger.

here,
A ratio of the weight of the inorganic particles (b2) in the composition (B-1) to the weight of the polyfunctional monomer (b1);
The preferred range of the ratio of the content weight of the inorganic particles (a2) in the composition (A-1) to the content weight of the polyfunctional monomer (a1) depends on the method for forming a laminate of the present invention. Is also different.

For example, as will be described later in the step (S5) in the section “Production Method of Laminate” below, when heating is performed prior to the curing of the composition (B-1), the above-mentioned polyfunctional monomer (b1) is added. There is a tendency that a laminate having a sufficiently high hardness can be obtained even if the amount of the inorganic particles (b2) is small as compared with the case where the heating is not performed. In this case, the ratio of the content weight of the inorganic particles (b2) in the composition (B-1) to the content weight of the polyfunctional monomer (b1) is the above-mentioned inorganic particles ( If it is larger than about 0.9 times the ratio of the content weight of a2) and the content weight of the polyfunctional monomer (a1), a laminate having a sufficiently high hardness may be obtained.

On the other hand, when heating is not performed prior to the curing of the composition (B-1), the weight of the inorganic particles (b2) in the composition (B-1) and the weight of the polyfunctional monomer (b1) The ratio is desirably larger than about 2.2 times the ratio of the content weight of the inorganic particles (a2) and the content weight of the polyfunctional monomer (a1) in the composition (A-1).

However, from the viewpoint of maintaining the antifogging property after repeated washing with water, the content of the inorganic particles (b2) in the composition (B-1) and the polyfunctional monomer (b1) regardless of the presence or absence of the heating. It is preferable that the ratio to the content weight of is greater than the ratio of the content weight of the inorganic particles (a2) to the content weight of the polyfunctional monomer (a1) in the composition (A-1).

Surfactant (b3)
The composition (B-1) used in the present invention can further contain a surfactant (b3). In a preferred embodiment of the present invention, the surfactant (b3) has a polyoxyalkylene structure.

Here, when the surfactant (b3) has a polyoxyalkylene structure, in a typical embodiment of the present invention, the surfactant (b3) preferably does not have an acrylic polymer structure or a methacrylic polymer structure. That is, the surfactant (b3) preferably does not have any of the structures represented by the following formulas (AC1) to (AC2):

In this case, the surfactant (b3) used in the present invention is
The surfactant is not particularly limited as long as it satisfies the following conditions: (i) having a polyoxyalkylene structure, (ii) not having any of the structures represented by the above formulas (AC1) to (AC2) It can be. However, in the present invention, as the surfactant (b3), one having no polymerizable property, particularly one containing no unsaturated bond in the molecule is used.

The specific configuration of the surfactant (b3) can be the same as that described above in the section “Surfactant (a3)”. One of the surfactants (b3) suitably used in the present invention is, for example, one having a structure represented by the above formula (SS1).

Examples of suitable surfactant (b3) include surfactants further having an anionic hydrophilic group such as polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, and mixtures thereof. Specific examples thereof include polyoxyethylene oleyl cetyl ether sulfate such as sodium polyoxyethylene oleyl cetyl ether sulfate and polyoxyethylene lauryl ether sulfate such as sodium polyoxyethylene lauryl ether sulfate.

The surfactant (b3) used in the present invention may be a nonionic surfactant having a polyoxyalkylene structure. Specific examples thereof include polyoxyalkylene alkyl ethers such as polyoxyalkylene monoalkyl ethers. , Polyoxyalkylene alkenyl ethers such as polyoxyalkylene monoalkenyl ether, and mixtures thereof. Here, examples of the polyoxyalkylene alkyl ether include polyoxyalkylene branched decyl ether, polyoxyalkylene dodecyl ether (polyoxyalkylene lauryl ether), polyoxyalkylene tridecyl ether, and polyoxyalkylene oleyl cetyl ether. Here, in an exemplary embodiment of the present invention, the polyoxyalkylene alkyl ether is a polyoxyethylene alkyl ether, and examples thereof include polyoxyethylene isodecyl ether and polyoxyethylene lauryl ether.

Here, when the surfactant (b3) has an anionic hydrophilic group, the anionic hydrophilic group is also suitable in the form of a free acid in the same manner as the anionic hydrophilic group that can constitute the surfactant (a3). Although it may be in the form of a salt with a cation, it often has the corresponding sodium, potassium or ammonium salt form. Among these salts, sodium salt is the most common, but this does not prevent the surfactant (b3) from having a salt form with other cations such as ammonium salt.

The surfactant (b3) that can be used in the present invention may be a single type or a combination of two or more types. The surfactant (b3) may be the same as the surfactant (a3) or may be different from each other.

In the present invention, the composition (B-1) may not contain the surfactant (b3). However, when the composition (B-1) further contains a surfactant (b3), the content of the surfactant (b3) relative to the total dry weight of the composition (B-1) is the composition (A- Less than the content of the surfactant (a3) relative to the total dry weight of 1).
The specific amount of the surfactant (b3) in the buffer layer (B) is usually more than 0% by weight and not more than 1% by weight, preferably 0.3% with respect to the total dry weight of the composition (B-1). ~ 0.6% by weight.

Other Surfactant The composition (B-1) used in the present invention has the above-mentioned surfactant activity for imparting leveling properties to the coating film or improving surface hydrophilicity regardless of the presence or absence of the surfactant (b3). Other surfactants (hereinafter referred to as “other surfactants”) not corresponding to the agent (b3) can be further included. Here, when the composition (B-1) further contains an anionic hydrophilic group-containing monomer described below, this “other surfactant” is used when forming a cured product of the composition (B-1). It may also be used to control the orientation of the anionic hydrophilic group-containing monomer.

The “other surfactant” is not particularly limited as long as it does not correspond to the surfactant (b3), and may be a conventionally known surfactant. Examples of “other surfactants” include various surfactants having no polyoxyalkylene structure such as dialkylsulfosuccinate, acrylic polymer structure, and methacrylic polymer structure.

The specific amount of “other surfactant” in the buffer layer (B) is usually more than 0% by weight and 2% by weight or less based on the total dry weight of the composition (B-1), preferably 0.8 to 1.2% by weight.

Anionic hydrophilic group-containing monomer The composition (B-1) used in the present invention may further contain an anionic hydrophilic group-containing monomer, in addition to the polyfunctional monomer (b1). When the composition (B-1) used in the present invention further contains an anionic hydrophilic group-containing monomer, the buffer layer (B) has an anionic hydrophilic group derived from the anionic hydrophilic group-containing monomer. . As a result, water molecules easily enter the buffer layer (B) from the outside, so that the surfactant (a3) from the storage layer (A) is easily replenished into the buffer layer (B), and the present invention. It becomes easy to recover the antifogging property of the laminate after washing the laminate. Therefore, in the present invention, the composition (B-1) preferably further contains an anionic hydrophilic group-containing monomer. When the anionic hydrophilic group-containing monomer is contained in the composition (B-1), the anionic hydrophilic group-containing monomer is converted from the polyfunctional monomer (b1) through curing of the composition (B-1). Incorporated into the resulting polymer, it becomes part of the polymer component in the buffer layer (B).

Here, the anionic hydrophilic group-containing monomer that can be used in the present invention is a compound having an anionic hydrophilic group and a functional group having a polymerizable carbon-carbon double bond such as a (meth) acryloyl group. Examples of such compounds include compounds exemplified as Compound (I) in International Publication No. 2007/064003, and preferred examples thereof include potassium 3-sulfopropyl acrylate.
The specific amount of the anionic hydrophilic group-containing monomer in the buffer layer (B) is usually 1 to 5% by weight, preferably 3 to 4% by weight, based on the total dry weight of the composition (B-1). .

Light Stabilizer The composition (B-1) used in the present invention preferably further contains a light stabilizer. Examples of the light stabilizer that can be used in the present invention include an ultraviolet absorber and a hindered amine light stabilizer.

The ultraviolet absorber is not particularly limited. For example, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzoate ultraviolet absorber, a propanedioic acid ester ultraviolet absorber, or an oxanilide type. Various ultraviolet absorbers such as an ultraviolet absorber can be used.

On the other hand, the hindered amine light stabilizer (Hindered Amine Light Stabilizers: abbreviated as HALS) is a general term for compounds having a 2,2,6,6-tetramethylpiperidine skeleton. These are roughly classified into high molecular weight HALS and reactive HALS. Examples of the hindered amine light stabilizer include ADK STAB LA-72, Tinuvin 123 and the like.

The specific content of the light stabilizer in the buffer layer (B) is preferably 3% by weight or more based on the total dry weight of the composition (B-1) so that sufficient light resistance can be secured. That is, the buffer layer (B) preferably contains 3% by weight or more of the light stabilizer with respect to the total dry weight of the composition (B-1). On the other hand, the upper limit of the content of the light stabilizer is not particularly limited as long as the light stabilizer is appropriately dispersed in the composition (B-1) and does not impair the antifogging property. ) Is preferably 4% by weight or less based on the total dry weight.

Configuration of Buffer Layer (B) In the present invention, the buffer layer (B) is a composition (B-1) containing the polyfunctional monomer (b1), the inorganic particles (b2), and the optional surfactant (b3). ) Can be obtained by curing. That is, the buffer layer (B) is a cured product of the composition (B-1).

