JP7179701B2 - Anti-fogging laminate and method for producing anti-fogging laminate - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to anti-fogging laminates and methods of manufacturing anti-fogging laminates.

Equipment and building materials that are installed indoors and outdoors and used for a long period of time are likely to be exposed to various environments. function and performance may not be maintained. As a technique for solving such a situation, for example, a technique for making the surface texture hydrophilic is being studied.

As a technique for making the surface property hydrophilic, a method of applying a hydrophilic layer to the target surface is known. materials (water-absorbing materials) and the like have been widely studied.

A hydrophilic material facilitates the formation of a water film on the surface of the material, thereby preventing the formation of water droplets that cause fogging. That is, the antifogging property becomes good. However, when the amount of adhering water is large, the thickness of the water film increases. Along with this, there are problems such as dripping of water droplets and problems such as deterioration of transparency due to fluctuations in transmission images, and their applications have been limited.

On the other hand, water-absorbing polymers are widely used for water-absorbing materials, and the water-absorbing polymers absorb water to prevent the formation of water droplets that cause fogging. However, since the material that absorbs water and swells is inferior in mechanical strength, there is a problem that it cannot be applied to applications involving frequent physical contact.

In addition, since the hydrophilic film has lipophilic properties, there is a problem that human-induced stains (sweat, fingerprints, etc.) tend to adhere to it.

As a technique focusing on antifogging properties, for example, Patent Document 1 discloses a cellulose ester film, a hydrophilic heat ray reflective layer laminated on one side of the cellulose ester film, and a hydrophilic heat ray reflecting layer laminated on one side of the cellulose ester film. and an antifogging layer formed by a heat treatment is described. Further, in Patent Document 2, in an antifogging agent composition comprising a copolymer, a polyfunctional block isocyanate compound, and a surfactant, the surfactant is 1 part by weight to 1 part by weight with respect to 100 parts by weight of the copolymer. It is described as containing 10 parts by weight of a betaine surfactant and 0.01 to 3 parts by weight of a cationic surfactant.

WO2015/083479 JP 2017-165886 A

However, the anti-fogging film disclosed in Patent Document 1 and the anti-fogging film formed using the anti-fogging agent composition disclosed in Patent Document 2 have anti-fogging properties, but transparency and scratch resistance. No consideration is given to compatibility between the properties, water drip resistance, and antifouling properties.

The present disclosure has been made in view of such circumstances. An object of the present invention is to provide an antifogging laminate excellent in stain resistance and a method for producing the antifogging laminate.

Specific means for solving the above problems include the following aspects.
<1> It has a water-absorbing resin layer and a hydrophilic oil-repellent layer disposed on the water-absorbing resin layer, and the hydrophilic oil-repellent layer contains a binder, a betaine-type fluorine compound and inorganic particles, or a binder and an anionic An antifogging laminate comprising a fluorine compound and anionic inorganic particles, or comprising a binder, a cationic fluorine compound and cationic inorganic particles.
<2> The antifogging laminate according to <1>, wherein the hydrophilic oil-repellent layer contains a binder, a betaine-type fluorine compound and inorganic particles, and the inorganic particles are silica particles or alumina particles.
<3> The antifogging laminate according to <1>, wherein the hydrophilic oil-repellent layer contains a binder, an anionic fluorine compound and anionic inorganic particles, and the anionic inorganic particles are silica particles.
<4> The antifogging laminate according to <1>, wherein the hydrophilic oil-repellent layer contains a binder, a cationic fluorine compound and cationic inorganic particles, and the cationic inorganic particles are alumina particles.
<5> The antifogging laminate according to <1> or <2>, wherein the content of the betaine-type fluorine compound is 0.5% by mass to 10% by mass with respect to the total amount of the hydrophilic oil-repellent layer.
<6> The antifogging laminate according to <1>, <2> or <5>, wherein the content of the inorganic particles relative to the content of the betaine-type fluorine compound is 0.5 to 30 on a mass basis.
<7> The antifogging laminate according to <1>, wherein each of the inorganic particles, the anionic inorganic particles, and the cationic inorganic particles has a primary particle size of 100 nm or less.
<8> The anti-fogging laminate according to any one of <1> to <7>, which has a non-water-absorbent support on the side opposite to the hydrophilic oil-repellent layer of the water-absorbent resin layer. .
<9> The antifogging property according to any one of <1> to <8>, which has an adhesive layer as the outermost layer on the side opposite to the side on which the hydrophilic oil-repellent layer of the water-absorbent resin layer is arranged. laminate.
<10> A coating liquid containing a binder, a betaine-type fluorine compound and inorganic particles, a coating liquid containing a binder, an anionic fluorine compound and anionic inorganic particles, or a coating liquid containing a binder, a cationic fluorine compound and cationic inorganic particles onto the water absorbent resin layer.

According to the present disclosure, an anti-fogging laminate having good anti-fogging properties and excellent transparency, scratch resistance, drip resistance, and antifouling properties, and a method for producing the anti-fogging laminate are provided. can be done.

FIG. 1 is a cross-sectional view showing an example of the lamination structure of an antifogging laminate in which the water-absorbing resin layer also serves as a support. FIG. 2 is a cross-sectional view showing an example of the lamination structure of an antifogging laminate in which a water-absorbing resin layer is provided on a non-water-absorbing support.

Hereinafter, the anti-fogging laminate and the method for producing the anti-fogging laminate of the present disclosure will be described in detail.

In this specification, the numerical range indicated using "to" means a range including the numerical values before and after "to" as the minimum and maximum values, respectively.
In the numerical ranges described stepwise in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. Moreover, in the numerical ranges described in this specification, the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.

As used herein, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means
In the present specification, a combination of two or more preferred aspects is a more preferred aspect.
In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. be
As used herein, "water absorption" means a water absorption rate of 12% or more as measured according to A method described in JIS K 7209:2000.

As used herein, "(meth)acrylate" is a concept that includes both acrylate and methacrylate. Moreover, "(meth)acryl" is a concept that includes both acryl and methacryl.

[Anti-fogging laminate]
The antifogging laminate of the present disclosure has a water-absorbing resin layer and a hydrophilic oil-repellent layer disposed on the water-absorbing resin layer, and the hydrophilic oil-repellent layer contains a binder, a betaine-type fluorine compound, and inorganic particles. or comprises a binder, an anionic fluorine compound and anionic inorganic particles; or comprises a binder, a cationic fluorine compound and cationic inorganic particles.

Anti-fogging materials are divided into a hydrophilic type and a water-absorbing type. In a hydrophilic material, when a large amount of water adheres, the thickness of the water film increases. Along with this, there are problems such as dripping of water droplets and problems such as deterioration of transparency due to fluctuations in transmitted images, and the use thereof has been limited. On the other hand, water-absorbing polymers are widely used for water-absorbing materials. there were. In addition, since the hydrophilic film has lipophilic properties, there is a problem that human-induced stains (sweat, fingerprints, etc.) tend to adhere to it.

In contrast, the antifogging laminate of the present disclosure has a water-absorbent resin layer and a hydrophilic oil-repellent layer disposed on the water-absorbent resin layer, and the hydrophilic oil-repellent layer comprises a binder, a betaine-type fluorine Since it contains a compound and inorganic particles, or contains a binder, an anionic fluorine compound and anionic inorganic particles, or contains a binder, a cationic fluorine compound and cationic inorganic particles, it has good antifogging properties, Excellent transparency, scratch resistance, drip resistance and stain resistance. In particular, in any combination of a betaine-type fluorine compound and inorganic particles, a combination of an anionic fluorine compound and anionic inorganic particles, and a combination of a cationic fluorine compound and cationic inorganic particles, they aggregate with each other. Since there is no haze, it has excellent transparency.

Patent Documents 1 and 2 above do not disclose a technique for combining a fluorine compound and inorganic particles so as not to agglomerate with each other, and cannot achieve properties other than anti-fog properties at the same time.

A specific embodiment of the antifogging laminate of the present disclosure will be described with reference to FIGS. 1 and 2. FIG.

The anti-fogging laminate 10 shown in FIG. 1 is an embodiment in which the water-absorbent resin layer also serves as a support. Specifically, the antifogging laminate 10 includes a water absorbent support 14 as a water absorbent resin layer, a hydrophilic oil-repellent layer 12 provided on one surface of the water absorbent support 14, and a water absorbent support 14. and an adhesive layer 16 provided on the other surface.

The antifogging laminate 20 shown in FIG. 2 is an embodiment in which the water-absorbing resin layer and the support are provided as separate layers. Specifically, the anti-fogging laminate 20 comprises a water-absorbent resin layer 24 and a hydrophilic oil-repellent layer 22 in this order on a non-water-absorbent support 26, and the water-absorbent resin layer 24 of the support 26 is An adhesive layer 28 is provided on the side opposite to the arranged side.

Hereinafter, details of each layer in the antifogging laminate of the present disclosure will be described.

(Water absorbent resin layer)
The water-absorbing resin layer is not particularly limited as long as it contains at least a resin and has water-absorbing properties. The water absorbent resin layer may be a single layer containing a water absorbent resin (water absorbent resin), or may be a plurality of layers.

The term "water absorption" in the absorbent resin layer refers to a property of 12% or more in water absorption measured according to Method A described in Japanese Industrial Standards (JIS) K 7209:2000.
Therefore, the water absorbent resin in the present disclosure refers to a resin with a water absorption rate of 12% or more, and a resin with a water absorption rate of less than 12% is distinguished from the water absorbent resin in the present disclosure as a non-water absorbent resin.

Examples of water absorbent resins include cellulose-based resins, polyvinyl alcohol-based resins, polyvinyl acetal-based resins, polyvinylpyrrolidone-based resins, polyvinyl acetate-based resins, and polyvinylacetamide-based resins. In addition, the cellulose-based resin refers to a resin containing at least cellulose, and the same applies to other resins.
Among them, cellulose-based resins are preferable from the viewpoint of excellent water absorption.

