JPWO2017217513A1 - Film-forming composition, laminate, and method for producing laminate - Google Patents

Abstract

Hydrolyzate of a compound represented by the following general formula (1), silica particles, an ionic surfactant having at least one of a phosphate group and a carboxy group, and a nonionic property having a hydrophilic / lipophilic balance of more than 15 A film-forming composition containing a surfactant and water and its application. In general formula (1), R1, R2, R3, and R4 each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 2 to 20.

Description

  The present disclosure relates to a film-forming composition, a laminate, and a method for producing the laminate.

  Equipment, building materials, etc. that are installed indoors or outdoors and used for a long period of time are used by being exposed to various environments, so they gradually accumulate dust, dust, gravel, etc., and get wet in rainwater during wind and rain. As a result, planned functions and performance may be impaired.

For this reason, measures are taken to protect the surfaces of the devices, building materials and the like with various protection means and to further improve the durability of the devices and the like. Examples of the protective means include disposing a protective member such as a cover or a protective sheet on the surface of the device or the like, and covering the surface of the device or the like with a protective film.
Even if protective means such as a protective film is provided on the surface, dust, dust or mud stains gradually accumulate on the surface over a long period of time, or it may become wet with rainwater during wind and rain. The desired function or performance of the protection means may not be exhibited.

Protective means for protecting the surface of surveillance camera protective covers, headlight protective covers, reflecting mirrors, traffic signs, etc. are usually used for a long time once a protected member or device is installed. It is. Therefore, the protection means is required to have protection performance for members, devices, and the like necessary for a long period of time and self-cleaning properties that do not require cleaning while maintaining light transmittance.
Usually, by making the surface of the protective member hydrophilic, a decrease in light transmittance due to clouding of the surface is suppressed, and aqueous stains are difficult to adhere.

  As a means for forming a hydrophilic film on the surface of a member, for example, a hydrolyzate of tetraalkoxysilane and / or a condensate thereof, a metal compound capable of interacting with a silanol group, an alkylene oxide unit, and an HLB (Hydrophyl Lipophile) An aqueous hydrophilization treatment agent comprising a nonionic surfactant having a balance of 10 to 15, acidic colloidal silica, and a hydrophilic organic solvent has been proposed (see Japanese Patent No. 4648667).

  Further, as another means for forming a hydrophilic film on the surface of a member, an aqueous coating material including a siloxane polymer, colloidal silica, and a nonionic surfactant having an HLB of 16 or more has been proposed (Japanese Patent Laid-Open No. 2006-2006). 69385).

  Furthermore, an aqueous coating composition for paints comprising a water-soluble polymer obtained by hydrolytic condensation of a silane compound in an aqueous solvent, colloidal inorganic particles, and a sulfosuccinic acid surfactant has been proposed (special feature). (See JP 2005-206701).

Equipment, components, building materials, etc. that are installed outdoors and are exposed to various changing environments such as wind and rain tend to deteriorate their intended functions as dirt adheres to them. It has become customary to periodically clean or replace parts.
However, even if dirt is attached to the protective member, for example, if it is a member having a so-called self-cleaning property that is easy to remove the dirt attached to the surface of the protective member when water adheres due to rain, cleaning or replacement of parts is possible. The work load can be greatly reduced. For this reason, the antifouling film | membrane which has a function close | similar to maintenance free which can maintain antifouling property and antifogging property over a long period of time is anxious.
Furthermore, according to the study by the present inventors, it contains a hydrophobic component such as a silicone-based adhesive, a butyl-based adhesive, and a plasticizer derived from the protective member, which are widely used when fixing the protective member or the like at a necessary position. When materials are used, the hydrophobic component gradually volatilizes over time, and the volatilized hydrophobic component affects the surface of the antifogging layer, etc. It became clear that the sex could not be obtained.

The hydrophilization treatment agent described in Japanese Patent No. 4648667 improves storage stability by containing a metal chelate compound, acidic colloidal silica, and a nonionic surfactant as hydrophilic components.
Further, the aqueous coating material described in JP-A-2006-69385 includes a colloidal silica, an alkali swelling thickener, and a nonionic surfactant, thereby forming a stain-resistant hydrophilic coating film. It is said that.
In the technique described in JP-A-2005-206701, the hydrophilicity of a coating film formed by the coexistence of colloidal inorganic particles and a sulfosuccinic acid surfactant in an aqueous coating composition for paints is improved.
However, the hydrophilic film formed from the composition described in Japanese Patent No. 4648667, Japanese Patent Application Laid-Open No. 2006-69385 and Japanese Patent Application Laid-Open No. 2005-206701 can exhibit a certain degree of hydrophilicity. However, the decrease in hydrophilicity of the hydrophilic film due to the coexistence with the hydrophobic substance such as the silicone-based adhesive described above has not been studied, and the temporal decrease in hydrophilicity due to the coexistence with the hydrophobic substance has not been studied. At present, almost no effect is obtained.

An object of one embodiment of the present invention is to provide a film-forming composition capable of forming a hydrophilic film that is excellent in hydrophilicity and in which a decrease in hydrophilicity after the coexistence of hydrophobic components is suppressed.
The problem of another embodiment of the present invention is a laminate having a hydrophilic film excellent in hydrophilicity and suppressed in hydrophilicity after the coexistence of hydrophobic components, or excellent in hydrophilicity and coexisting hydrophobic components. An object of the present invention is to provide a method for producing a laminate having a hydrophilic film in which a decrease in hydrophilicity after aging is suppressed.

Specific means for solving the problems include the following aspects.
<1> Hydrolyzate of siloxane compound represented by the following general formula (1), silica particles, an ionic surfactant having at least one of a phosphate group and a carboxy group, and a hydrophilic / lipophilic balance value of 15 A film-forming composition comprising a larger nonionic surfactant and water.

In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 2 to 20.
<2> The film forming composition according to <1>, wherein the ionic surfactant having at least one of a phosphoric acid group and a carboxy group has an acid value of 180 mgKOH / g or less.
<3> The film forming composition according to <1> or <2>, wherein the nonionic surfactant has a polyoxyalkylene group.
<4> The film-forming composition according to any one of <1> to <3>, further comprising a ketone solvent.

<5> An ionic interface having a base material, a hydrolyzate condensate of a siloxane compound represented by the following general formula (1), silica particles, and at least one of a phosphoric acid group and a carboxy group on the base material. A hydrophilic film containing an active agent and a nonionic surfactant having a hydrophilic / lipophilic balance value greater than 15, and the laminate is filled with a silicone sealant in an atmosphere of 65 ° C. and 25% RH. A laminated body having a pure water contact angle measured at 25 ° C. of 30 ° or less on the surface of the hydrophilic film after being placed in a constant temperature and humidity apparatus containing a glass container and kept for 150 hours.

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

<6> A method for producing a laminate comprising: providing a hydrophilic film by applying the film forming composition according to any one of <1> to <4> on a base material.
<7> The laminate is placed in a thermostatic chamber containing a glass container containing a silicone sealant in an atmosphere of 65 ° C. and 25% RH, and kept at 150 ° C. of the hydrophilic membrane surface after holding for 150 hours. The manufacturing method of the laminated body as described in <6> which is a laminated body whose pure water contact angle measured in (30) is 30 degrees or less.

According to one embodiment of the present invention, there is provided a film-forming composition capable of forming a hydrophilic film that is excellent in hydrophilicity and in which a decrease in hydrophilicity after the coexistence of hydrophobic components is suppressed.
According to another embodiment of the present invention, a laminated body having a hydrophilic film excellent in hydrophilicity and suppressed in hydrophilicity after the coexistence of hydrophobic components, or excellent in hydrophilicity and coexisting hydrophobic components. Provided is a method for producing a laminate having a hydrophilic film in which a decrease in hydrophilicity over time is suppressed.

Hereinafter, the film forming composition, the laminate, and the method for producing the laminate of the present disclosure will be described in detail.
In the present specification, a numerical range indicated using “to” means a range including the numerical values described before and after “to” as a minimum value and a maximum value, respectively.
In this specification, when referring to the amount of each component in the composition, when there are a plurality of substances corresponding to each component in the composition, a plurality of components present in the composition unless otherwise specified. Means the total amount.
In the numerical ranges described stepwise in this specification, 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 range. Good. Further, in the numerical ranges described in this specification, 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 specification, a combination of preferred embodiments is a more preferred embodiment.
The term “solid content” in the present specification means a component excluding a solvent, and liquid components such as low molecular weight components other than the solvent are also included in the “solid content” in the present specification.
In the present specification, the “solvent” means water, an organic solvent, and a mixed solvent of water and an organic solvent.

Hereinafter, the hydrophilic / lipophilic balance value may be referred to as an HLB value.
In the present specification, the hydrophilic film refers to a film having a pure water contact angle of 30 ° or less.
In this specification, the pure water contact angle is measured by dropping 1 μl (microliter) of pure water onto the surface of the film to be measured at 25 ° C. using a contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). The value obtained by the θ / 2 method is used, and the arithmetic average value of the values obtained by measuring five times is adopted as the pure water contact angle in this specification.
The pure water contact angle after the coexistence of the hydrophobic component of the hydrophilic membrane in this specification is determined by coexisting the hydrophilic membrane and the silicone sealant in the constant temperature and humidity device SH-641 manufactured by Espec Co., Ltd. at 65 ° C. and 25% RH. The pure water contact angle measured in the same manner as described above after standing for 150 hours.

<Film forming composition>
The film forming composition of the present disclosure includes an ionic surfactant (hereinafter referred to as a hydrolyzate of a siloxane compound represented by the following general formula (1), silica particles, and at least one of a phosphate group and a carboxy group. , A specific ionic surfactant), a nonionic surfactant having an HLB value greater than 15 (hereinafter sometimes referred to as a specific nonionic surfactant), and water. To do.
Hereinafter, the siloxane compound represented by the following general formula (1) may be referred to as a specific siloxane compound, and a hydrolyzate of the specific siloxane compound may be referred to as a specific siloxane hydrolyzate.

In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 2 to 20.
Hereinafter, each component that can be contained in the film-forming composition of the present disclosure will be described.

[Hydrolyzate of specific siloxane compound]
The film forming composition of the present disclosure contains at least one hydrolyzate of a specific siloxane compound.
When the film-forming composition contains a hydrolyzate of a specific siloxane compound, the hydrophilic film obtained by the film-forming composition has good retention of silica particles described later, and has good scratch resistance and hydrophilicity. Become.

  The film-forming composition contains a hydrolyzate of a specific siloxane compound, and is obtained by a film-forming composition containing a hydrolyzate of a specific siloxane compound. Including at least one of the following.

