WO2015083479A1

WO2015083479A1 - Heat-shielding antifog film and glass laminate

Info

Publication number: WO2015083479A1
Application number: PCT/JP2014/079306
Authority: WO
Inventors: 啓史別宮; 絢子稲垣; 梅田　博紀; 矢野　健太郎
Original assignee: コニカミノルタ株式会社
Priority date: 2013-12-05
Filing date: 2014-11-05
Publication date: 2015-06-11
Also published as: JPWO2015083479A1

Abstract

　A heat-shielding antifog film having heat-shielding and antifog functions, wherein the film is provided with a cellulose ester film (14), a hydrophilic heat ray reflecting layer (13) layered on one surface of the cellulose ester film (14), and an antifog layer (14a) formed by hydrophilizing the other surface of the cellulose ester film (14).

Description

Thermal barrier / antifogging film and glass laminate

The present invention relates to a heat-shielding and anti-fogging film having a heat-shielding function and an anti-fogging function, and a glass laminate having the same.

In recent years, interest in energy conservation measures has increased, and from the viewpoint of reducing the load on cooling equipment, there has been an increasing demand for heat ray reflective films that can be attached to window glass of buildings and vehicles to block the transmission of sunlight heat rays. ing.

The light emitted from the sun has a wide spectrum from the ultraviolet region to the infrared light region. Visible light has a wavelength range of 380 to 780 nm ranging from purple to yellow to red light, and occupies about 45% of sunlight. As for infrared light, those close to visible light are called near-infrared rays (wavelength 780 to 2500 nm), and more than that is called mid-infrared rays, accounting for about 50% of sunlight. The intensity of light energy in this region is as small as about one-tenth or less compared with ultraviolet light, but the thermal effect is large, and when absorbed by a substance, it is released as heat, resulting in an increase in temperature. For this reason, it is also called a heat ray, and by blocking these rays, the temperature rise in the room can be suppressed. Further, it is possible to suppress the heat of the winter in the cold region from being dissipated outside.

By the way, the glass used for window glass of buildings and vehicles, glass windows of freezers, water tanks, signboards, etc., water droplets adhere to the surface due to rain or moisture in the air condensing, and visibility is reduced. There's a problem. As a countermeasure, it has been proposed to attach an antifogging film to the surface of glass.

For example, Patent Document 1 discloses an agricultural film having an anti-fogging function and a heat shielding function.

JP 2010-220567 A

However, the film of Patent Document 1 is used for agriculture and is not suitable for window applications such as automobiles. This is because the visibility of a window of an automobile or the like corresponding to a rapid humidity change is important. Moreover, since it is necessary to stick a film on a window, the ease of construction such as a short construction time is also important.

In view of the above circumstances, the object of the present invention is to provide a heat-shielding and anti-fogging function that has a heat-shielding function, can be attached to glass in a short time by a material for water sticking, and has an anti-fogging property against a sudden change in humidity. To provide a film. Another object of the present invention is to provide a glass laminate in which the heat-shielding anti-fogging film and glass are adhered.

The above object of the present invention is achieved by the following configuration. That is, the heat-shielding and anti-fogging film of the present invention is a heat-shielding and anti-fogging film having a heat-shielding function and an anti-fogging function, and has a hydrophilic property laminated on one side of the cellulose ester film and the cellulose ester film. A heat ray reflective layer, and an antifogging layer formed by hydrophilizing the other surface of the cellulose ester film.

According to the above configuration, the heat-shielding anti-fogging film has a heat-shielding function by providing a heat ray reflective layer, and can be attached to glass in a short time with a water-adhesive adhesive due to the high moisture permeability of the cellulose ester film. By providing a defogging layer that has been subjected to a hydrophilic treatment, it has an defogging property against a sudden change in humidity.

It is sectional drawing which shows the structure of the glass laminated body of one Embodiment of this invention.

An embodiment of the present invention will be described below with reference to the drawings. In this specification, when the numerical range is expressed as A to B, the numerical value range includes the values of the lower limit A and the upper limit B.

[Configuration of glass laminate]
As shown in FIG. 1, the glass laminate 10 has a water-adhesive layer 12 (water-adhesive adhesive), a heat ray reflective layer 13, a cellulose ester film 14, and, if necessary, on one surface side of the glass 11. The hard coat layer 15 is laminated in this order. And the surface on the opposite side to the heat ray reflective layer 13 of the cellulose-ester film 14 is hydrophilized. The surface portion of the cellulose ester film 14 that has been hydrophilized is also referred to as a hydrophilic layer (antifogging layer) 14a, and the non-hydrophilic portion is also referred to as a non-hydrophilic layer 14b. Moreover, the heat ray reflective layer 13 and the cellulose ester film 14 are collectively referred to as a heat-shielding and anti-fogging film (which may include the water sticking pressure-sensitive adhesive 12 and / or the hard coat layer 15).

The glass 11 is assumed to be a window glass of a building or a vehicle, and its thickness is not particularly limited, but is usually 0.1 mm to 5 cm.

The adhesive 12 for water sticking is for sticking the heat ray reflective layer 13 to the glass 11. FIG. The water sticking pressure-sensitive adhesive 12 may be formed by applying a water-soluble water sticking pressure-sensitive adhesive to the glass 11, or the water sticking pressure-sensitive adhesive on the surface opposite to the cellulose ester film 14 of the heat ray reflective layer 13. You may form by apply | coating an agent. In addition, a type of adhesive (reactive adhesion) that reversibly cures and melts by water evaporation and rewetting is applied to the opposite side of the heat ray reflective layer 13 from the cellulose ester film 14. A heat-shielding and anti-fogging film may be prepared by drying, and when applied to a window glass or the like of a building or a vehicle, water may be sprayed on and adhered to the adhesive 12 for water application. Thereby, it can construct simply by using water.

