WO2019150780A1

WO2019150780A1 - Coating agent, laminate and method for producing laminate

Info

Publication number: WO2019150780A1
Application number: PCT/JP2018/045881
Authority: WO
Inventors: 明希中道; 北村　拓也
Original assignee: 富士フイルム株式会社
Priority date: 2018-01-31
Filing date: 2018-12-13
Publication date: 2019-08-08

Abstract

The present invention provides: a coating agent which contains (A) a siloxane compound that contains at least one of a compound represented by formula (1) and a hydrolysis-condensation product of a compound represented by formula (1), (B) inorganic oxide particles that include inorganic oxide particles having a refractive index of 1.60 or more, (C) a polymer dispersant that has an acid group, and (D) a dispersion medium; and applications of this coating agent. In formula (1), each of R¹, R², R³ and R⁴ independently represents a monovalent organic group having 1-6 carbon atoms; and n represents an integer of 1-20. AA Formula (1)

Description

COATING AGENT, LAMINATE, AND METHOD FOR PRODUCING LAMINATE

The present disclosure relates to a coating agent, a laminate, and a method for manufacturing the laminate.

Conventionally, a technique for forming a coating on a base material has been studied for the purpose of anti-fogging (that is, suppression of fogging) of the base material.

For example, Patent Document 1 does not require a baking process, and is a laminate that can maintain antifouling properties, antifogging properties, and adhesion to a resin base material for a long period of time even in an environment where the temperature difference is severe. An antifouling layer made of a coating composition is formed on the outermost surface of the composite containing at least a resin substrate, and the coating composition comprises (A) a metal oxide, (B) polymer emulsion particles, and (C) A laminate containing a hydrolyzable silicon compound and having a surface tension of 15 to 40 mN / m is disclosed.

Patent Document 2 discloses a hydrophilic member that is formed on the substrate and has hydrophilicity as a hydrophilic member that is not easily clouded and that is resistant to water droplets and dirt while maintaining sufficient film hardness and durability. A hydrophilic film comprising at least an inorganic amorphous substance, the hydrophilic film in a state in which excess water is removed by attaching water to the hydrophilic film and maintaining the film vertically. A hydrophilic member is disclosed in which the weight of the water film attached to the conductive coating is 0.25 to 0.50 g per 10 cm ² .

Patent Document 1: Japanese Patent Application Laid-Open No. 2014-205736 Patent Document 2: Japanese Patent Application Laid-Open No. 2000-318084

In the above-described technique for forming a coating on a substrate (ie, a technique for producing a laminate including a substrate and a coating), the coating is formed from the viewpoint of improving the antifogging property and the like of the laminate. The coating liquid (hereinafter referred to as “coating agent”) may contain a siloxane compound and silica particles (see, for example, Example 1 of Patent Document 1 above).
However, when a coating agent containing a siloxane compound and silica particles is used, particularly when the film to be formed is thin (for example, when the film is 2 μm or less), In some cases, rainbow-like unevenness (hereinafter referred to as “rainbow unevenness”) due to interference occurs. As a cause of rainbow unevenness, it can be considered that the refractive index of silica particles is low. Here, the refractive index of the silica particles is about 1.43. The refractive index of the coating tends to be lower than 1.43 due to voids present in the coating.

As a method for suppressing rainbow unevenness, it is conceivable to include inorganic oxide particles having a refractive index of 1.60 or more in the coating agent.
However, as a result of studies by the present inventors, it has been found that when the coating agent contains inorganic oxide particles having a refractive index of 1.60 or more, the haze of the resulting laminate may increase. .

The subject of 1 aspect of this indication is providing the coating agent which is excellent in anti-fogging property, the rainbow nonuniformity is suppressed, and the laminated body with which haze was reduced can be manufactured.
The subject of the other aspect of this indication is providing the laminated body which was excellent in anti-fogging property, the rainbow nonuniformity was suppressed, and the haze was reduced, and its manufacturing method.

Specific means for solving the problems include the following aspects.
<1> A siloxane compound (A) containing at least one of a compound represented by the following formula (1) and a hydrolysis condensate of a compound represented by the following formula (1);
Inorganic oxide particles (B) containing inorganic oxide particles having a refractive index of 1.60 or more;
A polymer dispersant (C) having an acid group;
A dispersion medium (D);
Containing a coating agent.

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

<2> The coating agent according to <1>, wherein the inorganic oxide particles (B) include silica particles.
<3> The coating agent according to <1> or <2>, wherein the dispersion medium (D) contains a solvent having a boiling point of 120 ° C. or higher.
<4> The coating agent according to any one of <1> to <3>, wherein the dispersion medium (D) contains water.
<5> The coating agent according to any one of <1> to <4>, further comprising a condensation catalyst (E) containing a metal chelate compound.
<6> The coating agent according to any one of <1> to <5>, wherein the content of the inorganic oxide particles (B) is 50% by mass or more based on the total solid content of the coating agent.
<7> The coating agent according to any one of <1> to <6>, wherein the inorganic oxide particles (B) include inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm.
<8> The coating agent according to any one of <1> to <7>, wherein the inorganic oxide particles (B) include inorganic oxide particles having a refractive index of 2.00 or more.
<9> The coating agent according to <8>, wherein the inorganic oxide particles having a refractive index of 2.00 or more are at least one selected from the group consisting of titanium oxide particles, cerium oxide particles, and zirconium oxide particles.
<10> A method for producing a laminate including a step of applying a coating agent according to any one of <1> to <9> on a substrate and drying to form a film.
The manufacturing method of the laminated body as described in <10> whose <11> base material is a glass base material, a polycarbonate base material, or a (meth) acrylic resin base material.
<12> including a base material and a film disposed on the base material,
The film is
A siloxane condensate (A1) containing a hydrolysis condensate of the compound represented by the following formula (1);
Inorganic oxide particles (B1) containing inorganic oxide particles having a refractive index of 1.60 or more;
A polymer dispersant (C1) having an acid group;
A laminate containing

<13> The laminate according to <12>, wherein the inorganic oxide particles (B1) include silica particles.
The laminated body as described in <12> or <13> whose content of <14> inorganic oxide particle (B1) is 50 mass% or more with respect to the total solid of a film.
<15> The laminate according to any one of <12> to <14>, wherein the inorganic oxide particles (B1) include inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm.
<16> The laminate according to any one of <12> to <15>, wherein the inorganic oxide particles (B1) include inorganic oxide particles having a refractive index of 2.00 or more.
<17> The laminate according to <16>, wherein the inorganic oxide particles having a refractive index of 2.00 or more are at least one selected from the group consisting of titanium oxide particles, cerium oxide particles, and zirconium oxide particles.
<18> The laminate according to any one of <12> to <17>, wherein the substrate is a glass substrate, a polycarbonate substrate, or a (meth) acrylic resin substrate.

According to one embodiment of the present disclosure, there is provided a coating agent that is excellent in antifogging property, suppresses rainbow unevenness, and can produce a laminate with reduced haze.
According to another aspect of the present disclosure, a laminated body that is excellent in anti-fogging property, that suppresses rainbow unevenness and has reduced haze, and a method for manufacturing the same are provided.

In the present disclosure, a numerical range indicated by using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the present disclosure, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, the plurality of components present in the composition unless otherwise specified. It means the total amount.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical description. . Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, the refractive index means a refractive index at a wavelength of 550 nm. The refractive index can be measured using, for example, an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.).
In the present disclosure, (meth) acrylic resin is a concept including both acrylic resin and methacrylic resin, and (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid. ) Acrylic acid ester is a concept including both acrylic acid ester and methacrylic acid ester.

[Coating agent]
The coating agent according to the present disclosure includes at least one of a compound represented by the following formula (1) and a hydrolysis condensate of a compound represented by the following formula (1) (hereinafter referred to as “compound represented by formula (1)”). And at least one of the hydrolysis condensates thereof), inorganic oxide particles (B) containing inorganic oxide particles having a refractive index of 1.60 or more, and polymer dispersion having an acid group An agent (C) and a dispersion medium (D) are contained.

According to the coating agent according to the present disclosure, it is possible to produce a laminate having excellent antifogging properties, suppressing rainbow unevenness, and reducing haze.
The reason why this effect is achieved is assumed as follows. However, the coating agent according to the present disclosure is not limited for the following reasons.