The buffer layer (B) in the present invention may have a plate shape or a film shape. However, in the present invention, the thickness of the buffer layer (B) is preferably 1 μm or more and 1.8 μm or more so that the buffer layer (B) can exhibit sufficiently high hardness and sufficient scratch resistance. It is more preferable.
On the other hand, the upper limit of the thickness of the buffer layer (B) is not particularly limited as long as the function of the laminate of the present invention is not impaired, but is usually 10 μm or less, and preferably 4 μm or less.
The specific conditions for forming the buffer layer (B) will be described later in the section of “Laminated body manufacturing method”.

<Base material>
Examples of the substrate used in the laminate of the present invention include a substrate made of an inorganic material such as glass, silica, metal, metal oxide, polymethyl methacrylate (PMMA), polycarbonate, polyallyl carbonate, polyethylene terephthalate, poly Organics such as acetylcellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene, polypropylene, polystyrene, polyurethane resin, epoxy resin, poly (meth) acrylate resin, vinyl chloride resin, silicone resin, paper, pulp, etc. Base materials made of materials, organic inorganic base materials such as SMC and BMC in which unsaturated polyester resin and filler such as calcium carbonate and glass fiber are combined, and these inorganic materials, organic materials, and organic-inorganic composite materials Become Coating the surface of the wood has been subjected, a substrate or the like having a coating cured layer.

In addition, for the purpose of activating the substrate surface, these substrate surfaces are activated, as necessary, by corona treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, chemicals, etc. A physical or chemical treatment such as an oxidation treatment or a flame treatment can be performed. In addition to or in addition to these treatments, primer treatment, undercoat treatment, and anchor coat treatment may be performed.

Examples of the coating agent used in the primer treatment, undercoat treatment, and anchor coat treatment include, for example, polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, and polyvinyl acetate resins. A coating agent containing a resin, a polyolefin resin such as polyethylene and polypropylene, or a copolymer or modified resin thereof, a resin such as a cellulose resin as a main component of the vehicle can be used. The coating agent used here may be a conventionally known coating agent usually used in the field to which the present invention belongs, and the coating agent can also be applied by a known coating method. The coating amount of the coating agent on the substrate is usually 0.5 μm to 10 μm in a dry state.

<Configuration of laminate>
As described above, the laminate according to the present invention includes the base material, the storage layer (A), and the buffer layer (B) in this order. Here, each of the storage layer (A) and the buffer layer (B) included in the laminate according to the present invention may be only one layer, or may be two or more layers, The storage layer (A) and the buffer layer (B) need to be in direct contact with each other.
In the laminate of the present invention, the ratio of the thickness of the storage layer (A) to the thickness of the buffer layer (B) (film thickness ratio) ensures sufficiently high antifogging properties and hydrophilicity after washing with water. From the viewpoint, it is preferably a certain value or more, specifically, usually 1.3 or more, preferably 1.5 or more, and more preferably 1.7 or more. On the other hand, the upper limit of the film thickness ratio is not particularly limited as long as the present invention can be practiced appropriately, but is usually 15 or less, preferably 5 or less, and more preferably 3.5 or less. In a typical embodiment of the present invention, the film thickness ratio is usually in the range of 1.3 to 15, preferably 1.5 to 5, and more preferably 1.7 to 3.5. When the film thickness ratio is in such a range, the laminate of the present invention tends to advantageously maintain high antifogging properties and high hydrophilicity even after washing with water, which is preferable.

Here, in one of preferred embodiments of the present invention, the laminate is composed of only the base material, the storage layer (A), and the buffer layer (B). However, the laminate of the present invention is not limited to these embodiments, and in addition to the substrate, the storage layer (A) and the buffer layer (B), the substrate and the storage layer ( You may further have other layers which are not any of A) and the said buffer layer (B).

Other layers In addition to the base material, the storage layer (A), and the buffer layer (B), the laminate of the present invention includes any of the base material, the storage layer (A), and the buffer layer (B). However, it may further have other layers (hereinafter, “other layers”).

Examples of such “other layers” include a primer layer, a hard coat layer, and an adhesive layer.
Here, the primer layer is a layer made of an adhesive (primer), and may be employed to improve the adhesion between two layers positioned so as to sandwich this layer. For example, when the substrate is polydiethylene glycol diallyl carbonate, polydiallyl carbonate, or the like, a primer layer may be present between the substrate and the storage tank layer (A). Furthermore, when the primer layer is present, the storage layer (A) may be made into two layers for the purpose of preventing the surfactant (a3) contained in the storage layer (A) from entering the primer. is there. In this case, the storage layer (A) has a two-layer structure of the “storage layer (A0)” and the “storage layer (A1)”, and the “storage layer (A0)” is the protective layer (P). Will be.

Further, the hard coat layer is the same layer as the layer provided as the hard coat layer in the prior art, and can be formed for the purpose of improving the hardness. The laminate of the present invention may have a hard coat layer directly on the substrate.

In addition, the laminate of the present invention has an adhesive layer on the side of the substrate opposite to the side having the storage layer (A) and the buffer layer (B) so that it can be attached to other objects. You may have.

Detailed description of these layers, including the formation method, will be described later in “Laminated body manufacturing method” below.
When mentioning a specific exemplary embodiment in which the laminate of the present invention includes "other layers", for example, in one of the preferred embodiments of the present invention, the laminate of the present invention comprises the above-described substrate, primer A layer, the storage layer (A), and the buffer layer (B) in this order.

<Method for producing laminate>
The typical manufacturing method of the laminated body of this invention is described below.
The method for producing the laminate of the present invention comprises:
(S1): For at least one surface of the layer containing the substrate,
The polyfunctional monomer (a1),
The inorganic particles (a2),
The surfactant (a3) and the solvent (a4)
Providing a coated layer (A2) of the composition (A-1a) containing:
(S2): A step of removing the solvent (a4) from the coated layer (A2) obtained in the step (S1),
(S3): After the step (S2), the coating layer (A2) is cured, and the coating layer (A2) is converted into a cured layer (A2 ′).
(S4): After the step (S3), on the cured product layer (A2 ′),
The polyfunctional monomer (b1),
The inorganic particles (b2), and the solvent (b4)
Providing a coated layer (B2) of the composition (B-1a) containing:
(S5): a step of removing the solvent (b4) from the coating layer (B2) obtained in the step (S4), and (S6): after the step (S5), the coating layer (B2) Curing, converting the coated layer (B2) into a cured layer (B2 ′),
including.

Step (S1)
In the production method of the present invention, the step (S1) is performed on at least one surface of the layer containing the substrate.
The polyfunctional monomer (a1),
The inorganic particles (a2),
The surfactant (a3) and the solvent (a4)
A coating layer (A2) of the composition (A-1a) containing

Here, as the “polyfunctional monomer (a1)”, “inorganic particles (a2)” and “surfactant (a3)”, the “polyfunctional monomer (A)” described above in the section “Storage layer (A)”, respectively. a1) ”,“ inorganic particles (a2) ”, and“ surfactant (a3) ”are used, respectively, and the amount of each is also the amount described above in the section“ Storage layer (A) ”. Can do. Further, as the “base material”, the base material described above in the section “Base material” is used.

On the other hand, “solvent (a4)” is not an essential component of the storage layer (A) by itself, and therefore is not an essential component of the composition (A-1). However, in a typical embodiment of the present invention, when the storage layer (A) is produced, a step of applying the composition (A-1) is performed. Therefore, the solvent (a4) is used so that the composition (A-1) is in a form suitable for coating. Here, in the present specification, the composition (A-1) containing the solvent (a4) is referred to as “composition (A-1a)”.

The type of the solvent (a4) is not limited, but a solvent that does not separate the components of the composition (A-1a) that is cured to form the storage layer (A) is preferable. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, n-hexanol, n-octanol, 2-ethyl-hexanol, 2-methoxyethanol 2-ethoxyethanol, 2-n-propoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-n-propoxy-2-propanol, Alcohols such as 1-isopropoxy-2-propanol and cyclohexanol, ethers such as diethyl ether, tetrahydrofuran and dioxane, nitriles such as acetonitrile, ethyl acetate, n-propyl acetate, n-butyl acetate Esters, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, N, N-dimethylformamide, N, N- dimethylacetamide amides such as, and water. As the solvent (a4) constituting the composition (A-1a), alcohols, ketones, and mixed solvents of alcohols and ketones are preferable. These solvents may be used alone or in combination of two or more.

Here, the composition (A-1a) can be obtained by mixing the polyfunctional monomer (a1), the inorganic particles (a2), the surfactant (a3), the solvent (a4) and the like. it can. At this time, the solvent (a4) may be added separately from the polyfunctional monomer (a1), the inorganic particles (a2), the surfactant (a3), or the like. Alternatively, the polyfunctional monomer It may be added together with one or more of (a1), the inorganic particles (a2), and the surfactant (a3). For example, when the inorganic particles (a2) are used in the form of sol or slurry, the solvent constituting the sol or slurry may constitute the solvent (a4). Moreover, when the said surfactant (a3) etc. are used in the form of a solution, the solvent which comprises the said solution may comprise the said solvent (a4).

The composition (A-1a) includes the polyfunctional monomer (a1), the inorganic particles (a2), the surfactant (a3), and the solvent (a4) in preparation for the step (S3) described later. In addition, a conventionally known photopolymerization initiator or thermal polymerization initiator may be appropriately added.

Here, examples of the photopolymerization initiator that can be added to the composition (A-1a) include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator. Among the polymerization initiators, a radical photopolymerization initiator is preferable.