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

The monovalent organic group having 1 to 6 carbon atoms in R ¹ , R ² , R ³ , and R ⁴ may be linear, branched, or cyclic. . Examples of the monovalent organic group include an alkyl group and an alkenyl group, and an alkyl group is preferable.
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, n-hexyl group, cyclohexyl group and the like can be mentioned.
In the specific siloxane compound, when the monovalent organic group in R ^{1 to} R ⁴ , preferably the alkyl group has 1 to 6 carbon atoms, the specific siloxane compound has good hydrolyzability. From the viewpoint of hydrolysis resistance is better, R ¹ to R ⁴ is more preferably each independently an alkyl group having 1 to 4 carbon atoms, is an alkyl group having 1 or 2 carbon atoms More preferably.

N in General formula (1) represents the integer of 2-20. When n in the general formula (1) is 2 or more, the reactivity of the specific siloxane compound can be easily controlled, and for example, a film having excellent surface hydrophilicity can be formed. When n is 20 or less, the viscosity of the film-forming composition does not become too high, and handling properties and uniform coating properties are improved. n is preferably from 3 to 12, and more preferably from 5 to 10.
In Table 1 below, examples of the specific siloxane compound are described by R ¹ , R ² , R ³ , R ⁴ , and n in the general formula (1). However, the specific siloxane compound in the present disclosure is not limited to the exemplified compounds described in Table 1.

The film-forming composition contains the hydrolyzate of the specific siloxane compound described above.
The specific siloxane compound is at least partially hydrolyzed by coexisting with water. The hydrolyzate of the specific siloxane compound reacts with the specific siloxane compound and water so that at least a part of OR ¹ , OR ² , OR ³ , and OR ⁴ bonded to the silicon atom of the specific siloxane compound is converted into a hydroxy group. It is presumed that a hydrophilic film formed by application and drying, for example, is a film having good surface hydrophilicity due to a hydroxy group which is a substituted compound and is a hydrophilic group.
In the hydrolysis reaction, it is not always necessary that all the terminal groups (that is, -OR ¹ , -OR ² , -OR ³ , or -OR ⁴ ) of the specific siloxane compound react, but for example, a coating solution for forming a hydrophilic film From the viewpoint of improving the hydrophilicity of the coating film obtained by coating and drying, it is preferable that more terminal groups are hydrolyzed.

When forming a hydrophilic film using the film-forming composition of the present disclosure, at least some of the hydroxy groups of the specific siloxane compound are bonded to each other and the specific siloxane compound is condensed. Therefore, the hydrophilic film obtained using the film-forming composition contains at least one kind of hydrolysis condensate of the specific siloxane compound.
The film-forming composition may contain only one type of hydrolyzate of a specific siloxane compound, or may contain two or more types.

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

  In the present specification, the weight average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation) is used, TSKgel, SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15 cm) are used as columns, and tetrahydrofuran is used as an eluent. It can be measured using (THF). 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 curve is “polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. , “F-4”, “F-40”, “F-128”, and “F-700” prepared from 10 samples can be used.

As described above, the film-forming composition contains a hydrolyzate of at least one specific siloxane compound. Furthermore, the film forming composition of the present disclosure may include partial cohydrolysis obtained using two or more silane compounds. As the two or more types of silane compounds, two or more types of specific siloxane compounds having different structures may be used, and the specific siloxane compound and the specific siloxane compound may be combined with another siloxane compound having a different structure. A hydrolyzate obtained from two or more kinds of siloxane compounds is sometimes referred to as “(co) hydrolyzate”, and a compound obtained by condensation of these is sometimes referred to as “(co) hydrolysis condensate”.
In this specification, the silane compound refers to a compound having at least one selected from a hydrolyzable silyl group and a silanol group. A bond is generated.

The film forming composition of the present disclosure contains at least one hydrolyzate containing a hydrolyzate obtained by hydrolyzing at least a part of the specific siloxane compound, and is formed by the film forming composition of the present disclosure. The hydrophilic film includes a hydrolyzed condensate obtained by hydrolyzing and condensing at least a part of the specific siloxane compound, so that the hydrophilic property of the surface is good, and a film strength having no practical problem can be obtained.
The siloxane compound represented by the general formula (1) is also available as a commercial product. For example, MKC (registered trademark) silicate MS51 (Mitsubishi Chemical Corporation) [R ¹ , R ² , R ³ , and R ⁴ : methyl group, n average: 5], silicate MS56 [R ¹ , R ² , R ³ , and R ⁴ : methyl group, n average: 11], silicate MS57 [R ¹ , R ² , R ³ , And R ⁴ : methyl group, n average: 13], silicate MS56S [R ¹ , R ² , R ³ , and R ⁴ : methyl group, n average: 16], methyl silicate 53A [R ¹ , R ² , R ³ and R ⁴ : methyl group, average of n: 7], ethyl silicate 40 [R ¹ , R ² , R ³ , and R ⁴ : ethyl group, average of n: 5], ethyl silicate 48 [R ^{1, R} 2, ^{R 3,} and ^R 4: Butyl group, the average of n: 10], and the like.

  The content of the specific siloxane compound in the film-forming composition is preferably 1% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, and more preferably 10% by mass with respect to the total solid content of the film-forming composition. % To 40% by mass is more preferable. When the content of the specific siloxane compound is in the above range, the contact angle of pure water on the surface of the hydrophilic film obtained by using the film-forming composition can be kept low, and antifouling properties and easy removal of dirt when soiled A film with good self-cleaning properties.

<Silica particles>
The film-forming composition contains at least one silica particle.
The silica particles have a function of enhancing the scratch resistance of the hydrophilic film formed by the film-forming composition and further exhibiting hydrophilicity. That is, the silica particles play a role as a hard filler, and the hydroxy group on the particle surface acts to contribute to the improvement of the hydrophilicity of the hydrophilic film.

Examples of the silica particles include fumed silica and colloidal silica.
Fumed silica can be obtained by reacting a compound containing a silicon atom with oxygen and hydrogen in the gas phase. Examples of the silicon compound 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. Examples of commercially available silica particles include AEROSIL (registered trademark) series manufactured by Evonik Japan, Snowtex (registered trademark) series (such as Snowtex O) manufactured by Nissan Chemical Industries, and Nalco manufactured by Nalco Chemical. (Registered trademark) series (for example, Nalco 8699, etc.), Quatron 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 even more preferably 30 nm or less, from the viewpoint of good film properties of the formed hydrophilic film. Particularly preferably, it is 15 nm or less. Moreover, the minimum of the average primary particle diameter of a silica particle is although it does not specifically limit, 2 nm or more is preferable from the point that the film property of the hydrophilic film | membrane formed is favorable.
The film-forming composition may contain only one kind of silica particles or may contain two or more kinds. 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.

  The average primary particle diameter of the silica particles is about 300 or more particles from the photograph obtained by observing the dispersed silica particles with a transmission electron microscope when the shape of the silica particles is a spherical shape or a substantially spherical shape with a cross-sectional ellipse shape. The projected area of the particles is measured, the equivalent circle diameter is determined from the projected area, and the obtained equivalent circle diameter is defined as the average primary particle diameter of the silica particles. When the shape of the silica particles is not spherical or substantially spherical, the average primary particle diameter of the silica particles is obtained using another method, for example, a dynamic light scattering method.

  The content of silica particles in the film forming composition is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and more preferably 20% by mass with respect to the total solid content of the film forming composition. -70 mass% is further more preferable, and 30 mass%-50 mass% is especially preferable. When the content of silica particles is within the above range, the hydrophilicity of the hydrophilic film obtained from the film-forming composition is improved, and the hydrophilic film is excellent in hardness, scratch resistance, and the like.

<Specific ionic surfactant>
The film-forming composition contains a specific ionic surfactant having at least one of a phosphate group and a carboxy group.
When the film forming composition contains the specific ionic surfactant, at least one functional group of the phosphate group and the carboxy group of the specific ionic surfactant functions as an acid-adsorbing group. Adsorption on the surface of the silica particles improves the dispersion stability of the silica particles, suppresses the adsorption of hydrophobic components to the surface of the silica particles, and reduces the hydrophilicity with time due to the adsorption of the hydrophobic components. Effectively suppressed.
The specific ionic surfactant is preferably an anionic surfactant in view of the adsorptivity with the silica particles.
Specific ionic surfactants include, as hydrophobic groups, aliphatic hydrocarbon groups having 1 to 36 carbon atoms, cyclohexyl groups, cyclobutyl groups and the like, and styryl groups, naphthyl groups, and phenyl groups. And a compound having a hydrocarbon group selected from aromatic hydrocarbon groups such as a phenylene ether group and having at least one of a phosphate group and a carboxy group as an acid-adsorbing group. Note that the hydrophobic group described above may further have a substituent.
The specific ionic surfactant may have an unsaturated bond in the molecule.

More preferably, the specific ionic surfactant has only a functional group selected from a phosphate group and a carboxy group as an acid-adsorbing group. Moreover, it is preferable that a specific ionic surfactant does not have acid adsorption groups other than a phosphoric acid group and a carboxy group, for example, a sulfonic acid group, a sulfuric acid group, etc.
An anionic surfactant known as an antistatic agent contained in the film-forming composition, more specifically, an anionic surfactant having a hydrophobic alkyl group and a hydrophilic sulfate group or sulfonate group. With a surfactant, the effect of suppressing the above-described decrease in hydrophilicity cannot be obtained.
In addition, an anionic surfactant containing a sulfosuccinic acid partial structure has a sulfonic acid group as an acid adsorbing group in the molecule. Even if exists, the effect of this indication mentioned above cannot be show | played.

  As the specific ionic surfactant, examples of the compound containing a phosphate group include alkyl phosphate ester salts and polyoxyethylene alkyl ether phosphates. Examples of the compound containing a carboxy group include N-acyl amino acid salts, polyoxyethylene alkyl ether carboxylates, aliphatic carboxylates, aliphatic dicarboxylates, polycarboxylic acid copolymers having a molecular weight of less than 25,000, and molecular weights. Examples include maleic acid copolymers having a molecular weight of less than 25,000.

The acid value of the specific ionic surfactant is preferably 180 mgKOH / g or less from the viewpoint of sufficiently covering the surface of the silica particles to improve the dispersibility and easily protect the surface. The following is more preferable.
In addition, although the lower limit of an acid value is not specifically limited, It is preferable to set it as 3 mgKOH / g or more from a viewpoint similar to the above.
When the acid value of the specific ionic surfactant is in the above-described range, both the dispersibility of the silica particles and the adsorption preventing ability of the hydrophobic component are improved.
The acid value of the specific ionic surfactant can be measured by titration of an indicator. Specifically, according to the method described in JIS K 0070, the acid component in 1 g of the solid content of the specific ionic surfactant It can be calculated by measuring the number of mg of potassium hydroxide to be summed.

  The specific ionic surfactant is also available as a commercial product. Examples of commercially available specific ionic surfactants that can be used in the film forming composition of the present disclosure include DISPERBYK (registered trademark) -2015 (acid-adsorbing group: carboxy group, acid value: 10 mgKOH / g) DISPERBYK. -180 (acid adsorbing group: phosphoric acid group, acid value: 94 mgKOH / g), TEG (registered trademark) Dispers 660C (acid adsorbing group: phosphoric acid group, acid value: 30 mgKOH / g), BYK P104 (acid adsorbing property) Group: carboxy group, acid value: 180 mgKOH / g) and the like.