The coating agent which concerns on this indication is used for formation of the film in the laminated body containing a base material and a film.
When the coating agent contains the siloxane compound (A) containing at least one of the compound represented by the formula (1) and its hydrolysis condensate and the inorganic oxide particles (B), the hydrophilicity of the coating film And voids are formed between the inorganic oxide particles. As a result, the antifogging property of the laminate is improved.
Further, the coating agent contains inorganic oxide particles (hereinafter also referred to as “high refractive index particles”) having a refractive index higher than that of silica particles (refractive index 1.43) and having a refractive index of 1.60 or more. Thereby, the rainbow nonuniformity of a laminated body is suppressed.
However, when the coating agent containing the siloxane compound (A) contains high refractive index particles, the haze of the resulting laminate may increase. Possible reasons for this increase in haze include aggregation of high refractive index particles and gelation of the siloxane compound (A). The reason for the gelation of the siloxane compound (A) is that since the high refractive index particles have basicity, the pH of the mixture of the high refractive index particles and the siloxane compound (A) is changed to the siloxane compound (A). ) In the basic region which is the gelation region.
In the coating agent which concerns on this indication, the haze of the laminated body mentioned above is reduced by containing the polymer dispersing agent (C) which has an acid group. The reason why the haze is reduced is that at least a part of the surface of the high refractive index particles is covered with the polymer dispersant (C) having an acid group, thereby suppressing aggregation of the high refractive index particles ( That is, the dispersion stability of the high refractive index particles is improved) and the gelation of the siloxane compound (A) is suppressed. The reason why the gelation of the siloxane compound (A) is suppressed is that at least a part of the surface of the basic high-refractive-index particles is coated with the polymer dispersant (C) having an acid group. It is considered that the basicity of the refractive index particles is weakened, and as a result, the pH of the mixture of the high refractive index particles and the siloxane compound (A) deviates from the gelation region (basic region) of the siloxane compound (A). .

As described above, according to the coating agent according to the present disclosure, the siloxane compound (A), the inorganic oxide particles (B) including the inorganic oxide particles having a refractive index of 1.60 or more, and the polymer dispersion having an acid group The combination with the agent (C) produces an effect of producing a laminate having excellent antifogging property, suppressing rainbow unevenness and reducing haze.
It goes without saying that the function of the dispersion medium (D) in the coating agent according to the present disclosure is a function as a dispersion medium for the inorganic oxide particles (B) and the like and a function of maintaining the liquid state of the coating agent.

The effect of suppressing rainbow unevenness by the coating agent according to the present disclosure is particularly effective when a glass substrate, a polycarbonate substrate, or a (meth) acrylic resin substrate is used as a substrate for forming a film. Played.
This is because the refractive indexes of the glass substrate, the polycarbonate substrate, and the (meth) acrylic resin substrate are about 1.55, about 1.59, and about 1.49, respectively, and are contained in the film. This is probably because the refractive index of the high refractive index particles is the same as or lower than the refractive index (refractive index of 1.60 or more).

The coating agent according to the present disclosure can be applied to any application that requires anti-fogging properties, rainbow unevenness suppression, and haze reduction.
Applications of the coating agent according to the present disclosure include formation of a coating on an automobile lamp (eg, head lamp, tail lamp, turn signal lamp, etc.); formation of a coating on an automobile glass (eg, windshield); surveillance camera, lighting, and building material , Formation of a coating on a sign, glasses, goggles and the like;

Hereinafter, each component that the coating agent according to the present disclosure may contain will be described.

<Siloxane compound (A)>
The coating agent which concerns on this indication contains the siloxane compound (A) containing at least one of the compound represented by Formula (1), and its hydrolysis-condensation product.
Here, the “siloxane compound (A)” means the entire siloxane compound contained in the coating agent according to the present disclosure.
The siloxane compound (A) exhibits a function of binding other components such as the inorganic oxide particles (B) in the resulting film (that is, a function as a binder). By exhibiting the function as the binder, the hydrophilicity of the resulting coating is improved, and voids are formed between the inorganic oxide particles (B) in the coating. By improving the hydrophilicity of the film and forming voids in the film, the antifogging property of the film is improved, and as a result, the antifogging property of the laminate is improved.
Further, the function of the siloxane compound (A) as the binder is exhibited, and the above-described function of the polymer dispersant (C) having an acid group is exhibited, thereby suppressing the haze of the coating. As a result, haze of the laminate is suppressed.

The compound represented by Formula (1) has a structure in which at least a part is hydrolyzed by coexisting with water. Specifically, by the reaction of the compound represented by the formula (1) with water, OR ¹ , OR ² , OR ³ , and OR ⁴ bonded to the silicon atom in the formula (1). A hydrolyzate having a structure in which at least one is substituted with a hydroxy group is produced.
The hydrolysis-condensation product of the compound represented by Formula (1) is a compound produced by condensing a plurality of molecules of hydrolysis product.

In the present disclosure, the concept of “hydrolysis condensate of compound represented by formula (1)” includes hydrolysis and condensation of the compound represented by formula (1) (hereinafter also referred to as “hydrolysis condensation”). As well as the product obtained by performing hydrolysis condensation several times on the compound represented by the formula (1) (for example, the compound represented by the formula (1)). Also included are products 2 obtained by further hydrolytic condensation of product 1 obtained by one hydrolytic condensation, products 3 obtained by further hydrolytic condensation of product 2, and the like. The

The siloxane compound (A) may contain at least one of the compound represented by the formula (1) and at least one of the hydrolysis condensates, or may contain both. .

In the formula (1), the monovalent organic group having 1 to 6 carbon atoms in R ¹ , R ² , R ³ , and R ⁴ may be linear or branched. It may be annular. Examples of the monovalent organic group include an alkyl group and an alkenyl group, and an alkyl group is preferable.
Examples of the alkyl group when R ¹ , R ² , R ³ , or R ⁴ represents an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n- A pentyl group, an n-hexyl group, a cyclohexyl group and the like can be mentioned.
In the compound represented by the formula (1), the compound represented by the formula (1) is hydrolyzed by setting the monovalent organic group in R ¹ to R ⁴ , preferably the alkyl group having 1 to 6 carbon atoms. Property is improved. From the viewpoint of better hydrolyzability, R ¹ to R ⁴ are more preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms. More preferably.

N in the general formula (1) represents an integer of 1 to 20. When n is 1 or more, the reactivity of the compound represented by the formula (1) can be easily controlled, and, for example, a film having excellent surface hydrophilicity can be formed. When n is 20 or less, the viscosity of the coating agent does not become too high, and handling properties and uniform coating properties are improved. n is preferably from 3 to 12, more preferably from 5 to 10, from the viewpoint of easy control of the hydrolysis reaction.

In Table 1 below, specific examples of the compound represented by the formula (1) are described by R ¹ , R ² , R ³ , R ⁴ and n in the formula (1). However, the compound represented by Formula (1) is not limited to the specific examples described in Table 1.

A commercial item can be used as a compound represented by Formula (1).
As an example of a commercial item of the compound represented by the formula (1), MKC (registered trademark) silicate MS51 [R ¹ , R ² , R ³ , and R ^{4 of} Mitsubishi Chemical Corporation]: methyl group, average of n 5], MKC® silicate MS56 [R ¹ , R ² , R ³ , and R ⁴ : methyl group, average of n: 11], MKC® silicate MS57 [R ¹ , R ² , R ³ and R ⁴ : methyl group, average of n: 13], MKC® silicate MS56S [R ¹ , R ² , R ³ , and R ⁴ : methyl group, average of n: 16], MKC (registered) Trademark) Methyl silicate 53A [R ¹ , R ² , R ³ , and R ⁴ : Methyl group, average of n: 7], MKC® ethyl silicate 40 [R ¹ , R ² , R ³ , and R ⁴ : Ethyl group, average of n: 5], M C (R) Ethyl silicate 48 ^[R ^1, R 2, ^{R 3,} and ^{R 4:} an ethyl group, the average of n: 10], MKC (R) EMS485 ^[R ^1, R 2, ^{R 3,} and R ⁴ : 50% each of methyl group and ethyl group, average n: 10], tetraethoxysilane of Tokyo Chemical Industry Co., Ltd. and the like.

In addition, in the hydrolysis condensate of the compound represented by the formula (1), the terminal group of the compound represented by the formula (1) (that is, —OR ¹ , —OR ² , —OR ³ , or —OR ⁴ ) is not necessarily used. However, from the viewpoint of increasing the hydrophilicity of the film formed by the coating agent, it is preferable that more terminal groups are reacted.

The weight average molecular weight of the compound represented by the formula (1) is preferably in the range of 300 to 1500, more preferably in the range of 500 to 1200.

In the present disclosure, the weight average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, HLC-8120GPC, SC-8020 (Tosoh Corporation) is used, TSKgel and SuperHM-H (Tosoh Corporation, 6.0 mm ID × 15 cm) are used as columns, and tetrahydrofuran (THF) is used as an eluent. ). Further, the conditions are as follows: sample concentration is 0.5 mass%, flow rate is 0.6 ml / min, sample injection amount is 10 μl (microliter), measurement temperature is 40 ° C., and a differential refractometer (RI) detector is used. Can be done. The calibration curves are Tosoh's “polystyrene standard sample TSK standard”: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500” Those prepared from 10 samples of “F-4”, “F-40”, “F-128”, and “F-700” can be used.

