JP4530351B2 - Anti-fogging laminate and method for producing the same - Google Patents

Description

  The present invention relates to an antifogging laminate having a transparent dry body of an organic-inorganic composite hydrogel formed on a base material, wherein a water-soluble organic polymer and a water-swellable clay mineral form a three-dimensional network, and a method for producing the same About.

  Cloudiness on the surface of the material is a phenomenon in which moisture in the air is condensed into small water droplets on the surface of the material (for example, glass or plastic) due to a decrease in the temperature of the atmosphere, and the originally transparent material becomes opaque. For example, many cloudy phenomena due to condensation are observed in daily life on glass parts of trains and cars, glass show windows, household window glass, and bathroom mirrors.

  Many measures have been taken to prevent this fogging phenomenon (usually anti-fogging or anti-fogging). For example, a hydrophilic surface treatment composition containing a copolymer composed of poly (meth) acrylic acid or a salt thereof and polystyrenesulfonic acid or a salt thereof is disclosed (see Patent Document 1). The surface treatment composition creates a hydrophilic film on the surface of another material to produce an antifogging effect. This hydrophilic film is composed of hydrophilic poly (meth) acrylic acid or a salt thereof and polystyrene sulfonic acid. Or it is a copolymer of the salt, and since it is easy to swell when exposed to water, the adhesiveness (especially when wet) between the hydrophilic film and various materials was insufficient. In particular, when the hydrophilic film is formed on a hydrophobic polymer, the problem of adhesion with the hydrophilic film is remarkable.

  Further, an anti-fogging composition mainly composed of three components of a clay clay mineral, an acrylic resin containing an acid group and a hydroxyl group and having a glass transition temperature of 40 ° C. to 75 ° C., and a nonionic surfactant, A film which is applied to a plastic resin film and has an antifogging property is disclosed (see Patent Document 2). However, the clay clay mineral in this composition is only dispersed in the acrylic resin via the surfactant, and no network structure is formed between the clay and the acrylic resin. Since the glass transition temperature of the resin is low, the deformation of the coating film is large at high temperatures, and the hardness of the formed antifogging coating film is also low.

  On the other hand, as a material having excellent mechanical strength, a polymer hydrogel in which a hydrophilic organic polymer and a clay mineral form a three-dimensional network or a dried product of the polymer hydrogel is disclosed (Patent Document 3, (See Patent Document 4). The dried hydrogel is a transparent and tough material, but is not disclosed to be homogeneously layered, and the formed dried hydrogel coating is an antifogging material. It was neither described nor suggested to be useful.

JP 2001-9361 A JP-A-9-40941 JP 2002-53762 A JP 2004-143212 A

  The problems to be solved by the present invention include an anti-fogging laminate having excellent adhesion to a substrate, high mechanical properties and heat resistance, and excellent transparency, and a uniform coating in a very short time. It is providing the manufacturing method of the anti-fogging laminated body which can form a film | membrane.

  As a result of intensive studies to solve the above problems, the present inventors have formed a three-dimensional network of the water-soluble organic polymer (A) and the water-swellable clay mineral (B), and has a thickness of 1 to 1. The said subject was solved by the anti-fogging laminated body which has a transparent gel dry body layer in the range of 500 micrometers on the base-material surface.

Furthermore, a composition (X) containing (I) an energy ray-curable water-soluble organic monomer (a), a water-swellable clay mineral (b), an aqueous medium (c) and a water-insoluble polymerization initiator (d) ) On the substrate,
(II) The coating film of the composition (X) applied on the substrate is irradiated with energy rays to react the water-soluble acrylic monomer (a) in the presence of the water-swellable clay mineral (b). A step of forming an organic-inorganic composite hydrogel layer on the substrate;
(III) a step of drying the organic-inorganic composite hydrogel layer to obtain a dried gel layer,
The above-described problems have been solved by a method for producing an antifogging laminate having the following.

  The antifogging laminate obtained by the present invention has a wide range of clay mineral content, the clay mineral is uniformly dispersed in the organic polymer, exhibits excellent mechanical properties and antifogging properties, etc. The mechanical properties of the dry layer (anti-fogging layer) and the adhesiveness with the base material are good, and the polymerization can be completed in a very short time. Used as various industrial materials.

  The dried transparent gel layer in the antifogging laminate of the present invention is formed by the interaction of the water-soluble organic polymer (A) and the water-swellable clay mineral (B) to form a three-dimensional network. Here, the water-soluble organic polymer includes a hydrophilic polymer that swells in water or absorbs a large amount of moisture in the air, in addition to those that dissolve in water. The interaction between the water-soluble organic polymer (A) and the water-swellable clay mineral (B) includes electrostatic interaction, interaction of hydrophobic part, hydrogen bond, interaction by coordination bond, or these interactions There are combinations. By these interactions, it is presumed that the mechanical properties (surface hardness), transparency and antifogging properties of the antifogging laminate of the present invention are very excellent.