The film-forming composition may contain only one type of specific ionic surfactant or two or more types.
The content of the specific ionic surfactant in the film-forming composition is preferably 50% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less based on the total solid content of the film-forming composition. Further preferred. The content of the specific ionic surfactant is preferably 0.05% by mass or more.
That is, the content of the specific ionic surfactant with respect to the total solid content of the film-forming composition is preferably 0.05% by mass or more and 50% by mass or less, and 0.5% by mass or more and 20% by mass or less. It is preferable that it is 1% by mass or more and 15% by mass or less.
When the content of the specific ionic surfactant is within the above range, the effect of preventing aggregation of silica particles and the effect of preventing the adsorption of hydrophobic components are improved, and the hydrophilic film is obtained by containing the specific ionic surfactant. It becomes easy to obtain the antifouling effect.
The content of the specific ionic surfactant described above does not include the content of ionic surfactants other than the specific ionic surfactant contained as an optional component.

<Specific nonionic surfactant>
The film-forming composition contains a nonionic surfactant (specific nonionic surfactant) having an HLB value greater than 15.
When the film-forming composition contains a specific nonionic surfactant, the hydrophilicity of the hydrophilic film obtained from the film-forming composition becomes better, and the ability to prevent adsorption of hydrophobic components to the silica particles Becomes better.

The specific nonionic surfactant is preferably a surfactant having a polyoxyalkylene group.
When the specific nonionic surfactant has a polyoxyalkylene group, the HLB value is in an appropriate range, and the ability to prevent a decrease in adsorptivity due to the hydrophobic component due to adsorption to the silica particles becomes better.
The polyoxyalkylene group is preferably a polyoxyethylene group from the viewpoint of better hydrophilicity.
The HLB value in this specification is a value calculated by the Griffin method (all revised edition, introduction to surfactant, p128) obtained by the following formula (I).

Nonionic surfactant HLB = (molecular weight of hydrophilic group portion / molecular weight of surfactant) × 20 (I)
The HLB value is preferably 15.5 or more, and the hydrophilicity of the resulting hydrophilic film is further increased, and the ability to prevent adsorption of hydrophobic components is further improved. 18 or more is particularly preferable.

  Specific nonionic surfactants having an HLB value exceeding 15 include, for example, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene aryl ethers, polyoxyalkylene alkyl aryl ethers, sorbitan derivatives, polyoxyalkylene aryls. Examples include a formalin condensate of ether, a formalin condensate of polyoxyalkylene alkylaryl ether, and polyethylene glycol. Among these, polyoxyalkylene alkyl ether is preferable.

Examples of the alkyl group of the polyoxyalkylene alkyl ether in the specific nonionic surfactant include a linear or branched alkyl group having 1 to 36 carbon atoms.
The oxyalkylene part of the polyoxyalkylene alkyl ether is preferably polyoxyethylene from the viewpoint that a hydrophilic film having particularly excellent hydrophilicity can be obtained. Further, the number of polyoxyethylene structural units possessed by the specific nonionic surfactant is preferably 6 or more, more preferably 10 or more, still more preferably 15 or more, and particularly preferably 20 or more. . From the viewpoint of solubility, the number of polyoxyethylene structural units can be 100 or less.

When the specific nonionic surfactant is a polyoxyalkylene alkyl ether, a surfactant represented by the following formula (II) is preferable.
_{RO- (C 2 H 4 0)} m-H (II)
(However, m represents an integer of 6 to 100. R represents a linear or branched alkyl group having 1 to 36 carbon atoms.)

  The specific nonionic surfactant is also available as a commercial product. Examples of commercially available specific nonionic surfactants that can be used in the film-forming composition of the present disclosure include Emalex 715 (HLB value: 15.6), 720 (HLB value: 16.5), and 730. (HLB value: 17.5) 750 (HLB value: 18.4) (above trade name: Nippon Emulsion Co., Ltd. polyoxyethylene lauryl ether), Rheodor TW-P120 (trade name, Kao Corp., polyoxyethylene) Sorbitan monopalmitate HLB value: 15.6), PEG2000 (trade name, Sanyo Chemical Industries, Ltd., HLB value: 19.9) and the like.

The content of the specific nonionic surfactant in the film-forming composition is preferably 0.01% by mass to 15% by mass, and 0.1% by mass with respect to the total solid content of the film-forming composition. % To 10% by mass is more preferable, and 1% to 10% by mass is even more preferable.
When the content of the specific nonionic surfactant is in the above-described range, the film-forming composition of the present disclosure has good hydrophilicity of the resulting hydrophilic film and has an ability to prevent adsorption of hydrophobic components. It is fully demonstrated.

<Water>
The film forming composition contains water.
As described above, water contributes to the hydrolytic condensation reaction of the specific siloxane compound.
The water that can be used for the film-forming composition is preferably ion-exchanged water, pure water, distilled water, or the like from the viewpoint that there are fewer impurities.
The water content is appropriately determined as necessary. For example, water may be contained in an amount of 1% by mass to 20% by mass, preferably 5% by mass to 15% by mass, and preferably 6% by mass to 12% by mass with respect to the total amount of solvent contained in the film-forming composition. % Is more preferable.

[Other ingredients]
The film-forming composition may contain other known components in addition to the specific siloxane hydrolyzate, silica particles, specific ionic surfactant, and specific nonionic surfactant as long as the effects are not impaired. Good. Examples of the other components include solvents other than water, antistatic agents, surfactants, catalysts that accelerate the condensation reaction of specific siloxane compounds, and the like, but are not limited to the components described above.

(Solvents other than water)
The film-forming composition can contain a solvent other than water as the solvent.
Examples of solvents other than water include ketone solvents, glycol solvents, alcohol solvents, glycol ether solvents, ether solvents, and the like.
Especially, it is preferable that a ketone solvent is included from a viewpoint that the adhesiveness of the film | membrane formed by the film forming composition and a base material becomes better.

-Ketone solvents-
The ketone solvent in the film-forming composition contributes to the adhesion between the hydrophilic film formed by the composition and the substrate.
The ketone solvent is not particularly limited, and examples thereof include acetone, diacetone alcohol, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and cyclopentanone.

The ketone solvent is preferably a ketone solvent having an SP value (solubility parameter) of 10.0 MPa ^1/2 or more from the viewpoint that a film having more excellent transparency can be formed. In addition, the upper limit of the SP value of the ketone solvent is not particularly limited. For example, from the viewpoint of effectively suppressing sheet-like failure such as coatability on a base material, for example, repellency during coating. It is preferably 0 MPa ^1/2 or less.

Specific examples of ketone solvents having an SP value of 10.0 MPa ^1/2 or more are shown below. However, the ketone solvent that can be used in the film-forming composition is not limited to the following specific examples. The numerical value in parentheses after the following specific example shows the SP value (unit: MPa ^1/2 ) of the ketone solvent written together.
Acetone (10.0), diacetone alcohol (10.2), acetylacetone (10.3), cyclopentanone (10.4).

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

  When the film forming composition of the present disclosure contains a ketone solvent, it may contain only one kind of ketone solvent, or may contain two or more kinds.

The content of the ketone solvent in the film-forming composition of the present disclosure is preferably 5% by mass to 95% by mass, and preferably 10% by mass to 60% by mass with respect to the total mass of the solvent contained in the film-forming composition. More preferably, it is 20% by mass or more and 50% by mass or less.
When the content of the ketone solvent in the film-forming composition is within the above range, a film that is more excellent in transparency and adhesion can be formed.

  Examples of other solvents that can be contained in the film-forming composition are shown below. In addition, the solvent which the composition for film formation can contain is not limited to the following exemplary solvent.

-Alcohol solvent-
The alcohol solvent in the present disclosure refers to a solvent having a structure in which one hydroxy group is substituted for one carbon atom of a hydrocarbon.
Examples of alcohol solvents include methanol, ethanol, butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, n-propanol, 2-propanol, tert-butanol, 2-butanol, and benzyl alcohol. .

-Glycol ether solvent-
The glycol ether solvent in the present disclosure refers to a solvent having a structure having one hydroxy group and at least one ether group in one molecule.
Examples of glycol ether solvents include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol mono Examples include hexyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, methyl cellosolve, ethyl cellosolve, and butyl cellosolve.

-Ether solvent-
The ether solvent in the present disclosure refers to a solvent having a structure having at least one ether group without having a hydroxy group in one molecule.
Examples of ether solvents include isopropyl ether, 1,4-dioxane, tert-butylmethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2 dimethoxyethane, diethyl ether and the like.

(Antistatic agent)
The film-forming composition preferably contains at least one antistatic agent.
By including an antistatic agent, antistatic property is imparted to the hydrophilic film obtained from the film-forming composition, the effect of preventing the adhesion of contaminants is improved, and the antifouling property is further improved.

The antistatic agent can be appropriately selected from compounds having an antistatic function, and may be either a compound showing surface activity or a compound not showing surface activity. Examples of the antistatic agent include ionic surfactants other than the specific ionic surfactants described above (hereinafter sometimes referred to as other ionic surfactants), metal oxide particles, and the like. . In addition, the above-mentioned silica particle is not contained in the metal oxide particle as an antistatic agent.
Other ionic surfactants as antistatic agents have the property of being easily segregated near the film surface of the coating film when, for example, a film-forming composition is applied to a substrate to form a hydrophilic film. Yes, the effect can be expected with a small amount of addition.
In addition, metal oxide particles as an antistatic agent may need to be added in a relatively large amount in order to impart antistatic properties to the hydrophilic film. However, since they are inorganic, they are scratch resistant to the hydrophilic film. Suitable for enhancing

  Examples of other ionic surfactants include alkyl sulfates (eg, sodium dodecyl sulfate, sodium lauryl sulfate, etc.), alkyl benzene sulfonates (eg, sodium dodecyl benzene sulfonate, sodium lauryl benzene sulfonate, etc.), And anionic surfactants such as alkylsulfosuccinate (eg, sodium di (2-ethylhexyl) sulfosuccinate); and cationic surfactants such as alkyltrimethylammonium salt and dialkyldimethylammonium salt.

When other ionic surfactant is used as the antistatic agent, the content of the other ionic surfactant is preferably 5% by mass or less based on the total solid content of the film-forming composition, 1 mass% or less is more preferable, and 0.5 mass% or less is further more preferable. When the content of the other ionic surfactant is within the above range, the antifouling property of the hydrophilic film can be enhanced while suppressing aggregation of the silica particles. The content of the other ionic surfactant is preferably 0.01% by mass or more from the viewpoint of the effect of improving the antifouling property of the hydrophilic film by including the ionic surfactant. .
In addition, when other ionic surfactants are added excessively to the film-forming composition, they affect the hydrophilicity-inhibiting effect caused by the hydrophobic component due to the specific ionic surfactant described above. Therefore, the content of the other ionic surfactant used as the antistatic agent is 0.1 parts by mass or less with respect to 1 part by mass of the specific ionic surfactant described above. It is preferable that it is 0.05 mass part or less.