As the photo radical polymerization initiator, known photo radical polymerization initiators can be used. For example, Irgacure 127 (manufactured by Ciba Specialty Chemicals), Irgacure 184 (manufactured by Ciba Specialty Chemicals) ), Darocur 1173 (manufactured by Ciba Specialty Chemicals), Irgacure 500 (manufactured by Ciba Specialty Chemicals), Irgacure 819 (manufactured by Ciba Specialty Chemicals), Darocur TPO (Ciba Specialty Chemicals) -Chemicals), Esacure ONE (Lamberti), Esacure KIP100F (Lamberti), Esacure KT37 (Lamberti), Esacure KTO46 (Lamberti), etc. .

On the other hand, also about a photocationic polymerization initiator and a photoanion polymerization initiator, a well-known photocationic polymerization initiator and a well-known photoanion polymerization initiator can be used similarly.
Moreover, when using the said photoinitiator, you may use a photoinitiator together. Examples of the photopolymerization accelerator include 2,2-bis (2-chlorophenyl) -4,5′-tetraphenyl-2′H- <1,2 ′> biimidazolol, tris (4-dimethylaminophenyl) methane, Examples include 4,4′-bis (dimethylamino) benzophenone, 2-ethylanthraquinone, camphorquinone, and the like.

On the other hand, as the thermal polymerization initiator that can be added to the composition (A-1a), a known thermal polymerization initiator can be used. Examples of thermal polymerization initiators include ketone peroxides, diacyl peroxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, and the like.

The amount of the photopolymerization initiator, photopolymerization accelerator, and thermal polymerization initiator used is usually 1 to 5% by weight, preferably 2 to 3% by weight, based on the total dry weight of the composition (A-1a). It is.
When forming the storage layer (A) by coating, the thickness of the storage layer (A) can be adjusted by adjusting the amount of the solvent (a4) contained in the composition (A-1a). Here, as described above in “Structure of storage layer (A)”, if the thickness of the storage layer (A) is too thin, sufficient anti-fogging property may not be exhibited after the laminate is washed with water. Accordingly, the total dry weight of the composition (A-1a) per 100 parts by weight of the composition (A-1a) is usually 46 so that the resulting storage layer (A) can have a sufficient thickness. It is preferably at least 55 parts by weight. On the other hand, the total dry weight of the composition (A-1a) occupying per 100 parts by weight of the composition (A-1a) is less than 100 parts by weight so that the fluidity necessary for coating can be obtained. Part or less.

The total dry weight of the composition (A-1a) is, for example, an inorganic composition composed of the polyfunctional monomer (a1), the inorganic particles (a2), and the first solvent. When composed of a particle sol, the surfactant (a3), the photopolymerization initiator, and a second solvent, the polyfunctional monomer (a1), the inorganic particles (a2), and the surfactant (a3) It refers to the total weight of the photopolymerization initiator.

Application of the composition (A-1a) to the substrate can be appropriately performed by a conventionally known method. Examples of such coating methods include spin coating, dip coating, spray coating, flow coating, brush coating, gravure coating, reverse roll coating, knife coating, and kiss coating. By this coating, a coated layer (A2) of the composition (A-1a) is obtained.

Here, prior to the step (S1), an adhesive (primer) may be applied and laminated between the base material and the storage layer (A) in order to improve adhesion, or the surface of the base material. May be subjected to surface treatment such as plasma treatment, corona treatment and polishing. In addition, for the purpose of improving hardness, a hard-coated material may be used as a base material, or a hard coat layer is laminated on the base material by a known method, and the storage layer (A) and the buffer are formed thereon. A layer (B) may be formed. Furthermore, for the purpose of imparting other functions, substances other than those described above may be laminated between the base material and the storage layer (A). Further, for example, the outermost buffer layer (B) may be subjected to a surface treatment for the purpose of controlling the surface energy of the outermost layer, or a graft treatment may be performed with a compound having reactivity with the outermost buffer layer (B). Also good.

In the case of a plastic substrate with a hard coat, the surface is first polished with an abrasive, and after washing and drying, surface treatment such as corona treatment is performed to improve wettability. Next, in order to improve the adhesion between the hard coat layer and the storage layer (A), a known primer is applied by a known application method (spin coating, dip coating, spray coating, flow coating, brush coating, etc.), and after drying The coated layer (A2) can be formed by coating the composition (A-1a) in the same manner as described above.

In any case, by this step (S1), a precursor laminate (PL1) having a base material and the coated product layer (A2) is obtained. This precursor laminate (PL1) is subjected to the step (S2) described below.

Step (S2)
Step (S2) is a step of removing the solvent (a4) from the coated layer (A2) obtained in the step (S1).

After the application of the composition (A-1a) to the base material, the solvent remaining immediately before the polymerization and curing tends to reduce the adhesion to the base material when the residual amount is large. For this reason, it is preferable that the residual solvent in the composition (A-1a) is small. Therefore, prior to polymerization and curing, the solvent (a4) is removed from the coated layer (A2).

This step (S2) may be performed by naturally drying the precursor laminate (PL1) obtained in the step (S1), or the precursor laminate (PL1) obtained in the step (S1). You may carry out by heating.

Step (S3)
The step (S3) is a step of curing the coated layer (A2) after the step (S2).
Curing of the coated layer (A2) can typically be performed by irradiation or heating.

Here, when the composition (A-1a) is polymerized and cured by radiation irradiation, for example, ultraviolet (UV) irradiation, a coating layer (A2) usually containing a photopolymerization initiator is used. In this case, the above-mentioned photopolymerization initiator is added to the composition (A-1a) produced in the step (S1).

When the composition (A-1a) is polymerized using radiation, energy rays having a wavelength range of 0.0001 to 800 nm can be used as the radiation. The radiation is classified into α rays, β rays, γ rays, X rays, electron rays, ultraviolet rays, visible light, and the like, and can be appropriately selected and used according to the composition of the composition (A-1a). Among these radiations, ultraviolet rays are preferable, and the output peak of ultraviolet rays is preferably in the range of 200 to 450 nm, more preferably in the range of 230 to 445 nm, still more preferably in the range of 240 to 430 nm, and particularly preferably in the range of 250 to 400 nm. When ultraviolet rays in the above output peak range are used, there are few problems such as yellowing and thermal deformation during polymerization, and the polymerization can be completed in a relatively short time even when an ultraviolet absorber is added. The irradiation time of radiation can be set as appropriate.

When the polymerization is carried out by heat, the coated layer (A2) usually contains a thermal polymerization initiator such as an organic peroxide. In this case, the above-described thermal polymerization initiator is added to the composition (A-1a) produced in the step (S1).

When the composition (A-1a) is polymerized by heat, it is heated in the range of room temperature to 150 ° C. or less. The heating time in this case can be set as appropriate.
The above polymerization can be carried out in the air, but it is preferable in that the polymerization time can be shortened when carried out in an inert gas atmosphere such as nitrogen.

By the irradiation or heating as described above, the polymerization reaction of the polyfunctional monomer (a1) contained in the coated layer (A2) proceeds and is converted into a corresponding polymer. As a result, the coated product layer (A2) is converted into a cured product layer (A2 ′) containing such a polymer. In other words, by this step (S3), a precursor laminate (PL3) having a base material and a cured product layer (A2 ′) is obtained. This precursor laminate (PL3) is subjected to the step (S4) described below.

Step (S4)
In the step (S4), after the step (S3), on the cured product layer (A2 ′),
The polyfunctional monomer (b1),
The inorganic particles (b2), and the solvent (b4)
A coating layer (B2) of the composition (B-1a) containing

Here, as “polyfunctional monomer (b1)” and “inorganic particle (b2)”, “polyfunctional monomer (b1)” and “inorganic particle (b2)” described above in the section of “buffer layer (B)”, respectively. ) "Is used.

The composition (B-1a) may or may not contain the “surfactant (b3)” described above in the section “Buffer layer (B)”. However, when the composition (B-1a) contains the surfactant (b3), the content of the surfactant (b3) relative to the total dry weight of the composition (B-1) is the composition (A-1 ) Less than the content of the surfactant (a3) with respect to the total dry weight. Further, the composition (B-1a) includes the “other surfactant”, “anionic hydrophilic group-containing monomer”, and “light stabilizer” described above in the section “Buffer layer (B)”. One or more may be further included.

The blending amounts of “polyfunctional monomer (b1)”, “inorganic particles (b2)”, and optional “surfactant (b3)” are also the amounts described above in the section “Buffer layer (B)”. can do.

On the other hand, “solvent (b4)” is not an essential component of the buffer layer (B) by itself, and therefore is not an essential component of the composition (B-1). However, in a typical embodiment of the present invention, when the buffer layer (B) is produced, a step of applying the composition (B-1) is performed. Therefore, the solvent (b4) is used so that the composition (B-1) is in a form suitable for coating. Here, in the present specification, the composition (B-1) containing the solvent (b4) is referred to as “composition (B-1a)”.

The type of the solvent (b4) is not limited, but a solvent that does not separate each component of the composition (B-1a) that is cured to form the buffer layer (B) is preferable. Specific examples of such a solvent (b4) include the same solvents as those listed above for the solvent (a1). The solvent (b4) may be the same as the solvent (a4) or may be different from each other.