The siloxane compound (A) may contain at least one of a siloxane compound other than the compound represented by the formula (1) (hereinafter referred to as “siloxane compound X”) and a hydrolysis condensate of the siloxane compound X.
Examples of the siloxane compound X include quaternary alkoxysilane compounds (excluding compounds corresponding to the compound represented by the formula (1)), tertiary alkoxysilane compounds, and the like.

The total content of the compound represented by formula (1) and the hydrolysis condensate thereof in the coating agent is preferably 5% by mass to 50% by mass with respect to the total solid content of the coating agent, and 10% by mass to 40% by mass. % Is more preferable, and 15% by mass to 35% by mass is even more preferable.

Here, the total solid content of the coating agent means all components obtained by removing the dispersion medium (D) from the coating agent (hereinafter the same).

The proportion of the compound represented by the formula (1) and the hydrolysis condensate thereof in the siloxane compound (A) (that is, the entire siloxane compound contained in the coating agent) is preferably 60% by mass or more, More preferably, it is 80 mass% or more, and it is still more preferable that it is 90 mass% or more.

The content of the siloxane compound (A) in the coating agent (that is, the entire siloxane compound contained in the coating agent) is preferably 5% by mass to 50% by mass, preferably 10% by mass to the total solid content of the coating agent. 40% by mass is more preferable, and 15% by mass to 35% by mass is even more preferable.

<Inorganic oxide particles (B)>
The coating agent according to the present disclosure contains inorganic oxide particles (B).
Here, the “inorganic oxide particles (B)” means the entire inorganic oxide particles contained in the coating agent according to the present disclosure.
The coating agent according to the present disclosure may contain only one kind of inorganic oxide particles, or may contain two or more kinds.
The inorganic oxide particles (B) contribute to improving the antifogging property of the coating film and the laminate, improving the strength (for example, scratch resistance) of the coating film, and improving the transparency of the coating film and the laminate.

As the inorganic oxide particles (B), metal oxide particles are preferable.
Here, the metal in the metal oxide particles includes semimetals such as B, Si, Ge, As, Sb, and Te.
As the metal oxide particles, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B Oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferred.
Moreover, a metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.

The surface of the inorganic oxide particles (B) may be treated with an organic material from the viewpoint of imparting dispersion stability.

From the viewpoint of the transparency of the coating agent and the coating, the average primary particle diameter of the inorganic oxide particles (B) is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, still more preferably 5 nm to 50 nm, and further preferably 5 nm to 20 nm. preferable.

In the present specification, the average primary particle diameter of particles refers to the arithmetic average of 200 particles measured by an electron microscope. When the particle shape is not spherical, the equivalent circle diameter calculated from the projected area is taken as the diameter.

The inorganic oxide particles (B) particularly preferably include inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm. Thereby, the anti-fogging property of a laminated body improves more. The reason for this is considered to be that the size of the voids in the coating is made more appropriate.
In this case, the proportion of the inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm in the inorganic oxide particles (B) (that is, the entire inorganic oxide particles contained in the coating agent) is preferably 60. It is at least mass%, more preferably at least 80 mass%.

The content of the inorganic oxide particles (B) in the coating agent according to the present disclosure is 30% by mass or more based on the total solid content of the coating agent from the viewpoint of further improving the antifogging property of the laminate. Preferably, it is more preferably 40% by mass or more, and further preferably 50% by mass or more.
Further, the content of the inorganic oxide particles (B) in the coating agent according to the present disclosure is preferably 80% by mass or less based on the total solid content of the coating agent from the viewpoint of storage stability of the coating agent. 70% by mass or less, more preferably 60% by mass or less.

When preparing the coating agent according to the present disclosure, a dispersion of inorganic oxide particles (B) may be used. The dispersion can be prepared by mixing and / or dispersing the inorganic oxide particles (B) in a suitable dispersant and solvent using a mixing device such as a ball mill or a rod mill.
Alternatively, the inorganic oxide particles (B) may be synthesized in a liquid phase using a precursor of inorganic oxide particles in an appropriate solvent, and the resulting sol may be used as a dispersion of the inorganic oxide particles (B). Good.
Examples of the solvent used for the preparation of the dispersion liquid include a dispersion medium (D) described below (preferably water or an alcohol solvent). A solvent can be used individually by 1 type or in mixture of 2 or more types.

(High refractive index particles)
The inorganic oxide particles (B) include high refractive index particles (that is, inorganic oxide particles having a refractive index of 1.60 or more).
As described above, the high refractive index particles contribute to the suppression of rainbow unevenness of the laminate. The high refractive index particles also contribute to improving the antifogging property of the laminate.
The inorganic oxide particles (B) may contain only one kind of high refractive index particles, or may contain two or more kinds.

The refractive index of the high refractive index particles is preferably 1.70 or more, more preferably 1.80 or more, further preferably 1.90 or more, and further preferably 2.00 or more.
The upper limit of the refractive index of the high refractive index particles is not particularly limited, but examples of the upper limit include 2.80.

As the high refractive index particles, aluminum oxide particles (refractive index 1.77), niobium oxide particles (refractive index 2.30), titanium oxide particles (refractive index 2.50-2.70), titanium composite oxide particles ( Refractive index 2.30-2.70), zinc oxide particles (refractive index 2.10), cerium oxide particles (refractive index 2.10), zirconium oxide particles (refractive index 2.10), indium / tin oxide particles (Refractive index of about 2.0) or antimony / tin oxide particles (refractive index of about 2.0) are preferable.
Yes.

The average primary particle diameter of the high refractive index particles is preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, still more preferably 5 nm to 50 nm, still more preferably 5 nm to 20 nm.

The content of the high refractive index particles in the coating agent according to the present disclosure is preferably 3% by mass or more based on the total solid content of the coating agent from the viewpoint of further suppressing rainbow unevenness of the laminate. % Or more is more preferable, and 5 mass% or more is still more preferable.
In addition, the content of the high refractive index particles in the coating agent according to the present disclosure is preferably 60% by mass or less, and more preferably 50% by mass or less, based on the total solid content of the coating agent.

When the inorganic oxide particles (B) include only high refractive index particles, the content of the high refractive index particles in the coating agent according to the present disclosure is 30% by mass or more with respect to the total solid content of the coating agent. Is preferable, and it is more preferable that it is 40 mass% or more.
When the inorganic oxide particles (B) include only high refractive index particles, the content of the high refractive index particles in the coating agent according to the present disclosure is 60% by mass or less with respect to the total solid content of the coating agent. Is preferable, and it is more preferable that it is 50 mass% or less.
When the inorganic oxide particles (B) include high refractive index particles and inorganic oxide particles other than the high refractive index particles, the content of the high refractive index particles in the coating agent according to the present disclosure is the total solid content of the coating agent. On the other hand, it is preferably 3% by mass or more, more preferably 4% by mass or more, and further preferably 5% by mass or more.
When the inorganic oxide particles (B) include high refractive index particles and inorganic oxide particles other than the high refractive index particles, the content of the high refractive index particles in the coating agent according to the present disclosure is the total solid content of the coating agent. On the other hand, it is preferable that it is 50 mass% or less, and it is more preferable that it is 45 mass% or less.

The inorganic oxide particles (B) preferably contain at least one kind of inorganic oxide particles having a refractive index of 2.00 or more as high refractive index particles. Thereby, the rainbow nonuniformity of a laminated body is suppressed more.
In this case, the proportion of the inorganic oxide particles having a refractive index of 2.00 or more in the high refractive index particles is preferably 50% by mass or more, more preferably 60% by mass or more, and 80% by mass or more. More preferably it is.

The inorganic oxide particles having a refractive index of 2.00 or more are preferably at least one selected from the group consisting of niobium oxide particles, titanium oxide particles, cerium oxide particles, and zirconium oxide particles.

The inorganic oxide particles having a refractive index of 2.00 or more are more preferably at least one selected from the group consisting of titanium oxide particles, cerium oxide particles, and zirconium oxide particles. Thereby, the haze of a laminated body is reduced more.

The inorganic oxide particles (B) may contain not only high refractive index particles but also inorganic oxide particles having a refractive index of less than 1.60 (for example, the following silica particles (refractive index 1.43)).

(Silica particles)
The inorganic oxide particles (B) preferably contain at least one silica particle.
Thereby, the anti-fogging property of a laminated body improves more. This reason is considered to be because the hydrophilicity of the coating is further improved.