There is no limitation in particular in the metal oxide particle used as an antistatic agent. Examples thereof include tin oxide particles, antimony-doped tin oxide particles, tin-doped indium oxide particles, and zinc oxide particles.
Two or more kinds of metal oxide particles having different sizes, shapes, or materials may be used. The particle shape of the metal oxide particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.
When the metal oxide particles have a large refractive index and a large particle size, loss due to excessive scattering of transmitted light is likely to occur. Therefore, the average primary particle size is preferably 100 nm or less, and preferably 50 nm or less. More preferably, it is more preferably 30 nm or less.
Regarding the average primary particle diameter of the metal oxide particles, when the particle shape is substantially spherical, such as a spherical shape or a cross-sectional ellipse, the dispersed particles are observed with a transmission electron microscope. It is obtained by measuring the projected area of the particles and determining the equivalent circle diameter from the projected area. In addition, when the shape of a metal oxide particle is not spherical, it calculates | requires using another method, for example, a dynamic light scattering method.

  When using metal oxide particles as an antistatic agent, the content of the metal oxide particles is preferably 40% by mass or less, more preferably 20% by mass or less, based on the total solid content of the film-forming composition. 10 mass% or less is still more preferable. When the content of the metal oxide particles is within the above range, the antistatic property can be effectively imparted without impairing the film formability when the hydrophilic film is formed by coating. In addition, the content of the metal oxide particles is desirably 1% by mass or more from the viewpoint of improving the antifouling property of the hydrophilic film by including the metal oxide particles.

(Catalyst promoting the condensation reaction of specific siloxane compounds)
The film-forming composition may contain at least one catalyst that promotes the condensation reaction of the specific siloxane compound (condensation promoting catalyst). The effect of the condensation accelerating catalyst will be described later.

There is no restriction | limiting in particular as a condensation promotion catalyst, For example, an acid catalyst, an alkali catalyst, an organometallic catalyst etc. are mentioned.
Examples of 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 , Dodecylbenzenesulfonic acid, polyphosphate, metaphosphate and the like.
Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium hydrogen carbonate, urea and the like.
Examples of organometallic catalysts include aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate; zirconium tetrakis (acetylacetonate) Zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate); titanium chelate compounds such as titanium tetrakis (acetylacetonate) and titanium bis (butoxy) bis (acetylacetonate); and dibutyltin diacetate, dibutyltin dilaurate , Organotin compounds such as dibutyltin dioctiate, aluminum ethylate, aluminum isopropylate, aluminum sec- Aluminum alkoxides such as tyrate, titanium (IV) ethoxide, titanium isopropoxide, titanium alkoxides such as titanium (IV) n-butoxide, zirconium (IV) ethoxide, zirconium (IV) n-propoxide, zirconium (IV) n- Zirconium alkoxides such as butoxide;

  Among these catalysts, the acid catalyst is preferably phosphoric acid, toluenesulfonic acid, polyphosphate, or metaphosphate, the alkali catalyst is preferably sodium bicarbonate or urea, the organometallic catalyst is an aluminum chelate compound, Titanium chelate compounds or zirconium chelate compounds are preferred. Among these catalysts, an organometallic catalyst is more preferable, and an aluminum chelate compound is particularly preferable.

  The content of the condensation accelerating catalyst in the total solid content of the film-forming composition is preferably 0.1% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and 5% by mass to 20% by mass. Further preferred. When the content of the condensation accelerating catalyst is within the above range, it is easy to form a hydrophilic film having scratch resistance. Moreover, it is excellent also in the formation property of a hydrophilic film | membrane.

(Other additives)
The film-forming composition may further contain other additives as necessary in addition to the components described above. As other additives, for example, other than the specific siloxane hydrolyzate described above, which is used for the purpose of improving the film properties of the hydrophilic film formed by the film-forming composition, improving the adhesion to the substrate, and the like. Examples thereof include adhesion assistants that are film-forming components.

Examples of the adhesion assistant include a film-forming component having no siloxane structure in the molecule, for example, a film-forming polymer compound, and more specifically, for example, polyurethane, (meth) acrylic resin, etc. And compounds having a polar group (for example, a hydroxyl group, a carboxy group, a phosphoric acid group, a sulfonic acid group, an amino group) at the terminal.
When the film-forming composition contains an adhesion assistant, the adhesion between the hydrophilic film obtained by the film-forming composition and the substrate, particularly, the polycarbonate substrate is further improved.
Among the adhesion assistants, a compound having a hydroxyl group, a carboxy group, or a phosphoric acid group at the terminal is preferable from the viewpoint that adhesion between the hydrophilic film and the base material is better. Polyurethane, acrylic resin, and polyphosphorus are preferable. Acid salts are more preferred.

The polyurethane is not particularly limited, and examples thereof include polyurethane having a soft segment / hard segment structure composed of a polyol skeleton and a polyisocyanate skeleton.
A commercially available polyurethane may be used. For example, Takerak (registered trademark) W series, WS series, WD series manufactured by Mitsui Chemicals, Ltd., Permarin (registered trademark) series manufactured by Sanyo Chemical Industries, Ltd., Registered trademark) series, uprene (registered trademark) series, and the like.
The (meth) acrylic resin is a resin containing at least one of acrylic acid and methacrylic acid as a structural unit, and is a homopolymer of (meth) acrylic acid (poly (meth) acrylic acid) or an ester of (meth) acrylic acid And a copolymer containing a (meth) acrylic acid derivative as a constituent unit.
Among the acrylic resins, polyacrylic acid is preferable, polyacrylic acid having a weight average molecular weight of 25,000 to 5,000,000 is preferable, 100,000 to 2,000,000 polyacrylic acid is more preferable, and 250,000 to 1,000,000 polyacrylic acid is further included. preferable.
The weight average molecular weight can be measured by the method described above.

  When the film-forming composition contains an adhesion assistant, the content of the adhesion assistant is preferably 0.001% by mass to 5% by mass with respect to the total solid content of the film-forming composition, and 0.01% by mass. % To 1% by mass is more preferable, and 0.05% to 0.5% by mass is more preferable. When the content of the adhesion assistant is within the above range, it is easy to form a hydrophilic film having excellent adhesion to the substrate.

  The film forming composition of the present disclosure described above is useful for forming a hydrophilic film on a substrate. The hydrophilic film obtained by the film forming composition of the present disclosure is excellent in hydrophilicity and contains a hydrophobic component, for example, a silicone adhesive or a protective member used for attaching a protective member to a necessary place. Even after aging in a state where it coexists with a silicone sealant used to suppress water intrusion from the peripheral edge of the film, it has a function of preventing the hydrophobic component from adsorbing to the hydrophilic film, particularly silica particles. Accordingly, the hydrophilic film obtained by the film-forming composition of the present disclosure has a good hydrophilicity because the decrease in hydrophilicity due to the adsorption of the hydrophobic component after coexistence with the hydrophobic component is suppressed. Maintained for a period of time.

[Laminate]
The laminate of the present disclosure includes a base material, a hydrolysis condensate of the compound represented by the general formula (1), silica particles, and at least one of a phosphate group and a carboxy group on the base material. A hydrophilic film containing an ionic surfactant having a nonionic surfactant having an HLB value greater than 15, and the laminate of the silicone sealant in an atmosphere of 65 ° C. and 25% RH The pure water contact angle measured at 25 ° C. on the surface of the hydrophilic film after being placed in a constant temperature and humidity apparatus containing the contained glass container and held for 150 hours is 30 ° or less.

<Base material>
The substrate used in the laminate of the present disclosure is not particularly limited, and may be appropriately selected from various materials such as glass, resin material (plastics material), metal, ceramics, etc. according to the purpose of use of the laminate. Can be used.

Glass is widely used as a substrate, and is suitable as a substrate for forming the laminate of the present invention. When glass is used as the substrate, condensation of hydroxy groups on silicon occurs even with the hydroxy groups on the glass surface, thereby forming a film having better adhesion to the substrate.
A resin material is also suitable as the base material. For example, a resin material is often used for a base material such as a protective material for a monitoring camera. Among the resin materials, polycarbonate and polymethyl methacrylate are preferable because they are excellent in durability against light and heat.
The substrate may be a composite material. As a base material, for example, any of a composite material including glass and a resin material, in which glass and a resin material are mixed and combined, or a resin composite material in which a plurality of types of resin materials are kneaded or bonded may be used.

There is no restriction | limiting in particular about the thickness of a base material, a shape, and a size, What is necessary is just to select suitably according to the use of a laminated body, a use purpose, etc.
As thickness of a base material, it can be set as 0.05 mm-10 mm, for example.

  The pure water contact angle can be determined by the θ / 2 method using a contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) at 25 ° C. by dropping 1 μl of pure water onto the surface of the film to be measured. . The pure water contact angle is measured five times by the method described above, and the arithmetic average value of the obtained values is used as the pure water contact angle value in this specification.

[Pure water contact angle]
The pure water contact angle of the hydrophilic membrane is 30 ° or less, preferably 20 ° or less, more preferably 15 ° or less, and even more preferably 10 ° or less. When the pure water contact angle is in the above range, the surface of the hydrophilic film is more hydrophilic. The method for measuring the pure water contact angle is as described above.

[Pure water contact angle after coexistence of hydrophobic components]
The hydrophilic film formed by the film-forming composition of the present disclosure decreases in hydrophilicity over time due to adsorption of the hydrophobic component to the hydrophilic film even after coexisting with a hydrophobic component such as silicone. Is suppressed.
The pure water contact angle after coexistence with the hydrophobic component of the hydrophilic film is measured by the following method. In this specification, silicone sealant 1527W (manufactured by Tianshan New Materials Co., Ltd.) is used as the hydrophobic component.
A glass containing the laminated body having a hydrophilic film and the above-described silicone sealant in a constant temperature and humidity device, coexisting in a constant temperature and humidity device SH-641 manufactured by ESPEC Co., Ltd. The container is put, sealed, and allowed to stand for 150 hours to obtain a laminated body coexisting with the hydrophobic component and aged. About the hydrophilic film | membrane of the obtained laminated body, a pure water contact angle is measured like the above.