Here, the composition (B-1a) can be obtained by mixing the polyfunctional monomer (b1), the inorganic particles (b2), the solvent (b4) and the like. At this time, the solvent (b4) may be added separately from the polyfunctional monomer (b1) and the inorganic particles (b2), or the polyfunctional monomer (b1) and the inorganic particles (b2). ) Etc. may be added along with one or more of the above. For example, when the inorganic particles (b2) are used in the form of sol or slurry, the solvent constituting the sol or slurry may constitute the solvent (b4). Further, when the surfactant (b3) or the like is used in the form of a solution in the composition (B-1a), the solvent constituting the solution may constitute the solvent (b4). .

In addition to the polyfunctional monomer (b1), the inorganic particles (b2), the solvent (b4) and the like, the composition (B-1a) is prepared by a conventionally known step in preparation for the step (S6) described later. A photopolymerization initiator or a thermal polymerization initiator may be appropriately added. The photopolymerization initiator and thermal polymerization initiator that can be added to the composition (B-1a) include a photopolymerization initiator and thermal polymerization initiator that can be added to the composition (A-1a), Each can be the same.

The amount of the photopolymerization initiator, photopolymerization accelerator, and thermal polymerization initiator used is usually 1 to 10% by weight, preferably 3 to 6% by weight, based on the total dry weight of the composition (B-1a). It is.
When the buffer layer (B) is formed by coating, the thickness of the buffer layer (B) can be adjusted by adjusting the amount of the solvent (b4) contained in the composition (B-1a). The total dry weight of the composition (B-1a) occupying per 100 parts by weight of the composition (B-1a) may have a thickness necessary for the obtained buffer layer (B) to have sufficient strength and the like. It is preferable that it is 35 weight part or more so that it can do, and it is more preferable that it is 37.5 weight part or more. On the other hand, the total dry weight of the composition (B-1a) occupying per 100 parts by weight of the composition (B-1a) is less than 100 parts by weight, so that the fluidity required for coating can be obtained. Part or less.

The total dry weight of the composition (B-1a) is, for example, an inorganic composition comprising the polyfunctional monomer (b1), the inorganic particles (b2), and the first solvent. Particle sol, dispersion comprising the surfactant (b3) and the second solvent, dispersion comprising the other surfactant and the third solvent, the anionic hydrophilic group-containing monomer and the fourth solvent And a dispersion comprising the above, the light stabilizer, the photopolymerization initiator, and a fifth solvent, the polyfunctional monomer (b1), the inorganic particles (b2), and the surfactant (b3) It refers to the total weight of the other surfactant, the anionic hydrophilic group-containing monomer, the light stabilizer, and the photopolymerization initiator.

Application of the composition (B-1a) to the cured product layer (A2 ′) can be performed in the same manner as the application of the composition (A-1a) described above in step (S1).
By this process (S4), the precursor laminated body (PL4) which has a base material, hardened | cured material layer (A2 '), and a coated material layer (B2) in this order is obtained. This precursor laminate (PL4) is subjected to the step (S5) described below.

Step (S5)
Step (S5) is a step of removing the solvent (b4) from the coated layer (B2) obtained in the step (S4).

This step (S5) may be performed by naturally drying the precursor laminate (PL4) obtained in the step (S4), or obtained by the step (S4), as in the step (S2). You may carry out by heating the obtained precursor laminated body (PL4). However, in this step (S5), if the precursor laminate (PL4) is heated at 50 to 90 ° C., that is, if the step (S5) is carried out at 50 to 90 ° C., the above polyfunctional monomer Even if there is little quantity of the said inorganic particle (b2) with respect to (b1), since the laminated body which has sufficiently high hardness can be obtained after a process (S6), it is preferable. This is presumably because the crosslinked state becomes denser during the curing in the subsequent step (S6) by performing the heating. Further, when this heating is performed, the content of the polyfunctional monomer (b1) with respect to the total dry weight of the composition (B-1) is changed so that the polyfunctional monomer (with respect to the total dry weight of the composition (A-1)) Even under a situation where the content is less than the content of a1), the degree of crosslinking of the buffer layer (B) obtained in the form of the cured product layer (B2 ′) after the step (S6) can be increased, which is advantageous.
The heating time in the case of performing the above heating in this step (S5) is usually 3 to 20 minutes.

Step (S6)
The step (S6) is a step of curing the coated layer (B2) after the step (S5) to convert the coated layer (B2) into a cured layer (B2 ′).
Here, when the composition (B-1a) is polymerized and cured by radiation irradiation, for example, ultraviolet (UV) irradiation, a coating layer (B2) usually containing a photopolymerization initiator is used. In this case, the above-mentioned photopolymerization initiator is added to the composition (B-1a) produced in the step (S4).

When the composition (B-1a) is polymerized using radiation, the wavelength and irradiation time of the radiation can be the same as those in the step (S4).
When it superposes | polymerizes with a heat | fever, what contains thermal polymerization initiators, such as an organic peroxide, is normally used as a coating material layer (B2). In this case, the above-described thermal polymerization initiator is added to the composition (B-1a) produced in the step (S4).
When the composition (B-1a) is polymerized by heat, the heating temperature and heating time can be the same as those in the step (S4).

By the irradiation or heating as described above, the polymerization reaction of the polyfunctional monomer (b1) contained in the coated layer (B2) proceeds and is converted into a corresponding polymer. As a result, the coated layer (B2) is converted into a cured product layer (B2 ′) containing such a polymer. In other words, a laminate having a base material, a cured product layer (A2 ′), and a cured product layer (B2 ′) in this order is obtained by this step (S6).

Through the above steps (S1) to (S6), the laminate of the present invention can be obtained. Here, the cured product layer (A2 ′) and the cured product layer (B2 ′) correspond to the storage layer (A) and the buffer layer (B), respectively.

Moreover, when a base material is a film, the below-mentioned adhesion layer can also be provided in the surface which does not form the said storage layer (A) and the said buffer layer (B), for example, Furthermore, it peels on the surface of an adhesion layer. A film can also be provided. When an adhesive layer is laminated on the other side of the base film, the laminated film having the laminate of the present invention is used as an antifogging film and an antifouling film, glass for vehicles and buildings; mirrors for bathrooms; displays, televisions It can be easily attached to the surface of display materials such as: information boards such as signboards, advertisements, and information boards; signs for railways, roads, etc .;

There is no restriction | limiting in particular in the adhesive used for an adhesion layer, A well-known adhesive can be used. Examples of the adhesive include acrylic adhesives, rubber adhesives, vinyl ether polymer adhesives, and silicone adhesives. The thickness of the adhesive layer is usually in the range of 2 to 50 μm, preferably in the range of 5 to 30 μm.

Further, by polymerizing the composition (A-1a) and / or the composition (B-1a) in a mold having various shapes, cross-linked resins having various shapes such as laminates and molded products can be obtained. It can also be obtained.

The laminate obtained by the present invention and the laminate comprising the laminate can be suitably used as an antifogging material, an antifouling material, a quick drying material, an anti-condensation material, an antistatic material and the like. Such a laminate of the present invention includes optical articles such as optical films, optical discs, optical lenses, spectacle lenses, glasses, sunglasses, goggles, helmet shields, headlamps, tail lamps, vehicle and building window glass, and materials thereof. It can be applied to various uses.

The laminate of the present invention can also be applied to an image recognition system using an in-vehicle camera that has been widely installed in vehicles in recent years. Specifically, the laminate of the present invention can be in the form of a vehicle window glass or a camera lens of an in-vehicle camera. The window glass and camera lens corresponding to the laminate of the present invention are formed by directly forming the storage layer (A) and the buffer layer (B) on the surface of a normal window glass and a normal camera lens. Can be obtained respectively. The window glass and camera lens corresponding to the laminate of the present invention can also be obtained by pasting the laminate of the present invention in the form of a film on the surface of a normal window glass and a normal camera lens, respectively. . That is, according to the present invention, the vehicle is equipped with an image recognition system using an in-vehicle camera, and includes (i) a window glass having the storage layer (A) and the buffer layer (B), or (ii) As a vehicle-mounted camera, there is provided a vehicle including a camera having a camera lens having the storage layer (A) and the buffer layer (B), or (iii) satisfying both (i) and (ii) Will be. In such a vehicle, the window glass and / or the camera lens are not easily fogged even under conditions where the inner window to which the laminate of the present invention is not applied is clouded, such as under low temperature and high humidity. The image recognition system installed in can properly recognize images.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited only to these Examples.
[Physical property evaluation of samples]
In the present invention, the physical properties of the samples were evaluated as follows.

1. Film thickness measurement The film thickness of each layer was calculated by spectroscopic measurement.
Specifically, using a film thickness measuring device ETA-ARC manufactured by OPTOTECH, the spectral reflectance is measured around the center of the film sample, and the film thickness of each single layer or two-layer laminated state by Fourier transform method Was calculated.