  The water-soluble organic polymer (A) used in the present invention can be suitably used as long as it interacts with the water-swellable clay mineral (B) to form a three-dimensional network and form a dried transparent gel layer, Since lamination is easy, it is preferable to be obtained from an energy ray-curable organic monomer. As the organic monomer, a water-soluble acrylic monomer can be suitably used from the viewpoint of ease of production by energy beam polymerization and physical properties of the gel obtained. Moreover, if the gel dry body layer can be formed, the other copolymerization monomer component may be included as a copolymerization component. Preferred examples of the water-soluble acrylic monomer (a) include acrylamide, methacrylamide, derivatives thereof (N- or N, N-substituted (meth) acrylamide, etc.), acrylic esters, and the like. Moreover, the monomer used for superposition | polymerization may be 1 type, or multiple types.

  In the present invention, among the water-soluble acrylic monomers, acrylamide, methacrylamide, or a derivative thereof (N- or N, N-substituted (meth) acrylamide) can be preferably used. At least one monomer selected from acrylic monomers represented by 1) to (6) can be preferably used.

(In Formulas (1) to (6), R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₄ is the number of carbon atoms. 1 to 2 alkyl groups, and n is 1 to 9.)

  By using these acrylic monomers, the water-insoluble photopolymerization initiator used at the time of polymerization can be dispersed more finely and uniformly, so that it is less susceptible to oxygen during polymerization by energy rays and has better physical properties. A body laminate is obtained.

  Examples of other copolymerization monomers include acrylic monomers having anionic groups such as sulfone groups and carboxyl groups, acrylic monomers having cationic groups such as quaternary ammonium groups, quaternary ammonium groups and phosphate groups. An acrylic monomer having a zwitterionic group having, an acrylic monomer having an amino acid residue having a carboxyl group and an amino group, an acrylic monomer having a sugar residue, an acrylic monomer having a hydroxyl group, polyethylene glycol, An acrylic monomer having a polypropylene glycol chain, an amphiphilic acrylic monomer having a hydrophilic chain such as polyethylene glycol and a hydrophobic group such as nonylphenyl group, polyethylene glycol diacrylate, N, N'-methylenebisacrylamide Na It can be used.

  Examples of the water-swellable clay mineral (B) used in the present invention include swellable clay minerals that can be peeled in layers, and preferably swell and uniformly disperse in water or a mixed solution of water and an organic solvent. Clay minerals are used, particularly preferably inorganic clay minerals that can be dispersed uniformly in water at molecular (single layer) or close to that level. Specific examples include water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorlite, water-swellable saponite, and water-swellable synthetic mica. You may mix and use these clay minerals.

  The weight ratio (A) / (B) of the water-soluble organic polymer (A) to the water-swellable clay mineral (B) in the dried transparent gel layer is preferably in the range of 0.01 to 10, The range of 0.03 to 5 is more preferable, and the range of 0.05 to 3 is particularly preferable. When the weight ratio (A) / (B) is 0.01 or more, the degree of swelling of the dried gel layer with water is small and sufficient mechanical properties can be obtained, and when it is 10 or less, the clay mineral is well dispersed. And a uniform gel is easily obtained.

  In the present invention, in the present invention, the strength and surface antifogging property can be exhibited as the surface layer of the antifogging laminate by setting the thickness of the gel dried body layer in the range of 1 to 500 μm. If the thickness of the dried gel layer is less than 1 μm, it is difficult to obtain a homogeneous film and the strength is not sufficient. If it exceeds 500 μm, the gel tends to be deformed or peeled off from the substrate during drying. The thickness of the dried gel layer is preferably 1 to 100 μm in terms of the anti-fogging property and smoothness of the dried gel layer and the adhesion to the hydrophobic polymer layer. 3 to 50 μm is more preferable.

  The substrate used in the antifogging laminate of the present invention is preferably a transparent substrate from the viewpoint of maintaining antifogging properties, that is, transparency. Examples thereof include glasses such as glass and mirrors, and transparent plastics such as polycarbonate and polyethylene.

  The dried gel layer formed on the substrate can be integrated by directly contacting the surface of the transparent substrate, or may be integrated via a transparent primer layer or adhesive layer between them. . It is desirable that the adhesive layer is a hydrophobic polymer made of a polymer of a hydrophobic acrylic monomer in terms of ease of production and adhesive strength.