The reason why the hydrophilic film in the laminate of the present disclosure can exhibit the above effect is not clear, but is presumed as follows.
The hydrophilic film in the present disclosure includes a hydrolytic condensate of a specific siloxane compound and silica particles. The hydrolyzed condensate of the specific siloxane compound formed by the condensation reaction of the hydrolyzate of the specific siloxane compound has a function as a binder that is a film-shaped component of the hydrophilic film. For this reason, a high density silanol group exists in the surface of the silica particle in the formed hydrophilic film | membrane, and it is thought that a hydrophilic film | membrane is excellent in hydrophilicity resulting from the silanol group of the silica particle surface.
Furthermore, the hydrophilic film in the present disclosure includes the specific ionic surfactant and the specific nonionic surfactant described above, and at least two types of surfactants adsorb to the silanol groups on the surface of the silica particles to form silica. It is thought to protect the particle surface. For this reason, even when coexisting with a hydrophobic component, the volatilized low-molecular hydrophobic component is prevented from adsorbing to silanol groups, and the surface hydrophilicity decrease due to the adsorption of the hydrophobic component is suppressed over a long period of time. It is estimated that you can.
Therefore, the hydrophilic film in the present disclosure maintains the physical properties such as hydrophilicity and scratch resistance due to the silica particles and the hydrolytic condensate of the specific siloxane compound in the conventional film, and the hydrophilic film due to adsorption of the hydrophobic component. It is considered that the decrease is suppressed.
Note that the present disclosure is not limited to the estimation mechanism.

  There is no restriction | limiting in particular in the thickness of a hydrophilic film | membrane, According to the objective, it selects suitably. When the laminate of the present disclosure is applied to a commonly used protective member, a range of 20 nm to 5 μm is preferable, a range of 50 nm to 1 μm is more preferable, a range of 75 nm to 500 nm is further preferable, and a range of 75 μm to 250 nm is more preferable. The following ranges are particularly preferred.

[Physical properties of hydrophilic film]
The hydrophilic film in the laminate of the present disclosure maintains hydrophilicity for a long time even in the presence of hydrophilic and hydrophobic components. Thereby, the hydrophilic film in the present disclosure is a member installed outdoors, such as a surveillance camera, a protective material for protecting lighting, a roof material for a garage, a protective material for a sign, a protective material for a wall material, etc. Is preferred.
By providing a laminate having a hydrophilic film as a protective member, fogging due to adhesion of moisture is suppressed, and adhesion of contaminants to the surface is also suppressed. Further, even when the hydrophilic property of the hydrophilic film is in the presence of a hydrophobic component, a decrease in hydrophilic property due to adsorption of the hydrophobic component is suppressed. Further, when the surface hydrophilicity is good and the contaminant adheres to the surface of the hydrophilic film, it can be easily removed by washing away the contaminant (for example, washing with water). There is also an effect that it is easily washed away by rain water or the like.
The preferred physical properties of the hydrophilic film in the present disclosure are listed below. The pure water contact angle that serves as a hydrophilic index is as described above.

[Haze]
Using a haze meter NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the haze of a laminate having a hydrophilic film produced by applying the film forming composition of the present disclosure onto a polycarbonate substrate as a base material. taking measurement. In addition, the haze is measured by directing the base material surface of the laminate, that is, the surface not having a hydrophilic film, to the light source.
The haze value is preferably 2.0 or less from the viewpoint of visibility, more preferably 1.5 or less, further preferably 1.0 or less, and particularly preferably 0.5 or less. .

[Adhesion]
A cross cut test of 25 squares is performed based on JIS (Japanese Industrial Standard) K5600. A sample that does not peel off even one square is considered acceptable. In addition, it is preferable that slight peeling is not recognized in the cross | intersection part of a crosscut, and it is more preferable that peeling is not recognized at all in the cut cross site | part and the edge part of a cut site | part.

[Coating suitability: Evaluation of dripping]
On a polycarbonate substrate as a base material, the film forming composition of the present disclosure was applied with a spray gun, allowed to stand at room temperature (25 ° C.) for 30 seconds, and then tilted vertically at 120 ° C. The surface state of the hydrophilic film after drying for 20 minutes is visually observed.
A sample in which sagging of the film-forming composition on the coated surface is clearly recognized visually is rejected. It is preferred that the trace of the film forming composition is slightly observed, and it is more preferable that the film forming composition is so smooth that the trace of the film forming composition cannot be visually confirmed.

The laminated body of the present disclosure includes a protective material (so-called protective cover) for protecting surveillance cameras, lighting, sensor lamps, and the like, roofing materials for garages for vehicles such as automobiles and bicycles, and protection for signs such as road signs. It is suitably used as a transparent protective material for materials, sound barriers for highway road shoulder installations, railways, etc., automobile bodies such as automobiles and motorcycles, glass, mirrors, and headlights.
Above all, in order to protect the use of materials containing hydrophobic components such as silicone adhesives and silicone sealants, such as surveillance cameras, lighting, and sensor lamps, for fixing protective members or waterproofing the ends of fixed members It can apply suitably for the use of the protective material of this, and the transparent protective material of a headlight.

<Method for producing laminate>
The manufacturing method of the laminated body of this indication includes providing the film forming composition of this indication mentioned above on a base material, and obtaining a hydrophilic film | membrane. That is, applying a film-forming composition containing a specific siloxane hydrolyzate, silica particles, a specific ionic surfactant, and a specific nonionic surfactant to a substrate by a coating method or the like. Including.
Furthermore, the manufacturing method of a laminated body has preparing the composition for film formation of this indication, and drying the composition for film formation provided to the base material at the temperature of 20 to 150 degreeC. Is preferred.

Preparation of a film forming composition in the production method of the present disclosure will be described.
The film-forming composition can be prepared by mixing a specific siloxane hydrolyzate, silica particles, a specific ionic surfactant, and a specific nonionic surfactant.
In preparing the film-forming composition, it is preferable to further mix a catalyst that promotes the condensation reaction of the specific siloxane compound (condensation promoting catalyst).

The film-forming composition is prepared, for example, by bringing a specific siloxane compound and water into contact with each other and preparing a mixed solution containing a hydrolyzate of the specific siloxane compound, and then having an average primary particle diameter of 2 nm or more and 100 nm in the prepared mixed solution. The method of adding the following silica particles is mentioned. The specific nonionic surfactant is preferably contained in the mixed solution. The specific ionic surfactant preferably contains a dispersion of silica particles as described later.
Although the hydrolysis reaction of the specific siloxane compound proceeds even at room temperature (25 ° C.), in order to promote the reaction, after preparing the mixed solution by bringing the specific siloxane compound and water into contact with each other, the obtained mixed solution is heated to 30 ° C. You may heat to about -50 degreeC. A longer reaction time for the hydrolysis reaction is preferred because the reaction proceeds more. For this reason, it is also preferable to make it react for 1 to 36 hours in a heated state from a viewpoint of making a hydrolysis reaction fully advance.
Further, by allowing a catalyst for promoting the hydrolysis reaction of the specific siloxane compound to coexist in the mixed solution, it is possible to obtain a hydrolyzate of the specific siloxane compound necessary for hydrophilicity even for about half a day.

The hydrolysis reaction of the specific siloxane compound is a reversible reaction. Therefore, when water is removed from the mixed solution, the condensation reaction between the hydroxy groups of the hydrolyzate of the specific siloxane compound starts and proceeds. Therefore, when a hydrolyzate of a specific siloxane compound is obtained by a hydrolysis reaction in a mixed liquid containing a specific siloxane compound and preferably a large excess of water, the liquid mixture is not isolated without isolating the hydrolyzate. It is preferable to prepare a film-forming composition by adding silica particles as it is.
When the film-forming composition is applied to the substrate, the condensation reaction of the hydrolyzate of the specific siloxane compound proceeds in the film-forming composition, so the hydrophilic film formed by the film-forming composition is the specific siloxane. Hydrolysis condensates of compounds are included.

From the viewpoint of suppressing the aggregation of silica particles, it is preferable to contain a specific ionic surfactant as a dispersant.
By containing the specific ionic surfactant as a dispersant, the phosphate groups and carboxy groups, which are the acid adsorption groups of the specific ionic surfactant, are adsorbed on the surface of the silica particles, effectively aggregating the silica particles. It is considered to be suppressed.
The specific ionic surfactant used as the dispersant may be used alone or in combination of two or more.

  When the specific ionic surfactant is contained as a dispersant in the film-forming composition, the content is within a preferable content range with respect to the total solid content of the film-forming composition, and the silica particles The range of 1% by mass to 500% by mass is preferable, and the range of 10% by mass to 100% by mass is more preferable.

  In the preparation of the film-forming composition, the specific ionic surfactant may be added at the end of the preparation. A liquid mixture that has been mixed and stirred in advance with silica particles is prepared, and the prepared liquid mixture is used as the film-forming composition. As a component of the product, it may be added to a mixed solution containing the above-mentioned specific siloxane hydrolyzate.

The film forming composition may further contain a viscosity modifier.
When the film-forming composition of the present disclosure further contains a viscosity modifier, the viscosity of the film-forming composition is increased, and dripping of the film-forming composition is less likely to occur during coating, thereby improving the coating suitability. .
It does not specifically limit as a viscosity modifier, A well-known thickener, a solvent with a high viscosity, etc. are mentioned. The viscosity modifier can be appropriately selected depending on the method for applying the film-forming composition to the substrate.

It does not specifically limit as a thickener, It is preferable to use and select suitably according to the kind of solvent of the composition for film formation. The thickener is preferably a thickener having a weight average molecular weight of 3,000 or more and 10,000,000 or less from the viewpoint that the effect of thickening can be obtained by adding a relatively small amount. Note that the thickener in the present disclosure does not include acrylic acid homopolymer (polyacrylic acid), acrylic acid derivatives such as acrylic acid and its esters, and methacrylic acid derivatives such as methyl methacrylate.
The weight average molecular weight of the thickener can be measured by the method described above.

  As the thickener, commercially available products may be used. Examples of commercially available products include SEPIGEL 305 from Seiwa Kasei Co., Ltd., DISPERBYK 410, 411, 415, 420, 425, 428, 430, 431 from BYK Chemie. 7410ET, 7411ES, 7420ES, Koskat GA468, Osaka Organic Chemical Industry Co., Ltd., inorganic materials (silicate (water-soluble alkali silicate), montmorillonite, organic montmorillonite, colloidal alumina, etc.), fibrin derivative-based material ( Carboxymethylcellulose, methylcellulose, hydroxycellulose, etc.), protein materials (casein, sodium caseinate, ammonium caseinate, etc.), alginic acid materials (sodium alginate, etc.), polyvinyl materials (polyvinyl alcohol, polyvinylpyrrolidone, Rivinyl benzyl ether copolymer, etc.), polyether materials (pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, polyether urethane modified products, polyether epoxy modified products, etc.), maleic anhydride copolymer based materials (Partial ester of vinyl ether-maleic anhydride copolymer, drying oil fatty acid allyl alcohol ester-half ester of maleic anhydride, etc.). In addition to the above, examples of the thickener include polyamide wax salt, acetylene glycol, zentane gum, oligomer or polymer having a polar group at the molecular end or side chain.

  When the film forming composition of the present disclosure further includes a thickener as a viscosity modifier, only one type of thickener may be included, or two or more types may be included.

  When the film forming composition of the present disclosure further contains a viscosity modifier, the viscosity modifier content in the film forming composition is 0.01% by mass to 20% with respect to the total mass of the film forming composition. % By mass is preferable, 0.1% by mass to 10% by mass is more preferable, and 0.5% by mass to 5% by mass is more preferable.