The heat ray reflective layer 13 has hydrophilicity that can be attached to the glass 11 by the water sticking pressure-sensitive adhesive 12, and the material and the layer structure are not particularly limited as long as the heat ray transmission of sunlight can be blocked. In the present embodiment, a layer in which high refractive index layers and low refractive index layers are alternately stacked is used. The high refractive index layer and the low refractive index layer each contain a water-soluble polymer, and are formed on the cellulose ester film 14 by aqueous coating. Here, it is desirable that the cellulose ester film 14 has a moisture permeability that allows moisture to escape quickly during drying after aqueous application. For example, as the cellulose ester film 14, it is preferable to use a moisture permeable film having a moisture permeability of 100 g / m ² · 24 hr or more at 40 ° C. and 90% RH measured in accordance with JIS Z 0208. Since moisture does not remain in the heat ray reflective layer 13, the change in the film thickness of the heat ray reflective layer 13 is small due to environmental fluctuations (temperature change), and the change in reflectance can be suppressed.

The cellulose ester film 14 is a base material that supports the heat ray reflective layer 13 and has heat resistance. The cellulose ester film 14 is an antifogging film whose surface has been subjected to a hydrophilic treatment. It is preferable that the change in haze before and after applying steam to the cellulose ester film 14 is small (for example, within 3%). In this case, it can be said that the deterioration of the anti-fogging function of the cellulose ester film 14 after applying the steam is suppressed.

Moreover, in the cellulose ester film 14, since the fall of the anti-fogging function after applying a vapor | steam is suppressed, adhesion of the water droplet to a film surface can be suppressed and back visibility can be improved (rearward visibility by the surface water droplet) Can be reduced).

The hydrophilic treatment for imparting antifogging properties can be performed by light irradiation or saponification. When performing by light irradiation, the surface of a cellulose-ester film is irradiated with the light which has photon energy of 155 kcal / mol or more, for example. On the other hand, when the saponification is performed, for example, the surface of the cellulose ester film is subjected to alkali saponification treatment using an aqueous NaOH solution for 60 minutes, and then washed with water and dried.

In the light irradiation treatment, a uniform antifogging property can be imparted to the surface of the cellulose ester film, and sufficient antifogging property can be obtained by a thin hydrophilic layer as compared with the case where the hydrophilic layer is formed by a saponification treatment. Can be granted. Furthermore, since a light irradiation process can be performed with respect to the single side | surface of a film, the cellulose-ester film 14 obtained is hard to produce sticking and can be wound up in elongate form. Moreover, since it becomes unnecessary to pinch | protect the protective film for preventing sticking at the time of winding, cost is also reduced.

It is presumed that the ester group substituted on the side chain of the glucose ring is easily converted into a hydroxyl group by the above light irradiation on the cellulose ester film, and the hydrophilic layer 14a is reliably formed on the surface of the cellulose ester film 14. This is because the anti-fogging property can be reliably imparted to the cellulose ester film 14. Moreover, since cellulose ester itself has a hygroscopic property, the water vapor | steam which generate | occur | produced by the environmental change can also be taken in the inside (non-hydrophilic layer 14b) of the cellulose-ester film 14, and since an anti-fogging effect is acquired, it is preferable.

When the cellulose ester film 14 is immersed in methylene chloride, the non-hydrophilic layer 6b is dissolved, and the hydrophilic layer 6a is not dissolved but remains as a powder. From this, it can be said that the non-hydrophilic layer 6b is a methylene chloride-soluble layer and the hydrophilic layer 6a is a methylene chloride-insoluble layer.

The hard coat layer 15 is formed of, for example, an ultraviolet curable acrylate resin. Here, it is desirable that the hard coat layer 15 has a moisture permeability that allows moisture to escape quickly during drying after the application of the water sticking pressure-sensitive adhesive. For example, the hard coat layer 15 is preferably a moisture permeable layer having a moisture permeability of not less than 300 g / m ² · 24 hr at 40 ° C. and 90% RH as measured in accordance with JIS Z 0208. When the moisture in the water sticking adhesive 12 evaporates in a short time, the sticking is completed in a short time when the heat shielding and antifogging film is applied to the glass 11.

According to the configuration of the above-described heat-shielding and anti-fogging film, since it has a heat-shielding function and an anti-fogging function, it is exposed to sunlight or high humidity in the state of the glass laminate 10 mounted on the window glass of a building or vehicle. Suitable for use in such an environment.

[Details of each layer]
Hereinafter, the detail of each layer which comprises the glass laminated body 10 is demonstrated.

(Adhesive for water application)
The adhesive for water application may be selected from, for example, rubber-based, acrylic-based, silicon-based, and urethane-based pressure-sensitive adhesives, depending on the purpose. Since there is no yellowing over time, acrylic and silicon are preferable, and acrylic is most preferable in that a general-purpose release sheet can be used. The thickness of the adhesive layer for water application is preferably in the range of 5 μm to 30 μm. If it is 5 μm or less, the tackiness is unstable, and if it is 30 μm or more, the pressure-sensitive adhesive protrudes from the side of the film, resulting in inconvenience in handling.

(Heat ray reflective layer)
As the heat ray reflective layer of this embodiment, a layer in which high refractive index layers and low refractive index layers are alternately laminated is used.