2. Adhesion The coating film is cut with a cutter so that it reaches the surface of 11 substrates at 1 mm intervals in the vertical and horizontal directions using a cutter, and the part is adhered by cross-cut method using Nichiban cellophane adhesive tape CT405AP-18 A visual inspection was conducted to determine the ratio of the film peeling area after the three peel tests to 100 squares. At that time, the evaluation when the area of the part where the film was not peeled and the film remained exceeded 90% was “◯”, the evaluation when 50% to 90% was “Δ”, and the evaluation when the area was less than 50% was “×” "

3. Scratch resistance test Using steel wool # 0000, a sample was placed on the steel wool, and a weight of 300 g or 1 kg was placed on the sample and a load was applied. In this state, the sample was reciprocated 10 times on steel wool. This reciprocating motion was performed using a reciprocating friction tester Type: 30s (manufactured by Shinto Kagaku Co., Ltd.). The scratches on the surface of the coating film were visually evaluated by performing this reciprocating motion, and five-level ranking was performed.
The ranks of scratches are as follows.
Rank 1: A state in which the entire width of the steel wool is scratched and the coat film is peeled off entirely.
Rank 2: The entire width of the steel wool is deeply scratched, but the coat film remains.
Rank 3: A state in which several to ten large scratches entered.
Rank 4: A state in which several to ten thin scratches have entered.
Rank 5: There is almost no visible scratch.
Here, the ranks represented by decimal numbers, such as “3.5” and “4.5”, are evaluated between rank 3 and rank 4, and between rank 4 and rank 5, respectively. Represents an evaluation.

4). Exhalation anti-fogging property Exhalation was blown on the sample surface for several seconds to confirm the presence or absence of fogging on the sample surface. Here, the evaluation when the sample surface was not clouded even when exhalation was performed was `` ○ '', and the evaluation when the sample surface was fogged when exhalation was performed was `` x '' did. The test was conducted at room temperature of 22 ° C. for 1 hour, and the test was performed at the same temperature.
In each of the following Examples and Comparative Examples, the “initial breath anti-fogging property” refers to the breath anti-fogging property of a sample before performing “evaluation after water washing” described later.

5. Water contact angle The contact angle of pure water was measured with a contact angle meter. The measurement was performed at three locations for one sample, and the average of these values was taken as the value of the water contact angle. Here, as the value of the water contact angle, the contact angle after 22 seconds from the landing is described.
As a contact angle meter used for the measurement, a contact angle meter DropMaster Model DMs-401 of Kyowa Interface Science was used.
In each of the following Examples and Comparative Examples, “initial water contact angle” refers to the water contact angle of a sample before performing “evaluation after water washing” described later.

6. Steam defogging at 50 ° C. Pure water is put in a beaker, and the sample to be evaluated is placed on the top of the beaker while being heated to 50 ° C. and held for 60 seconds, and then evaluated as it is. The sample was observed by viewing from above. As this sample to be evaluated, a sample which had been allowed to stand at 22 ° C. for 1 hour or more in advance was used. The evaluation when the sample was clouded or the image was distorted within 60 seconds from the start of the holding was “x”, and the evaluation when it was not so was “◯”.

7. Evaluation after water washing The sample surface was washed for 5 seconds while rubbing with Crecia Techno Wipe C100-S (Nippon Paper Crecia Co., Ltd.) in running water, dried by air blow, and then allowed to stand at room temperature for 2 hours. After the first, third, and fifth cycles, the breath antifogging property and contact angle were measured. Based on this, anti-fogging durability was evaluated by evaluating exhalation anti-fogging properties and the change in contact angle according to the number of repeated washings.
In addition, after the third and fifth cycles, the evaluation “−” for the antifogging property and the contact angle indicates that the measurement of the antifogging property and / or the contact angle was not performed.

8). Light resistance test The sample was irradiated with light in an environment of a temperature of 40 ° C. and a humidity of 60% to perform a light resistance test. Here, as a light source, a Xenon weather tester, a Suga tester, was used, and the irradiation intensity was 75 W / m ² . The irradiation time (hereinafter referred to as “endurance time”) from the start of light irradiation to the appearance of cracking or peeling on the sample was measured, and the light resistance was evaluated using this endurance time.

[Synthesis Example A1] <Preparation of Storage Layer Forming Composition A1>
Under a normal temperature and pressure environment, weigh 1.0 parts by weight of Daiichi Kogyo's surfactant Hytenol 08E (polyoxyethylene oleyl cetyl ether sulfate) into a glass screw tube, and then make it from Nissan Chemical Industries 66.5 parts by weight of organosilica sol PGM-AC-2140Y (surface modification grade of propylene glycol monomethyl ether-dispersed silica sol: silica particle content 42%; particle size 10 to 15 nm) was added. Further, 3.3 parts by weight of methyl isobutyl ketone was added as a solvent, and the mixture was stirred with a magnetic stirrer and a stir bar until Haitenol 08E was completely dissolved. Next, 27.9 parts by weight of acrylate NK ester A-600 (polyethylene glycol # 600 diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. was added and stirred well until compatible. Next, Irgacure 127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one manufactured by BASF was used as a photopolymerization initiator. 1.3 parts by weight) and stirred until completely dissolved to obtain a liquid composition (hereinafter referred to as “storage layer forming composition A1”).

This storage layer forming composition A1 corresponds to a composition containing inorganic particles modified with a functional group containing an acryloyl group as inorganic particles and an anionic surfactant as a surfactant. Here, the organosilica sol PGM-AC-2140Y corresponds to inorganic particles modified with a functional group containing an acryloyl group.

[Synthesis Example A2] <Preparation of Storage Layer Forming Composition A2>
A liquid composition was prepared in the same manner as in Synthesis Example A1, except that the surfactant Neugen LP-80 (polyoxyalkylene lauryl ether) manufactured by Daiichi Kogyo Seiyaku was used in place of Haitenol 08E as the surfactant. A composition for forming a storage layer A2.
This storage layer forming composition A2 corresponds to a composition containing inorganic particles modified with a functional group containing an acryloyl group as inorganic particles and a nonionic surfactant as a surfactant.

[Synthesis Example A3] <Preparation of Storage Layer Forming Composition A3>
The amount of organosilica sol PGM-AC-2140Y is 61.6 parts by weight, the amount of methyl isobutyl ketone is 3.5 parts by weight, the amount of NK ester A-600 is 32.4 parts by weight, and the amount of Irgacure 127 is 1. A liquid composition was prepared in the same manner as in Synthesis Example A1 except that the amount was changed to 5 parts by weight, and designated as storage layer forming composition A3.

[Synthesis Example A4] <Preparation of storage layer forming composition A4>
The amount of surfactant Haitenol 08E is 1.1 parts by weight, the amount of organosilica sol PGM-AC-2140Y is 55.2 parts by weight, the amount of methyl isobutyl ketone is 3.2 parts by weight, and the NK ester A- A liquid composition was prepared in the same manner as in Synthesis Example A1, except that the amount of 600 was changed to 38.7 parts by weight and the amount of Irgacure 127 was changed to 1.8 parts by weight, and this was designated as storage layer forming composition A4. .

[Synthesis Example A5] <Preparation of storage layer forming composition A5>
Under a normal temperature and normal pressure environment, weigh 0.8 parts by weight of a surfactant Hytenol 08E manufactured by Daiichi Kogyo Seiyaku into a glass screw tube, and then organosilica sol PGM-ST (propylene glycol monomethyl ether) manufactured by Nissan Chemical Industries Dispersed silica sol: silica particle content 30%; particle diameter 10-15 nm) was added at 73.5 parts by weight. Further, 2.6 parts by weight of methyl isobutyl ketone was added as a solvent, and the mixture was stirred with a magnetic stirrer and a stirring bar until Hitenol 08E was completely dissolved. Next, 22.0 parts by weight of acrylate NK ester A-600 manufactured by Shin-Nakamura Chemical Co., Ltd. was added and stirred well until they were compatible. Next, 1.1 parts by weight of ISFacure 127 manufactured by BASF was added as a photopolymerization initiator and stirred until completely dissolved to obtain a liquid composition (hereinafter referred to as “storage layer forming composition A5”).
This storage layer forming composition A5 corresponds to a composition containing inorganic particles not modified with a functional group containing a (meth) acryloyl group as inorganic particles and an anionic surfactant as a surfactant.

[Synthesis Example A6] <Preparation of Storage Layer Forming Composition A6>
A liquid composition was prepared in the same manner as in Synthesis Example A1 except that the surfactant was not added, and designated as storage layer forming composition A6.
This storage layer forming composition A6 is a composition containing inorganic particles modified with a functional group containing an acryloyl group as inorganic particles, but not containing a surfactant.

[Synthesis Example A7] <Preparation of storage layer forming composition A7>
Under a normal temperature and normal pressure environment, 0.7 parts by weight of a surfactant Hytenol 08E manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was weighed into a glass screw tube, and then an organosilica sol PGM-AC-2140Y manufactured by Nissan Chemical Industries Co., Ltd. 9 parts by weight were added. Further, 4.6 parts by weight of methyl isobutyl ketone and 28.6 parts by weight of propylene glycol monomethyl ether were added as a solvent, and the mixture was stirred with a magnetic stirrer and a stirring bar until Hitenol 08E was completely dissolved. Next, 19.3 parts by weight of NK ester A-600 of acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. was added and stirred well until they were compatible. Next, 0.9 part by weight of ISFacure 127 manufactured by BASF was added as a photopolymerization initiator and stirred until completely dissolved to obtain a liquid composition (hereinafter referred to as “storage layer forming composition A7”).

The compositions of the respective storage layer forming compositions obtained in Synthesis Examples A1 to A7 are summarized in Table 1 below.
Here, the value enclosed in parentheses in the weight shown in Table 1 below represents a value obtained by calculation.