Examples of the silica particles include fumed silica and colloidal silica.
Fumed silica can be obtained by reacting a compound containing a silicon atom (hereinafter also referred to as “silicon compound”) with oxygen and hydrogen in a gas phase. Examples of the silicon compound used as a raw material include silicon halide (for example, silicon chloride).
Colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed. Examples of the raw material compound for colloidal silica include alkoxy silicon (for example, tetraethoxysilane), halogenated silane compound (for example, diphenyldichlorosilane) and the like.

The shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a plate shape, a needle shape, a bead shape, or a shape in which two or more of these are combined. The term “spherical” as used herein includes not only true spherical shapes but also spheroids, oval shapes, and the like.

Silica particles are also available as commercial products.
Commercially available silica particles include AEROSIL (registered trademark) series from Evonik, Snowtex (registered trademark) series (for example, Snowtex O) from Nissan Chemical Industries, Ltd., and Nalco (registered from Nalco Chemical). (Trademark) series (for example, Nalco 8699), Quartron PL series (for example, PL-1) of Fuso Chemistry, and the like.

The average primary particle diameter of the silica particles is preferably 100 nm or less, more preferably 50 nm or less, and more preferably 30 nm or less from the viewpoint of good film properties of the formed film and low haze. More preferably, it is particularly preferably 20 nm or less. The lower limit of the average primary particle diameter of the silica particles is not particularly limited, but is preferably 2 nm or more from the viewpoint of handleability, and is 5 nm or more from the viewpoint of easy formation of voids for developing antifogging properties. More preferably, 10 nm or more is more preferable.
In particular, the average primary particle diameter of the silica particles is preferably 10 nm to 20 nm from the viewpoint of improving antifogging properties and stain resistance.

When inorganic oxide particle (B) contains a silica particle, inorganic oxide particle (B) may contain only 1 type of silica particles, and may contain 2 or more types.
When two or more types of silica particles are included, particles having at least one of size and shape different from each other may be included.

When the inorganic oxide particles (B) include silica particles, the content of the silica particles in the coating agent is 10% by mass with respect to the total solid content of the coating agent from the viewpoint of further improving the antifogging property of the laminate. The above is preferable, 30 mass% or more is more preferable, and 40 mass% or more is still more preferable.
Further, the upper limit of the content of the silica particles is preferably 70% by mass and more preferably 60% by mass with respect to the total solid content of the coating layer from the viewpoint of storage stability of the coating agent.

<Polymer dispersant having acid group (C)>
The coating agent according to the present disclosure contains a polymer dispersant (C) having an acid group.
The polymer dispersant (C) having an acid group contributes to a reduction in haze of the laminate.
Here, the “polymer dispersant having an acid group (C)” means the entire polymer dispersant having an acid group contained in the coating agent according to the present disclosure.
The coating agent which concerns on this indication may contain only 1 type of polymer dispersing agents which have an acid group, and may contain 2 or more types.

The acid group in the polymer dispersant (C) having an acid group is not limited as long as it is an acid group having a dispersion performance (that is, adsorption performance) with respect to the inorganic oxide particles (B) (for example, high refractive index particles). For example, a carboxy group, a sulfonic acid group, and a phosphoric acid group are mentioned.

The acid value of the polymer dispersant (C) having an acid group is such that the adsorption performance for the inorganic oxide particles (B) (for example, high refractive index particles) and the inorganic oxide particles (B) (for example, high refractive index particles) From the viewpoint of improving dispersibility, it is preferably 180 mgKOH / g or less, and more preferably 100 mgKOH / g or less.
The lower limit of the acid value is not particularly limited, but is preferably 3 mgKOH / g or more.

The acid value of the polymer dispersant (C) having an acid group can be measured by titration of an indicator. Specifically, according to the method described in JIS K K0070, the solid content of the polymer dispersant having an acid group is 1 g. It can be calculated by measuring the number of mg of potassium hydroxide that neutralizes the acid component therein.

In addition, the weight average molecular weight (Mw) of the polymer dispersant (C) having an acid group is preferably 1000 to 200000, more preferably 1000 to 50000, and further preferably 5000 to 30000.

A commercially available product may be used as the polymer dispersant (C) having an acid group.
Commercially available polymer dispersants having acid groups include, for example, DISPERBYK (registered trademark) -2015 (acid group: carboxy group, acid value: 10 mgKOH / g), DISPERBYK (registered trademark) -2010 (acid group) manufactured by BYK Chemie. : Carboxy group, acid value: 20 mg KOH / g), DISPERBYK (registered trademark) -194 (acid group: carboxy group, acid value: 70 mg KOH / g), Aron (registered trademark) A-6012 (acid) of Toagosei Co., Ltd. Group: sulfonic acid group, weight average molecular weight: 10,000), Aron (registered trademark) A-6001 (acid group: carboxy group, pH: 7 to 9 (aqueous solution concentration), weight average molecular weight: 8000), Aron (registered trademark) SD-10 (acid group: carboxy group, pH: 2 to 5 (concentration in aqueous solution), weight average molecular weight: 10,000), T of Evonik GO (TM) Dispers651 (acid group: phosphoric acid group, acid value: 30 mgKOH / g), and the like.

The content of the polymer dispersant (C) in the coating agent is preferably in the range of 10% by mass to 60% by mass, and in the range of 20% by mass to 50% by mass with respect to the inorganic oxide particles (B). The range of 20% by mass to 40% by mass is more preferable.

<Dispersion medium (D)>
The coating agent according to the present disclosure contains a dispersion medium (D).
Here, the “dispersion medium (D)” means the entire dispersion medium contained in the coating agent according to the present disclosure.
The coating agent according to the present disclosure may contain only one type of dispersion medium, or may contain two or more types.

The content of the dispersion medium (D) in the coating agent according to the present disclosure is preferably 80% by mass to 99% by mass, more preferably 85% by mass to 99% by mass, and more preferably 90% by mass to 98% by mass with respect to the total amount of the coating agent. More preferred is mass%.

(water)
The dispersion medium (D) preferably contains water.
As water, ion-exchanged water, pure water, distilled water, and the like are preferable from the viewpoint of fewer impurities.

The content of water in the dispersion medium (D) is preferably 10% by mass to 60% by mass, more preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 45% by mass with respect to the total amount of the dispersion medium (D). % Is more preferable.

(Organic solvent with boiling point less than 120 ° C)
The dispersion medium (D) may contain at least one organic solvent having a boiling point of less than 120 ° C.
Examples of organic solvents having a boiling point of less than 120 ° C. include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3- Alcohol solvents such as pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol;
Glycol ether solvents such as dipropylene glycol methyl ether;
Ether solvents such as isopropyl ether, 1,4-dioxane, tert-butyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, diethyl ether;
Ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone;
Etc.
As the organic solvent having a boiling point of less than 120 ° C., an alcohol solvent is preferable from the viewpoint of low surface energy and enhancing spreadability of the coating agent.
Here, the alcohol solvent refers to a solvent having a structure in which one hydroxy group is substituted for one carbon atom of a hydrocarbon.

When the dispersion medium (D) contains an organic solvent having a boiling point of less than 120 ° C., the content of the organic solvent having a boiling point of less than 120 ° C. in the dispersion medium (D) is 10% by mass to 60% with respect to the total amount of the dispersion medium (D). % By mass is preferable, 20% by mass to 50% by mass is more preferable, and 25% by mass to 45% by mass is still more preferable.

(Solvent with boiling point of 120 ° C or higher)
The dispersion medium (D) preferably contains a solvent having a boiling point of 120 ° C. or higher (hereinafter also referred to as “high boiling solvent”).
Thereby, the leveling property (flatness) of a film improves. Thereby, the haze of a laminated body is reduced more and the anti-fogging property of a laminated body improves more.

The boiling point of the high boiling point solvent is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, from the viewpoint of further improving the leveling property of the coating and obtaining a laminate having a lower haze.
In addition, the upper limit of the boiling point of the high boiling point solvent is preferably 230 ° C. from the point of suppressing poor drying of the film by the coating agent.