In general, it is preferable to design a large difference in refractive index between the high refractive index layer and the low refractive index layer from the viewpoint that the infrared reflectance can be increased with a small number of layers. For example, in at least one of the units composed of a high refractive index layer and a low refractive index layer, the refractive index difference between the adjacent high refractive index layer and the low refractive index layer is preferably 0.1 or more, more Preferably it is 0.3 or more, More preferably, it is 0.35 or more, Most preferably, it is 0.4 or more. In the case of having a plurality of these units, it is preferable that the refractive index difference between the high refractive index layer and the low refractive index layer in all the units is within the preferable range. However, regarding the outermost layer and the lowermost layer, a configuration outside the above preferred range may be used. The preferred refractive index of the high refractive index layer is 1.80 to 2.50, more preferably 1.90 to 2.20. The preferred refractive index of the low refractive index layer is 1.10 to 1.60, more preferably 1.30 to 1.50.

The reflectance in a specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of layers, and the larger the difference in refractive index, the same reflectance can be obtained with a smaller number of layers. The refractive index difference and the required number of layers can be calculated using commercially available optical design software. For example, in order to obtain an infrared reflectance of 90% or more, if the difference in refractive index is less than 0.1, it is necessary to laminate 200 layers or more, which not only decreases productivity but also scattering at the interface of the layers. Becomes larger, the transparency is lowered, and it becomes very difficult to manufacture without failure. From the standpoint of improving reflectivity and reducing the number of layers, there is no upper limit to the difference in refractive index, but practically about 1.4 is the limit.

Further, as the optical characteristics of the heat ray reflective layer of this embodiment, the transmittance in the visible light region shown in JIS R3106-1998 is preferably 50% or more, preferably 75% or more, more preferably 85% or more. In addition, it is preferable that the region having a wavelength of 900 nm to 1400 nm has a region with a reflectance exceeding 50%.

The heat ray reflective layer of the present embodiment may have a configuration including at least one unit composed of a high refractive index layer and a low refractive index layer. As the number of layers of the high refractive index layer and the low refractive index layer, from the above viewpoint, the range of the total number of layers is 100 layers or less, that is, 50 units or less, more preferably 40 layers (20 units) or less. More preferably, it is 20 layers (10 units) or less.

The thickness per layer of the low refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 350 nm. On the other hand, the thickness per layer of the high refractive index layer is preferably 20 to 800 nm, and more preferably 50 to 350 nm.

Further, the high refractive index layer and the low refractive index layer in this embodiment each contain a water-soluble polymer, and are formed on the cellulose ester film by aqueous coating.

<Water-soluble polymer>
Examples of water-soluble polymers applicable to the high refractive index layer and the low refractive index layer include synthetic polymers, such as polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymers, Acrylic resins such as potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, or acrylic acid-acrylic ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer Styrene acrylic resin such as styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, or styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer , Styrene-sodium styrene sulfonate copolymer, steel Len-2-hydroxyethyl acrylate copolymer, styrene-2-hydroxyethyl acrylate-potassium styrene sulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer Vinyl acetate copolymers such as polymers, vinyl naphthalene-maleic acid copolymers, vinyl acetate-maleic acid ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and the like Salt. Among these, particularly preferable examples include polyvinyl alcohol, polyvinyl pyrrolidones, and copolymers containing the same.

The weight average molecular weight of the water-soluble polymer is preferably 1,000 or more and 200,000 or less. Furthermore, 3,000 or more and 40,000 or less are more preferable.

The polyvinyl alcohol preferably used includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a terminal cation modified or anionic modified polyvinyl alcohol having an anionic group. It is.

As the polyvinyl alcohol obtained by hydrolyzing vinyl acetate, those having an average degree of polymerization of 1,000 or more are preferably used, and those having an average degree of polymerization of 1,500 to 5,000 are particularly preferably used. The degree of saponification is preferably 70 to 100%, particularly preferably 80 to 99.5%.

Examples of the cation-modified polyvinyl alcohol have primary to tertiary amino groups and quaternary ammonium groups in the main chain or side chain of the polyvinyl alcohol as described in JP-A-61-10383. Polyvinyl alcohol, which is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride. N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl- (2-methacrylamidopropyl) ammonium chloride, N- (1, And 1-dimethyl-3-dimethylaminopropyl) acrylamide. The ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 to 10 mol%, preferably 0.2 to 5 mol%, relative to vinyl acetate.

Anion-modified polyvinyl alcohol is, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, as described in JP-A-61-237681 and JP-A-63-307979, Examples thereof include a copolymer of vinyl alcohol and a vinyl compound having a water-soluble group, and modified polyvinyl alcohol having a water-soluble group as described in JP-A-7-285265.

Nonionic modified polyvinyl alcohols include, for example, polyvinyl alcohol derivatives obtained by adding a polyalkylene oxide group to a part of vinyl alcohol as described in JP-A-7-9758, and described in JP-A-8-25795. And a block copolymer of a vinyl compound having a hydrophobic group and vinyl alcohol. Polyvinyl alcohol may use 2 or more types together, such as a polymerization degree and a different kind of modification | denaturation.

In this embodiment, a curing agent may be used together with the water-soluble polymer. When the water-soluble polymer is polyvinyl alcohol, boric acid and its salts and epoxy curing agents are preferred.

The content of the water-soluble polymer contained in the high refractive index layer and the low refractive index layer is 50 to 150% by mass with respect to 100% by mass of metal oxide particles (details will be described later) contained in the layer. It is preferably 80 to 120% by mass. If the amount of the water-soluble polymer is too small, the strength of the film may decrease, and if it is too large, the refractive index of the film may decrease. The water-soluble polymers contained in the high refractive index layer and the low refractive index layer may be the same or different from each other, but are preferably the same.

《Metal oxide particles》
Examples of the metal oxide particles that can be used in this embodiment include titanium dioxide, zirconium oxide, zinc oxide, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, lead titanate, red lead, yellow lead, and zinc. Examples thereof include yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, niobium oxide, europium oxide, lanthanum oxide, zircon, and tin oxide.