  The hydrophobic polymer is preferably a hydrophobic polymer made of a polymer of a hydrophobic acrylic monomer because it has excellent adhesion to the dried transparent gel layer. Specific examples of hydrophobic acrylic monomers include, for example, acrylic esters having one or more acryloyl groups in one molecule, epoxy esters of acrylic acid, urethane oligomers having one or more acryloyl groups in one molecule, etc. Is mentioned.

  The antifogging laminate of the present invention can widely adjust the hardness of the gel dried body layer according to demands such as abrasion resistance, and the surface hardness is a surface pencil from the viewpoint of ordinary handling ease. The hardness is preferably HB or higher, and particularly preferably H or higher.

  The anti-fogging laminate of the present invention can adjust its anti-fogging properties by appropriately adjusting the degree of hydrophilicity (water contact angle) on the surface of the dried gel layer. As a range that can be particularly suitably used as the antifogging material, the water contact angle on the surface of the dried gel layer is desirably 40 ° or less, and more desirably 20 ° or less. The degree of hydrophilicity of the dried gel layer can be prepared by appropriately selecting the type of water-soluble organic polymer and a copolymer of the water-soluble organic polymer and other hydrophobic polymers.

The antifogging laminate of the present invention can be suitably produced by the following steps (I) to (III).
(I) A composition (X) containing an energy ray-curable water-soluble organic monomer (a), a water-swellable clay mineral (b), an aqueous medium (c) and a water-insoluble polymerization initiator (d). Applying on the substrate,
(II) The coating film of the composition (X) applied on the substrate is irradiated with energy rays to react the water-soluble acrylic monomer (a) in the presence of the water-swellable clay mineral (b). A step of forming an organic-inorganic composite hydrogel layer on the substrate;
(III) A step of drying the organic-inorganic composite hydrogel layer to obtain a dried gel layer.

  The energy ray-curable water-soluble organic monomer (a), the water-swellable clay mineral (b) and the base material in the composition (X) each obtain the water-soluble organic polymer (A) in the dried gel layer described above. The same water-soluble organic monomers, water-swellable clay mineral (B) and base materials used in the process can be preferably used.

  The aqueous medium (c) can include a water-soluble acrylic monomer, a water-swellable clay mineral, and the like, and is not particularly limited as long as an organic-inorganic composite hydrogel having good mechanical properties can be obtained by polymerization using energy rays. For example, it may be water or an aqueous solution containing a solvent miscible with water and / or other compounds, and further includes antiseptics, antibacterial agents, coloring agents, fragrances, enzymes, proteins, saccharides, amino acids. , Cells, DNAs, salts, water-soluble organic solvents, surfactants, leveling agents and the like.

  Examples of the water-insoluble polymerization initiator (d) used in the present invention include acetophenones such as p-tert-butyltrichloroacetophenone, benzophenones such as 4,4′-bisdimethylaminobenzophenone, and 2-methylthioxanthone. Examples include ketones, benzoin ethers such as benzoin methyl ether, α-hydroxy ketones such as hydroxycyclohexyl phenyl ketone, phenylglyoxylates such as methylbenzoyl formate, and metallocenes.

  The term “water-insoluble” as used herein means that the amount of polymerization initiator dissolved in water is 0.5% by weight or less. If the solubility in water is high, the mechanical properties of the resulting hydrogel tend to be insufficient, which is not preferable.

  In the production method of the present invention, a composition containing an energy ray-curable water-soluble organic monomer (a), a water-swellable clay mineral (b), an aqueous medium (c) and a water-insoluble polymerization initiator (d). The product (X) may be directly applied to the substrate and irradiated with energy rays, or when it is necessary to increase the adhesion between the gel and the substrate, a primer (e.g. hydrophilic Or the composition (Y) containing a hydrophobic acrylic monomer and a polymerization initiator is applied to a substrate and remains uncured or still has a double bond. In a semi-cured state, the composition (X) containing a water-soluble acrylic monomer, a water-swellable clay mineral, an aqueous medium and a polymerization initiator is applied, and the whole is irradiated with energy rays. It is what is polymerized. At this time, the composition (X) containing the water-soluble acrylic monomer, water-swellable clay mineral, aqueous medium and polymerization initiator is applied to a substrate and irradiated with energy rays through a mask. An antifogging laminate having an arbitrary pattern can also be produced.