Cellulosic resins include, for example, triacetyl cellulose (TAC), nitrocellulose, hydroxypropyl cellulose, and hydroxyethyl cellulose. The cellulose-based resin may be a commercial product on the market. Commercially available products include, for example, saponified triacetyl cellulose manufactured by Tochisen Co., Ltd. (saponified TAC, saponified layer thickness: 0.5 μm, water absorption: 5%), and Sumitomo Seika Co., Ltd. HEC AL-15 (hydroxyethyl cellulose)”.

Polyvinyl alcohol-based resins include, for example, polyvinyl alcohol and partially saponified polyvinyl alcohol. The polyvinyl alcohol-based resin may be a commercial product on the market. Commercially available products include Kuraray Poval series manufactured by Kuraray Co., Ltd., for example.

Examples of polyvinyl acetal-based resins include polyvinyl acetal and polyvinyl butyral. The polyvinyl acetal-based resin may be a commercial product on the market. Commercially available products include, for example, “S-Lec (polyvinyl acetal)” manufactured by Sekisui Chemical Co., Ltd.

Examples of polyvinylpyrrolidone-based resins include polyvinylpyrrolidone and vinylpyrrolidone-vinyl acetate copolymers. The polyvinylpyrrolidone-based resin may be a commercial product on the market. Commercially available products include, for example, "Pitzcol (polyvinylpyrrolidone)" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

Examples of polyvinyl acetate-based resins include polyvinyl acetate and vinylpyrrolidone-vinyl acetate copolymers. The polyvinyl acetate-based resin may be a commercial product on the market. Examples of commercially available products include "PVP/VA S-630 (vinylpyrrolidone-vinyl acetate copolymer)" manufactured by Ashland Japan.

Examples of polyvinylacetamide-based resins include poly-N-vinylacetamide. The polyvinylacetamide-based resin may be a commercial product on the market. Commercially available products include, for example, "GE191 (poly-N-vinylacetamide)" manufactured by Showa Denko.

The water absorbent resin layer may contain only one type of absorbent resin, or may contain two or more types.

The water-absorbing resin layer may be a resin layer containing a water-absorbing resin, a water-absorbing resin molding, or a laminate having a water-absorbing resin molding and a water-absorbing surface treatment layer.

The resin layer containing a water-absorbing resin includes, for example, a resin layer formed by preparing a coating liquid containing a water-absorbing resin and a solvent and coating the coating liquid on a non-water-absorbing support.

Examples of molded products of the water absorbent resin include films or sheets obtained by molding the water absorbent resin into a film (for example, by melt extrusion).

As a laminate having a water-absorbing resin molding and a water-absorbing surface treatment layer, for example, a film or sheet formed by molding a water-absorbing resin into a film (for example, by melt extrusion) is subjected to a hydrophilic treatment, and the surface has a surface. One having a treated layer formed thereon can be mentioned. Here, the hydrophilization treatment includes, for example, saponification treatment and oxygen plasma treatment.

The saponification method is not particularly limited, and known methods can be applied.
As a saponification treatment method, for example, a method of immersing the film in an alkaline aqueous solution can be mentioned. The alkaline aqueous solution includes, for example, an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide. As the film used in the saponification method, a cellulose ester film is preferred, and a triacetyl cellulose film is more preferred. That is, in the antifogging laminate of the present disclosure, it is preferable to use a triacetyl cellulose film having a saponified layer on at least one surface as the water absorbent resin layer.

The concentration of the alkaline component in the alkaline aqueous solution and the immersion time of the film in the alkaline aqueous solution are not particularly limited, and can be appropriately set according to the design thickness of the surface treatment layer and the type of film.

The thickness of the surface treatment layer is preferably 5 μm to 15 μm, more preferably 5 μm to 12 μm, from the viewpoint of water absorption. Layer thickness is measured in the following manner. First, an arithmetic average value of thicknesses measured at ten randomly selected locations is obtained in a cross-sectional observation image in the thickness direction. The obtained value is taken as the thickness of the layer. A cross-sectional observation image in the thickness direction of the layer can be obtained using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Any layer in the present disclosure can be measured in a similar manner.

The thickness of the water-absorbing resin layer may be appropriately selected depending on the application, purpose or structure. When the anti-fogging laminate of the present disclosure has the structure shown in FIG. 1, the thickness is preferably several tens of μm to several hundreds of μm from the viewpoint of ensuring water absorption ability and functioning as a support. 20 μm to 400 μm is more preferable. Further, when the anti-fogging laminate of the present disclosure has the structure shown in FIG. 2, from the viewpoint of ensuring water absorption, the thickness is preferably several μm to several tens of μm, more preferably 5 μm to 30 μm.

(Hydrophilic oil-repellent layer)
The hydrophilic oil-repellent layer is a layer arranged on the water absorbent resin layer. The hydrophilic oil-repellent layer contains a binder, a betaine-type fluorine compound and inorganic particles, a binder, an anionic fluorine compound and anionic inorganic particles, or a binder, a cationic fluorine compound and cationic inorganic particles.

From the viewpoint of transparency, the thickness of the hydrophilic oil-repellent layer is preferably 100 nm to 10 μm, more preferably 200 nm to 8 μm.

<When binder, betaine-type fluorine compound and inorganic particles are included>
A case where the hydrophilic oil-repellent layer contains a binder, a betaine-type fluorine compound, and inorganic particles will be described.

- Betaine-type fluorine compounds -
The betaine-type fluorine compound used in the hydrophilic oil-repellent layer in the antifogging laminate of the present disclosure is not particularly limited as long as it is a fluorine compound having an anion structure and a cation structure in one molecule. The antifogging laminate of the present disclosure is excellent in antifouling properties because the hydrophilic oil-repellent layer contains a betaine-type fluorine compound that exhibits a hydrophilic oil-repellent function.

The hydrophilic oil-repellent layer in the present disclosure may contain only one betaine-type fluorine compound, or may contain two or more betaine-type fluorine compounds.

The betaine-type fluorine compounds used in the present disclosure may be of the carbobetaine, sulfobetaine, amine oxide betaine or phosphobetaine type. From the viewpoint of antifogging properties, the betaine-type fluorine compound is preferably a compound represented by the following formula (1).

In formula (1), Rf ¹ and Rf ² are each independently a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.

A perfluoroalkyl group refers to a group in which all hydrogen atoms of an alkyl group are substituted with fluorine. A perfluoroalkylene group refers to a group in which all hydrogen atoms of an alkylene group are substituted with fluorine. Examples of perfluoroalkyl groups include trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, nonafluoro-n-butyl group, nonafluoroisobutyl group, undecafluoro-n- Pentyl groups and tridecafluoro-n-hexyl groups are included.

In Formula (1), R is a divalent organic group. R may be linear or branched. Also, R may contain one or more bonds selected from an ether bond, an ester bond, an amide bond and a urethane bond in the molecular chain. The divalent organic group is preferably an alkylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 30 carbon atoms, and an alkylene group having 2 to 20 carbon atoms. is more preferred, and an alkylene group having 2 to 8 carbon atoms is particularly preferred.

When R is an alkylene group, the alkylene group may have a linear structure, a branched structure, or a cyclic structure. Examples of the alkylene group include -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -CH ₂ -, -CH ₂ C(CH ₃ ) ₂ CH ₂ -, -C ₆ H ₁₂ - , -C ₄ H ₇ (C ₄ H ₉ )C ₄ H ₈ -, -C ₁₈ H ₃₆ -, 1,4-trans-cyclohexylene group, -C ₂ H ₄ -OCO-NH-C ₂ H ₄ - , -C ₂ H ₄ -OCO-C ₂ H ₄ -, -C ₂ H ₄ -O-, -C ₂ H ₄ -O-C ₅ H ₁₀ -O-, -C ₂ H ₄ -NH-COO- , -C ₂ H ₄ -O-CH ₂ -CH(OH)-CH ₂ -OCO-, -CH ₂ -CH(OH)-CH ₂ -, -C ₂ H ₄ -OCO-, -C ₂ H ₄ -O- _C5H10- , _-CH2 -O _{- C5H9 ( C5H11} )-, _{-C2H4 -} NH _- COO _{- C2H4-} , _{-C2H4 -} CONH _-C2H4- , _{-C4H8 - OCONH - C6H12-} , _{-CH2 - OCONHC10H20-} , _-CH2CH (OH)CH2- _, and -CONH _{- C3H6} - includes.

Arylene groups include, for example, phenylene groups, biphenylene groups, —C ₆ H ₄ —CO—C ₆ H ₄ —, —C ₆ H ₄ —S—, and naphthylene groups.

The aralkylene group includes, for example, -C ₃ H ₆ -C ₆ H ₄ -, -C ₂ H ₄ -C ₆ H ₄ -C ₆ H ₄ -, -CH ₂ -C ₆ H ₄ -C ₆ H ₄ - Mention may be made of C ₂ H ₄ -, -C ₂ H ₄ -OCO-C ₆ H ₄ -, and -C ₂ H ₄ -O-C ₂ H ₄ -C ₆ H ₄ -S-.

In formula (1), X is a group having any structure selected from the group consisting of carbobetaine type, sulfobetaine type, amine oxide type and phosphobetaine type. X is, at the end, a carbobetaine type "-N ⁺ R ⁸ R ⁹ (CH ₂ ) _n CO ₂ ^- ", a sulfobetaine type "-N ⁺ R ⁸ R ⁹ (CH ₂ ) _n SO ₃ ^- ", It has an amine oxide type “—N ⁺ R ⁸ R ⁹ O ⁻ ” or a phosphobetaine type “—OPO ₃ ⁻ (CH ₂ ) _n N ⁺ R ⁸ R ⁹ R ¹⁰ ”. n is an integer from 1 to 5; R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Specific examples of the carbobetaine-type compound represented by formula (1) include the following compounds.