In order to form a transparent high refractive index layer having a higher refractive index, the high refractive index layer may contain high refractive index metal oxide fine particles such as titanium and zirconia, that is, fine titanium oxide particles and fine zirconia oxide particles. preferable. In particular, it is preferable to contain rutile (tetragonal) titanium oxide particles having a volume average particle diameter of 100 nm or less.

The volume average particle size of the titanium oxide particles or zirconia particles used in this embodiment is preferably 100 nm or less, more preferably 4 to 50 nm, and even more preferably 4 to 40 nm. A volume average particle diameter of 100 nm or less is preferable from the viewpoint of low haze and excellent visible light transmittance.

Here, the volume average particle diameter is a volume average particle diameter of primary particles or secondary particles dispersed in a medium, and can be measured by a laser diffraction / scattering method, a dynamic light scattering method, or the like.

When measuring the average diameter of the particles present in each layer, specifically, the particles themselves or the particles appearing on the cross section or surface of the refractive index layer are observed with an electron microscope, and 1,000 arbitrary particles are observed. In the group of metal oxide particles, each having a particle diameter of d1, d2,..., Dk, and n1, n2,. When the volume per unit is vi, the average particle diameter weighted by the volume represented by the volume average particle diameter mv = {Σ (vi · di)} / {Σ (vi)} is calculated.

Furthermore, the titanium oxide particles or zirconia oxide particles used in the present embodiment are preferably monodispersed. The monodispersion here means that the monodispersity obtained by the following formula is 40% or less. This monodispersity is more preferably 30% or less, and particularly preferably 0.1 to 20%.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 10

As the titanium oxide particles used in the present embodiment, the surface of the titanium oxide particles of an aqueous titanium oxide sol having a pH of 1.0 to 3.0 and a positive zeta potential of the titanium particles is hydrophobized to an organic solvent. It is preferable to use a dispersion-dispersible material.

Examples of a method for preparing an aqueous titanium oxide sol that can be used in the present embodiment include JP-A 63-17221, JP-A 7-819, JP-A 9-165218, and JP-A 11-43327. Reference can be made to the matters described in JP-A No. 63-17221, JP-A No. 7-819, JP-A No. 9-165218, JP-A No. 11-43327, and the like.

The content of the metal oxide particles in the high refractive index layer is preferably 15 to 70% by mass and more preferably 20 to 65% by mass with respect to 100% by mass of the solid content of the high refractive index layer. Preferably, it is 30 to 60% by mass.

On the other hand, the metal oxide particles contained in the low refractive index layer are preferably silicon dioxide, and examples thereof include synthetic amorphous silica and colloidal silica. Of these, acidic colloidal silica sol is more preferably used, and colloidal silica sol dispersed in an organic solvent is more preferably used. In order to further reduce the refractive index, it is particularly preferable to use hollow fine particles having pores inside the particles as metal oxide fine particles, and hollow fine particles of silicon dioxide (silica) are most preferred.

The volume average particle size of the metal oxide particles contained in the low refractive index layer is preferably 3 to 100 nm, more preferably 3 to 50 nm, and even more preferably 3 to 30 nm.

The volume average particle diameter of the metal oxide fine particles contained in the low refractive index layer is determined by the same method as the measurement of the average particle diameter of the metal oxide particles contained in the high refractive layer.

The colloidal silica used in this embodiment is obtained by heating and aging a silica sol obtained by metathesis of sodium silicate with an acid or the like or passing through an ion exchange resin layer. For example, JP-A-57-14091 JP, 60-219083, JP 60-218904, JP 61-20792, JP 61-188183, JP 63-17807, JP 4-207 No. 93284, JP-A-5-278324, JP-A-6-92011, JP-A-6-183134, JP-A-6-297830, JP-A-7-81214, JP-A-7-101142 Publications, JP-A-7-179029, JP-A-7-137431, and WO94 / 26530. Are those described.

Such colloidal silica may be a synthetic product or a commercially available product.

The surface of the colloidal silica may be cation-modified, or may be treated with Al, Ca, Mg, Ba or the like.

The hollow fine particles used in this embodiment preferably have an average particle pore size of 3 to 70 nm, more preferably 5 to 50 nm, and even more preferably 5 to 45 nm. The average particle pore size of the hollow fine particles is an average value of the inner diameters of the hollow fine particles. In the present invention, when the average particle pore diameter of the hollow fine particles is within the above range, the refractive index of the low refractive index layer is sufficiently lowered. The average particle diameter is 50 or more at random, which can be observed as an ellipse in a circular, elliptical or substantially circular shape by electron microscope observation, and obtains the pore diameter of each particle. Is obtained. In the present specification, as the average particle pore diameter, the minimum distance among the distances between the outer edges of the pore diameter that can be observed as a circle, an ellipse, a substantially circle or an ellipse, between two parallel lines Means.

The hollow fine particles used in this embodiment preferably have an average outer thickness of 10 nm or less, more preferably 1 to 7 nm, and even more preferably 1 to 5 nm. In addition, in this specification, the outer side part of the void | hole in a hollow microparticle is called outline. A thickness of the outer shell of 10 nm or less is preferable because the haze is small and the light transmittance of the glass laminate is excellent. If the thickness of the outer shell is 1 nm or more, the mechanical strength of the particles is increased and the shape can be maintained in the low refractive index layer, so that formation of pores is facilitated. The average thickness of the outer shell is observed by electron microscope observation, and the average thickness of the outer shell of the pores that can be observed as a circle, ellipse, or substantially circular as an ellipse is randomly observed, and 50 or more of the outer shell of each particle is observed. The average thickness is obtained, and the number average value is obtained.