When forming the hydrophobic polymer layer on the substrate, the hydrophobic polymer layer and the dried hydrogel layer have excellent adhesion due to the production method in the following steps (i) to (iii). Can be obtained.
(I) A composition (X) containing an energy ray-curable water-soluble organic monomer (a), a water-swellable clay mineral (b), an aqueous medium (c) and a water-insoluble polymerization initiator (d). Applying the composition (Y) containing the energy ray-curable hydrophobic monomer (e) and the polymerization initiator (f) on the coated substrate,
(Ii) The coating film of the composition (X) applied on the substrate is irradiated with energy rays to react the water-soluble acrylic monomer (a) in the presence of the water-swellable clay mineral (b). And a step of reacting a hydrophobic monomer together to form a hydrophobic polymer layer and an organic-inorganic composite hydrogel layer on the substrate,
(Iii) A step of drying the organic-inorganic composite hydrogel layer to obtain a dried gel layer.

  As the energy ray-curable hydrophobic monomer (e) in the composition (Y), a hydrophobic monomer capable of forming the above-described hydrophobic polymer layer can be preferably used.

  As the polymerization initiator (f), the same water-insoluble polymerization initiator (d) as that described above can be preferably used.

  In the present invention, it is important to disperse the water-insoluble polymerization initiator (d) in the aqueous medium (c) and irradiate it with energy rays in this state for polymerization. At this time, in order to disperse the polymerization initiator (d), it is preferable to disperse it in a state dissolved in the solvent (g).

  The solvent (g) used here is a water-soluble solvent that can dissolve the water-insoluble polymerization initiator, or an acrylic solvent that dissolves the water-insoluble polymerization initiator and has an HLB (hydrophilic hydrophobic balance) value of 8 or more. Monomers can be used. The HLB value here is a value determined according to the Davis formula ("Surfactant-Physical Properties / Application / Chemical Ecology", edited by Fumio Kitahara, Kodansha, p24-27 (1979)). For example, polypropylene glycol diacrylates such as tripropylene glycol diacrylate, polyethylene glycol diacrylates, polypropylene glycol acrylates such as pentapropylene glycol acrylate, polyethylene glycol acrylates, methoxyethyl acrylate, methoxytriethylene glycol acrylate Examples thereof include non-methyl polyethylene glycol acrylates, nonyl phenoxy polyethylene glycol acrylates, N-substituted acrylamides such as dimethyl acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, and the like. It is preferable that the acrylic monomer as the solvent has an HLB value of 8 or less because it is excellent in solubility or dispersibility in an aqueous medium. These acrylic monomers can be used by mixing one or more.

  Further, as the solvent (g), a solvent capable of dissolving the water-insoluble polymerization initiator (d) and having a certain level of water solubility can be used. The water-soluble solvent mentioned here is preferably a solvent that can dissolve 50 g or more with respect to 100 g of water. If the solubility in water is less than 50 g, the dispersibility of the water-insoluble polymerization initiator in the aqueous medium is lowered, and the resulting gel dried body layer may have low mechanical properties, which is not desirable.

  For example, examples of the water-soluble solvent include amides such as dimethylacetamide and dimethylformamide, alcohols such as dimethyl sulfoxide, methanol and ethanol, and tetrahydrofuran. You may mix and use these solvents.

  The weight ratio / the ratio of the water-insoluble polymerization initiator (g) to the solvent (g) in the solution obtained by dissolving the water-insoluble polymerization initiator (d) in the solvent (g) is 0.001 to 0.1. Preferably, 0.01 to 0.05 is more preferable. When the amount is 0.001 or more, a sufficient amount of radicals are generated by irradiation with energy rays, so that the polymerization reaction can be suitably performed. When the amount is 0.1 or less, coloring by an initiator and odor are caused. It does not occur substantially and the cost can be reduced.

  A solution in which the water-insoluble polymerization initiator (d) is dissolved in the solvent (g) in the case of using any of these acrylic monomers having an HLB (hydrophilic / hydrophobic balance) value of 8 or more and a water-soluble solvent. The amount of dispersion in the composition (X) is preferably 0.1% by weight to 5% by weight, and preferably 0.2% by weight to 2% by weight, based on the total weight of the composition (X). Is more preferable. When it is 0.1% by weight or more, the polymerization is favorably started, and when it is 5% by weight or less, generation of odor due to generation of a linear polymer not participating in the composite gel or increase of the polymerization initiator in the gel. This is preferable because it hardly occurs, and re-aggregation of the once-dispersed polymerization initiator or the solution of the polymerization initiator and the solvent hardly occurs.

  In order to obtain a dried gel layer having good mechanical properties in the present invention, it is preferable to disperse a solution obtained by dissolving a polymerization initiator in a solvent in an aqueous medium to 1 μm or less, particularly preferably 0.1 μm or less, 0 .01 μm or less is most preferable. If it is 1 μm or less, the uniformity of the reaction solution (aqueous medium) is excellent, so that a more uniform and transparent hydrogel can be obtained.