As the viscosity modifier, a solvent having a high viscosity is preferable in that no viscosity modifier component remains in the formed film.
In the present specification, “a solvent having a high viscosity” refers to a solvent having a viscosity at 25 ° C. of 30 mPa / s or more, for example.
The “high viscosity solvent” used as a viscosity modifier functions as a solvent in addition to the function as a viscosity modifier in the film-forming composition, and is removed in the same way as other solvents during film formation. As a result, there is an advantage that it does not remain in the film formed as described above.
In addition, the viscosity in this specification is the value measured at room temperature (25 degreeC) using the Toki Sangyo company B-type viscosity meter TVB-10.
Examples of the solvent having a high viscosity that can be used as the viscosity modifier include glycol solvents.

In the present specification, the “glycol-based solvent” refers to one having a structure in which two or more carbon atoms of a hydrocarbon are each substituted with a hydroxy group.
Examples of glycol solvents include ethylene glycol, diethylene glycol, triethylene glycol, glycerin, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, , 4-butanediol, diethanolamine, triethanolamine and the like.
Among these, the glycol solvent is preferably at least one selected from propylene glycol and dipropylene glycol from the viewpoint of dispersibility of the silica particles and drying properties when applied.

  When the film forming composition of the present disclosure further includes a glycol solvent as a viscosity modifier, it may include only one glycol solvent or two or more glycol solvents.

When the film forming composition of the present disclosure contains a glycol solvent as a viscosity modifier, the content of the glycol solvent in the film forming composition is based on the total mass of the solvent contained in the film forming composition. , 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
While the content of the glycol-based solvent is 40% by mass or less with respect to the total mass of the solvent contained in the film-forming composition, while suppressing dripping of the film-forming composition during coating, A film having excellent adhesion can be formed.
In addition, the content of the glycol-based solvent in the film-forming composition is based on the total mass of the solvent contained in the film-forming composition from the viewpoint of the effect of improving the coating suitability by further including the glycol-based solvent. It is preferable that it is 0.1 mass% or more.

  When the film forming composition of the present disclosure further contains a viscosity modifier, the viscosity may be adjusted by using a thickener and a solvent having a high viscosity in combination. The optimum viscosity of the film-forming composition of the present disclosure varies depending on the application method to the substrate. For example, in the case of spray coating, the viscosity of the film-forming composition is 2 mPa / s or more and 200 mPa / s or less. It is preferably 3 mPa / s or more and 100 mPa / s or less, more preferably 4 mPa / s or more and 50 mPa / s or less.

  In preparing the film forming composition, as described above, other components such as a condensation accelerating catalyst, an antistatic agent, and an adhesion improving agent can be added to the film forming composition as necessary.

  When the composition for film formation contains the specific siloxane compound and the condensation accelerating catalyst, the condensation reaction of the specific siloxane compound is promoted, and the formation of the hydrolysis condensate of the specific siloxane compound is promoted. Thereby, a hydrophilic film | membrane becomes a film | membrane excellent in scratch resistance.

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

  The amount of the condensation accelerating catalyst added to the film-forming composition is preferably 0.1% by mass to 40% by mass and more preferably 1% by mass to 30% by mass with respect to the total solid content of the film-forming composition. 5 mass%-20 mass% are still more preferable. When the content of the condensation accelerating catalyst is within the above range, it is easy to form a hydrophilic film having scratch resistance. Moreover, it is excellent also in the formation property of a hydrophilic film | membrane.

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

  It is preferable that the prepared film forming composition does not contain a photopolymerization initiator and a thermal polymerization initiator. By not using a photopolymerization initiator and a thermal polymerization initiator, light irradiation or heat treatment can be omitted when forming the hydrophilic film. Moreover, it is preferable not to contain a photoinitiator and a thermal polymerization initiator from the viewpoint of the storage stability of the film-forming composition.

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

In the method for producing a laminate of the present disclosure, the method for applying the film-forming composition to the substrate is not particularly limited, and any of a coating method, a transfer method, a dipping method, and the like may be used.
From the viewpoint of good uniformity and productivity of the film to be formed, a method of applying the film-forming composition to the substrate is preferable as a method of applying the film-forming composition to the substrate.
There is no particular limitation on the coating method for coating the film-forming composition on the substrate. For example, a known method such as spray coating, brush coating, roller coating, bar coating, dip coating (dip coating) can be applied. it can. In particular, spray coating is preferred when applying to a three-dimensional structure having various shapes such as curves and irregularities, such as in the field used for manufacturing the laminate of the present disclosure, and the laminate is highly productive. Can be manufactured.

  When the film-forming composition of the present disclosure is applied to a substrate by a spray coating method, the method for setting the substrate is not particularly limited. Depending on the shape of the substrate, the substrate can be applied while changing the direction of the substrate appropriately with respect to the application direction, such as the horizontal direction and the vertical direction. In order to make the coating film thickness uniform, it is preferable to apply the coating by applying the spray nozzle to the substrate by arranging the spray nozzle at a position where the distance between the spray nozzle and the substrate is equal. The distance is preferably 10 mm or more and 1000 mm or less.

As a method for supplying the film-forming composition of the present disclosure to the coating apparatus, any of a pumping type, a suction type, and a gravity type can be used.
The nozzle diameter of the spray nozzle is preferably 0.1 mmφ to 1.8 mmφ, and the air pressure is preferably 0.02 MPa to 0.60 MPa. By coating under such conditions, the coating film thickness can be made more uniform. In order to form a more suitable coating film by spray coating, it is sometimes necessary to adjust at least one of the air amount, the ejection amount of the film-forming composition, the pattern opening, etc. in spray coating. .

  When the film forming composition of the present disclosure is applied to a substrate by spray coating, the amount of air at the time of spray coating is preferably 5 L / min to 600 L / min, and the paint ejection amount is 5 L / min to 600 L / min. The pattern opening is preferably 40 mm or more and 450 mm or less.

In spray coating, the environment during coating also affects the formation of the coating film. The temperature condition is preferably 15 ° C. or more and 35 ° C. or less, and the humidity condition is preferably 80% RH or less.
The cleanliness is not particularly limited, but for example, from the viewpoint of suppressing surface failure due to fine particles (that is, particles) in the coating environment, the cleanliness is preferably class 10,000 or higher, and class 1,000 or higher is preferable. More preferably, it is clean.

The coating amount of the film-forming composition is not particularly limited, and should be appropriately set in consideration of operability and the like according to the solid content concentration, desired film thickness, etc. in the film-forming composition. Can do. The coating amount of the film forming composition ^is preferably ^{1mL / m 2 ~400mL / m 2} , more preferably ^{2mL / m 2 ~100mL / m 2} , 4mL / m 2 ~40mL / m 2 still more ^preferably, it is particularly preferably ^{6mL / m 2 ~20mL / m 2} . When the coating amount of the film-forming composition is within the above range, the coating accuracy tends to be good.

  The manufacturing method of the laminated body of this indication can include drying the coating film of the composition for film formation provided on the base material by application | coating etc. at the temperature of 20 to 150 degreeC.

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

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

The drying conditions for the film-forming composition are not particularly limited, and can be appropriately set in consideration of the curability of the coating film.
Drying of the film-forming composition may be performed under a constant temperature condition where a predetermined set temperature is kept constant, or the temperature condition may be changed stepwise.
The drying conditions for the film-forming composition in the former case are preferably drying conditions in which the film-forming composition is heated at a surface temperature of 20 ° C. to 150 ° C. for 1 minute to 60 minutes, and the surface temperature is 40 ° C. More preferred is a drying condition of heating at 150 ° C. or lower for 1 minute to 60 minutes, and further preferred is a drying condition of heating at a surface temperature of 60 ° C. or higher and 150 ° C. or lower for 1 minute to 60 minutes.
The film-forming composition in the latter case is preferably dried separately in preliminary drying and main drying. The conditions for the preliminary drying are preferably conditions in which the surface temperature is set to 20 ° C. or more and 60 ° C. or less and heated for 5 seconds to 10 minutes.
The surface temperature can be measured with an infrared thermometer or the like.

  When drying the film-forming composition by blowing dry air, the air volume of the dry air can be appropriately set in consideration of the optimum temperature when reaching the substrate. However, in consideration of drying unevenness, it is preferable to suppress the air volume as much as possible, and it is more preferable to perform the drying under the condition of no air, that is, the dry air does not directly hit the substrate.

  In addition, the base material which apply | coated the composition for film formation may be dried by placing directly on the pedestal (that is, flatly) and heating depending on the shape of the base material, or by standing and drying. Alternatively, it may be hung and dried.

  For cleaning the spray gun instrument parts and the coating apparatus after use for coating, a solvent such as thinner, water, alcohol, and a surfactant may be used. Further, in order to effectively clean the dirt adhered to the scale and the like, the remaining film-forming composition, and the like, it is preferable to wash using an acidic or alkaline aqueous solution, and an aqueous solution having a pH of 3.0 or less or pH 8. It is more preferable to wash with zero or more aqueous solutions. The temperature of the cleaning liquid is preferably room temperature or higher, and more preferably 50 ° C. or higher.

The storage container for the film-forming composition is not particularly limited, and may be a metal container such as a canister or a royal can, or may be a polyethylene container.
The storage temperature of the film forming composition is preferably 0 ° C. or higher and 50 ° C. or lower.

The coating after drying, that is, the formed hydrophilic film, preferably has a film thickness of 20 nm or more. When the film thickness is 20 nm or more, the hydrophilic film is more excellent in scratch resistance.
The formed hydrophilic film preferably has a thickness of 20 nm to 1 μm, more preferably 50 nm to 500 nm, and particularly preferably 75 nm to 250 nm.
Moreover, when using a hydrophilic film | membrane as an anti-fogging film | membrane, it is more preferable that they are 20 nm or more and 5000 nm or less, 50 nm or more and 1000 nm or less are still more preferable, 75 nm or more and 500 nm or less are especially preferable.

  Since the hydrophilic film in the laminate of the present disclosure is formed using the film forming composition of the present disclosure described above, the laminate of the present disclosure contains a silicone sealant in an atmosphere of 65 ° C. and 25% RH. After being placed in a constant temperature and humidity apparatus containing a glass container and held for 150 hours, the surface of the hydrophilic film is a laminate having a pure water contact angle measured at 25 ° C. of 30 ° or less.

The hydrophilic membrane of the present disclosure is used for a protective material (so-called protective cover) for protecting a surveillance camera, lighting, sensor lamp, and the like, a roof material of a garage for vehicles such as automobiles and bicycles, and a sign for road signs and the like. It is suitably used for a protective material, a soundproof wall for highway road shoulder installation or railroad use, and a transparent protective material for vehicle bodies such as automobiles and motorcycles, glass, mirrors, and headlights.
Especially, it can apply suitably for the use of the protection material (what is called a camera cover) for surveillance cameras which protects an imaging device, and the protection material of a motor vehicle (for example, headlight cover of a motor vehicle).