Specific examples of the sulfobetaine-type compound represented by formula (1) include the following compounds.

Specific examples of the amine oxide type compound represented by Formula (1) include the following compounds.

Specific examples of the phosphobetaine-type compound represented by formula (1) include the following compounds.

The betaine-type fluorine compound may be a commercially available product such as Efrontia A0111 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.).

The number of fluorine atoms contained in the betaine type fluorine compound is preferably 10 at % (atomic %) to 80 at %, more preferably 20 at % to 60 at %, based on the total number of atoms in the betaine type fluorine compound. When the number of fluorine atoms is 10 at % or more, the hydrophilic and oil-repellent function is more exhibited, and an antifogging film having more excellent antifouling properties can be formed. Further, when the number of fluorine atoms is 80 at % or less, the betaine-type fluorine compound is easily dissolved in the coating liquid, and the content of the betaine-type fluorine compound can be increased. As a result, the hydrophilic and oil-repellent function can be exhibited more effectively, and an antifogging film having more excellent antifouling properties can be formed. The number of fluorine atoms in each betaine-type fluorine compound is obtained by analyzing the structure of the compound using ¹⁹ F-NMR (fluorine 19 nuclear magnetic resonance) and dividing the number of fluorine atoms by the number of atoms in the entire compound. can be calculated.

The content of the betaine-type fluorine compound in the hydrophilic oil-repellent layer is preferably 0.5% by mass to 10% by mass, more preferably 2% by mass to 8% by mass, based on the total amount of the hydrophilic oil-repellent layer. When the content of the betaine-type fluorine compound is 0.5% by mass or more, the antifouling property is more excellent. When the content of the betaine-type fluorine compound is 10% by mass or less, the antifogging property is more excellent.

-Inorganic particles-
In the anti-fogging laminate of the present disclosure, by including inorganic particles in the hydrophilic oil-repellent layer, the hardness of the hydrophilic oil-repellent layer can be improved, and the scratch resistance of the anti-fogging laminate can be improved. In addition, since the inorganic particles do not aggregate even when combined with the betaine-type fluorine compound, the haze can be kept low and the transparency is excellent. When combined with a betaine-type fluorine compound, the inorganic particles may be either anionic inorganic particles or cationic inorganic particles.

The hydrophilic oil-repellent layer in the present disclosure may contain one type of inorganic particles, or may contain two or more types of inorganic particles. When two or more kinds of inorganic particles are included, at least one of size and shape may be different from each other.

As the inorganic particles, inorganic oxide particles are preferable, and metal oxide particles are more preferable. Here, the metals in the metal oxide particles include semimetals such as B, Si, Ge, As, Sb and Te.

Metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B , Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferred. In addition, from the viewpoint of improving scratch resistance, metal oxide particles having a Mohs hardness of 6 or more are preferable. Examples of metal oxide particles having a Mohs hardness of 6 or more include silica particles, titania particles, zirconia particles and alumina particles, with silica particles or alumina particles being preferred.

Silica particles are not particularly limited, and known ones can be used. Silica particles include, for example, fumed silica and colloidal silica.

Fumed silica can be obtained by reacting a compound containing silicon atoms with oxygen and hydrogen in the gas phase. Examples of silicon compounds used as raw materials include silicon halides (eg, silicon chloride).

Colloidal silica can be synthesized by a sol-gel method in which raw material compounds are hydrolyzed and condensed. Raw material compounds for colloidal silica include, for example, alkoxy silicon (eg, tetraethoxysilane) and halogenated silane compounds (eg, diphenyldichlorosilane).

The inorganic particles may be commercially available products on the market.
Commercial products of silica particles include, for example, Evonik's AEROSIL (registered trademark) series, Nissan Chemical Industries' Snowtex (registered trademark) series (e.g., Snowtex OXS, Snowtex O-33, and Snowtex OL). , Nalco's Nalco® series (eg, Nalco 8699), and Fuso Chemical Industries' Quatron PL series (eg, PL-1).

Commercial products of alumina particles include, for example, the Aluminasol series (eg, Alumisol F-3000) manufactured by Kawaken Fine Chemicals Co., Ltd., and the Vilar series (eg, AL-7) manufactured by Taki Chemical Co., Ltd.

Examples of the shape of the inorganic particles include a spherical shape, a plate shape, a needle shape, a beaded shape, and a shape in which two or more of these shapes are united. In addition, the spherical shape includes not only the shape of a true sphere but also shapes such as a spheroid and an oval. Moreover, the inorganic particles preferably have a shape with a large average aspect ratio from the viewpoint of improving scratch resistance. Specifically, the aspect ratio of the inorganic particles is preferably 5-3000, more preferably 30-1000.

From the viewpoint of improving transparency, the average primary particle size of the inorganic particles is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 30 nm or less, and particularly preferably 20 nm or less. . In addition, the average primary particle size of the inorganic particles is preferably 2 nm or more, more preferably 8 nm or more, from the viewpoint of maintaining good antifogging properties. The average primary particle size of the inorganic particles is preferably 8 nm to 20 nm from the viewpoint of compatibility between transparency and antifogging properties.

The average primary particle size of the inorganic particles is the arithmetic mean value of equivalent circle diameters measured by the following method. The projected area of the primary particles of 300 inorganic particles selected from the observation image obtained using a transmission electron microscope is measured. From the obtained projected area, the equivalent circle diameter of each inorganic particle is determined. The arithmetic average value of the equivalent circle diameters of the inorganic particles is determined, and the obtained value is defined as the average primary particle diameter of the inorganic particles.

The content of the inorganic particles in the hydrophilic oil-repellent layer is preferably 5% by mass to 70% by mass, more preferably 8% by mass to 60% by mass, and 10% by mass with respect to the total amount of the hydrophilic oil-repellent layer. It is particularly preferred that it is up to 40% by mass. When the content of the inorganic particles is 5% by mass or more, the hardness of the hydrophilic oil-repellent layer can be further improved. When the content of the inorganic particles is 70% by mass or less, the decrease in transparency can be further suppressed.

The ratio of the content of the inorganic particles to the content of the betaine-type fluorine compound is preferably 0.5 to 30 on the mass basis. If the ratio is 30 or less, the decrease in transparency can be further suppressed.

-binder-
The binder is not particularly limited as long as it is a polymer capable of forming a layer containing a betaine-type fluorine compound and inorganic particles. From the viewpoint of hardness, the binder is preferably a siloxane polymer or an organic crosslinked polymer.

The hydrophilic oil-repellent layer in the present disclosure may contain one binder, or may contain two or more binders.

(1) Siloxane polymer The hydrophilic oil-repellent layer in the present disclosure can be formed by applying a hydrophilic oil-repellent layer-forming coating liquid onto the water-absorbent resin layer and drying the coating liquid. When inorganic particles, a betaine-type fluorine compound, alkoxysilane, water, etc. are mixed when preparing a coating liquid for forming a hydrophilic oil-repellent layer, the alkoxysilane is hydrolyzed and silanol is dehydrated and condensed to form a siloxane polymer that serves as a binder. be done. In the present disclosure, the inorganic particles are preferably chemically bonded with a siloxane polymer that serves as a binder.

Alkoxysilanes include, for example, compounds represented by the following general formula (3).
Si(OR ⁴ ) _x (R ⁵ ) _4-x (3)
In formula (3), R ⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ⁵ represents an organic group having 1 to 15 carbon atoms and not containing an amino group. In addition, x represents an integer of 2 to 4. When x is 2, it represents a bifunctional alkoxysilane, when x is 3, it represents a trifunctional alkoxysilane, and when x is 4, it represents a tetrafunctional alkoxysilane.

When R ⁴ is an alkyl group, if the number of carbon atoms is 4 or less, the hydrolysis rate of the alkoxysilane when mixed with acidic water does not become too slow, and dissolution to a uniform aqueous solution is required. less time. Examples of R ⁴ include hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group and phenyl group. Among them, a methyl group and an ethyl group are preferred. Moreover, a hydrophilic oil-repellent layer has sufficient hardness as carbon number of R5 is ¹⁵ or less. The organic group represented by ^R5 may have heteroatoms such as oxygen, nitrogen and sulfur.

Alkoxysilane may be used alone or in combination of two or more.

Specific examples of the compound represented by formula (3) are shown below.
Examples of the tetrafunctional alkoxysilane in which x is 4 in the general formula (3) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, Tetraphenoxysilane can be mentioned. The tetrafunctional alkoxysilane may be a commercial product. Commercially available products include, for example, tetraethoxysilane (product name “KBE-04”, manufactured by Shin-Etsu Chemical Co., Ltd.).

In the general formula (3), trifunctional alkoxysilanes in which x is 3 include, for example, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane Silane, propyltrimethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-ureidopropyltriethoxysilane , methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane and phenyltrimethoxysilane. Among them, methyltriethoxysilane and methyltrimethoxysilane are preferred. Trifunctional alkoxysilanes may be commercially available. Commercially available products include, for example, methyltriethoxysilane (product name “KBE-13”, manufactured by Shin-Etsu Chemical Co., Ltd.).

In the general formula (3), bifunctional alkoxysilanes in which x is 2 include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane. silanes, di-n-propyldiethoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane and diphenyldimethoxysilane. Bifunctional alkoxysilanes may be commercially available. Commercially available products include, for example, dimethyldiethoxysilane (product name “KBE-22”, manufactured by Shin-Etsu Chemical Co., Ltd.).