Further, the “solid content” with respect to the amount of the inorganic particles (a2) means that when the inorganic particles (a2) are used in the form of the corresponding sol, the weight of components other than the contained solvent in the weight of the sol. Represents. The “total dry weight” is the sum of the total weight of the solvent specified in the “Solvent” section and the total weight of the solvent components that can be contained in components other than the “solvent” from the total weight of the composition. It represents the weight after subtraction.

[Synthesis Example B1] <Preparation of Composition B1 for Forming Buffer Layer>
Organo silica sol PGM-AC-2140Y manufactured by Nissan Chemical Industries, Ltd. (surface modification grade of propylene glycol monomethyl ether-dispersed silica sol: 42% silica particle content; particle diameter 10-15 nm) Next, 19.5 parts by weight of propylene glycol monomethyl ether was added as a solvent, and 11.7 of NK ester A-600 (polyethylene glycol # 600 diacrylate) of acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. was added. The mixture was thoroughly stirred with a magnetic stirrer and a stir bar until the parts were added and dissolved. Next, 3-sulfopropyl acrylate potassium salt (SPA-K) dispersion (SPA-K 30.0 wt%, water 9.0 wt%, propylene glycol monomethyl ether 61.0 wt%) dispersed in propylene glycol monomethyl ether Was added and stirred well until completely compatible. Next, 3.2 parts by weight of Pelex TR dispersion (Pelex TR (sodium dialkylsulfosuccinate) 10.0% by weight, 90.0% by weight of propylene glycol monomethyl ether) was added, and the mixture was stirred well until it was completely compatible. Next, Irgacure 127 (2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one manufactured by BASF was used as a photopolymerization initiator. 1.6 parts by weight) and stirred until completely dissolved to obtain a liquid composition (hereinafter referred to as “buffer layer forming composition B1”).
This buffer layer forming composition B1 corresponds to a composition containing inorganic particles modified with a functional group containing an acryloyl group as inorganic particles and an anionic surfactant as a surfactant.

[Synthesis Example B2] <Preparation of buffer layer forming composition B2>
Under a normal temperature and pressure environment, weigh 59.2 parts by weight of an organosilica sol PGM-AC-2140Y (silica particle content 42%) manufactured by Nissan Chemical Industries into a glass screw tube, and then use propylene glycol monomethyl ether 19 as a solvent. Then, 2 parts by weight were added, and 11.4 parts by weight of NK ester A-600 of acrylate made by Shin-Nakamura Chemical Co., Ltd. was further added and stirred well with a magnetic stirrer and a stir bar until they were compatible. Next, 3.3 parts by weight of a SPA-K dispersion (SPA-K 30.0 wt%, water 9.0 wt%, propylene glycol monomethyl ether 61.0 wt%) dispersed in propylene glycol monomethyl ether was added, Stir well until completely compatible. Next, 3.1 parts by weight of PELEX TR dispersion (PELEX TR 10.0% by weight / propylene glycol monomethyl ether 90.0% by weight) was added, and the mixture was stirred well until it was completely compatible. Next, a high-tenol 08E dispersion composed of 10.0% by weight of high tenol 08E (polyoxyethylene oleyl cetyl ether sulfate; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 90.0% by weight of propylene glycol monomethyl ether was 2.2% by weight. Partly added and stirred well. Next, 1.6 parts by weight of ISFacure 127 manufactured by BASF was added as a photopolymerization initiator and stirred until completely dissolved to obtain a liquid composition (hereinafter referred to as “buffer layer forming composition B2”).

This buffer layer forming composition B2 corresponds to a composition containing inorganic particles modified with a functional group containing an acryloyl group as inorganic particles and an anionic surfactant as a surfactant. However, unlike the buffer layer forming composition B1, the buffer layer forming composition B2 further includes an anionic surfactant having a polyoxyethylene structure as a surfactant.

[Synthesis Example B3] <Preparation of buffer layer forming composition B3>
Disperse SPA-K in 47.4 parts by weight of organosilica sol PGM-AC-2140Y, 25.2 parts by weight of propylene glycol monomethyl ether, and 15.3 parts by weight of NK ester A-600. The amount of the liquid is 4.4 parts by weight, the amount of the Perex TR dispersion is 4.1 parts by weight, the amount of the Haitenol 08E dispersion is 1.9 parts by weight, and the amount of Irgacure 127 is 1.7 parts by weight. Except for each change, a liquid composition was prepared in the same manner as in Synthesis Example B2 to obtain a buffer layer forming composition B3.

[Synthesis Example B4] <Preparation of Buffer Layer Forming Composition B4>
The amount of organosilica sol PGM-AC-2140Y is 44.8 parts by weight, the amount of propylene glycol monomethyl ether is 24.2 parts by weight, and the amount of NK ester A-600 is 17.3 parts by weight. The amount of the liquid is 5.0 parts by weight, the amount of the Perex TR dispersion is 4.7 parts by weight, the amount of the Haitenol 08E dispersion is 2.1 parts by weight, and the amount of Irgacure 127 is 1.9 parts by weight. Except for each change, a liquid composition was prepared in the same manner as in Synthesis Example B2 to obtain a buffer layer forming composition B4.

[Synthesis Example B5] <Preparation of buffer layer forming composition B5>
Disperse SPA-K with 39.5 parts by weight of organosilica sol PGM-AC-2140Y, 27.2 parts by weight of propylene glycol monomethyl ether, 19.0 parts by weight of NK ester A-600 The amount of the liquid is 5.5 parts by weight, the amount of the Perex TR dispersion is 4.3 parts by weight, the amount of the Haitenol 08E dispersion is 2.4 parts by weight, and the amount of Irgacure 127 is 2.1 parts by weight. Except for each change, a liquid composition was prepared in the same manner as in Synthesis Example B2, and designated as buffer layer forming composition B5.

[Synthesis Example B6] <Preparation of buffer layer forming composition B6>
78.8 parts by weight of an organosilica sol PGM-ST (propylene glycol monomethyl ether-dispersed silica sol: 30% silica particle content; particle size 10 to 15 nm) manufactured by Nissan Chemical Industries in a glass screw tube bottle at room temperature and normal pressure Next, 10.9 parts by weight of NK ester A-600 of acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. was added and stirred well with a magnetic stirrer and a stir bar until they were compatible. Next, 3.1 parts by weight of SPA-K dispersion (SPA-K 30.0% by weight, water 9.0% by weight, propylene glycol monomethyl ether 61.0% by weight) dispersed in propylene glycol monomethyl ether was added, Stir well until completely compatible. Next, 3.6 parts by weight of Pelex TR dispersion (Pelex TR 10.0% by weight, propylene glycol monomethyl ether 90.0% by weight) was added and stirred well until completely compatible. Next, 2.1 parts by weight of Hightenol 08E dispersion (Hightenol 08E 10.0% by weight / propylene glycol monomethyl ether 90.0% by weight) was added and stirred well. Next, 1.5 parts by weight of ISFacure 127 manufactured by BASF was added as a photopolymerization initiator and stirred until it was completely dissolved to obtain a liquid composition (hereinafter referred to as “buffer layer forming composition B6”).

This buffer layer forming composition B6 corresponds to a composition containing inorganic particles not modified with a functional group containing a (meth) acryloyl group as inorganic particles and an anionic surfactant as a surfactant. This buffer layer forming composition B6 further contains an anionic surfactant containing a polyoxyethylene structure in addition to an anionic surfactant not containing a polyoxyethylene structure as a surfactant.

[Synthesis Example B7] <Preparation of buffer layer forming composition B7>
Under a normal temperature and normal pressure environment, 38.7 parts by weight of organosilica sol PGM-AC-2140Y (silica particle content 42%) manufactured by Nissan Chemical Industries was weighed into a glass screw tube, and further, organosilica sol PGM-ST (silica particles) Weighed 13.5 parts by weight, and then added 19.4 parts by weight of propylene glycol monomethyl ether as a solvent, and further added 15.6 parts by weight of NK ester A-600 made by Shin-Nakamura Chemical Co., Ltd. Stir well with a magnetic stirrer and stir bar until compatible. Next, 4.5 parts by weight of SPA-K dispersion (SPA-K 30.0% by weight, water 9.0% by weight, propylene glycol monomethyl ether 61.0% by weight) dispersed in propylene glycol monomethyl ether was added, Stir well until completely compatible. Next, 4.2 parts by weight of PELEX TR dispersion (PELEX TR 10.0% by weight / propylene glycol monomethyl ether 90.0% by weight) was added and stirred well until it was completely compatible. Next, 2.0 parts by weight of Hightenol 08E dispersion (Hightenol 08E 10.0% by weight / propylene glycol monomethyl ether 90.0% by weight) was added and stirred well. Next, 2.1 parts by weight of ISFacure 127 manufactured by BASF was added as a photopolymerization initiator and stirred until completely dissolved to obtain a liquid composition (hereinafter referred to as “buffer layer forming composition B7”).

This buffer layer-forming composition B7 uses an inorganic particle not modified with a functional group containing a (meth) acryloyl group as an inorganic particle and an inorganic particle modified with a functional group containing an acryloyl group as an anionic surfactant. This corresponds to a composition containing a surfactant. This buffer layer forming composition B7 further contains an anionic surfactant containing a polyoxyethylene structure in addition to an anionic surfactant not containing a polyoxyethylene structure as a surfactant.