Embodiments of the present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless the gist of the present invention is exceeded.
In Tables 2 to 3, the components shown below may be indicated by the abbreviations shown in brackets [].

Example 1
The laminated body of Example 1 was produced by the following method.
-Preparation of hydrolyzed liquid 1A-
Each component having the following composition was mixed and stirred at 25 ° C. for 12 hours to prepare hydrolyzed liquid 1A.
(Composition 1A)
MKC (registered trademark) silicate MS-51 (Mitsubishi Chemical Corporation)
: Specific siloxane compound [MS-51] 0.63 parts by mass Distilled water [water] 2.80 parts by mass Propylene glycol monomethyl ether:
Solvent (manufactured by Nippon Emulsifier Co., Ltd., MFG)
(Hereafter, it may be called MFG.) 1.32 parts by mass / 0.1 mol / l hydrochloric acid 0.07 parts by mass

-Preparation of silica dispersion 1B-
Each component having the following composition was mixed and stirred at 25 ° C. for 1 hour to prepare silica dispersion 1B.
(Composition 1B)
・ Snowtex OUP (Nissan Chemical Co., Ltd., solid content 15%): silica particles
11.92 parts by mass-DISPERBYK (registered trademark) -2015 (by Big Chemie,
(Solid content 40%, acid value: 10 mgKOH / g)
: Specific ionic surfactant [BYK-2015])
(Content relative to total solid content of composition: 0.356004 parts by mass)
0.89 parts by mass / propylene glycol monomethyl ether: solvent [MFG]
14.52 parts by mass

-Preparation of hydrophilic coating solution 1C-
Each component having the following composition was mixed with the hydrolyzed liquid 1A obtained above to prepare a hydrophilic coating liquid 1C which is a film forming composition of the present disclosure.
Propylene glycol monomethyl ether: solvent [MFG]
72.29 parts by mass, aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluent) 3.57 parts by mass Emalex 715 (manufactured by Nippon Emulsion Co., Ltd.,
MFG 10% by weight diluent: specific nonionic surfactant,
(HLB: 15.6) 1.32 parts by mass. 1.32 parts by mass of di (2-ethylhexyl) sulfosuccinate sodium (manufactured by NOF, water / MFG mixed solvent (mixing ratio, 1: 4 (mass basis))
0.2% by weight diluted solution): antistatic agent,
Content based on total solid content of composition: 0.00264 parts by mass)
Silica dispersion 1B (dispersion obtained above) 13.66 parts by mass Polyacrylic acid (molecular weight 250,000: adhesion aid,
MFG 0.1% by weight diluted solution) [PA] 3.00 parts by mass

-Fabrication of laminates-
The obtained hydrophilic coating solution 1C was spray gun (Anest Iwata, W-101) on one surface of a polycarbonate substrate (Carbo Glass C-110, Asahi Glass Co., Ltd., thickness: 0.5 mm) as a base material. -101G), allowed to stand at 30 ° C. for 10 minutes, and then dried at 120 ° C. for 20 minutes to obtain a laminate having a hydrophilic film with a thickness of 100 nm after drying on the substrate.
The polycarbonate substrate was abbreviated as “PC” in Tables 2 to 3.

-Evaluation-
The following measurements or evaluations were performed using the prepared laminate. The evaluation results are shown in Tables 2 to 3 below.

(1) Pure water contact angle The pure water contact angle was obtained by dropping 1 μl of pure water onto the surface of the hydrophilic film in the laminate at 25 ° C. using a contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). , Θ / 2 method. The same measurement was performed 5 times, and the arithmetic average value was defined as the pure water contact angle of the hydrophilic membrane. The results are shown in Tables 2 to 3 below.
The smaller the value of the pure water contact angle, the better the surface hydrophilicity, and the allowable value was a pure water contact angle of 30 ° or less.

(2) Contact angle of pure water after lapse of hydrophobic component coexistence In the constant temperature and humidity device SH-641 manufactured by Espec, the laminate obtained in Example 1 and silicone sealant 1527W (manufactured by Tianshan New Materials Co., Ltd.) The glass container was put in and sealed, kept at 65 ° C. and 25% RH, left for 150 hours, and coexisting with the hydrophobic component and aged.
Then, the pure water contact angle was measured about the hydrophilic film | membrane of the laminated body similarly to the measuring method of (1) pure water contact angle. The results are shown in Tables 2 to 3 below.
It is evaluated that a decrease in surface hydrophilicity is suppressed as the value of the pure water contact angle after the coexistence with the hydrophobic component is smaller. The pure water contact angle after the coexistence with the hydrophobic component was 30 ° or less as an allowable value.

(3) Haze Using a haze meter NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the composition for film formation of the present disclosure is placed on a Carboglass C-110 manufactured by Asahi Glass Co., Ltd., on a polycarbonate substrate having a thickness of 0.5 mm. The haze of the laminate having a hydrophilic film with a film thickness of 100 nm prepared by applying was measured. The results are shown in Tables 2 to 3 below.
In addition, the measurement of the haze was performed by directing the substrate surface of the laminate, that is, the surface having no hydrophilic film, to the light source. The smaller the haze value, the better the laminate has better transparency.

(4) Adhesiveness Based on JIS K5600, the hydrophilic film in the laminate was subjected to a 25-mass cross-cut test and evaluated according to the following evaluation criteria. In this cross-hatch test, the cut interval was 2 mm, and 25 square grids of 2 mm square were formed. The results are shown in Tables 2 to 3 below.
Ranks A and B are levels that are not problematic in practice.
A: There is no peeling visually recognized over the entire surface.
B: Slight peeling is observed on the cut line of the cross cut.
C: Slight peeling is observed at the crossing portion of the crosscut.
D: Peeling is recognized in one or more squares of the cross cut.

(5) Coating suitability: Evaluation of liquid dripping On a polycarbonate substrate (200 mm × 200 mm × 0.5 mm thickness) as a base material, the hydrophilic coating liquid C1 which is the film forming composition obtained in Example 1 is applied to a spray gun. After coating and standing at room temperature (25 ° C.) for 30 seconds, the surface of the hydrophilic film after being dried at 120 ° C. for 20 minutes in a vertically tilted state is visually observed and evaluated as follows. Evaluation was based on criteria. The results are shown in Tables 2 to 3 below.
Ranks A and B are levels that are not problematic in practice.
A: There is no sag observed visually over the entire surface.
B: Although there is no big dripping, fine dripping can be visually recognized slightly. Specifically, a sagging trace having a width of less than 1 cm and a length of less than 1 cm can be visually recognized.
C: A large sag is visually recognized. Specifically, a sagging trace having a width of 1 cm or more and a length of 1 cm or more can be visually recognized.

(Examples 2 to 12, Comparative Examples 1 to 6)
In Example 1, a laminate having a hydrophilic film was produced in the same manner as in Example 1 except that the various components were changed to the formulations shown below. Further, measurement and evaluation were performed in the same manner as in Example 1.
Tables 2 to 3 show the main components of the film-forming composition, the results of measurement and evaluation. In Tables 2 to 3, “-” indicates that the component is not included.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that the silica dispersion 1B was changed to the silica dispersion 2B having the following composition.
-Composition of silica dispersion 2B-
-Snowtex OUP 11.92 mass parts-Dispers 660C (acid value: 30 mgKOH / g):
Specific ionic surfactant (EVONIK, MFG 40% by weight dilution)
0.89 parts by mass / MFG: 14.54 parts by mass of solvent

(Example 3)
A laminate was obtained in the same manner as in Example 1 except that the silica dispersion 1B was changed to the silica dispersion 3B having the following composition.
-Composition of silica dispersion 3B-
Snowtec OUP 11.92 parts by mass DISPERBYK (registered trademark) -180 (acid value: 94 mgKOH / g)
: Specific nonionic surfactant [BYK-180] (by Big Chemie,
MFG 40% by weight diluted solution) 0.89 parts by mass MFG: solvent 14.52 parts by mass

Example 4
A laminate was obtained in the same manner as in Example 1 except that the silica dispersion 1B was changed to the silica dispersion 4B having the following composition.
-Composition of silica dispersion 4B-
Snowtech OUP 11.92 parts by mass BYK-P104 (acid value: 180 mgKOH / g):
Specific nonionic surfactant (by Big Chemie, MFG 40% by weight dilution)
0.89 parts by mass / MFG: 14.54 parts by mass of solvent

(Example 5)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to the hydrophilic coating solution 5C having the following composition.
-Composition of hydrophilic coating solution 5C-
-MFG: Solvent 60.40 parts by mass-Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluted solution) 3.57 parts by mass / Reodol TW-P120 (manufactured by Kao Corporation, MFG 1% by weight diluted solution: specific nonionic surfactant: HLB: 15.6) 13.21 parts by mass / di ( 2-Ethylhexyl) sodium sulfosuccinate 1.32 parts by mass (manufactured by NOF, water / MFG 0.2% by weight dilution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Example 6)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to the hydrophilic coating solution 6C having the following composition.
-Composition of hydrophilic coating solution 6C-
MFG: Solvent 60.40 parts by mass Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd., MFG 10% by mass)
Diluent) 3.57 parts by mass Emalex 720 (manufactured by Nippon Emulsion Co., Ltd., MFG 1% by weight diluent)
: Specific nonionic surfactant HLB: 16.5) 13.21 parts by mass / di (2-ethylhexyl) sodium sulfosuccinate 1.32 parts by mass (manufactured by NOF, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Example 7)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to a hydrophilic coating solution 7C having the following composition.
-Composition of hydrophilic coating solution 7C-
MFG: Solvent 60.40 parts by mass Aluminum chelate D (manufactured by Kawaken Fine Chemicals Co., Ltd., 3.57 parts by mass MFG 10% by weight diluted solution)
・ Emalex 730 (manufactured by Nippon Emulsion Co., MFG 1% by weight dilution)
: Specific nonionic surfactant HLB: 17.5 13.21 parts by mass. Sodium di (2-ethylhexyl) sulfosuccinate 1.32 parts by mass (manufactured by NOF, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Example 8)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to a hydrophilic coating solution 8C having the following composition.
-Composition of hydrophilic coating solution 8C-
-MFG: Solvent 60.40 parts by mass-Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluent) 3.57 parts by mass Emalex 750 (manufactured by Nippon Emulsion Co., Ltd., MFG 1% by weight diluent)
: Specific nonionic surfactant HLB: 18.4 13.21 parts by mass / di (2-ethylhexyl) sodium sulfosuccinate 1.32 parts by mass (manufactured by NOF, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