In the present disclosure, it is preferable to use a combination of a tetrafunctional alkoxysilane and an epoxy group-containing bifunctional alkoxysilane or an epoxy group-containing trifunctional alkoxysilane. The epoxy group-containing bifunctional alkoxysilane or epoxy group-containing trifunctional alkoxysilane may have one or more epoxy groups in one molecule, and the number of epoxy groups is not particularly limited.

Examples of epoxy group-containing bifunctional alkoxysilanes and epoxy group-containing trifunctional alkoxysilanes include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, 3-glycides xypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and 3-glycidoxypropylmethyldiethoxysilane. The epoxy group-containing bifunctional alkoxysilane and epoxy group-containing trifunctional alkoxysilane may be commercially available products. Commercially available products include, for example, 3-glycidoxypropyltriethoxysilane (product name “KBE-403”, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropylmethyldiethoxysilane (product name “KBE-402”). , manufactured by Shin-Etsu Chemical Co., Ltd.).

Also, a silane coupling agent may be mixed when preparing the hydrophilic oil-repellent layer-forming coating liquid. By mixing a silane coupling agent, a stronger hydrophilic oil-repellent layer can be formed. The silane coupling agent is preferably a silane compound having a terminal functional group, and examples of the functional group include amino group, hydroxyl group, vinyl group and carboxy group. A commercial item may be sufficient as a silane coupling agent. Commercially available products include, for example, silane coupling agents containing alkylene glycol (product name “X-12-1098”, manufactured by Shin-Etsu Chemical Co., Ltd.).

Moreover, when preparing the coating liquid for hydrophilic oil-repellent layer formation, you may mix a curing catalyst. The curing catalyst is preferably water soluble. The curing catalyst has a function of promoting dehydration condensation of silanol to promote formation of siloxane bonds. Curing catalysts include, for example, water-soluble inorganic acids, organic acids, inorganic acid salts, organic acid salts, metal alkoxides, and metal complexes. As the metal complex, a metal complex containing a metal selected from the group consisting of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf and Zr is preferred.

Inorganic acids include, for example, boric acid, phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid. Organic acids include, for example, acetic acid, formic acid, oxalic acid, citric acid, malic acid, and ascorbic acid.

Examples of inorganic acid salts include aluminum chloride, aluminum sulfate, aluminum nitrate, zinc chloride, zinc sulfate, zinc nitrate, magnesium chloride, magnesium sulfate, magnesium nitrate, zirconium chloride, zirconium sulfate, and zirconium nitrate.

Organic acid salts include, for example, aluminum acetate, aluminum oxalate, zinc acetate, zinc oxalate, magnesium acetate, magnesium oxalate, zirconium acetate, and zirconium oxalate.

Metal alkoxides include, for example, aluminum alkoxides, titanium alkoxides, and zirconium alkoxides.

Examples of metal complexes include aluminum ethylacetoacetate diisopropylate, aluminum tris(ethylacetoacetate), aluminum alkylacetoacetate diisopropylate, aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris(acetylacetonate), and the like. aluminum chelate;
magnesium chelates such as magnesium ethylacetoacetate monoisopropylate, magnesium bis(ethylacetoacetate), magnesium alkylacetoacetate monoisopropylate, magnesium bis(acetylacetonate);
Zirconium chelates such as zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium acetylacetonate bis(ethylacetoacetate);
Manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate, and titanium oxyacetylacetonate.

Among others, aluminum ethylacetoacetate diisopropylate, aluminum tris(acetylacetonate), aluminum tris(ethylacetoacetate), aluminum monoacetylacetonate bis(ethylacetoacetate), magnesium bis(acetylacetonate), magnesium bis(ethyl acetoacetate) and zirconium tetraacetylacetonate are preferred. Further, from the viewpoint of storage stability and availability, aluminum ethylacetoacetate diisopropylate and aluminum monoacetylacetonate bis(ethylacetoacetate) are more preferable. Commercially available products include, for example, aluminum ethylacetoacetate diisopropylate (product name "ALCH", manufactured by Kawaken Fine Chemicals) and aluminum monoacetylacetonate bis(ethylacetoacetate) (product name "ALCH-D", Kawaken manufactured by Fine Chemicals).

(2) Organic Crosslinked Polymer The hydrophilic oil-repellent layer in the present disclosure can be formed by applying a coating liquid for forming a hydrophilic oil-repellent layer onto the water-absorbing resin layer and drying it. When preparing the coating liquid for forming the hydrophilic oil-repellent layer, it is possible to obtain an organic crosslinked polymer as a binder by mixing and reacting raw materials for forming an organic crosslinked polymer together with inorganic particles and a betaine-type fluorine compound. can. The raw materials for forming the organic crosslinked polymer are preferably a water absorbent polymer and a crosslinker. Moreover, a curing catalyst may be used in addition to the water absorbing polymer and the cross-linking agent, and other additives may be used.

The water-absorbent polymer is preferably at least one polymer selected from the group consisting of polyvinyl alcohol polymers, polysaccharides, and (meth)acrylic polymers. By using a water-absorbing polymer, it is possible to improve the anti-fogging property and strength due to the water-absorbing function.

In the present disclosure, "polyvinyl alcohol-based polymer" means a polymer containing vinyl alcohol units (--CH.sub.2-- _CHOH-- ), and includes homopolymers and copolymers unless otherwise specified. Vinyl alcohol units can be formed, for example, by saponifying vinyl ester units (eg, vinyl acetate units).

Polyvinyl alcohol-based polymers include, for example, polyvinyl alcohol and modified polyvinyl alcohol.

Modified polyvinyl alcohol is a partially modified compound of polyvinyl alcohol (also referred to as a polyvinyl alcohol derivative). Examples of modified polyvinyl alcohol include acetoacetyl-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, and silanol-modified polyvinyl alcohol. Among them, the polyvinyl alcohol-based polymer is preferably acetoacetyl-modified polyvinyl alcohol.

From the viewpoint of antifogging properties, the polyvinyl alcohol polymer is preferably a partially saponified polyvinyl alcohol polymer. The degree of saponification of the partially saponified polyvinyl alcohol-based polymer is preferably 80 mol% or more and less than 98 mol%, more preferably 80 mol% to 95 mol%, from the viewpoint of antifogging properties. It is more preferably 85 mol % to 95 mol %, particularly preferably 88 mol % to 95 mol %.
The degree of saponification is measured according to the method described in JIS K 6726:1994.

A commercial item may be sufficient as a polyvinyl-alcohol-type polymer. Commercially available products include, for example, Kuraray Poval series manufactured by Kuraray Co., Ltd. (e.g., PVA-205 (degree of saponification 86.5 mol% to 89 mol%), and PVA-220 (degree of saponification 87 mol% to 89 mol% )), and Nippon Synthetic Chemical Co., Ltd. Gohsenex (registered trademark, hereinafter the same. For example, Z-100 (degree of saponification 98.5 mol% or more), Z-200 (degree of saponification 99 mol% or more), and Z -220 (degree of saponification 90.5 mol% to 92.5 mol% or more)).

From the viewpoint of hardness, the polymerization degree of the polyvinyl alcohol polymer is preferably 600 or more, more preferably 1000 or more, and even more preferably 1200 or more. The upper limit of the polymerization degree of the polyvinyl alcohol-based polymer is not particularly limited, and can be appropriately selected within the range of 5000 or less, for example.

Polysaccharides are a general term for substances in which monosaccharide molecules are polymerized by glycosidic bonds, and include, for example, agarose, dextran, carrageenan, alginic acid, hyaluronic acid, chitin, chitosan, starch, and cellulosic compounds. Among polysaccharides, cellulosic compounds are preferred.

Cellulosic compounds include cellulose and modified cellulose. Modified cellulose is a compound obtained by partially modifying cellulose. Modified celluloses include, for example, acetylcellulose, triacetylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropylmethylcellulose.

The cellulose-based compound may be a commercially available product on the market. Commercially available products include, for example, Daicel Finechem SP200, SP400, SP500, SP600, SP850, SP900 (hydroxyethyl cellulose), and 1110, 1120, 1130, 1140, 1150, 1160, 1170, 1180, 1190, 1220, 1240, 1250, 1260, 1330, 1350, 1380, 1390, 2200, 2260, 2280 (carboxymethyl cellulose).

From the viewpoint of hardness, the weight average molecular weight of the cellulose compound is preferably 500,000 or more, more preferably 800,000 or more, and even more preferably 1,000,000 or more. The upper limit of the weight-average molecular weight of the cellulose-based compound is not particularly limited, and can be appropriately selected within the range of, for example, 3,000,000 or less.

The weight average molecular weight (Mw) in the present disclosure is a value measured by a gel permeation chromatography (GPC) analyzer.
Specifically, measurement by GPC uses HLC-8120GPC and SC-8020 (both manufactured by Tosoh Corporation) as measuring devices, and TSKgel (registered trademark) Super HM-H (6.0 mm ID × 15 cm, Tosoh Corporation) as a column. Co., Ltd.), and water or a mixed solvent of water and dimethylsulfoxide (DMSO) is used as the eluent. The measurement conditions are a sample concentration of 0.5% by mass, a flow rate of 0.6 ml/min, a sample injection volume of 10 μl, and a measurement temperature of 40° C., using a refractometer (RI) detector. . The calibration curve is "Standard sample TSK standard, polystyrene" 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" made from 10 samples can be used.

The (meth)acrylic polymer means a polymer containing structural units derived from a (meth)acrylic monomer, and is selected from water-absorbing (meth)acrylic polymers. The (meth)acrylic polymer may be either a homopolymer or a copolymer unless otherwise specified.

(Meth)acrylic monomers include, for example, (meth)acrylic acid, (meth)acrylamide, and (meth)acrylic esters.

(Meth)acrylamides include, for example, acrylamide, methacrylamide, N-methylacrylamide, N,N'-dimethylacrylamide, N,N'-dimethylmethacrylamide, and N-methylolacrylamide.