  As the energy rays used in the present invention, electron beams, γ rays, X rays, ultraviolet rays, visible light, and the like can be used. Among these, it is preferable to use ultraviolet rays because of the simplicity of the apparatus and handling. The intensity of the irradiated ultraviolet light is preferably 10 to 500 mW / cm 2, and the irradiation time is generally about 0.1 to 200 seconds. In radical polymerization by normal heating, oxygen acts as an inhibitor of polymerization, but in the present invention, it is not always necessary to prepare a solution and perform polymerization by irradiation with energy rays in an atmosphere in which oxygen is cut off. Is possible. However, it may be desirable that the polymerization rate can be further increased by performing ultraviolet irradiation in an inert gas atmosphere.

  The coating method of the composition (X) and the composition (Y) in the method for producing an antifogging laminate in the present invention can be appropriately selected as necessary. For example, methods such as coating with a coater, dipping or spraying can be used. Further, by using a belt-like support, a single-wafer type or continuous anti-fogging laminate can be produced.

The antifogging laminate obtained by the present invention is a homogeneous film in which the dried gel layer (antifogging layer) on the surface has a clay mineral content uniformly dispersed in an organic polymer in a wide range of clay mineral content. Therefore, it has excellent mechanical properties (surface hardness), antifogging properties and transparency. Furthermore, the dried gel layer (anti-fogging layer) has excellent adhesion to the substrate, and particularly when the dried gel layer and the hydrophobic polymer layer are covalently bonded, extremely excellent adhesion is obtained. Have. In addition, since the polymerization can be completed in a very short time and a homogeneous film can be formed, the production efficiency is very high, and it is used as a medical or nursing tool or various industrial materials.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the scope of the present invention is not limited only to these Examples.

Example 1
[Preparation of aqueous medium containing water-soluble acrylic monomer and water-swellable clay mineral]
2 g of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd.) as a water-soluble acrylic monomer, 0.8 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as a clay mineral, and 20 g of water are uniformly mixed to form an aqueous medium. (C1) was prepared.

[Solution in which polymerization initiator is dissolved in solvent]
As a solvent, 98 g of polyoxypropylene monoacrylate “Blenmer AP-400” (manufactured by NOF Corporation) and 2 g of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) as a polymerization initiator were mixed uniformly. Solution 1 was prepared.

[Preparation of organic-inorganic composite hydrogel / substrate composite]
50 μl of Solution 1 is added to the total amount of the aqueous medium (c1), and uniformly dispersed with an ultrasonic disperser. The solution is applied to a 3 mm thick glass plate using a bar coater to a thickness of 150 μm. An organic / inorganic composite hydrogel / substrate composite (DNC5M1 / glass) was prepared by polymerizing N, N-dimethylacrylamide by irradiating ultraviolet rays having an ultraviolet intensity at 365 nm of 40 mW / cm ² for 120 seconds.

[Production of dried gel laminate]
The organic-inorganic composite hydrogel / substrate composite (DNC5M1 / glass) was dried with a hot air dryer at 80 ° C. for 20 minutes to prepare a gel dried product laminate DNC5M1glass.

[Physical properties of dried gel laminate]
The gel dried product laminate DNC5M1glass produced above was visually colorless and transparent. The surface hardness of the gel dried body laminate measured by the pencil method on the gel dried body side was H. As a result of measurement using a contact angle measuring device (CA-X200 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle was 31 °.

[Anti-fogging property test of dried gel laminate]
The prepared dried gel laminate DNC5M1glass was covered on a 200 ml beaker containing 100 ml of hot water at 60 ° C. so that the dried gel was faced down, and it was confirmed that it did not cloud for 1 minute. After the test, there was no swelling of the gel dried body and no peeling from the glass plate.

(Example 2)
[Preparation of aqueous medium containing water-soluble acrylic monomer and water-swellable clay mineral]
2.3 g of N-isopropylacrylamide (manufactured by Kojin Co., Ltd.) as a water-soluble acrylic monomer, 1.28 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as a clay mineral, and 20 g of water are uniformly mixed in an aqueous medium. (C2) was prepared.

[Solution in which polymerization initiator is dissolved in solvent]
Solution 2 is obtained by uniformly mixing 95 g of 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent and 5 g of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) as a polymerization initiator. Was prepared.