Such hollow fine particles may be a synthetic product or a commercially available product. Here, as hollow fine particles of silicon dioxide (silica), for example, an organic silicon compound (for example, alkoxysilane such as tetraethoxysilane) is added to a calcium carbonate aqueous dispersion under alkaline conditions (for example, addition of ammonia). , Stir. Thereafter, the mixture is heated to 50 to 80 ° C. and stirred to obtain a silica-coated calcium carbonate dispersion. The silica-coated calcium carbonate dispersion is decomposed under acidic conditions (for example, acetic acid is added) to decompose calcium carbonate and generate carbon dioxide to elute calcium carbonate. After adding distilled water to the obtained dispersion, ultrafiltration is performed on the dispersion until the same amount of distilled water as that added is discharged. By performing the ultrafiltration 1 to 5 times, a dispersion containing silica hollow fine particles can be obtained.

The content of the metal oxide particles in the low refractive index layer is preferably 0.1 to 50% by mass, and preferably 0.5 to 45% by mass with respect to 100% by mass of the solid content of the low refractive index layer. More preferred is 1 to 40% by mass, still more preferred is 5 to 30% by mass.

<Thermal gelling agent>
As for the heat ray reflective layer of this embodiment, it is desirable that at least one of the high refractive index layer and the low refractive index layer contains a thermal gelling agent. By setting it as such a structure, the crack in a heat ray reflective layer, the nonuniformity, and also the mixing of the particle | grains between a high refractive index layer and a low refractive index layer are prevented. As a result, a heat ray reflective layer excellent in flexibility, transparency, and infrared shielding property can be produced with high productivity.

In the present specification, the “thermal gelling agent” is a substance that has a property of dissolving in water, forming a thickened gel by heating, and forming a sol by cooling. Although there is no restriction | limiting in particular about the temperature which a thermogelling agent gelatinizes, Preferably it is 40 degreeC or more, More preferably, it is 50 degreeC or more, More preferably, it is 60 degreeC or more. As long as the above definition is satisfied, there is no limitation on the specific form of the thermal gelling agent used in the present embodiment. For example, examples of the thermal gelling agent include curdlan, methyl cellulose (MC), hydroxyethyl methyl cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl cellulose (HEC), egg white, soybean globulin, and the like. . At this time, hydroxypropyl methylcellulose may be appropriately selected from those having preferable properties since the viscosity and solubility at the time of dissolution differ depending on the molecular weight and the methoxy group / propyl group content. In the produced glass laminate, the thermal gelling agent is usually already in a gelled state. Also in such a case, it is understood that “including a thermal gelling agent”. The same applies to the “low temperature gelling agent” described later.

As described above, in this embodiment, at least one of the high refractive index layer and the low refractive index layer may contain a thermal gelling agent, but at least one layer of the high refractive index layer may contain a thermal gelling agent. preferable. Moreover, it is more preferable that all the high refractive index layers contain a thermal gelling agent. In still another preferred form, at least one of both the high refractive index layer and the low refractive index layer preferably contains a thermal gelling agent, and all the high refractive index layers and all the low refractive index layers are thermal gels. More preferably, an agent is included.

The content of the thermal gelling agent contained in each layer is not particularly limited, but when the high refractive index layer contains a thermal gelling agent, the content of the thermal gelling agent in the high refractive index layer is that of the high refractive index layer. The content is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and further preferably 7 to 20% by mass with respect to 100% by mass of the solid content. When the low refractive index layer contains a thermal gelling agent, the content of the thermal gelling agent in the low refractive index layer is 3 to 30% by mass with respect to 100% by mass of the solid content of the low refractive index layer. It is preferably 5 to 25% by mass, more preferably 7 to 20% by mass.

《Low temperature gelling agent》
In a more preferred form of the present embodiment, at least one of the high refractive index layer and the low refractive index layer contains a low temperature gelling agent. By adopting such a configuration, there is an advantage that it is possible to further ensure the expression of the above-described operational effects exhibited by the use of the thermal gelling agent.

In the present specification, the “low temperature gelling agent” is a substance that has the property of dissolving in an aqueous solution, forming a thickened gel upon cooling, and forming a sol upon heating. Although there is no restriction | limiting in particular about the temperature which a low temperature gelatinizer gelatinizes, Preferably it is 10 degrees C or less, More preferably, it is 15 degrees C or less, More preferably, it is 20 degrees C or less. As long as such a definition is satisfied, there is no limitation on the specific form of the thermal gelling agent used in this embodiment. For example, gelatin, carrageenan, gellan gum, pectin, sodium alginate and the like have been developed as low temperature gelling agents. In addition, there are many that cause thickening gelation by cooling by coexisting with other components, for example, a combination of galactoxycycloglucan and alcohol, a combination of polyvinyl alcohol, boric acid, silica, etc. can be preferably used. .

As for the low temperature gelling agent, when at least one of the high refractive index layer and the low refractive index layer contains a low temperature gelling agent, it is preferable that at least one layer of the high refractive index layer contains a low temperature gelling agent. More preferably, all the high refractive index layers contain a low temperature gelling agent. In still another preferred embodiment, at least one of both the high refractive index layer and the low refractive index layer preferably contains a low temperature gelling agent, and all the high refractive index layers and all the low refractive index layers are low temperature gels. More preferably, an agent is included.