The (meth)acrylic ester is preferably an alkyl (meth)acrylate, more preferably an alkyl (meth)acrylate having 1 to 4 carbon atoms in the alkyl moiety. (Meth)acrylic esters include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate.

(Meth)acrylic polymers include, for example, polyacrylic acid, polymethacrylic acid, (meth)acrylamide polymers, and (meth)acrylic ester polymers.

(Meth)acrylamide polymers include, for example, polyacrylamide, polymethacrylamide, acrylamide-acrylic acid copolymer, acrylamide-methacrylic acid copolymer, acrylamide-methyl acrylate copolymer, acrylamide-methyl methacrylate copolymer polymers, and N,N'-dimethylacrylamide-N-methylolacrylamide-methyl methacrylate copolymers.

(Meth)acrylic ester polymers include, for example, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and polyisobutyl (meth)acrylate.

The weight average molecular weight of the (meth)acrylic polymer is preferably 15,000 or more, more preferably 20,000 or more, and even more preferably 25,000 or more, from the viewpoint of wet rubbing resistance and hardness. The upper limit of the weight average molecular weight of the (meth)acrylic polymer is not particularly limited, and can be appropriately selected within the range of, for example, 50,000 or less.

The content of the water-absorbing polymer in the hydrophilic oil-repellent layer is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 50% by mass, based on the total amount of the hydrophilic oil-repellent layer, from the viewpoint of strength and hardness.

Among them, the water-absorbing polymer more preferably contains a polyvinyl alcohol-based polymer because it has high water-absorbing property and further improves the antifogging property.

The cross-linking agent is preferably at least one selected from the group consisting of melamine resins, blocked isocyanates and metal chelates.

As the melamine resin, a melamine resin having a hydroxyl group is preferable in terms of cross-linking reaction, and a methylol melamine resin is preferable. The methylol melamine resin may be a commercial product on the market. Examples of commercially available products include Nikalac MX-035 manufactured by Nippon Carbide Co., Ltd.

A blocked isocyanate has a structure in which an isocyanate group of an isocyanate compound is protected with a blocking agent. When heated, the blocking agent is dissociated and the isocyanate groups are regenerated.

Examples of isocyanate compounds constituting blocked isocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4 - tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2′-diethyl ether diisocyanate, diphenylmethane-4,4′-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylenebis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane -1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methyleneditrylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, Norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate.

Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are preferred.

The parent structure of the blocked isocyanate may be biuret type, isocyanurate type, adduct type, or bifunctional prepolymer type.

Blocking agents that protect isocyanate groups of isocyanate compounds include, for example, oxime compounds, lactam compounds, phenol compounds, alcohols, amines, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds and imide compounds. Among them, blocking agents selected from oxime compounds, lactam compounds, phenol compounds, alcohols, amines, active methylene compounds, and pyrazole compounds are particularly preferred.

Moreover, a commercial item may be sufficient as a blocked isocyanate. Commercially available blocked isocyanates include, for example, Duranate (registered trademark) series manufactured by Asahi Kasei Corporation (eg, Duranate WM44-L70G), Takenate (registered trademark) series manufactured by Mitsui Chemicals (eg, Takenate WXB-F206), Meisei Meikanate series manufactured by Kagaku Kogyo Co., Ltd. (eg, Meikanate TP-10) can be mentioned.

As the metal chelate, a chelate compound having a metal selected from Zr, Ti and Al as a ligand and a metal selected from Zr, Ti and Al as a ligand, or R ^A OH (R ^A : an alkyl group having 1 to 10 carbon atoms) and an alcohol represented by R ^B COCH ₂ COR ^C (R ^B : alkyl group having 1 to 10 carbon atoms, R ^C : alkyl group having 1 to 10 carbon atoms or alkoxy group having 1 to 10 carbon atoms) A chelate compound having a metal selected from Zr, Ti and Al as a central metal and having a compound as a ligand can be used.

Examples of metal chelates include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis(ethylacetoacetate) zirconium, n-butoxytris(ethylacetoacetate) zirconium, tetrakis(n-propylacetoacetate) zirconium, Zirconium chelates such as tetrakis(acetylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium;
Titanium chelates such as titanium lactate, titanium lactate ammonium salt, diisopropoxy bis(ethylacetoacetate) titanium, diisopropoxy bis(acetylacetate) titanium, diisopropoxy bis(acetylacetone) titanium;
Diisopropoxyethylacetoacetate aluminum, Diisopropoxyacetylacetonate aluminum, Isopropoxybis(ethylacetoacetate)aluminum, Isopropoxybis(acetylacetonate)aluminum, Tris(ethylacetoacetate)aluminum, Tris(acetylacetonate) Examples include aluminum chelates such as aluminum and monoacetylacetonate/bis(ethylacetoacetate)aluminum.

Also, the metal chelate may be a commercial product on the market. Commercially available products include, for example, titanium lactate ammonium salt (product name "Orgatics TC-300", manufactured by Matsumoto Fine Chemicals Co., Ltd.), titanium lactate (product names "Orgatics TC-310" and "Orgatics TC-315", Matsumoto Fine Chemicals Co., Ltd.), and zirconium chloride compounds (product names “Orgatics ZC-126” and “Orgatics ZC-300, Matsumoto Fine Chemicals Co., Ltd.).

The curing catalyst is not particularly limited, and can be selected from known curing catalysts according to the types of water-absorbing polymer and cross-linking agent. Examples of curing catalysts include photoacid generators, thermal acid generators, photobase generators, thermal base generators, and photopolymerization initiators.

Among them, the curing catalyst is preferably a thermal acid generator (also referred to as a thermosetting catalyst). By including a thermal acid generator in the hydrophilic oil-repellent layer-forming coating liquid, the curing reaction by heating can be accelerated. Thermal acid generators include, for example, p-toluenesulfonic acid, phosphoric acid, and dodecylbenzenesulfonic acid. The hydrophilic oil-repellent layer-forming coating liquid may contain one curing catalyst, or two or more curing catalysts.

The content of the binder in the hydrophilic oil-repellent layer is preferably from 10% by mass to 95% by mass, more preferably from 20% by mass to 90% by mass, and from 50% by mass to the total amount of the hydrophilic oil-repellent layer. 90% by mass is particularly preferred. When the content of the binder is 10% by mass or more, the inorganic particles used in combination can be sufficiently retained. When the content of the binder is 95% by mass or less, the content of the inorganic particles can be ensured, and the hardness can be further improved.

The hydrophilic oil-repellent layer in the antifogging laminate of the present disclosure may contain components other than the binder, the betaine-type fluorine compound, and the inorganic particles. The hydrophilic oil-repellent layer may contain, for example, an ultraviolet absorber, an antioxidant, and the like for the purpose of improving weather resistance.

<Binder, anionic fluorine compound and anionic inorganic particles included>
A case where the hydrophilic oil-repellent layer contains an anionic fluorine compound and anionic inorganic particles will be described.

- Anionic fluorine compounds -
The anionic fluorine compound used in the hydrophilic oil-repellent layer in the antifogging laminate of the present disclosure is not particularly limited as long as it is a fluorine compound having an anionic group in one molecule. The antifogging laminate of the present disclosure is excellent in antifouling properties because the hydrophilic oil-repellent layer contains an anionic fluorine compound that exhibits a hydrophilic oil-repellent function.

Anions contained in the anionic fluorine compound include, for example, COO ⁻ , PO ₃ ⁻ and SO ₃ ⁻ .

An anionic fluorine surfactant can be used as an anionic fluorine compound. The anionic fluorine compound may be a commercial product on the market. Commercially available anionic fluorine compounds include, for example, Megafac F-114 and Megafac F-410 manufactured by DIC, and Futergent 100 and Futergent 150 manufactured by Neos.

The content of the anionic fluorine compound in the hydrophilic oil-repellent layer is preferably 0.5% by mass to 10% by mass, more preferably 2% by mass to 8% by mass, relative to the total amount of the hydrophilic oil-repellent layer. When the content of the anionic fluorine compound is 0.5% by mass or more, the antifouling property is excellent. When the content of the anionic fluorine compound is 10% by mass or less, the antifogging property is more excellent.

- Anionic inorganic particles In the anti-fogging laminate of the present disclosure, the hydrophilic oil-repellent layer contains anionic inorganic particles, thereby improving the hardness of the hydrophilic oil-repellent layer and increasing the scratch resistance of the anti-fogging laminate. can be improved. In addition, since the anionic inorganic particles do not aggregate even when combined with an anionic fluorine compound, the haze can be kept low and the transparency is excellent.

In the present disclosure, anionic inorganic particles refer to inorganic particles whose surfaces are negatively charged in water. As the anionic inorganic particles, anionic inorganic oxide particles are preferred, and anionic metal oxide particles are more preferred. Silica particles are preferred as the anionic metal oxide particles.

Silica particles are not particularly limited, and known ones can be used. Silica particles include, for example, fumed silica and colloidal silica.

Fumed silica can be obtained by reacting a compound containing silicon atoms with oxygen and hydrogen in the gas phase. Examples of silicon compounds used as raw materials include silicon halides (eg, silicon chloride).

Colloidal silica can be synthesized by a sol-gel method in which raw material compounds are hydrolyzed and condensed. Raw material compounds for colloidal silica include, for example, alkoxy silicon (eg, tetraethoxysilane) and halogenated silane compounds (eg, diphenyldichlorosilane).

The anionic inorganic particles may be commercially available products on the market.
Commercially available silica particles include Evonik's AEROSIL® series, Nissan Chemical Industries' Snowtex® series (e.g., Snowtex OXS, Snowtex O-33, and Snowtex OL), Nalco company's Nalco® series (eg, Nalco 8699), and Fuso Chemical Industries, Ltd.'s Quatron PL series (eg, PL-1).