[Preparation of organic-inorganic composite hydrogel / substrate composite]
100 μl of the solution 2 is added to the total amount of the aqueous medium (c2) and uniformly dispersed by an ultrasonic disperser, and then a hydrophobic urethane acrylate (V) containing 2% by weight of 1-hydroxycyclohexyl phenyl ketone as an adhesive layer in advance. -4263, Dainippon Ink and Chemicals and Inc.) was applied to the coated polycarbonate plate so that the thickness of about 20 [mu] m (thickness 3 mm), 120 seconds irradiation adhesive layer UV intensity ultraviolet radiation 40 mW / cm ² at 365nm The portion and N-isopropylacrylamide were polymerized to prepare an organic-inorganic composite hydrogel / adhesive layer / substrate composite (NNC8M1 / PC).

[Production of dried gel laminate]
The organic-inorganic composite hydrogel / adhesive layer / substrate composite (NNC8M1 / PC) was dried with a hot air dryer at 80 ° C. for 20 minutes to prepare a gel dried product laminate NNC8M1PC.

[Physical properties of dried gel laminate]
The gel dried product laminate NNC8M1PC produced above was visually colorless and transparent. The surface hardness of the substrate on the gel dried body side measured by a pencil method was H. As a result of measurement using a contact angle measuring device (CA-X200 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle was 30 °.

[Anti-fogging property test of dried gel laminate]
The prepared dried gel laminate NNC8M1PC was placed on a 200 ml beaker containing 100 ml of hot water at 60 ° C. so that the dried gel was faced down, and it was confirmed that it did not cloud for 1 minute. After the test, there was no swelling of the gel dry body or peeling from the PC plate.

(Example 3)
[Preparation of aqueous medium containing water-soluble acrylic monomer and water-swellable clay mineral]
2.8 g of acryloyl morpholine (manufactured by Kojin Co., Ltd.) as a water-soluble acrylic monomer, 1.6 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as a clay mineral, and 20 g of water are uniformly mixed to form an aqueous medium (c3 ) Was prepared.

[Solution in which polymerization initiator is dissolved in solvent]
As a solvent, 95 g of N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 g of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) as a polymerization initiator were mixed to give a solution 3 Was prepared.

[Preparation of organic-inorganic composite hydrogel / substrate composite]
80 μl of the solution 3 is put in the total amount of the aqueous medium (c3), and the solution is uniformly mixed with a mixer, and then the solution is applied to a polyethylene terephthalate (PET) sheet having a thickness of 200 μm using a bar coater to a thickness of 150 μm. The mixture was applied and irradiated with ultraviolet rays having an ultraviolet intensity at 365 nm of 40 mW / cm ² for 120 seconds to polymerize acryloylmorpholine to prepare an organic-inorganic composite hydrogel / substrate composite (ACMONC10M1 / PET).

[Production of dried gel laminate]
The organic-inorganic composite hydrogel / substrate composite (ACMONC10M1 / PET) was dried with a hot air dryer at 80 ° C. for 20 minutes to prepare a gel dry body laminate ACMONC10M1PET.

[Physical properties of dried gel laminate]
The produced organic-inorganic composite gel dried laminate ACMONC10M1PET was colorless and transparent visually. The surface hardness of the substrate on the gel dried body side measured by a pencil method was 2H. As a result of measurement using a contact angle measuring device (CA-X200 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle was 33 °.

[Anti-fogging property test of dried gel laminate]
The prepared organic-inorganic composite gel dried product laminate ACMONC10M1PET was placed on a 200 ml beaker containing 100 ml of hot water at 60 ° C. so that the dried gel product faced down, and it was confirmed that it did not cloud for 1 minute. After the test, there was no swelling of the gel dry body or peeling from the PC plate.

(Comparative Example 1)
[Preparation of acrylic monomer composition]
4.5 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 3.5 g of butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 1 g of hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), acrylic acid (stock of Wako Pure Chemical Industries, Ltd.) Acrylic monomer composition AC1 is prepared by uniformly mixing 0.3 g of company), 0.2 g of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 10 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.). did.

[Preparation of clay mineral dispersion]
0.4 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as a clay mineral (B) is dispersed in a mixed solution of 4.8 g of 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.8 g of water, Mineral dispersion 1 was prepared.

[Preparation of antifogging composition]
Antifogging composition 1 was prepared by uniformly mixing 0.2 g of acrylic monomer composition AC1 prepared above, 5 g of clay mineral dispersion 1, 20 g of 2-propanol, and 30 g of water.

[Preparation of anti-fogging coating film]
The antifogging composition 1 was applied to a glass plate using a bar coater having a coating thickness of 10 μm, and heat-dried in a hot air dryer at 90 ° C. for 10 minutes to prepare an antifogging coating film.