[Synthesis Example B8] <Preparation of Composition B8 for Forming Buffer Layer>
Under a normal temperature and normal pressure environment, weigh 46.8 parts by weight of an organosilica sol PGM-AC-2140Y (silica particle content 42%) manufactured by Nissan Chemical Industries into a glass screw tube, and then use propylene glycol monomethyl ether 24 as a solvent. Further, 4 parts by weight were added, and 15.1 parts by weight of NK ester A-600 of acrylate made by Shin-Nakamura Chemical Co., Ltd. was further added and stirred well with a magnetic stirrer and a stir bar until they were compatible. Next, 4.4 parts by weight of SPA-K dispersion (SPA-K 30.0% by weight, water 9.0% by weight, propylene glycol monomethyl ether 61.0% by weight) dispersed in propylene glycol monomethyl ether was added, Stir well until completely compatible. Next, 4.1 parts by weight of PELEX TR dispersion (PELEX TR 10.0% by weight / propylene glycol monomethyl ether 90.0% by weight) was added, and the mixture was stirred well until it was completely compatible. Next, 2.0 parts by weight of Hightenol 08E dispersion (Hightenol 08E 10.0% by weight / propylene glycol monomethyl ether 90.0% by weight) was added and stirred well. Next, 1.6 parts by weight of Adeka Stab LA-72 manufactured by Adeka as a light stabilizer was added and stirred. Next, 1.6 parts by weight of ISFacure 127 manufactured by BASF was added as a photopolymerization initiator and stirred until completely dissolved to obtain a liquid composition (hereinafter, “buffer layer forming composition B8”).

This buffer layer forming composition B8 corresponds to a composition containing inorganic particles modified with a functional group containing an acryloyl group as inorganic particles and an anionic surfactant as a surfactant. This buffer layer forming composition B8 further contains an anionic surfactant containing a polyoxyethylene structure in addition to an anionic surfactant not containing a polyoxyethylene structure as a surfactant. Moreover, this buffer layer forming composition B8 contains a light stabilizer.

[Synthesis Example B9] <Preparation of buffer layer forming composition B9>
The amount of organosilica sol PGM-AC-2140Y was 46.9 parts by weight, the amount of propylene glycol monomethyl ether was 24.9 parts by weight, the amount of Haitenol 08E dispersion was 1.9 parts by weight, A liquid composition was prepared in the same manner as in Synthesis Example B8, except that the amount was changed to 1.2 parts by weight, and designated as buffer layer forming composition B9.

[Synthesis Example B10] <Preparation of buffer layer forming composition B10>
The amount of organosilica sol PGM-AC-2140Y was 47.1 parts by weight, the amount of propylene glycol monomethyl ether was 25.0 parts by weight, the amount of Haitenol 08E dispersion was 1.9 parts by weight, A liquid composition was prepared in the same manner as in Synthesis Example B8, except that the amount was changed to 0.8 parts by weight, and designated as buffer layer forming composition B10.

The compositions of the buffer layer forming compositions obtained in Synthesis Examples B1 to B10 are summarized in Tables 2-1 to 2-2 below.
Here, the “solid content” with respect to the amount of the inorganic particles (b2) means that when the inorganic particles (b2) are used in the form of the corresponding sol, components other than the contained solvent in the weight of the sol. Represents weight. Further, “effective component amount” per amount of the surfactant (b3) and the like represents the weight of components other than the contained solvent in the weight of each dispersion. The “total dry weight” is the sum of the total weight of the solvent specified in the “Solvent” section and the total weight of the solvent components that can be contained in components other than the “solvent” from the total weight of the composition. It represents the weight after subtraction.

[Example 1]
The storage layer forming composition A1 was applied to a polycarbonate plate (length 65 mm × width 65 mm × thickness 2 mm) by spin coating. The spin coating uses the storage layer forming composition A1 as a coating solution, and while the polycarbonate plate is rotated at 500 rpm for 10 seconds, the coating solution is allowed to flow over the polycarbonate plate and is gradually spread on the plate, and then at 10 The first coating film was obtained by rotating for a second.

Subsequently, the first coating film thus formed on the polycarbonate plate was cured with a UV irradiation apparatus. As the UV irradiation apparatus, a UV irradiation apparatus UB012-0BM manufactured by Eye Graphics Co., Ltd. is used, and the first coating film is cured by irradiating the coating film with UV light for 5 seconds with a 1 kw light source. The cured film (hereinafter referred to as “cured film A1”) was obtained. Integrated light quantity at that time was 1300 mJ / cm ² at 350mJ / cm ^2, UV-A with UV-C. The cured film A1 obtained by this UV irradiation constitutes a storage layer.

Next, the buffer layer forming composition B1 was applied onto the cured film A1 by spin coating. The application of the buffer layer forming composition B1 was performed under the same spin coat application conditions as when the coating film A1 was formed, thereby obtaining a second coating film. The second coating film was directly irradiated with UV for 30 seconds by the UV irradiation apparatus, and a second cured film (hereinafter referred to as “cured film B1”) was obtained. The cured film B1 obtained by this UV irradiation constitutes a buffer layer.

By the above operation, a transparent laminate (hereinafter referred to as “laminate 1”) having a polycarbonate plate, a cured film A1, and a cured film B1 in this order was obtained. In the obtained laminate 1, the thickness of the cured film A1 (storage layer) was 5.8 μm, and the thickness of the cured film B1 (buffer layer) was 2.6 μm.

[Example 2]
When the buffer layer was formed, each layer was formed in the same manner as in Example 1 except that the buffer layer forming composition B2 was used instead of the buffer layer forming composition B1, and a laminated body (hereinafter referred to as “laminated body”) was formed. 2 ").

[Example 3]
When the buffer layer is formed, the buffer layer forming composition B3 is used in place of the buffer layer forming composition B1, and after the second coating film is obtained, the second coating film is irradiated with UV. Each layer was formed in the same manner as in Example 1 except that the intermediate laminate having the second coating film was once dried in an electric furnace at 80 ° C. for 5 minutes. Body 3 ") was obtained.

[Example 4]
When the storage layer was formed, each layer was formed in the same manner as in Example 3 except that the storage layer forming composition A2 was used instead of the storage layer forming composition A1, and a laminate (hereinafter referred to as “laminated body”) was formed. 4 ").

[Example 5]
When forming the buffer layer, each layer was formed in the same manner as in Example 3 except that the buffer layer forming composition B4 was used instead of the buffer layer forming composition B3. 5 ").

[Example 6]
When forming the buffer layer, each layer was formed in the same manner as in Example 3 except that the buffer layer forming composition B5 was used in place of the buffer layer forming composition B3, and a laminate (hereinafter referred to as “laminate”) was formed. 6 ").

[Example 7]
When forming the storage layer, the storage layer forming composition A3 is used instead of the storage layer forming composition A1, and when forming the buffer layer, the buffer layer forming composition B3 is replaced with a buffer. Each layer was formed in the same manner as in Example 3 except that the layer forming composition B4 was used to obtain a laminate (hereinafter referred to as “laminate 7”).

[Example 8]
When forming the storage layer, each layer was formed in the same manner as in Example 3 except that the storage layer forming composition A4 was used instead of the storage layer forming composition A1, and a laminate (hereinafter referred to as “laminated body”) was formed. 8 ”).

[Example 9]
In this example, as inorganic particles constituting the first cured film (storage layer), inorganic particles modified with a functional group containing an acryloyl group are used as inorganic particles constituting the second cured film (buffer layer). Inorganic particles not modified with a functional group containing a (meth) acryloyl group were employed.
When the buffer layer was formed, each layer was formed in the same manner as in Example 1 except that the buffer layer forming composition B6 was used instead of the buffer layer forming composition B1, and a laminated body (hereinafter referred to as “laminated body”) was formed. 9 ").

[Example 10]
In this example, the inorganic particles constituting the first cured film (storage layer) and the inorganic particles constituting the second cured film (buffer layer) are both modified with a functional group containing a (meth) acryloyl group. Untreated inorganic particles were adopted.
When the storage layer is formed, the storage layer forming composition A5 is used instead of the storage layer forming composition A1, and when the buffer layer is formed, the buffer layer is replaced with the buffer layer forming composition B1. Each layer was formed in the same manner as in Example 1 except that the layer forming composition B6 was used to obtain a laminate (hereinafter referred to as “laminate 10”).

[Example 11]
In this example, as inorganic particles constituting the first cured film (storage layer), inorganic particles modified with a functional group containing an acryloyl group are used as inorganic particles constituting the second cured film (buffer layer). A mixture of inorganic particles not modified with a functional group containing a (meth) acryloyl group and inorganic particles modified with a functional group containing an acryloyl group was employed.
When the buffer layer was formed, each layer was formed in the same manner as in Example 3 except that the buffer layer forming composition B7 was used instead of the buffer layer forming composition B3, and a laminate (hereinafter referred to as “laminate”) was formed. 11 ").

[Comparative Example 1]
In this comparative example, unlike the above examples, only the first cured film (storage layer) was formed, and the second cured film (buffer layer) was not formed.
Here, the first cured film (storage layer) was formed in the same manner as in Example 10. The laminated body having the first cured film (storage layer) obtained in this way was used as it is as the laminated body C1 without performing the coating / film forming process for forming the buffer layer.

[Comparative Example 2]
In this comparative example, unlike the above examples, only the first cured film (storage layer) was formed, and the second cured film (buffer layer) was not formed.
Here, the first cured film (storage layer) was formed in the same manner as in Example 1. The laminated body having the first cured film (storage layer) obtained in this way was used as it is as the laminated body C2 without performing the coating / film forming process for forming the buffer layer.