Examples of the shape of the anionic inorganic particles include spherical, plate-like, needle-like, bead-like, and a combination of two or more of these. In addition, the spherical shape includes not only the shape of a true sphere but also shapes such as a spheroid and an oval. Moreover, the inorganic particles preferably have a shape with a large average aspect ratio from the viewpoint of improving scratch resistance. Specifically, the aspect ratio of the inorganic particles is preferably 5-3000, more preferably 30-1000.

From the viewpoint of improving transparency, the average primary particle size of the anionic inorganic particles is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 30 nm or less, and 20 nm or less. Especially preferred. In addition, the average primary particle size of the anionic inorganic particles is preferably 2 nm or more, more preferably 8 nm or more, from the viewpoint of maintaining good antifogging properties. The average primary particle size of the anionic inorganic particles is preferably 8 nm to 20 nm from the viewpoint of compatibility between transparency and antifogging properties.

The content of the anionic inorganic particles in the hydrophilic oil-repellent layer is preferably 5% by mass to 70% by mass, more preferably 8% by mass to 50% by mass, relative to the total mass of the hydrophilic oil-repellent layer. 10% by mass to 40% by mass is particularly preferred. When the content of the anionic inorganic particles is 5% by mass or more, the hardness of the hydrophilic oil-repellent layer can be further improved. When the content of the anionic inorganic particles is 70% by mass or less, a decrease in transparency can be further suppressed.

-binder-
As for the binder, the same binder as the binder described above can be used, so the description thereof is omitted.

The content of the binder in the hydrophilic oil-repellent layer is preferably from 10% by mass to 95% by mass, more preferably from 20% by mass to 90% by mass, and from 50% by mass to the total amount of the hydrophilic oil-repellent layer. 90% by mass is particularly preferred. When the content of the binder is 10% by mass or more, the inorganic particles used in combination can be sufficiently retained. When the content of the binder is 95% by mass or less, the content of the inorganic particles can be ensured, and the hardness can be further improved.

The hydrophilic oil-repellent layer in the antifogging laminate of the present disclosure may contain components other than the binder, the anionic fluorine compound and the anionic inorganic particles. The hydrophilic oil-repellent layer may contain, for example, an ultraviolet absorber, an antioxidant, and the like for the purpose of improving weather resistance.

<Binder, cationic fluorine compound and cationic inorganic particles included>
A case where the hydrophilic oil-repellent layer contains a binder, a cationic fluorine compound and cationic inorganic particles will be described.

- Cationic Fluorine Compound -
The cationic fluorine compound used in the hydrophilic oil-repellent layer in the antifogging laminate of the present disclosure is not particularly limited as long as it is a fluorine compound having a cationic group in one molecule. The antifogging laminate of the present disclosure is excellent in antifouling properties because the hydrophilic oil-repellent layer contains a cationic fluorine compound that exhibits a hydrophilic oil-repellent function.

The cation contained in the cationic fluorine compound is preferably a quaternary ammonium cation.

A cationic fluorine surfactant can be used as the cationic fluorine compound. The cationic fluorine compound may be a commercial product on the market. Commercially available cationic fluorine compounds include Surflon S-221 manufactured by AGC Seichemical Co., Ltd. and Futergent 320 manufactured by Neos.

The content of the cationic fluorine compound in the hydrophilic oil-repellent layer is preferably 0.5% by mass to 10% by mass, more preferably 2% by mass to 8% by mass, based on the total amount of the hydrophilic oil-repellent layer. When the content of the cationic fluorine compound is 0.5% by mass or more, the antifouling property is excellent. When the content of the cationic fluorine compound is 10% by mass or less, the antifogging property is excellent.

- Cationic inorganic particles In the anti-fogging laminate of the present disclosure, the hydrophilic oil-repellent layer contains cationic inorganic particles, so that the hardness of the hydrophilic oil-repellent layer can be improved, and the scratch resistance of the anti-fogging laminate can be improved. can be improved. Moreover, since the cationic inorganic particles do not aggregate even when combined with a cationic fluorine compound, the haze can be kept low and the transparency is excellent.

In the present disclosure, cationic inorganic particles refer to inorganic particles whose surfaces are positively charged in water. As the cationic inorganic particles, cationic inorganic oxide particles are preferred, and cationic metal oxide particles are more preferred. Examples of cationic metal oxide particles include titanium particles and alumina particles, with alumina particles being preferred.

The cationic inorganic particles may be commercial products on the market.
Commercial products of alumina particles include, for example, the Aluminasol series (eg, Alumisol F-3000) manufactured by Kawaken Fine Chemicals Co., Ltd., and the Vilar series (eg, AL-7) manufactured by Taki Chemical Co., Ltd.

Examples of the shape of the cationic inorganic particles include a spherical shape, a plate shape, a needle shape, a beaded shape, and a shape in which two or more of these shapes are combined. In addition, the spherical shape includes not only the shape of a true sphere but also shapes such as a spheroid and an oval. Moreover, the inorganic particles preferably have a shape with a large average aspect ratio from the viewpoint of improving scratch resistance. Specifically, the aspect ratio of the inorganic particles is preferably 5-3000, more preferably 30-1000.

From the viewpoint of improving transparency, the average primary particle size of the cationic inorganic particles is preferably 100 nm or less, more preferably 50 nm or less, even more preferably 30 nm or less, and 20 nm or less. Especially preferred. In addition, the average primary particle size of the cationic inorganic particles is preferably 2 nm or more, more preferably 8 nm or more, from the viewpoint of maintaining good antifogging properties. The average primary particle size of the cationic inorganic particles is preferably 8 nm to 20 nm from the viewpoint of compatibility between transparency and antifogging properties.

The content of the cationic inorganic particles in the hydrophilic oil-repellent layer is preferably 5% by mass to 70% by mass, more preferably 8% by mass to 50% by mass, relative to the total mass of the hydrophilic oil-repellent layer. 10% by mass to 40% by mass is particularly preferred. When the content of the cationic inorganic particles is 5% by mass or more, the hardness of the hydrophilic oil-repellent layer can be further improved. When the content of the cationic inorganic particles is 70% by mass or less, a decrease in transparency can be further suppressed.

-binder-
As for the binder, the same binder as the binder described above can be used, so the description thereof is omitted.

The content of the binder in the hydrophilic oil-repellent layer is preferably from 10% by mass to 95% by mass, more preferably from 20% by mass to 90% by mass, and from 50% by mass to the total amount of the hydrophilic oil-repellent layer. 90% by mass is particularly preferred. When the content of the binder is 10% by mass or more, the inorganic particles used in combination can be sufficiently retained. When the content of the binder is 95% by mass or less, the content of the inorganic particles can be ensured, and the hardness can be further improved.

The hydrophilic oil-repellent layer in the antifogging laminate of the present disclosure may contain components other than the binder, cationic fluorine compound and cationic inorganic particles. The hydrophilic oil-repellent layer may contain, for example, an ultraviolet absorber, an antioxidant, and the like for the purpose of improving weather resistance.

(Non-water absorbing support)
The anti-fogging laminate of the present disclosure may have a non-water-absorbent support on the side of the water-absorbent resin layer opposite to the side on which the hydrophilic oil-repellent layer is arranged. When the anti-fogging laminate has a pressure-sensitive adhesive layer, which will be described later, it is preferred that a non-water-absorbent support is arranged between the water-absorbing resin layer and the pressure-sensitive adhesive layer.

Materials for the non-water-absorbing support can be appropriately selected from various materials such as glass, resins (including plastics), metals, and ceramics, and resins are preferred.

When the antifogging laminate of the present disclosure is applied to, for example, a protective material for automobile lights or a protective material for surveillance cameras, it is preferable to use a resin base material because of its light weight and excellent strength.

The non-water-absorbing support is preferably a support using acrylic resin, polycarbonate, polyolefin or polyethylene terephthalate. Further, from the viewpoint of forming a laminate having excellent adhesion, a support using acrylic resin or polycarbonate is more preferable, and a support using polymethyl methacrylate or polycarbonate is even more preferable.

As the material for the non-absorbent support, a composite material formed from a plurality of materials may be used. It may be a composite material that is made into a composite material, or a resin composite material in which a plurality of types of resin materials are kneaded or bonded together.

The thickness and shape of the non-water-absorbent support are not particularly limited, and can be appropriately selected according to the application. The thickness of the non-water-absorbent support can be several tens of μm to several hundred μm.

Moreover, the surface of the non-water-absorbent support may be subjected to surface treatment, if necessary. The surface treatment method is not particularly limited, and known methods such as corona discharge treatment can be used.

(Adhesive layer)
The anti-fogging laminate of the present disclosure may have an adhesive layer as the outermost layer on the side of the water-absorbing resin layer opposite to the side on which the hydrophilic oil-repellent layer is arranged. By having a pressure-sensitive adhesive layer, adhesion to various adherends can be improved.

The material of the pressure-sensitive adhesive layer is not particularly limited, and is selected from known materials depending on the material of the adherend. Examples include polyvinyl butyral, acrylics, styrene/acrylics, polyurethanes, and polyesters. The pressure-sensitive adhesive layer may contain an antistatic agent, lubricant or antiblocking agent, if necessary.

The thickness of the adhesive layer is preferably 0.1 μm to 30 μm.

(other layers)
The antifogging laminate of the present disclosure may optionally have layers other than the above-described water-absorbing resin layer, hydrophilic oil-repellent layer, and pressure-sensitive adhesive layer (hereinafter also referred to as "other layers"). good. Other layers include protective layers (eg, protective films) and adhesion layers. The adhesion layer can improve the adhesion between the layers by, for example, being arranged between the layers.