There is no particular restriction on the content of the low temperature gelling agent contained in each layer when the low temperature gelling agent is used, but the low refractive index gelation in the high refractive index layer when the high refractive index layer contains the low temperature gelling agent. The content of the agent is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and 7 to 20% by mass with respect to 100% by mass of the solid content of the high refractive index layer. More preferably. When the low refractive index layer contains a low temperature gelling agent, the content of the low temperature gelling agent in the low refractive index layer is 3 to 30% by mass with respect to 100% by mass of the solid content of the low refractive index layer. It is preferably 5 to 25% by mass, more preferably 7 to 20% by mass.

《Other additives》
Various additives can be used in the high refractive index layer and the low refractive index layer as necessary. One example is described below.

[Amino acids with an isoelectric point of 6.5 or less]
The high refractive index layer or the low refractive index layer may contain an amino acid having an isoelectric point of 6.5 or less. By including an amino acid, the dispersibility of the metal oxide particles in the high refractive index layer or the low refractive index layer can be improved.

Here, an amino acid is a compound having an amino group and a carboxyl group in the same molecule, and may be any type of amino acid such as α-, β-, and γ-. Some amino acids have optical isomers, but in the present invention, there is no difference in effect due to optical isomers, and any isomer can be used alone or in racemic form.

For a detailed explanation of amino acids, refer to the description on pages 268 to 270 of the 1st edition of the Chemistry Dictionary (Kyoritsu Shuppan; published in 1960).

Specific examples of preferred amino acids include aspartic acid, glutamic acid, glycine, serine, and the like, with glycine and serine being particularly preferred.

The isoelectric point of an amino acid refers to this pH value because an amino acid balances the positive and negative charges in the molecule at a specific pH and the overall charge is zero. The isoelectric point of each amino acid can be determined by isoelectric focusing at a low ionic strength.

[Emulsion resin]
The high refractive index layer or the low refractive index layer may further contain an emulsion resin. By including the emulsion resin, the flexibility of the film is increased and the workability such as sticking to glass is improved.

An emulsion resin is a resin in which fine resin particles having an average particle diameter of about 0.01 to 2.0 μm, for example, are dispersed in an emulsion state in an aqueous medium. Obtained by emulsion polymerization using a molecular dispersant. There is no fundamental difference in the polymer component of the resulting emulsion resin depending on the type of dispersant used. Examples of the dispersant used in the polymerization of the emulsion include polyoxyethylene nonylphenyl ether in addition to low molecular weight dispersants such as alkylsulfonate, alkylbenzenesulfonate, diethylamine, ethylenediamine, and quaternary ammonium salt. , Polymer dispersing agents such as polyoxyethylene lauryl ether, hydroxyethyl cellulose, and polyvinylpyrrolidone. When emulsion polymerization is performed using a polymer dispersant having a hydroxyl group, the presence of hydroxyl groups is estimated on at least the surface of fine particles, and the emulsion resin polymerized using other dispersants has chemical and physical properties of the emulsion. Different.

The polymer dispersant containing a hydroxyl group is a polymer dispersant having a weight average molecular weight of 10,000 or more, and has a hydroxyl group substituted at the side chain or terminal. For example, an acrylic polymer such as sodium polyacrylate or polyacrylamide is used. Examples of such polymers include 2-ethylhexyl acrylate copolymer, polyethers such as polyethylene glycol and polypropylene glycol, and polyvinyl alcohol. Polyvinyl alcohol is particularly preferable.

Polyvinyl alcohol used as a polymer dispersant is an anion-modified polyvinyl alcohol having an anionic group such as a cation-modified polyvinyl alcohol or a carboxyl group in addition to ordinary polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate. Further, modified polyvinyl alcohol such as silyl-modified polyvinyl alcohol having a silyl group is also included. Polyvinyl alcohol has a higher effect of suppressing the occurrence of cracks when forming the ink absorbing layer when the average degree of polymerization is higher, but when the average degree of polymerization is within 5000, the viscosity of the emulsion resin is not high, and at the time of production Easy to handle. Accordingly, the average degree of polymerization is preferably 300 to 5000, more preferably 1500 to 5000, and particularly preferably 3000 to 4500. The saponification degree of polyvinyl alcohol is preferably 70 to 100 mol%, more preferably 80 to 99.5 mol%.

Examples of the resin that is emulsion-polymerized with the above polymer dispersant include homopolymers or copolymers of ethylene monomers such as acrylic acid esters, methacrylic acid esters, vinyl compounds, and styrene compounds, and diene compounds such as butadiene and isoprene. Examples of the polymer include acrylic resins, styrene-butadiene resins, and ethylene-vinyl acetate resins.

[Other additives]
In addition, the high refractive index layer or the low refractive index layer is, for example, an ultraviolet absorber described in JP-A-57-74193, JP-A-57-87988 and JP-A-62-261476, -74192, 57-87989, 60-72785, 61-146591, JP-A-1-95091, 3-3-1376, etc., Various anionic, cationic or nonionic surfactants such as JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-228771 and JP-A-4-219266 The optical brighteners described, pH adjusters such as sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, Foams, lubricants such as diethylene glycol, preservatives, antistatic agents, may contain various known additives such as a matting agent.

[Method for forming heat ray reflective layer]
The method for forming the heat ray reflective layer includes a coating solution for a high refractive index layer containing a first water-soluble polymer and first metal oxide particles, a second water-soluble polymer and second metal oxide particles. A step (application step) of applying a coating solution for a low refractive index layer. In at least one of the coating steps, the high refractive index layer coating liquid or the low refractive index layer coating liquid contains a thermal gelling agent, and the coating film of the coating liquid containing the thermal gelling agent is heated to form a thermal gel. It further includes a heating gelation step of gelling the agent.