[Physical properties of anti-fogging coating film]
The produced anti-fogging coating film was visually white and cloudy. This was because clay did not dissolve in the mixture of water and 2-propanol. The surface hardness of the anti-fogging coating film measured by the pencil method was B. As a result of measurement using a contact angle measuring device (CA-X200 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle was 32 °.

[Anti-fogging test of anti-fogging coating film]
The prepared anti-fogging coating film was covered on a 200 ml beaker containing 100 ml of hot water at 60 ° C. so that the coating film faced downward, and it was confirmed that the film was clouded for 1 minute. After the test, there was no swelling of the coating film or peeling from the glass plate.

(Comparative Example 3)
[Preparation of aqueous medium containing water-soluble acrylic monomer and water-swellable clay mineral]
2 g of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd.) as a water-soluble acrylic monomer, 0.5 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as a clay mineral, and 50 g of water are uniformly mixed in an aqueous medium. (C3 ′) was prepared.

[Solution in which polymerization initiator is dissolved in solvent]
As a solvent, 98 g of polyoxypropylene monoacrylate “Blenmer AP-400” (manufactured by NOF Corporation) and 2 g of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) as a polymerization initiator were mixed uniformly. To prepare solution 3 ′.

[Preparation of organic-inorganic composite hydrogel / substrate composite]
150 μl of Solution 1 is placed in the total amount of the above aqueous medium (c3 ′), and uniformly dispersed with an ultrasonic disperser. The solution is then applied to a 3 mm thick glass plate using a bar coater to a thickness of 10 μm. Then, ultraviolet rays having an ultraviolet intensity at 365 nm of 40 mW / cm ² were irradiated for 120 seconds to polymerize N, N-dimethylacrylamide to produce an organic-inorganic composite hydrogel / substrate composite.

[Production of dried gel laminate]
The organic-inorganic composite hydrogel / substrate composite was dried with a hot air dryer at 80 ° C. for 20 minutes to prepare a gel dried product laminate. The thickness of the dried gel layer was about 0.5 μm.

[Physical properties of dried gel laminate]
The produced gel dried product laminate was visually colorless and transparent. The surface hardness of the gel dried body laminate measured by the pencil method on the gel dried body side was B. As a result of measurement using a contact angle measuring device (CA-X200 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle was 42 °.

[Anti-fogging property test of dried gel laminate]
The gel dried body laminate prepared above was placed on a 200 ml beaker containing 100 ml of hot water at 60 ° C. so that the gel dried body faced downward, and left to stand for 1 minute. The gel dried body layer side was slightly cloudy. . After the test, there was no swelling of the gel dried body and no peeling from the glass plate.

(Comparative Example 4)
A glass plate (thickness 3 mm) previously coated with a hydrophobic urethane acrylate (V-4263, manufactured by Dainippon Ink & Chemicals, Inc.) containing 2% by weight of 1-hydroxycyclohexyl phenyl ketone as an adhesive layer to a thickness of about 20 μm. ) With a silicone plate having a thickness of about 4 mm and a width of about 5 mm, and an aqueous medium c1 containing the water-soluble acrylic monomer of Example 1 and a water-swellable clay mineral is poured therein (thickness is about 4 mm). ) Irradiation with ultraviolet rays at 365 nm of 40 mW / cm ² for 120 seconds was performed to polymerize the adhesive layer portion and N, N-dimethylacrylamide to produce an organic-inorganic composite hydrogel / substrate composite.

  The organic-inorganic composite hydrogel / substrate composite was dried with a hot air dryer at 80 ° C. for 20 minutes to prepare a gel dried product laminate. The thickness of the dried gel layer was about 550 μm.

[Physical properties of anti-fogging coating film]
The anti-fogging coating film produced above was slightly thick for 4 weeks, slightly thin at the center, and slightly uneven in thickness. The place which peeled a little from the glass plate in the peripheral part of the gel dried body was seen. The surface hardness of the anti-fogging coating film measured by a pencil method was H. As a result of measurement using a contact angle measuring device (CA-X200 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle was 30 °.

[Anti-fogging property test of dried gel laminate]
The prepared dried gel laminate was covered on a 200 ml beaker containing 100 ml of hot water at 60 ° C. so that the dried gel was faced down, and it was confirmed that it did not cloud for 1 minute. After the test, there was no swelling of the gel dry body due to moisture absorption or peeling from the glass plate.

As is clear from the above Examples and Comparative Examples, the antifogging laminate of the present invention has a uniform gel dry body layer (antifogging layer) and has excellent mechanical properties, antifogging properties and transparency. And the adhesiveness between a gel dry body layer and a base material was favorable.