Examples of the high boiling point solvent include the following. The numerical value in parentheses after the high boiling point solvent shown below indicates the boiling point.
Alcohol solvents such as 1,3-butanediol (207 ° C.), 1,4-butanediol (228 ° C.), benzyl alcohol (205 ° C.), terpionol (217 ° C.);
Glycol solvents such as ethylene glycol (197 ° C.), diethylene glycol (244 ° C.), triethylene glycol (287 ° C.), propylene glycol (187 ° C.), dipropylene glycol (230 ° C.);
Diethylene glycol monomethyl ether (194 ° C), diethylene glycol monoethyl ether (202 ° C), diethylene glycol monobutyl ether (231 ° C), triethylene glycol monomethyl ether (249 ° C), propylene glycol monomethyl ether (121 ° C), propylene glycol monobutyl ether (170 ° C), propylene glycol monopropyl ether (150 ° C), 3-methoxy-3-methyl-1-butanol (174 ° C), diethylene glycol monohexyl ether (over 261 ° C), propylene glycol monomethyl ether propionate (160 ° C) ), Methyl cellosolve (ethylene glycol monomethyl ether, 125 ° C.), ethyl cellosolve (ethylene glycol monoethyl ether) 135 ° C), butyl cellosolve (ethylene glycol monobutyl ether, 171 ° C), ethylene glycol mono-tert-butyl ether (153 ° C), tripropylene glycol monomethyl ether (243 ° C), dipropylene glycol monomethyl ether (188 ° C), etc. Glycol ether solvents;
Ether solvents such as diethylene glycol dimethyl ether (162 ° C.), diethylene glycol ethyl methyl ether (176 ° C.), diethylene glycol isopropyl methyl ether (179 ° C.), triethylene glycol dimethyl ether (216 ° C.);
Ester solvents such as ethylene glycol monomethyl ether acetate (145 ° C), diethylene glycol monoethyl ether acetate (217 ° C), ethyl acetate (154 ° C), ethyl lactate (154 ° C), 3-methoxybutyl acetate (172 ° C);
Ketone solvents such as diacetone alcohol (169 ° C.), cyclohexanone (156 ° C.), cyclopentanone (131 ° C.);
Etc.

Here, the glycol solvent refers to a solvent having a structure in which one hydroxyl group is substituted on each of two or more carbon atoms of a hydrocarbon.
The glycol ether solvent refers to a solvent having a structure having one hydroxy group and at least one ether group in one molecule.
The ether solvent refers to a solvent having a structure having at least one ether group without having a hydroxy group or an ester group in one molecule.
The ester solvent refers to a solvent having a structure having at least one ester group in one molecule.
The ketone solvent refers to a solvent having a structure having at least one ketone group in one molecule.

As the high boiling point solvent, it is preferable to use a glycol ether solvent from the viewpoint that the surface energy is low and the leveling property of the film is further improved.
For the same reason, it is preferable to use a solvent having a branched alkyl group as the high boiling point solvent contained in the coating agent.

The dispersion medium (D) may contain only one kind of high boiling point solvent or may contain two or more kinds.
When the dispersion medium (D) contains two or more high boiling solvents, it is preferable to contain a glycol ether solvent as one of them. By including the glycol ether solvent, the leveling property of the coating is further improved.

When the dispersion medium (D) includes a high boiling point solvent, the content of the high boiling point solvent in the dispersion medium (D) is preferably 10% by mass to 60% by mass, and 20% by mass with respect to the total amount of the dispersion medium (D). Is more preferably from 50% by weight, and even more preferably from 20% by weight to 40% by weight.

<Condensation catalyst (E)>
The coating agent according to the present disclosure preferably further contains a condensation catalyst (E) containing a metal chelate compound.
Here, the “condensation catalyst (E)” means the entire condensation catalyst contained in the coating agent.
When the coating agent according to the present disclosure further contains a condensation catalyst (E) containing a metal chelate compound, the coating agent according to the present disclosure may contain only one type of condensation catalyst that is a metal chelate compound. It may be good and may contain 2 or more types. The coating agent according to the present disclosure may contain at least one condensation catalyst other than the metal chelate compound.

When the coating agent according to the present disclosure further contains a condensation catalyst (E) containing a metal chelate compound, the haze of the laminate is further reduced, and the antifogging property of the laminate is further improved. The reason for this is considered to be that the condensation reaction of the siloxane compound (A) is further enhanced, and as a result, the leveling property of the film is improved and the film forming property of the film is further improved.

Examples of condensation catalysts that are metal chelate compounds include aluminum chelate compounds such as aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), aluminum ethylacetoacetate diisopropylate; zirconium tetrakis (acetylacetate) ), Zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate); titanium chelate compounds such as titanium tetrakis (acetylacetonate) and titanium bis (butoxy) bis (acetylacetonate); and the like.

Examples of condensation catalysts other than metal chelate compounds include organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin dioctate; aluminum alkoxides such as aluminum ethylate, aluminum isopropylate, and aluminum sec-butyrate; titanium (IV) ethoxide, And titanium alkoxides such as titanium isopropoxide and titanium (IV) n-butoxide; zirconium alkoxides such as zirconium (IV) ethoxide, zirconium (IV) n-propoxide and zirconium (IV) n-butoxide;

Examples of the condensation catalyst other than the metal chelate compound include an acid catalyst and an alkali catalyst.
Acid catalysts include nitric acid, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, chloroacetic acid, formic acid, oxalic acid, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, dinonylnaphthalene monosulfonic acid, dinonylnaphthalenedisulfonic acid, dodecyl Examples thereof include benzenesulfonic acid, polyphosphate, and metaphosphate, and phosphoric acid, toluenesulfonic acid, polyphosphate, and metaphosphate are preferable.
Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium hydrogen carbonate, urea and the like, and sodium hydrogen carbonate or urea is preferable.

When the coating agent according to the present disclosure includes a condensation catalyst that is a metal chelate compound, the content of the condensation catalyst that is a metal chelate compound is 0.1% by mass to 30% by mass with respect to the total solid content of the coating agent. It is preferably 2% by mass to 20% by mass, more preferably 3% by mass to 10% by mass.

When the coating agent according to the present disclosure includes the condensation catalyst (E), the proportion of the condensation catalyst in the condensation catalyst (E) (that is, the entire condensation catalyst contained) is preferably 60% by mass or more, and 70 More preferably, it is more than 80 mass%, and still more preferably 80 mass% or more.

When the coating agent according to the present disclosure includes the condensation catalyst (E), the content of the condensation catalyst (E) (that is, the content of the entire condensation catalyst contained) is 0 with respect to the total solid content of the coating agent. It is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 20% by mass, and still more preferably 3% by mass to 10% by mass.

<Other ingredients>
The coating agent which concerns on this indication may contain other components other than the component mentioned above.
Examples of other components include adhesion assistants, antistatic agents, ultraviolet absorbers, antioxidants, surfactants (for example, nonionic surfactants), and the like.

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

A commercially available product may be used as the nonionic surfactant.
Examples of commercially available nonionic surfactants include EMALEX (registered trademark) 715 (HLB value: 15.6), EMALEX (registered trademark) 720 (HLB value: 16.5), EMALEX (Japan Emulsion Co., Ltd.). (Registered Trademark) 730 (HLB value: 17.5), EMALEX (Registered Trademark) 750 (HLB value: 18.4) (both trade names, polyoxyethylene lauryl ether), Leodol TW-P120 (trade name) of Kao Corporation Product name, polyoxyethylene sorbitan monopalmitate, HLB value: 15.6), PEG2000 (trade name, HLB value: 19.9) of Sanyo Chemical Industries, Ltd., and the like.
Here, the HLB value is a value that is defined by the following formula (I) by the Griffin method (all revised edition, introduction to surfactants, p128) and obtained by arithmetic.
HLB value of surfactant = (molecular weight of hydrophilic group portion / molecular weight of surfactant) × 20 (I)
The HLB value of the nonionic surfactant is preferably 15.5 or more, more preferably 16 or more, still more preferably 17 or more, and particularly preferably 18 or more.
The upper limit of the HLB value of a nonionic surfactant is not specifically limited, For example, 20 or less is preferable.

<Method for preparing coating agent>
The coating agent which concerns on this indication may be prepared by mixing each component mentioned above.
The following method is mentioned as an example of a preparation method.
First, a compound represented by the formula (1) and water are mixed to produce a hydrolysis condensate of the compound represented by the formula (1), and a liquid containing the hydrolysis condensate (hereinafter referred to as “liquid A”). Is also prepared). The liquid A may contain components other than the compound represented by the formula (1), the hydrolysis condensate, and water.
Next, with respect to the obtained liquid A, inorganic oxide particles (B), a polymer dispersant (C) having an acid group, a dispersion medium (D), and, if necessary, other such as a condensation catalyst (E) The coating agent which concerns on this indication is obtained by adding the component of.
Needless to say, when preparing the coating agent according to the present disclosure, a dispersion (hereinafter, also referred to as “raw material dispersion”) of components (for example, high refractive index particles) other than the dispersion medium (D) is used. When used, the dispersion medium in the raw material dispersion is also included in the dispersion medium (D) (the entire dispersion medium included in the coating agent).

The storage container for the coating agent according to the present disclosure is not particularly limited, and may be a metal container such as a Ito can or a royal can, or a resin container such as polyethylene or polypropylene. Glass containers such as coat bottles and gallon bottles may be used.
The storage temperature of the coating agent according to the present disclosure is preferably 0 ° C. or higher and 50 ° C. or lower.