<Method for manufacturing laminate>
The method for producing a laminate of the present disclosure includes a coating liquid containing a binder, a betaine-type fluorine compound and inorganic particles, a coating liquid containing a binder, an anionic fluorine compound and anionic inorganic particles, or a binder, a cationic fluorine compound and a cationic a step of applying a coating liquid containing organic inorganic particles onto the water-absorbing resin layer; The method for manufacturing a laminate of the present disclosure may further have other steps. A hydrophilic oil-repellent layer is formed by applying a hydrophilic oil-repellent layer-forming coating liquid onto the water-absorbing resin layer.

The hydrophilic oil-repellent layer-forming coating liquid can be prepared by mixing raw materials for forming a binder, a betaine-type fluorine compound, inorganic particles, and, if necessary, other components. Moreover, the hydrophilic oil-repellent layer-forming coating liquid can be prepared by mixing raw materials for forming the binder, the anionic fluorine compound, the anionic inorganic particles, and, if necessary, other components. Moreover, the hydrophilic oil-repellent layer-forming coating liquid can be prepared by mixing raw materials for forming a binder, a cationic fluorine compound, cationic inorganic particles, and, if necessary, other components.

As for the betaine-type fluorine compound, anionic fluorine compound, cationic fluorine compound, inorganic particles, anionic inorganic particles and cationic inorganic particles, the above-described ones can be used, and thus the description thereof is omitted.

When the binder is a siloxane polymer, raw materials for forming the binder include, for example, alkoxysilanes, silane coupling agents, and curing catalysts. The alkoxysilane, the silane coupling agent, and the curing catalyst are the same as those described above, so the description thereof is omitted.

When the binder is an organic crosslinked polymer, raw materials for forming the binder include, for example, a water absorbing polymer, a crosslinking agent and a curing catalyst. As for the water-absorbing polymer, the cross-linking agent and the curing catalyst, the above-mentioned ones can be used, so the description is omitted.

The coating liquid for forming the hydrophilic oil-repellent layer preferably contains a solvent. The solvent is not particularly limited, and can be selected from known solvents according to the type, solubility, and dispersibility of components contained in the hydrophilic oil-repellent layer-forming coating liquid. Solvents include, for example, water and alcohols.

Alcohols include, for example, ethanol, propanol, and butanol. The coating liquid for forming the hydrophilic oil-repellent layer may contain one kind of solvent, or may contain two or more kinds of solvents.

The solid content concentration of the hydrophilic oil-repellent layer-forming coating liquid can be appropriately set according to the design thickness of the hydrophilic oil-repellent layer and coating suitability. The solid content concentration of the hydrophilic oil-repellent layer-forming coating liquid can be appropriately set, for example, within the range of 5% by mass to 20% by mass.

The coating method is not particularly limited, and can be selected from known coating methods. Examples of coating methods include spray coating, slit coating, roll coating, blade coating, spin coating, bar coating, and dip coating. The coating device used in the coating method is not particularly limited, and can be selected from known coating devices.

After the coating step, it is preferable to dry the hydrophilic oil-repellent layer-forming coating solution applied on the water-absorbing resin layer. When the coating liquid for forming the hydrophilic oil-repellent layer contains a curing catalyst, the curing reaction can be accelerated by heating the coating liquid for forming the hydrophilic oil-repellent layer. The method for forming the hydrophilic oil-repellent layer may have an exposure step, if necessary.

A drying method is not particularly limited, and a known drying method can be applied. Drying methods include, for example, natural drying, heat drying, and vacuum drying. Drying devices include, for example, ovens and electric furnaces.

The drying temperature is not particularly limited, and can be appropriately set in the range of, for example, 20°C to 150°C.

The drying time is not particularly limited, and can be appropriately set, for example, in the range of 1 minute to 60 minutes.

EXAMPLES Hereinafter, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to the following examples as long as the gist thereof is not exceeded.

(Example 1)
[Preparation of coating solution for forming hydrophilic oil-repellent layer]
First, while vigorously stirring the acetic acid aqueous solution, 3-glycidoxypropyltriethoxysilane (product name “KBE-403”, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100% by mass) was added to the acetic acid aqueous solution and stirred for 30 minutes. continued. Next, tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., solid content: 100% by mass) was added to the acetic acid aqueous solution with vigorous stirring, and stirring was continued for 1 hour. The obtained solution was designated as solution 1-A.

Next, aluminum ethyl acetoacetate diisopropylate (product name "ALCH", alumina sol (product name "Alumisol F-1000", short diameter 4 nm × long diameter 1400 nm, manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 75% by mass) Ken Fine Chemical Co., Ltd., solid content 100% by mass) was added, and the mixture was stirred for 12 hours. Further, half of solution 1-A was added and stirred for 1 hour. The obtained solution was designated as solution 1-B.

Aluminum monoacetylacetonate bis(ethylacetoacetate) (product name “ALCH-D”, manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 75% by mass) was added to the remaining half of solution 1-A and stirred for 1 hour. continued. The obtained solution was designated as solution 1-C.

Solution 1-B, solution 1-C, silane coupling agent (product name “X-12-1098”, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 30% by mass), water and ethanol are mixed and stirring is continued for 1 hour. rice field. The obtained solution was designated as Solution 1-D.

Betaine-type fluorine compound 1 (product name “Efrontier A0111”, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., solid content 1% by mass) is added to solution 1-D and stirred for 30 minutes to form a hydrophilic oil-repellent layer coating liquid. got

[Preparation of anti-fogging laminate]
Saponified triacetyl cellulose (manufactured by Tochisen Co., Ltd., thickness: 127 μm (including thickness of saponified layer: 7 μm to 8 μm), which is a water absorbent film that functions as a base material, water absorption: 70% to 85 %) on one surface (surface of the saponified layer) is coated with a coating liquid for forming a hydrophilic oil-repellent layer by a bar coating method, and the coating film is dried at 150 ° C. for 10 minutes to form a hydrophilic oil-repellent layer with a thickness of 6 μm. formed. An antifogging laminate of Example 1 was obtained, in which the hydrophilic oil-repellent layer was disposed on the absorbent film.

(Examples 2 to 9, Example 14, Example 15, Comparative Examples 1 to 8)
The binder raw material, inorganic particles and fluorine compound used in Example 1 were changed to the types and contents shown in Tables 1 and 2, and in the same manner as in Example 1, Examples 2 to 9 and Examples 14, Example 15, and Comparative Examples 1 to 8 were prepared. In Comparative Example 8, a water-soluble non-fluorine compound was used, which is described in the "fluorine compound" column.
In Comparative Example 7, the fluorine compound was not dissolved in the mixed solution of water and ethanol, and the hydrophilic oil-repellent layer-forming coating liquid could not be prepared.
For Examples 2 to 9, Example 14, Example 15, Comparative Examples 1 to 6, and Comparative Example 8, antifogging laminates were produced in the same manner as in Example 1.

(Example 10)
[Preparation of coating solution for forming hydrophilic oil-repellent layer]
After mixing the components shown below so as to have the contents shown in Tables 1 and 2, betaine-type fluorine compound 1 (product name “Efrontia A0111A0111”, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., solid content 1% by mass ) was added and stirred for 30 minutes to obtain a coating liquid for forming a hydrophilic oil-repellent layer.
・ Acetoacetyl-modified polyvinyl alcohol (product name “Gohsenex Z-220”, manufactured by Nippon Synthetic Chemical Co., Ltd., degree of polymerization 1200, degree of saponification 90.5 to 92.5, solid content 100% by mass) ・ Melamine resin cross-linking agent (product Name “Nikalac MX-035”, manufactured by Nippon Carbide Co., Ltd., solid content 70% by mass)
・ p-toluenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., solid content 100% by mass)
・ Alumina sol (product name “Aluminum Sol F-1000”, short diameter 4 nm × long diameter 1400 nm, manufactured by Kawaken Fine Chemicals, solid content 75% by mass)
・Water/ethanol

[Preparation of anti-fogging laminate]
An antifogging laminate of Example 10 was produced in the same manner as in Example 1.

(Example 11 and Example 12)
The binder raw material, inorganic particles and fluorine compound used in Example 10 were changed to the types and contents shown in Tables 1 and 2, and the antifogging of Examples 11 and 12 was performed in the same manner as in Example 10. A flexible laminate was produced.

(Example 13)
[Preparation of coating solution for forming hydrophilic oil-repellent layer]
By the same method as in Example 1, a coating liquid for forming a hydrophilic oil-repellent layer was obtained.

[Preparation of anti-fogging laminate]
On a polyethylene terephthalate base material (product name “A4300”, manufactured by Toyobo Co., Ltd., thickness 75 μm), acetoacetyl-modified polyvinyl alcohol (product name “Gohsenex Z-220” manufactured by Nippon Synthetic Chemical Co., Ltd., degree of polymerization 1200, degree of saponification 90.5 to 92.5, solid content 100 mass %) was applied by a bar coating method, and the coating film was dried at 150° C. for 5 minutes to form a 5 μm thick water absorbent resin layer.

Next, a hydrophilic oil-repellent layer-forming coating liquid was applied by a bar coating method, and the coating film was dried at 150° C. for 10 minutes to form a hydrophilic oil-repellent layer having a thickness of 6 μm. An anti-fogging laminate of Example 13 was obtained in which a water-absorbing resin layer and a hydrophilic oil-repellent layer were arranged in this order on a polyethylene terephthalate base material, which is a non-water-absorbing support.

The antifogging laminates of Examples and Comparative Examples were evaluated for antifogging properties, water drip resistance, pencil hardness, antifouling properties and transparency. The evaluation method is as follows. Table 2 shows the evaluation results. In Comparative Example 9, the coating liquid for forming the hydrophilic oil-repellent layer could not be prepared, and the antifogging laminate could not be produced, so no evaluation was performed. Therefore, "-" was entered in the evaluation column.