The method for forming each refractive index layer on the cellulose ester film is not particularly limited, but a high refractive index layer coating solution and a low refractive index layer coating solution are alternately applied and dried to form a laminate. Is preferred. Specific examples include the following: (1) A high refractive index layer coating solution is applied onto a film and dried to form a high refractive index layer, and then a low refractive index layer coating solution is applied and dried. Forming a low refractive index layer and forming a heat ray reflective layer; (2) applying a low refractive index layer coating solution on the film and drying to form a low refractive index layer; then applying a high refractive index layer A method of forming a heat-reflective layer by applying a liquid and drying to form a heat-reflective layer; (3) On the film, a high refractive index layer coating liquid and a low refractive index layer coating liquid are alternately layered successively. A method of forming a heat ray reflective layer including a high refractive index layer and a low refractive index layer by coating and drying; (4) a high refractive index layer coating solution and a low refractive index layer coating solution on a film; And a method of forming a heat ray reflective layer including a high refractive index layer and a low refractive index layer by simultaneously applying multiple layers and drying. Among these, the method (4), which is a simpler manufacturing process, is preferable.

Examples of the coating method include a roll coating method, a rod bar coating method, an air knife coating method, a spray coating method, a curtain coating method, or US Pat. Nos. 2,761,419 and 2,761,791. A slide bead coating method using an hopper, an extrusion coating method, or the like is preferably used.

The solvent for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited, but water, an organic solvent, or a mixed solvent thereof is preferable.

Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol, and 1-butanol, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethyl ether. And ethers such as propylene glycol monomethyl ether and ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, and ketones such as acetone, methyl ethyl ketone, acetylacetone and cyclohexanone. These organic solvents may be used alone or in combination of two or more. From the viewpoint of environment and simplicity of operation, the solvent of the coating solution is preferably water or a mixed solvent of water and methanol, ethanol, or ethyl acetate, and more preferably water.

The concentration of the water-soluble polymer in the high refractive index layer coating solution is preferably 1 to 10% by mass. The concentration of the metal oxide particles in the high refractive index layer coating solution is preferably 1 to 50% by mass. Further, when the coating solution for high refractive index layer contains a thermal gelling agent, the concentration thereof is preferably 0.1 to 3% by mass, more preferably 1 to 2% by mass. If this density | concentration is 0.1 mass% or more, the gelatinization by the heating in the heating gelation process mentioned later can fully advance. On the other hand, if this concentration is 3% by mass or less, the occurrence of unevenness due to non-uniform gelation by heating in the heating gelation step can be suppressed. Further, when the coating solution for the high refractive index layer contains a low temperature gelling agent, the concentration is preferably 0.3 to 10% by mass, more preferably 0.5 to 3% by mass. More preferably, the content is 0.7 to 2% by mass. If the concentration is 0.3% by mass or more, sufficient mixing of the particles can be expected. On the other hand, if the concentration is 10% by mass or less, the uniformity of the coating film can be sufficiently ensured.

The concentration of the water-soluble polymer in the low refractive index layer coating solution is preferably 1 to 10% by mass. The concentration of the metal oxide particles in the low refractive index layer coating solution is preferably 1 to 50% by mass. Further, for the same reason as in the case of the coating liquid for the high refractive index layer described above, the concentration when the coating liquid for the low refractive index layer contains a thermal gelling agent is preferably 0.1 to 3% by mass. More preferably, it is 1 to 2% by mass. When the low refractive index layer coating solution contains a low-temperature gelling agent, the concentration is preferably 0.3 to 10% by mass, more preferably 0.5 to 3% by mass. More preferably, the content is 0.7 to 2% by mass. If the concentration is 0.3% by mass or more, sufficient mixing of the particles can be expected. On the other hand, if the concentration is 10% by mass or less, the uniformity of the coating film can be sufficiently ensured.

The method for preparing the high refractive index layer coating solution and the low refractive index layer coating solution is not particularly limited, and includes, for example, a water-soluble polymer, metal oxide particles, a thermal gelling agent and a low temperature gelling agent, and as necessary. Examples include a method of adding other additives to be added and stirring and mixing. At this time, the order of addition of the respective components is not particularly limited, and the respective components may be sequentially added and mixed while stirring, or may be added and mixed at one time while stirring. If necessary, it is further adjusted to an appropriate viscosity using a solvent.

In this embodiment, it is preferable to form the high refractive index layer using an aqueous high refractive index coating solution prepared by adding and dispersing rutile type titanium oxide having a volume average particle size of 100 nm or less. At this time, the rutile type titanium oxide is added to the high refractive index layer coating solution as an aqueous titanium oxide sol having a pH of 1.0 or more and 3.0 or less and a positive zeta potential of the titanium particles. It is preferable to prepare.

When the slide bead coating method is used, the viscosity of the high refractive index layer coating solution and the low refractive index layer coating solution in the simultaneous multilayer coating (4) is preferably in the range of 5 to 100 mPa · s. More preferably, it is in the range of 10 to 50 mPa · s. When the curtain coating method is used, the range of 5 to 1200 mPa · s is preferable, and the range of 25 to 500 mPa · s is more preferable.

The viscosity of the coating solution at 15 ° C. is preferably 100 mPa · s or more, more preferably 100 to 30,000 mPa · s, still more preferably 3,000 to 30,000 mPa · s, and most preferably 10 , 30,000 to 30,000 mPa · s.