[Method for producing laminate]
The manufacturing method of the laminated body which concerns on this indication includes the process (henceforth a "film formation process") which apply | coats the coating agent which concerns on this indication on a base material, and makes it dry and forms a film.
This manufacturing method may include other processes other than the film forming process.

<Film formation process>
This manufacturing method includes a film forming step in which a coating agent according to the present disclosure is applied onto a substrate and dried to form a film.

As described above, the substrate is preferably a glass substrate, a polycarbonate substrate, or a (meth) acrylic resin substrate.
Here, the (meth) acrylic resin in the (meth) acrylic resin substrate represents a resin containing a structural unit derived from a (meth) acrylic ester.
As the (meth) acrylic resin, one kind of (meth) acrylic acid ester homopolymer, two or more kinds of (meth) acrylic acid ester copolymers, one or more kinds of (meth) acrylic acid esters and one kind Examples thereof include copolymers with other monomers (for example, (meth) acrylic acid).
As the (meth) acrylic resin, a resin containing a structural unit derived from methyl (meth) acrylate is preferable, and a homopolymer of methyl methacrylate (PMMA) is particularly preferable.

Also, as the base material, a composite material formed from a plurality of materials can be used. For example, the material of the base material may include glass and a resin material, a composite material in which glass and a resin material are mixed to be composited, a resin composite material in which a plurality of types of resin materials are kneaded or bonded, and the like. Good.

Further, as the substrate, a substrate having a refractive index of 1.45 to 1.70 (more preferably 1.49 to 1.59) is preferable.

Moreover, as a base material, the base material which has transparency is preferable.
Here, having transparency means that the transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more (preferably 90% or more).

The thickness and shape of the substrate are not particularly limited, and are appropriately set according to the application target.
Further, the surface of the base material may be subjected to a surface treatment as necessary. There is no restriction | limiting in particular as a surface treatment method, A well-known method can be used.

The coating method may be determined according to the shape, size, thickness of the coating, etc., for example, spray coating, brush coating, roller coating, bar coating, dip coating (so-called dip coating), etc. The known coating method can be applied.
Among these, spray coating is preferable when applying to three-dimensional structures having various surface shapes such as curved surfaces and unevenness.

As a method of drying the coating film obtained by applying the coating agent, heat drying is preferred in which the coating film is dried by heating.
The heat drying temperature is preferably 40 ° C. to 150 ° C., more preferably 60 ° C. to 150 ° C., and still more preferably 90 ° C. to 150 ° C.
The temperature here means the temperature of the surface of the coating film. The surface temperature of the coating film can be measured with an infrared thermometer or the like.
The heat drying time is preferably 1 minute to 60 minutes, and more preferably 5 minutes to 40 minutes.
Before performing heat drying, for example, the coating film may be allowed to stand at a temperature of 15 ° C. or higher and lower than 40 ° C. for a time of 1 second or longer and 3 minutes or shorter.

You may perform heat drying using a well-known heating apparatus.
As the heating device, an oven, an electric furnace, or the like, or a heating device uniquely manufactured according to the production line can be used.

[Laminate]
The laminate according to the present disclosure includes a base material and a coating film disposed on the base material, and the coating film includes a siloxane condensate (A1) including a hydrolysis condensate of a compound represented by the following formula (1): And a laminate containing inorganic oxide particles (B1) containing inorganic oxide particles having a refractive index of 1.60 or more and a polymer dispersant (C1) having an acid group.

In the laminate according to the present disclosure, the coating film may be disposed on a part of the base material, or may be disposed on the entire base material.
Moreover, the coating film may be disposed in direct contact with the base material, or may be disposed on the base material via another layer (for example, an undercoat layer).

In the laminate according to the present disclosure, the preferred embodiment of the substrate is the same as the preferred embodiment of the substrate in the method for producing a laminate described above.

In the coating film in the laminate according to the present disclosure, the siloxane condensate (A1) includes a hydrolysis condensate of the compound represented by the formula (1).
The compound represented by the formula (1) which is a raw material of the siloxane condensate (A1) has the same meaning as the compound represented by the formula (1) in the coating agent according to the present disclosure, and the preferred embodiment is also the same.

As described above, the concept of “hydrolysis condensate of compound represented by formula (1)” includes only a product obtained by subjecting the compound represented by formula (1) to one hydrolysis condensation. In addition, a product obtained by subjecting the compound represented by the formula (1) to hydrolytic condensation multiple times is also included.
Therefore, for example, the coating in the laminate according to the present disclosure is a coating agent according to the present disclosure, and a hydrolysis condensate (hereinafter referred to as “hydrolysis condensate X1”) of the compound represented by the formula (1) In the siloxane condensate (A1), the “hydrolysis condensate of the compound represented by the formula (1)” is a hydrolyzed product. The decomposition condensate X1 may be a hydrolysis condensate obtained by further hydrolytic condensation one or more times.

The inorganic oxide particles (B1) and the polymer dispersant (C1) having an acid group in the coating agent according to the present disclosure have the inorganic oxide particles (B) and the acid group in the coating agent according to the present disclosure, respectively. It is synonymous with a polymer dispersing agent (C), and its preferable aspect is also the same.
The film in the laminate according to the present disclosure may contain other components other than the siloxane condensate (A1), the inorganic oxide particles (B1), and the polymer dispersant (C1) having an acid group. Examples of the other components include components in the coating agent according to the present disclosure.

In short, the preferred embodiments of the components of the coating film in the laminate according to the present disclosure (excluding the siloxane condensate (A1)) include the solid content (that is, the siloxane compound (A) and the dispersion medium ( This is the same as the preferred embodiment of the component (other than D).
Therefore, for the preferred embodiments of the film components (excluding the siloxane condensate (A1)) in the laminate according to the present disclosure, the description of the coating agent according to the present disclosure can be referred to as appropriate. However, “the total solid content of the coating agent” in the description of the coating agent according to the present disclosure is read as “the total solid content of the coating film”.
Here, the total solid content of the coating means all components excluding the dispersion medium (D) in the coating when the dispersion medium (D) remains in the coating, and the dispersion medium in the coating When (D) does not remain, it means all components of the coating (hereinafter the same).

The content of the hydrolysis-condensation product of the compound represented by the formula (1) in the coating in the laminate according to the present disclosure is preferably 5% by mass to 50% by mass with respect to the total solid content of the coating, and is preferably 10% by mass to 40% by mass is more preferable, and 15% by mass to 30% by mass is even more preferable.
The proportion of the hydrolysis condensate of the compound represented by formula (1) in the siloxane condensate (A1) is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass. % Or more is more preferable.
In addition, the content of the siloxane condensate (A1) in the coating in the laminate according to the present disclosure is preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass with respect to the total solid content of the coating. More preferably, the content is 15% by mass to 30% by mass.

The laminate according to the present disclosure includes the following preferred embodiments.
The aspect in which an inorganic oxide particle (B1) contains a silica particle.
A mode in which the content of the inorganic oxide particles (B1) is 50% by mass or more based on the total solid content of the coating.
The inorganic oxide particles (B1) include inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm.
The aspect in which an inorganic oxide particle (B1) contains the inorganic oxide particle of refractive index 2.00 or more.
A mode in which the inorganic oxide particles having a refractive index of 2.00 or more are at least one selected from the group consisting of titanium oxide particles, cerium oxide particles, and zirconium oxide particles.
The aspect whose base material is a glass base material, a polycarbonate base material, or a (meth) acrylic resin base material.

In the laminate according to the present disclosure, the thickness of the coating is not particularly limited.
The thickness of the coating is preferably 10 nm to 2000 nm, more preferably 10 nm to 1000 nm, and still more preferably 50 nm to 1000 nm.
When the thickness of the coating is 10 nm or more, it is advantageous in terms of ease of forming the coating.
When the thickness of the coating is 2000 nm or less, it is advantageous in that cracks in the coating can be suppressed.

Moreover, it is preferable that the film in the laminated body which concerns on this indication has a space | gap from a viewpoint of improving the anti-fogging property of a laminated body more. The voids can exist mainly between the inorganic oxide particles (B1) in the coating.
Here, that the coating has voids means that the porosity of the coating is 5% or more.
The porosity of the coating is preferably 5% to 50%, more preferably 10% to 50%.
The porosity of the coating is a value measured using an automatic porosimeter (Shimadzu Corporation, Autopore IV 9520).

Moreover, it is preferable that the haze of the laminated body which concerns on this indication is 2.0% or less.
The haze is a measured value obtained using a haze meter (for example, “NDH 5000” manufactured by Nippon Denshoku Industries Co., Ltd.).

Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples.
Hereinafter, “%” means “mass%” unless otherwise specified.
“High refractive index particles” means inorganic oxide particles having a refractive index of 1.60 or more, and “high boiling point solvents” mean solvents having a boiling point of 120 ° C. or more. The term “solvent” means an organic solvent other than the high boiling point solvent.

[Example 1]
<Preparation of liquid A>
MKC (registered trademark) silicate MS51 (siloxane compound represented by the formula (1), Mitsubishi Chemical Corporation) and ethanol were mixed. Next, ion-exchanged water (hereinafter simply referred to as “water”) is added thereto, and the mixture is stirred at room temperature (25 ° C., the same shall apply hereinafter) for 24 hours or longer to hydrolyze the siloxane compound represented by the formula (1). A liquid A containing the siloxane compound (A) containing the condensate (composition: siloxane compound (A) 27%, water 50%, and ethanol 23%) was obtained.

<Preparation of coating agent>
Liquid A, Bilal (registered trademark) Al-ML15 (dispersion of aluminum oxide particles as high refractive index particles, solid content: 15%, dispersion medium: water), DISPERBYK (registered trademark) -2015 (acid group) As an aqueous solution of a polymer dispersant having a carboxy group, solid content 40%), water, and ethanol, the composition shown in Table 2 (the composition of the solid content, the composition of the dispersion medium (D), and A coating agent having a solid content concentration) was obtained.

In Table 2, a blank means that the corresponding component is not contained.
In Table 2, in the “Solid content” column, each component (siloxane compound (A), high refractive index particles in inorganic oxide particles (B), and polymer dispersant (C) having an acid group) The material abbreviations (MS51, Al-ML15, and BYK2015) corresponding to are shown.
In Table 2, the amount of each component in the “Composition of solid content” column indicates the amount of each component (solid content in the corresponding material).
For example, the notation “48” next to “Al-ML15” means that the amount of solids (ie, alumina particles) in Al-ML15 is 48% by mass with respect to the total solids of the coating agent. And the notation of “25” next to “BYK2015” means that the amount of solids in BYK2015 (that is, the polymer dispersant having a carboxy group) is 25% by mass with respect to the total solids of the coating agent. It means that. The notation of “27” next to “MS51” means that the amount of MS51 which is a material of the siloxane compound (A) is 27% by mass with respect to the total solid content of the coating agent.

<Manufacture of laminates>
The above coating agent was spray gun (Anest Iwata (Anesto Iwata (Asahi Glass Co., Ltd., Carbo Glass C-110, thickness: 0.5 mm, A4 size)) on one side of the coating agent. Co., Ltd., W-101-101G), allowed to stand at 30 ° C. for 1 minute, and then dried at 120 ° C. for 20 minutes to form a film having a dried film thickness of 300 nm on the substrate. Coating with a spray gun was performed under the following conditions, and the discharge amount was appropriately adjusted according to the liquid composition. As described above, a laminate composed of the base material and the coating film disposed on the base material was obtained.
-Painting conditions with a spray gun-
Distance between spray nozzle and substrate: 150mm
Nozzle diameter: 1.0mmφ
Air pressure: 0.15 MPa
Ejection amount: 95 ml / min

<Evaluation of laminate>
The following evaluation was implemented about the obtained laminated body.
The results are shown in Table 2.

(Haze)
About a laminated body, haze was measured using the haze meter NDH5000 (Nippon Denshoku Industries Co., Ltd.). The haze was measured by placing a light source on the film side of the laminate. Based on the obtained results, the haze of the laminate was evaluated according to the following evaluation criteria.
If the haze is greater than 2.0%, the rainbow unevenness described later cannot be evaluated.

-Evaluation criteria for haze-
5: The haze of the laminate is 0.3% or less.
4: The haze of the laminate is greater than 0.3% and 1.0% or less.
3: The haze of the laminate is greater than 1.0% and not more than 2.0%.
2: The haze of the laminate is greater than 2.0% and 3.0% or less.
1: The haze of the laminate is greater than 3.0%.

(Rainbow unevenness)
The film side of the laminate was visually observed from various angles, and rainbow unevenness was evaluated according to the following evaluation criteria.

-Evaluation criteria for rainbow unevenness-
5: No rainbow unevenness is seen at all from any angle.
4: Although very thin rainbow unevenness may be visually recognized depending on the viewing angle, rainbow unevenness is not visually recognized at most angles.
3: The rainbow unevenness may be visually recognized depending on the viewing angle, but the angle range where the rainbow unevenness is not visually recognized is wider than the range of the angle where the rainbow unevenness is visually recognized.
2: Rainbow irregularities are visible when viewed from almost any angle (except for cases corresponding to 1).
1: Rainbow irregularities are visible when viewed from any angle.

(Anti-fogging property)
Vapor generated from water heated to 60 ° C. is applied to the coating in the laminated body at a distance of 20 mm from the water surface for 1 minute, and the fogging of the subsequent coating is visually observed. evaluated.

-Evaluation criteria for anti-fogging properties-
5: There is no cloudiness on the film, and a clean water film is formed on the film.
4: The film is not cloudy and a water film is formed on the film, but the formed water film is slightly shaken.
3: The film is not cloudy and a water film is formed on the film, but the formed water film is shaking.
2: A water film is unevenly formed on the coating.
1: A water film is not formed on a film and a film becomes cloudy.

[Examples 2 to 24 and 27 to 29]
The same as in Example 1 except that the type and amount of materials used are appropriately changed so that the composition of the solid content, the composition of the dispersion medium (D), and the solid content concentration shown in Table 2 below are obtained. The operation was performed.
The results are shown in Table 2.
In Examples 2 to 24 and 27 to 29, the silica particles, the condensation catalyst (E), and the high boiling point solvent are all mixed with the liquid A at the stage after the preparation of the liquid A containing the siloxane compound (A). By doing so, it was included in the coating agent.

[Examples 25 and 26]
The same operation as in Example 21 was performed except that the type of the substrate was changed as shown in Table 2.
The results are shown in Table 2.
In Examples 25 and 26, as glass and PMMA, the following glass substrates and PMMA substrates were used, respectively.
Glass… Glass substrate (Non-alkali glass “OA-10” manufactured by Nippon Electric Glass Co., Ltd., thickness 1 mm)
PMMA ... Polymethylmethacrylate (PMMA) base material ("Comoglas (registered trademark)" manufactured by Kuraray Co., Ltd., thickness 1 mm)

[Comparative Examples 1 to 3]
The same as in Example 1 except that the type and amount of materials used are appropriately changed so that the composition of the solid content, the composition of the dispersion medium (D), and the solid content concentration shown in Table 2 below are obtained. The operation was performed.
The results are shown in Table 2.
In Comparative Examples 1 to 3, the silica particles, the condensation catalyst (E), and other components were all contained in the coating agent by mixing with the liquid A at the stage of “preparation of the coating agent”.

Each material in Table 2 is as follows.
-Raw material of siloxane compound (A) (compound represented by formula (1))-
MS51: MKC (registered trademark) silicate MS51 (R ¹ , R ² , R ³ , and R ⁴ in formula (1): methyl group, average of n: 5, Mitsubishi Chemical Corporation)
・ TEOS: Tetraethoxysilane (Tokyo Chemical Industry Co., Ltd.)

-Material of inorganic oxide particles (B)-
--- Materials of high refractive index particles--
Al-ML15: Vilaral (registered trademark) Al-ML15 (a dispersion of aluminum oxide particles having a refractive index of 1.77 and an average primary particle diameter of less than 5 nm, solid content: 15%, dispersion medium: water, many Ki Chemical Co., Ltd.)
Al-C20: BIRAL (registered trademark) Al-C20 (a dispersion of aluminum oxide particles having a refractive index of 1.77 and an average primary particle diameter of 15 nm to 20 nm, solid content: 20%, dispersion medium: water, Taki Chemical Co., Ltd.)
AS-L10: Viral (registered trademark) AS-L10 (a dispersion of aluminum oxide / silicon oxide composite particles having a refractive index of 1.63 and an average primary particle diameter of 5 nm to 50 nm, solid content: 10%, dispersion Medium: Water, Taki Chemical Co., Ltd.)
Nb-G6600: Bayal (registered trademark) Nb-G6600 (dispersion liquid of niobium oxide particles having a refractive index of 2.30 and an average primary particle diameter of 5 nm or less, solid content: 6%, dispersion medium: water, many Ki Chemical Co., Ltd.)
TKS-203: TKS-203 (dispersion liquid of titanium oxide particles having a refractive index of 2.50 to 2.70 and an average primary particle diameter of 6 nm, solid content: 20%, dispersion medium: water, Teika Corporation ))
B-10: Niedral (registered trademark) B-10 (dispersion of cerium oxide particles having a refractive index of 2.10 and an average primary particle diameter of 8 nm, solid content: 10%, dispersion medium: water, Taki Chemical Co., Ltd.)
SZR-W: SZR-W (dispersion of zirconium oxide particles having a refractive index of 2.10 and an average primary particle diameter of 5 nm, solid content: 30%, dispersion medium: water, Sakai Chemical Co., Ltd.)
--Material of silica particles--
ST-OXS: Snowtex (registered trademark) OXS (aqueous dispersion of silica particles having a refractive index of 1.43 and an average primary particle diameter of 4 nm to 6 nm, solid content of 10%, Nissan Chemical Industries, Ltd.)
ST-O33: Snowtex (registered trademark) O33 (aqueous dispersion of silica particles having a refractive index of 1.43 and an average primary particle diameter of 10 nm to 15 nm, solid content 15%, Nissan Chemical Industries, Ltd.)