Claims (19)

The water-soluble organic polymer (A) and the water-swellable clay mineral (B) form a three-dimensional network, and a transparent gel dried body layer having a thickness in the range of 1 to 500 μm is laminated with a base material. Cloudy material . The antifogging material according to claim 1, wherein the dried transparent gel layer is polymerized by irradiation with energy rays. The antifogging material according to claim 1 or 2, wherein the base material is a base material having a hydrophobic polymer layer formed on a surface thereof. The anti-fogging material according to any one of claims 1 to 3, wherein the substrate is transparent. The antifogging material according to any one of claims 1 to 4, wherein a surface pencil hardness of the dried transparent gel layer is HB or more. The antifogging material according to any one of claims 1 to 5, wherein a contact angle with water on the surface of the dried transparent gel layer is 40 ° or less. The anti-fogging material according to any one of claims 1 to 6, wherein the water-soluble organic polymer (A) is a polymer comprising a water-soluble acrylic monomer. The water-soluble organic polymer (A) is a polymer composed of at least one selected from acrylamide, methacrylamide, acrylamide derivatives, methacrylamide derivatives, and (meth) acrylic acid esters. Anti-fogging material . The water-soluble organic polymer (A) is represented by the following formulas (1) to (6).

(In Formulas (1) to (6), R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₄ is the number of carbon atoms. 1 to 2 alkyl groups, and n is 1 to 9.)
The antifogging material according to any one of claims 1 to 8, which is a polymer composed of at least one selected from the group consisting of: The water-swellable clay mineral (B) is at least one selected from water-swellable hectorite, water-swellable montmorillonite, water-swellable saponite, and water-swellable synthetic mica. Anti-fogging material . The weight ratio (A) / (B) of the water-soluble organic polymer (A) and the water-swellable clay mineral (B) in the dried transparent gel layer is in the range of 0.01 to 10. 10. The antifogging material according to any one of 10 above. The manufacturing method of the anti-fogging material which has the following process.
(I) A composition (X) containing an energy ray-curable water-soluble organic monomer (a), a water-swellable clay mineral (b), an aqueous medium (c) and a water-insoluble polymerization initiator (d). Applying on the substrate,
(II) The coating film of the composition (X) applied on the substrate is irradiated with energy rays to react the water-soluble acrylic monomer (a) in the presence of the water-swellable clay mineral (b). A step of forming an organic-inorganic composite hydrogel layer on the substrate;
(III) A step of drying the organic-inorganic composite hydrogel layer to obtain a dried gel layer. The manufacturing method of the anti-fogging material which has the following process.
(I) A composition (X) containing an energy ray-curable water-soluble organic monomer (a), a water-swellable clay mineral (b), an aqueous medium (c) and a water-insoluble polymerization initiator (d). Applying the composition (Y) containing the energy ray-curable hydrophobic monomer (e) and the polymerization initiator (f) on the coated substrate,
(Ii) The coating film of the composition (X) applied on the substrate is irradiated with energy rays to react the water-soluble acrylic monomer (a) in the presence of the water-swellable clay mineral (b). And a step of reacting a hydrophobic monomer to form a hydrophobic polymer layer and an organic-inorganic composite hydrogel layer on the substrate (iii) a step of drying the organic-inorganic composite hydrogel layer to obtain a dried gel layer. The water-insoluble polymerization initiator (d) in the composition (X) is dissolved in a solvent (g) and then dispersed in an aqueous medium (c). Manufacturing method of anti-fogging material . The method for producing an antifogging material according to claim 12, wherein the solvent (g) is an acrylic monomer that dissolves a water-insoluble polymerization initiator and has an HLB value of 8 or more. The method for producing an antifogging material according to claim 14, wherein the solvent (g) is a water-soluble solvent capable of dissolving a water-insoluble polymerization initiator. The weight ratio (d) / (g) of the water-insoluble polymerization initiator (d) to the solvent (g) in a solution in which the water-insoluble polymerization initiator (d) is dissolved in the solvent (g), It exists in the range of 0.001-0.1, The manufacturing method of the anti-fogging material in any one of Claims 12-16. In the composition (X), a dispersion amount of a solution in which the water-insoluble polymerization initiator (d) is dissolved in the solvent (g) is 5% by weight or less with respect to the total weight of the composition (X). It is a range, The manufacturing method of the anti-fogging material in any one of Claims 12-17. The antifogging according to any one of claims 12 to 18, wherein a dispersion diameter when a solution obtained by dissolving the water-insoluble polymerization initiator (d) in a solvent (g) is dispersed in an aqueous medium is 1 µm or less. Material manufacturing method.