Example 9
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to a hydrophilic coating solution 9C having the following composition.
-Composition of hydrophilic coating solution 9C-
-MFG: Solvent 60.40 parts by mass-Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluent) 3.57 parts by mass PEG2000 (manufactured by Shonan Wako Pure Chemical Industries, Ltd., MFG 1% by weight diluent)
: Specific nonionic surfactant HLB: 19.9 3.21 parts by mass / di (2-ethylhexyl) sodium sulfosuccinate 1.32 parts by mass (manufactured by NOF, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Example 10)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to the hydrophilic coating solution 10C having the following composition.
-Composition of hydrophilic coating solution 10C-
MFG: solvent 33.17 parts by mass Diacetone alcohol: solvent 39.12 parts by mass Aluminum chelate D (manufactured by Kawaken Fine Chemicals Co., Ltd., 3.57 parts by mass MFG 10% by weight diluted solution)
・ Emalex 715 (manufactured by Nippon Emulsion Co., MFG 1% by weight dilution)
: Specific nonionic surfactant HLB: 15.6 parts by mass 1.32 parts by weight of sodium di (2-ethylhexyl) sulfosuccinate 1.32 parts by weight (manufactured by NOF, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Example 11)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to the hydrophilic coating solution 11C having the following composition.
-Composition of hydrophilic coating solution 11C-
MFG: solvent 28.28 parts by mass Diacetone alcohol: solvent 39.12 parts by mass Propylene glycol: solvent 4.89 parts by mass Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluent) 3.57 parts by mass Emalex 715 (manufactured by Nippon Emulsion Co., Ltd., MFG 1% by weight diluent)
: Specific nonionic surfactant HLB: 15.6 parts by mass 1.32 parts by weight of sodium di (2-ethylhexyl) sulfosuccinate 1.32 parts by weight (manufactured by NOF Corporation, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Example 12)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to the hydrophilic coating solution 12C having the following composition.
-Composition of hydrophilic coating solution 12C-
MFG: solvent 16.39 parts by mass Diacetone alcohol: solvent 39.12 parts by mass Propylene glycol: solvent 4.89 parts by mass Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluent) 3.57 parts by mass Emalex 715 (manufactured by Nippon Emulsion Co., Ltd., MFG 1% by weight diluent)
: Specific nonionic surfactant HLB: 15.6 parts by mass 1.32 parts by weight of sodium di (2-ethylhexyl) sulfosuccinate 1.32 parts by weight (manufactured by NOF Corporation, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to a comparative hydrophilic coating solution 13C having the following composition.
-Composition of comparative hydrophilic coating solution 13C-
-MFG: Solvent 67.61 parts by mass-Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.)
MFG 10% by weight diluted solution) 3.57 parts by mass di (2-ethylhexyl) sodium sulfosuccinate 1.32 parts by mass (manufactured by NOF Corporation, water / MFG 0.2% by weight diluted solution)
Silica dispersion (similar to that obtained in Example 1) 3.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight diluted solution)

(Comparative Example 2)
A laminate was obtained in the same manner as in Example 1 except that the silica dispersion 1B in Example 1 was changed to a comparative silica dispersion 14B having the following composition.
-Composition of Comparative Silica Dispersion 14B-
・ Snowtex OUP (Nissan Chemical Co., Ltd., solid content 15% by mass)
11.92 parts by mass / sodium di (2-ethylhexyl) sulfosuccinate 0.89 parts by mass (manufactured by NOF Corporation, MFG 40% by weight diluted solution)
* MFG: Solvent 14.52 mass parts

(Comparative Example 3)
A laminate was obtained in the same manner as in Example 1 except that the silica dispersion 1B in Example 1 was changed to a comparative silica dispersion 15B having the following composition.
-Composition of Comparative Silica Dispersion 15B-
・ Snowtex OUP (Nissan Chemical Co., Ltd., solid content 15% by mass)
11.92 parts by mass-DISPERBYK (registered trademark) -184 0.89 parts by mass (by Big Chemie, MFG 40% by weight diluted solution)
* MFG: Solvent 14.52 mass parts

(Comparative Example 4)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to a comparative hydrophilic coating solution 16C having the following composition.
-Composition of comparative hydrophilic coating solution 16C-
-MFG: Solvent 72.29 parts by mass-Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluted solution) 3.57 parts by mass Emalex 705 (manufactured by Nippon Emulsion Co., Ltd., MFG 10% by weight diluted solution)
: Comparative nonionic surfactant HLB: 10.8 1.32 parts by mass. Sodium di (2-ethylhexyl) sulfosuccinate (manufactured by NOF Corporation, water / MFG 0.2% by mass diluted solution) 1.32 parts by mass Silica dispersion (similar to that obtained in Example 1) 13.66 parts by mass Polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

(Comparative Example 5)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to a comparative hydrophilic coating solution 17C having the following composition.
-Composition of comparative hydrophilic coating solution 17C-
-MFG: Solvent 72.29 parts by mass-Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluted solution) 3.57 parts by mass Cotamin 24P (Made by Kao, MFG 10% by weight diluted solution)
: Comparative surfactant 1.32 parts by mass / di (2-ethylhexyl) sodium sulfosuccinate (manufactured by NOF Corporation, water / MFG 0.2% by mass diluted solution) 1.32 parts by mass / silica dispersion (Example 1) 13.66 parts by mass of polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight diluted solution)

(Comparative Example 6)
A laminate was obtained in the same manner as in Example 1 except that the hydrophilic coating solution 1C in Example 1 was changed to a comparative hydrophilic coating solution 17C having the following composition.
-Composition of comparative hydrophilic coating solution 17C-
-MFG: Solvent 72.29 parts by mass-Aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd.,
MFG 10% by weight diluted solution) 3.57 parts by mass Amphital 20N (manufactured by Kao Corporation, MFG 10% by weight diluted solution)
: Comparative surfactant 1.32 parts by mass MFG 10% by weight diluted solution)
・ Sodium di (2-ethylhexyl) sulfosuccinate (manufactured by NOF Corporation, water / MFG 0.2% by mass diluted solution) 1.32 parts by mass. Silica dispersion (same as that obtained in Example 1) 13.66 Part by mass / polyacrylic acid: molecular weight 250,000 3.00 parts by mass (MFG 0.1% by weight dilution)

As shown in Tables 2 to 3, the film forming compositions obtained in the examples have good coating suitability, do not cause dripping during spray coating, and are obtained from the film forming compositions. It can be seen that the hydrophilic film in the laminate having the hydrophilic film has good transparency, shows good hydrophilicity, and suppresses the decrease in hydrophilicity after the coexistence with the hydrophobic component.
In addition, from comparison with Example 1- Example 9 and Example 10- Example 12, in addition to the effect as stated above, the film-forming composition contains a ketone solvent, and further, a substrate and a formation. It can be seen that the adhesion to the formed film is further improved.
On the other hand, in Comparative Examples 1 to 6, the hydrophilic film surface obtained initial hydrophilicity to some extent, but a decrease in hydrophilicity was observed after coexistence with the hydrophobic component. The composition for film shape of the comparative example was inferior in the effect of suppressing the decrease in hydrophilicity compared to the composition for film shape of the example.

(Example 13 to Example 24)
-Production of surveillance camera cover-
A housing replacement cover RCP7C for an outdoor dome housing A-ODP7C1A for a network camera manufactured by Sony Corporation was prepared. W-101-101G) was applied by spraying and dried at 120 ° C. for 20 minutes to obtain a surveillance camera cover having a hydrophilic film having a thickness (film thickness after drying) of 100 nm formed on the inner surface.

-Evaluation-
(Anti-fogging property)
Applying steam from warm water heated to 60 ° C. for 2 minutes to the inner surface (surface having a hydrophilic film) of the surveillance camera cover produced above, and then observing the appearance visually, antifogging properties evaluated. When the steam was applied, the distance between the hot water surface and the coating surface was 50 mm.
As a comparison, a surveillance camera cover (uncoated product) not coated with the antifogging film composition was prepared, and the same operation was performed.
As a result, although the uncoated product was clouded by steam, the surveillance camera cover in which the hydrophilic film was formed by the film-forming composition of Examples 1 to 12 did not fog, and was not fogged. It can be seen that a film excellent in property, that is, hydrophilicity is formed.

(Example 25 to Example 36)
-Production of headlight cover-
A W219 repair headlight lens manufactured by Office Kei Co., Ltd. was prepared, and the film-forming compositions obtained in Examples 1 to 12 were applied to a spray gun (Anest Iwata, W-101-101G). A headlight lens on which a hydrophilic film having a thickness (film thickness after drying) of 100 nm is formed by spraying and coating on the inner surface of the headlight lens under the same conditions as above and drying at 120 ° C. for 20 minutes. Produced.

-Evaluation-
(Anti-fogging property)
Applying steam from warm water heated to 60 ° C. to the inner surface (surface having a hydrophilic film) of the headlight cover produced above for 2 minutes, and then visually observing the appearance, anti-fogging properties are achieved. evaluated. When the steam was applied, the distance between the hot water surface and the coating surface was 50 mm.
As a comparison, a headlight cover (uncoated product) not coated with the antifogging film composition was prepared, and the same operation was performed.
As a result, the uncoated product was clouded by steam, but the headlight covers in which the hydrophilic film was formed by the film forming compositions of Examples 1 to 12 were not fogged and were not fogged. It can be seen that a film excellent in property, that is, hydrophilicity is formed.

The disclosure of Japanese Patent Application No. 2016-121287 filed on June 17, 2016 is incorporated herein by reference.
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 (7)

A hydrolyzate of a siloxane compound represented by the following general formula (1), silica particles, an ionic surfactant having at least one of a phosphate group and a carboxy group, and a hydrophilic / lipophilic balance value greater than 15. A film-forming composition comprising an ionic surfactant and water.

In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 2 to 20.   The film-forming composition according to claim 1, wherein an acid value of the ionic surfactant having at least one of the phosphoric acid group and the carboxy group is 180 mgKOH / g or less.   The film forming composition according to claim 1, wherein the nonionic surfactant has a polyoxyalkylene group.   Furthermore, the composition for film formation of any one of Claims 1-3 containing a ketone solvent. A base material, a hydrolysis condensate of a siloxane compound represented by the following general formula (1), silica particles, and an ionic surfactant having at least one of a phosphate group and a carboxy group on the base material; A non-ionic surfactant having a hydrophilic / lipophilic balance value greater than 15, and a hydrophilic film containing the laminate,
The laminate was placed in a constant temperature and humidity apparatus containing a glass container containing a silicone sealant in an atmosphere of 65 ° C. and 25% RH, and after maintaining for 150 hours, the surface of the hydrophilic film was kept at 25 ° C. A laminate having a pure water contact angle measured by measuring 30 ° or less.

In General Formula (1), R ¹ , R ² , R ³ , and R ⁴ each independently represent a monovalent organic group having 1 to 6 carbon atoms. n represents an integer of 2 to 20.   The manufacturing method of a laminated body including providing the film forming composition of any one of Claims 1-4 on a base material, and obtaining a hydrophilic film | membrane.   The laminate was placed in a thermo-hygrostat with a glass container containing a silicone sealant in an atmosphere of 65 ° C. and 25% RH, and after maintaining for 150 hours, the surface of the hydrophilic film was kept at 25 ° C. The method for producing a laminate according to claim 6, wherein the laminate has a pure water contact angle measured by measuring 30 ° or less.