-Materials for polymer dispersants with acid groups-
BYK2015: DISPERBYK (registered trademark) -2015 (aqueous solution of polymer dispersant having a carboxy group, solid content 40%, acid value: 10 mgKOH / g, Big Chemie Japan Co., Ltd.)
BYK180: DISPERBYK (registered trademark) -180 (aqueous solution of polymer dispersant having a phosphate group, solid content 40%, acid value: 94 mgKOH / g, Big Chemie Japan Co., Ltd.)
A-6012: Aron (registered trademark) A-6012 (aqueous solution of a polymer dispersant having a sulfonic acid group, solid content 40%, weight average molecular weight: 10,000, Toagosei Co., Ltd.)

-Material of condensation catalyst (E)-
AL-D: Aluminum chelate D (76% aqueous solution of aluminum chelate compound, Kawaken Fine Chemical Co., Ltd.)

-Other ingredients-
-PVA: polyvinyl alcohol (weight average molecular weight: 20000, Tokyo Chemical Industry Co., Ltd.)

-High boiling point solvent-
MFG: propylene glycol monomethyl ether (boiling point 121 ° C., surface tension 27.7, Tokyo Chemical Industry Co., Ltd.)
ETB: ethylene glycol mono-tert-butyl ether (boiling point 153 ° C., surface tension 24.6, Tokyo Chemical Industry Co., Ltd.)

-Other solvents-
EtOH: ethanol (boiling point 78 ° C., Tokyo Chemical Industry Co., Ltd.)
-water-
Water: ion exchange water (boiling point 100 ° C.)

As shown in Table 2, containing a siloxane compound (A), inorganic oxide particles (B) containing high refractive index particles, a polymer dispersant (C) having an acid group, and a dispersion medium (D) The laminates of Examples 1 to 29 using the coating agent having excellent antifogging properties, haze reduction, and rainbow unevenness were suppressed.

Compared with Examples 1 to 29, the rainbow unevenness deteriorated in the laminate of Comparative Example 1 using a coating agent containing no high refractive index particles.
In the laminate of Comparative Example 2 produced using a coating agent that does not contain the polymer dispersant (C) having an acid group, the haze increased.
In the laminate of Comparative Example 3 produced using a coating agent containing no siloxane compound (A), the antifogging property was lowered and the haze was increased.

From the comparison between Example 1 and Example 2, it can be seen that when the inorganic oxide particles (B) contain silica particles (Example 2), the antifogging property of the laminate is further improved. This reason is considered to be because the hydrophilicity of the coating is further improved.

From the comparison between Example 1 and Examples 3 and 4, when the dispersion medium (D) contains a high-boiling solvent (Examples 3 and 4), the haze of the laminate is further reduced and anti-fogging is achieved. It can be seen that the property is further improved. The reason for this is considered to be that the leveling property (smoothness) of the coating is improved during drying after application of the coating agent.

From a comparison between Example 1 and Example 5, when the coating agent contains a condensation catalyst (E) containing a metal chelate compound (Example 5), the haze of the laminate is further reduced and the coating is prevented. It turns out that cloudiness improves more. The reason for this is considered to be that the leveling property (smoothness) of the coating is improved during drying after application of the coating agent.

From the comparison between Example 1 and Example 6, when the content of the inorganic oxide particles (B) is 50% by mass or more based on the total solid content of the coating agent (Example 6), a laminate is obtained. It can be seen that the antifogging property of the toner is further improved. The reason for this is considered to be that the void amount of the coating is made more appropriate.

From the comparison between Example 1 and Examples 8 to 10, when the inorganic oxide particles (B) include inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm (Examples 8 to 10), a laminate is obtained. It can be seen that the antifogging property of the toner is further improved. The reason is considered to be that the void size of the coating is made more appropriate.

From the comparison between Example 1 and Examples 12 to 15, the inorganic oxide particles (B) contain inorganic oxide particles having a refractive index of 2.00 or more as high refractive index particles (Examples 12 to 15). It can be seen that rainbow unevenness of the laminate is further suppressed.

From a comparison between Example 12 and Examples 13 to 15, the inorganic oxide particles having a refractive index of 2.00 or more are at least one selected from the group consisting of titanium oxide particles, cerium oxide particles, and zirconium oxide particles. It can be seen that in some cases (Examples 13 to 15), the haze of the laminate is further improved.

Next, transmission electron microscope (SEM) images of the cross sections of the laminates in Examples 1 to 29 were acquired, and the obtained cross-sectional SEM images were binarized using image processing software (for example, ImageJ, manufactured by Wayne Rasband). Based on the binarized cross-sectional SEM images, the porosity of the coatings in Examples 1 to 29 were measured.
As a result, in Examples 1 to 10 and 12 to 29, the porosity of the coating was 14%, and in Example 11, the porosity of the coating was 21%.

The disclosure of Japanese Patent Application No. 2018-014679 filed on Jan. 31, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims

A siloxane compound (A) containing at least one of a compound represented by the following formula (1) and a hydrolysis condensate of the compound represented by the following formula (1);
Inorganic oxide particles (B) containing inorganic oxide particles having a refractive index of 1.60 or more;
A polymer dispersant (C) having an acid group;
A dispersion medium (D);
Containing a coating agent.

In formula (1), R 1 , R 2 , R 3 and R 4 each independently represents a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 20.
The coating agent according to claim 1, wherein the inorganic oxide particles (B) contain silica particles.
The coating agent according to claim 1 or 2, wherein the dispersion medium (D) contains a solvent having a boiling point of 120 ° C or higher.
The coating agent according to any one of claims 1 to 3, wherein the dispersion medium (D) contains water.
The coating agent according to any one of claims 1 to 4, further comprising a condensation catalyst (E) containing a metal chelate compound.
The coating agent according to any one of claims 1 to 5, wherein the content of the inorganic oxide particles (B) is 50% by mass or more based on the total solid content of the coating agent.
The coating agent according to any one of claims 1 to 6, wherein the inorganic oxide particles (B) include inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm.
The coating agent according to any one of claims 1 to 7, wherein the inorganic oxide particles (B) contain inorganic oxide particles having a refractive index of 2.00 or more.
The coating agent according to claim 8, wherein the inorganic oxide particles having a refractive index of 2.00 or more are at least one selected from the group consisting of titanium oxide particles, cerium oxide particles, and zirconium oxide particles.
A method for producing a laminate comprising a step of applying a coating agent according to any one of claims 1 to 9 on a substrate and drying to form a coating film.
The method for producing a laminate according to claim 10, wherein the substrate is a glass substrate, a polycarbonate substrate, or a (meth) acrylic resin substrate.
A substrate and a coating disposed on the substrate;
The coating is
A siloxane condensate (A1) containing a hydrolysis condensate of the compound represented by the following formula (1);
Inorganic oxide particles (B1) containing inorganic oxide particles having a refractive index of 1.60 or more;
A polymer dispersant (C1) having an acid group;
A laminate containing

In formula (1), R 1 , R 2 , R 3 and R 4 each independently represents a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 1 to 20.
The laminate according to claim 12, wherein the inorganic oxide particles (B1) include silica particles.
The laminate according to claim 12 or 13, wherein the content of the inorganic oxide particles (B1) is 50% by mass or more based on the total solid content of the coating film.
The laminate according to any one of claims 12 to 14, wherein the inorganic oxide particles (B1) include inorganic oxide particles having an average primary particle diameter of 5 nm to 20 nm.
The laminate according to any one of claims 12 to 15, wherein the inorganic oxide particles (B1) include inorganic oxide particles having a refractive index of 2.00 or more.
The laminate according to claim 16, wherein the inorganic oxide particles having a refractive index of 2.00 or more are at least one selected from the group consisting of titanium oxide particles, cerium oxide particles, and zirconium oxide particles.
The laminate according to any one of claims 12 to 17, wherein the substrate is a glass substrate, a polycarbonate substrate, or a (meth) acrylic resin substrate.