<Anti-fogging property>
A hot water bath at 40° C. was prepared, and only a predetermined 5 cm×5 cm area of the hydrophilic oil-repellent layer of the obtained laminate was exposed to steam from the hot bath, and the time until fogging occurred was measured. Evaluation criteria are as follows. Evaluation made A and B into the pass.
A: No fogging for 1 minute and 30 seconds or more, and no fluctuation that makes the transmitted image look blurred.
B: 30 seconds or more and less than 1 minute and 30 seconds.
C: Clouding occurs in less than 30 seconds, and a transmitted image cannot be seen.

<Water drip resistance>
A sample having a size of 10 cm×10 cm was prepared, and 10 mL of water was sprayed onto the surface of the hydrophilic oil-repellent layer by spraying to forcibly form a water film. After that, it was allowed to stand and dried while standing vertically. After repeating this operation 10 times, the presence or absence of dripping traces (that is, dripping traces) was visually observed. Evaluation criteria are as follows. Evaluation made A the pass.
A: No trace of dripping B: Trace of dripping is slightly visible C: Trace of dripping is clearly visible

<Pencil hardness>
A sample with a size of 10 cm×10 cm was prepared, and a pencil hardness test was performed on the surface of the hydrophilic oil-repellent layer under the conditions of JIS K 5600 5-4 (1999). The higher the pencil hardness, the better the scratch resistance. HB, H, 2H and 3H were evaluated as acceptable. More preferably, the evaluation is H or higher.

<Transparency>
The haze of the laminate was measured using a haze meter (model number: NDH 5000, manufactured by Nippon Denshoku Industries Co., Ltd.). The obtained measured value was used as an index for evaluating transparency. In order to remove the difference due to the base material, the haze was calculated by subtracting the measured value of the base material alone from the measured value of the laminate. The measurement was performed with the substrate surface of the laminate, that is, the surface of the laminate opposite to the surface on which the hydrophilic oil-repellent layer was formed, facing the light source. The lower the haze, the better the transparency. Evaluation criteria are as follows. Evaluation made A and B into the pass.
A: Less than 0.9% haze B: 0.9% or more and less than 1.5% haze C: 1.5% or more haze

<Stain resistance>
A sample having a size of 10 cm×10 cm was prepared, and 1 μL of n-hexadecane was dropped onto the surface of the hydrophilic oil-repellent layer. At room temperature (25±1° C.), the angle (unit: degree) formed by the contact portion between the surface of the hydrophilic oil-repellent layer and the droplet was measured using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The larger the angle, the better the antifouling property. Evaluation criteria are as follows. Evaluation made A the pass.
A: 80° or more B: 30° or more and less than 80° C: less than 30°

The abbreviations listed in Table 1 mean the following compounds.
· KBE-403 ... 3-glycidoxypropyltriethoxysilane (product name "KBE-403", manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100% by mass)
・ Z-220 ... acetoacetyl-modified polyvinyl alcohol (product name “Gohsenex Z-220”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., degree of polymerization 1200, degree of saponification 90.5 to 92.5, solid content 100% by mass)
・ TEOS ... tetraethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., solid content 100% by mass)
· X-12-1098 ... silane coupling agent (product name "X-12-1098", manufactured by Shin-Etsu Chemical Co., Ltd., solid content 30% by mass)
・ MX-035 ... melamine resin having an imino group and a methylol group (product name "Nikalac MX-035", manufactured by Nippon Carbide Co., Ltd., solid content 70% by mass)
· WM44-L70G ... blocked isocyanate cross-linking agent (product name "Duranate WM44-L70G", manufactured by Asahi Kasei Chemicals, solid content 70% by mass)
· ALCH ... aluminum ethyl acetoacetate diisopropylate (product name "ALCH", manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 100% by mass)
· ALCH-D ... aluminum monoacetylacetonate bis (ethyl acetoacetate) (product name "ALCH-D", manufactured by Kawaken Fine Chemicals Co., Ltd., solid content 75% by mass)
・ p-TS ... p-toluenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd., solid content 100% by mass)

The abbreviations listed in Table 2 refer to the following compounds.
· Cationic inorganic particles: alumina ... alumina sol (product name "Aluminumsol F-1000", short diameter 4 nm × long diameter 1400 nm, manufactured by Kawaken Fine Chemicals, solid content 75% by mass)
・ Anionic inorganic particles: silica ... colloidal silica (product name “Snowtex O33”, primary particle size 10 nm to 15 nm, manufactured by Nissan Chemical Industries, Ltd., solid content 33% by mass)
・Betaine-type fluorine compound 1: Betaine-type fluorine compound (product name “A0111”, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), fluorine atom number 36 at%
・Betaine-type fluorine compound 2: A betaine-type fluorine compound having the following structure, 24 at% of fluorine atoms
Cationic fluorine compound 1: Cationic fluorine compound having the following structure Cationic fluorine compound 2: Cationic fluorine compound having the following structure Anionic fluorine compound 1: Anionic fluorine compound having the following structure Anion Fluorine compound 2: anionic fluorine compound/water-insoluble fluorine compound having the following structure: fluorine-containing group/lipophilic group-containing oligomer (product name “Megafac F-552”, manufactured by DIC Corporation)
・Water-soluble non-fluorine compound ... polyoxyethylene lauryl ether (product name "Emulgen 103", manufactured by Kao Corporation)
・ UG-4040 ... epoxy group-containing acrylic polymer (product name “ARUFON (registered trademark) UG-4040”, weight average molecular weight 11000, epoxy value 2.1 meq / g, manufactured by Toagosei Co., Ltd.)
・Saponified TAC: saponified triacetyl cellulose (manufactured by Tochisen Co., Ltd., thickness: 127 μm (including thickness of saponified layer: 7 μm to 8 μm), water absorption: 70% to 85%)
・ A4300 ... polyethylene terephthalate base material (product name "A4300", manufactured by Toyobo Co., Ltd., thickness 75 μm)

(Betaine-type fluorine compound 2)

(Cationic fluorine compound 1)

(Cationic fluorine compound 2)

(Anionic fluorine compound 1)

(Anionic fluorine compound 2)

As shown in Table 2, the antifogging laminates of Examples 1 to 15 each have a water-absorbent resin layer and a hydrophilic oil-repellent layer disposed on the water-absorbent resin layer, and the hydrophilic oil-repellent layer contains a binder, a betaine-type fluorine compound and inorganic particles; or contains a binder, an anionic fluorine compound and anionic inorganic particles; It was found to be excellent in transparency, scratch resistance, drip resistance and antifouling property while having fogging properties. In particular, in the antifogging laminates of Examples 1 to 3, the content of the betaine-type fluorine compound is 0.5% by mass to 10% by mass with respect to the total amount of the hydrophilic oil-repellent layer, so the antifogging laminates of Example 14 It was found that the antifouling property was superior to that of the antifogging laminate of Example 15, and the antifogging property was superior to that of the antifogging laminate of Example 15.

On the other hand, Comparative Examples 1 and 2 were inferior in antifogging properties because they did not have a water absorbent resin layer. In Comparative Example 3, since the hydrophilic oil-repellent layer did not contain inorganic particles, the scratch resistance was poor. In Comparative Example 4, since the hydrophilic oil-repellent layer did not contain a fluorine compound, the antifouling property was inferior. In Comparative Example 5, the hydrophilic oil-repellent layer contained the cationic inorganic particles and the anionic fluorine compound, so the transparency was poor. In Comparative Example 6, since the hydrophilic oil-repellent layer contained anionic inorganic particles and a cationic fluorine compound, the transparency was poor. In Comparative Example 8, since the hydrophilic oil-repellent layer contained a non-fluorine compound instead of a fluorine compound, the antifouling property was poor.

As described above, the antifogging laminate of the present disclosure has a water-absorbent resin layer and a hydrophilic oil-repellent layer disposed on the water-absorbent resin layer, and the hydrophilic oil-repellent layer comprises a binder, a betaine-type fluorine compound and Since it contains inorganic particles, or contains a binder, an anionic fluorine compound and anionic inorganic particles, or contains a binder, a cationic fluorine compound and cationic inorganic particles, it has good antifogging properties and transparency. , Excellent scratch resistance, drip resistance and stain resistance.

Reference Signs List 10, 20 Anti-fogging laminate 12, 22 Hydrophilic oil-repellent layers 14, 24 Water-absorbing resin layers 16, 28 Adhesive layer 26 Non-water-absorbing support

Claims (9)

a water absorbent resin layer;
a hydrophilic oil-repellent layer disposed on the water-absorbing resin layer,
The hydrophilic oil-repellent layer is an antifogging laminate containing a binder, a betaine-type fluorine compound, and alumina particles . The antifogging laminate according to claim 1, wherein the water absorbent resin layer contains a cellulose resin. 3. The antifogging laminate according to claim 2, wherein the cellulosic resin contains triacetyl cellulose. The antifogging laminate according to any one of claims 1 to 3 , wherein the content of the betaine-type fluorine compound is 0.5% by mass to 10% by mass with respect to the total amount of the hydrophilic oil-repellent layer. . The antifogging laminate according to any one of claims 1 to 4, wherein the content of the alumina particles with respect to the content of the betaine-type fluorine compound is 0.5 to 30 on a mass basis. The antifogging laminate according to any one of claims 1 to 5, wherein the alumina particles have a primary particle size of 100 nm or less. The antifogging laminate according to any one of claims 1 to 6 , which has a non-water-absorbent support on the side of the water-absorbent resin layer opposite to the side on which the hydrophilic oil-repellent layer is arranged. The antifogging laminate according to any one of claims 1 to 7 , which has an adhesive layer as an outermost layer on the side of the water-absorbing resin layer opposite to the side on which the hydrophilic oil-repellent layer is arranged. body. A method for producing an antifogging laminate comprising the step of applying a coating liquid containing a binder, a betaine-type fluorine compound and alumina particles onto a water absorbent resin layer.

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