[Comparative Example 3]
In this comparative example, unlike the above examples, the storage layer was formed using a composition containing no surfactant.
That is, when the storage layer is formed, the storage layer forming composition A6 is used instead of the storage layer forming composition A1, and when the buffer layer is formed, it is replaced with the buffer layer forming composition B1. Each layer was formed in the same manner as in Example 1 except that the buffer layer forming composition B2 was used to obtain a laminate (hereinafter referred to as “laminate C3”).

[Comparative Example 4]
In this comparative example, unlike the above examples, only the second cured film (buffer layer) was formed, and the first cured film (storage layer) was not formed.
That is, the second cured film (buffer layer) was formed in the same manner as in Example 9 except that the buffer layer forming composition B6 was directly applied to the polycarbonate plate. A laminate having no layer (hereinafter referred to as “laminate C4”) was obtained.

[Comparative Example 5]
In this comparative example, unlike the above examples, only the second cured film (buffer layer) was formed, and the first cured film (storage layer) was not formed.
That is, the second cured film (buffer layer) was formed in the same manner as in Example 2 except that the application of the buffer layer forming composition B2 was directly performed on the polycarbonate plate, and the buffer layer had a storage although it had a buffer layer. A laminate having no layers (hereinafter referred to as “laminate C5”) was obtained.

[Comparative Example 6]
In this comparative example, as the first cured film (storage layer), a laminate having a thickness thinner than that of each of the above examples was formed.
When the storage layer was formed, each layer was formed in the same manner as in Example 3 except that the storage layer forming composition A7 was used instead of the storage layer forming composition A1, and a laminate (hereinafter referred to as “laminated body”) was formed. C6 ").

[Comparative Example 7]
In this comparative example, as the inorganic particles constituting the first cured film (storage layer), inorganic particles not modified with a functional group containing a (meth) acryloyl group are used, and the second cured film (buffer layer) is constituted. As the inorganic particles, inorganic particles modified with a functional group containing an acryloyl group were employed.
When the storage layer is formed, the storage layer forming composition A5 is used instead of the storage layer forming composition A1, and when the buffer layer is formed, the buffer layer is replaced with the buffer layer forming composition B1. Each layer was formed in the same manner as in Example 1 except that the layer forming composition B2 was used to obtain a laminate (hereinafter referred to as “laminate C7”).

The evaluation results for each of Examples 1 to 11 and Comparative Examples 1 to 7 are shown in Tables 3-1 to 3-5 below. Here, the definitions of “solid content”, “active ingredient amount”, and “total dry weight” described in Tables 3-1 to 3-5 are as described in Tables 2-1 to 2-2 above. This is the same as “solid content”, “active ingredient amount”, and “total dry weight”.

The following Examples 12, 13, R1 and R2 were carried out in order to confirm the light resistance by adding the light stabilizer.

[Example 12]
When forming the buffer layer, each layer was formed in the same manner as in Example 3 except that the buffer layer forming composition B8 was used instead of the buffer layer forming composition B3. 12 ").

[Example 13]
When forming the buffer layer, each layer was formed in the same manner as in Example 3 except that the buffer layer forming composition B9 was used instead of the buffer layer forming composition B3. 13 ").

[Example R1]
When forming the buffer layer, each layer was formed in the same manner as in Example 3 except that the buffer layer forming composition B10 was used instead of the buffer layer forming composition B3. R1 ").

[Example R2]
As the laminate without the light stabilizer, the laminate obtained in the same manner as in Example 3 was used as “Laminate R2”.
The evaluation results are shown in Table 4 below for each of Examples 12, 13, R1, and R2. Here, the definitions of “solid content”, “active ingredient amount”, and “total dry weight” described in Table 4 are “solid content”, “effective content” described in Table 2-1 to Table 2-2 above. This is the same as “component amount” and “total dry weight”.

Claims

Including a substrate, a storage layer (A), and a buffer layer (B) in this order;
The storage layer (A) and the buffer layer (B) are in direct contact with each other;
The ratio of the thickness of the storage layer (A) to the thickness of the buffer layer (B) is in the range of 1.3-15,
The storage layer (A) is
A polyfunctional monomer (a1) having two or more (meth) acryloyl groups,
Inorganic particles (a2), and surfactant (a3)
A cured product of the composition (A-1) comprising:
The buffer layer (B)
A polyfunctional monomer (b1) having two or more (meth) acryloyl groups, and inorganic particles (b2)
A cured product of the composition (B-1) comprising:
The composition (B-1) further contains or does not contain a surfactant (b3);
When the composition (B-1) further contains the surfactant (b3), the content of the surfactant (b3) relative to the total dry weight of the composition (B-1) Less than the content of the surfactant (a3) relative to the total dry weight of A-1); and
The inorganic particles (a2) include inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group, or
The inorganic particles (a2) are inorganic particles (a2-0) not modified with a functional group containing a (meth) acryloyl group, and the inorganic particles (b2) are modified with a functional group containing a (meth) acryloyl group Inorganic particles (b2-0) that are not
Laminated body.
The inorganic particles (a2) include inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group;
The laminate according to claim 1, wherein the inorganic particles (b2) include inorganic particles (b2-1) modified with a functional group containing a (meth) acryloyl group.
The inorganic particles (a2-1) and the inorganic particles (b2-1) are independently modified with a silica particle modified with a functional group containing a (meth) acryloyl group and a functional group containing a (meth) acryloyl group. The laminate according to claim 2, which is at least one selected from the group consisting of zirconia particles formed.
The inorganic particles (b2) include inorganic particles (b2-0) not modified with a functional group containing a (meth) acryloyl group, and
The weight of the inorganic particles (b2-1) modified with the functional group containing the (meth) acryloyl group in the composition (B-1) is modified with the functional group containing the (meth) acryloyl group. The laminate according to claim 2 or 3, wherein the amount of the inorganic particles (b2-0) is larger than the content weight of the inorganic particles (b2-0).
The content of the polyfunctional monomer (b1) relative to the total dry weight of the composition (B-1) is greater than the content of the polyfunctional monomer (a1) relative to the total dry weight of the composition (A-1). The laminate according to any one of claims 1 to 4, wherein the laminate is small.
The laminate according to any one of claims 1 to 5, comprising a polyfunctional monomer represented by the following formula (1) as the polyfunctional monomer (a1) and the polyfunctional monomer (b1).

(In the above formula (1), n represents an integer of 1 to 30.)
The laminate according to any one of claims 1 to 6, wherein the surfactant (a3) and the surfactant (b3) have a polyoxyalkylene structure.
The surfactant (a3) and the surfactant (b3) are any one or more selected from the group consisting of polyoxyethylene lauryl ether sulfate, polyoxyethylene oleyl cetyl ether sulfate, and polyoxyalkylene lauryl ether The laminate according to any one of claims 1 to 7, comprising:
The laminate according to any one of claims 1 to 8, wherein the content of the inorganic particles (b2) is 40 to 70 wt% with respect to the total dry weight of the composition (B-1).
The laminate according to any one of claims 1 to 9, wherein the content of the surfactant (a3) with respect to the total dry weight of the composition (A-1) is 1.0 to 5.0 wt%. .
The laminate according to any one of claims 1 to 10, wherein the composition (B-1) further comprises a compound having a (meth) acryloyl group and an anionic hydrophilic group.
The laminate according to any one of claims 1 to 11, wherein the buffer layer (B) contains a light stabilizer in an amount of 3% by weight or more based on the total dry weight of the composition (B-1).
The laminate according to any one of claims 1 to 12, wherein the storage layer (A) has a thickness of 4.0 µm or more.
(S1): For at least one surface of the layer containing the substrate,
The polyfunctional monomer (a1),
The inorganic particles (a2),
The surfactant (a3) and the solvent (a4)
Providing a coated layer (A2) of the composition (A-1a) containing:
(S2): A step of removing the solvent (a4) from the coated layer (A2) obtained in the step (S1),
(S3): After the step (S2), the coating layer (A2) is cured, and the coating layer (A2) is converted into a cured layer (A2 ′).
(S4): After the step (S3), on the cured product layer (A2 ′),
The polyfunctional monomer (b1),
The inorganic particles (b2), and the solvent (b4)
Providing a coated layer (B2) of the composition (B-1a) containing:
(S5): a step of removing the solvent (b4) from the coating layer (B2) obtained in the step (S4), and (S6): after the step (S5), the coating layer (B2) Curing, converting the coated layer (B2) into a cured layer (B2 ′),
Including:
The total dry weight of the composition (A-1a) per 100 parts by weight of the composition (A-1a) is 46 parts by weight or more and less than 100 parts by weight;
The composition (B-1a) further contains or does not contain the surfactant (b3);
When the composition (B-1) further contains the surfactant (b3), the content of the surfactant (b3) relative to the total dry weight of the composition (B-1) Less than the content of the surfactant (a3) relative to the total dry weight of A-1); and
The inorganic particles (a2) include inorganic particles (a2-1) modified with a functional group containing a (meth) acryloyl group, or
The inorganic particles (a2) are inorganic particles (a2-0) not modified with a functional group containing a (meth) acryloyl group, and the inorganic particles (b2) are modified with a functional group containing a (meth) acryloyl group Inorganic particles (b2-0) that are not
The manufacturing method of the laminated body of Claim 1.
The manufacturing method according to claim 14, wherein the step (S5) is performed under heating at 50 to 90 ° C.