Any method can be used as a coating and drying method. The temperature of the coating solution when applying the coating solution is preferably 15 to 40 ° C., more preferably 30 to 40 ° C. And, for example, after performing simultaneous multi-layer coating, if the low-temperature gelling agent is not included, the thermal gelling agent is gelled by heat treatment to thicken the coating solution (heating gelation step), A heat ray reflective layer can be manufactured, suppressing mixing of the particle | grains contained in the high refractive index layer and the low refractive index layer by heat-drying with warm air etc. as needed. At this time, with respect to the heating conditions in the heating gelation step, the temperature is preferably 60 to 150 ° C., and the heating time is preferably 10 to 60 seconds. The drying conditions after the heat gelation step are preferably 50 ° C. or more, and more preferably, the drying conditions are a wet bulb temperature of 50 ° C. to 150 ° C. and a film surface temperature of 50 ° C. to 100 ° C. It is to be performed under the conditions of. Moreover, it is preferable to carry out by the horizontal set system from a viewpoint of the formed coating-film uniformity as a heating system in the heating gelation process immediately after application | coating.

On the other hand, when a low-temperature gelling agent is used in combination, for example, after simultaneous multi-layer coating, the low-temperature gelling agent is gelled by cooling (such as using cold air) to thicken the coating solution (cooling gelation step) ), And then the heat gelling agent is gelled by heat treatment to increase the viscosity of the coating solution (heating gelation step), and if necessary, by heating and drying with warm air or the like, the high refractive index layer and A heat ray reflective layer can be produced while suppressing mixing of particles contained in the low refractive index layer. At this time, the temperature during cooling in the cooling gelation step is preferably 1 to 15 ° C., more preferably 10 to 15 ° C. The cooling time is preferably 10 to 60 seconds. In addition, as a cooling system in a cooling gelation process, it is preferable to carry out by a horizontal set system from a viewpoint of the formed coating-film uniformity. The temperature during the heat treatment in the heat gelation step after the cooling gelation step is preferably 10 ° C. or higher, more preferably under conditions of a wet bulb temperature of 5 to 58 ° C. and a film surface temperature of 10 to 80 ° C. Is to do.

In each of the above-described forms, any heating method such as warm air heating, infrared heating, or microwave heating can be used as the heating method in the heating gelation step for gelling the thermal gelling agent. However, from the viewpoint of productivity and cost, it is necessary to raise the temperature of the coating liquid to the gelation temperature using infrared heating that has a high rate of temperature rise and does not lose heat by evaporation, and to dry the hot air after the coating liquid is gelled. To preferred.

(Cellulose ester film)
The cellulose ester film is mainly composed of a cellulose ester resin composition (hereinafter also simply referred to as cellulose ester), and if necessary, a plasticizer, an ultraviolet absorber, fine particles, a dye, a sugar ester compound, an acrylic copolymer, which will be described later. It is a film containing additives such as coalescence. In the present specification, the cellulose ester is a part or all of hydrogen atoms of hydroxyl groups (—OH) at the 2nd, 3rd and 6th positions in the β-1,4 bonded glucose units constituting cellulose. Refers to a cellulose acylate resin substituted with an acyl group.

In addition, it is desirable that a phosphoric acid plasticizer is not added to the cellulose ester film. This is to prevent the film from deteriorating due to hydrolysis.

The cellulose ester is not particularly limited. Examples thereof include cellulose ester resins substituted with an aliphatic acyl group having 2 to 20 carbon atoms. Among these, those having an acyl group having 2 to 4 carbon atoms are preferable, and an acetyl group, a propionyl group, and a butanoyl group are more preferable. Note that the acyl group in the cellulose ester may be a single species or a combination of a plurality of acyl groups.

Specific preferred cellulose esters include cellulose acylate resins such as cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, and cellulose acetate propionate, and more preferably cellulose triacetate, cellulose diacetate, and cellulose ester pro Examples thereof include cellulose acylate resins such as pionate. These cellulose esters may be used singly or in combination of two or more. Among these, acetylcellulose is preferable.

The cellulose used as the raw material for the cellulose ester is not particularly limited, and examples thereof include cotton linters, wood pulp (derived from conifers and hardwoods), kenaf and the like. Moreover, the cellulose ester obtained from these can be mixed and used for each arbitrary ratio.

The cellulose ester can be produced by a known method. Generally, cellulose is esterified by mixing cellulose as a raw material, a predetermined organic acid (such as acetic acid or propionic acid), an acid anhydride (such as acetic anhydride or propionic anhydride), and a catalyst (such as sulfuric acid). The reaction proceeds until the triester is formed. In the triester, the three hydroxyl groups of the glucose unit are substituted with an acyl group of an organic acid. When two kinds of organic acids are used at the same time, a mixed ester type cellulose ester such as cellulose acetate propionate or cellulose acetate butyrate can be produced. Subsequently, a cellulose ester having a desired degree of acyl substitution can be synthesized by hydrolyzing the cellulose triester. Thereafter, a cellulose ester is finally produced through steps such as filtration, precipitation, washing with water, dehydration, and drying.

More specifically, the cellulose ester can be synthesized with reference to the methods described in JP-A-10-45804, JP-A-2005-281645, JP-A-2003-270442, and the like. Commercially available films include Konica Minolta KC4UAW, KC6UAW, N-TAC KC4KR, FUJIFILM UZ-TAC, TD-80UL, and materials manufactured by Daicel Corporation. L20, L30, L40, and L50, Ca398-3, Ca398-6, Ca398-10, Ca398-30, Ca394-60S manufactured by Eastman Chemical Japan Co., Ltd., and the like can be mentioned.

The degree of substitution of the acyl group of the cellulose ester is preferably 2.0 or more from the viewpoint of antifogging properties and production stability in the production process. On the other hand, the substitution degree of the acyl group is preferably 3.0 or less from the viewpoint of durability with time of the film. In the present specification, the degree of substitution of acyl groups refers to the average number of acyl groups per glucose unit, and any one of the hydrogen atoms of hydroxyl groups at the 2nd, 3rd and 6th positions of the 1 glucose unit is an acyl group. Indicates the percentage replaced. That is, when all of the hydrogen atoms of the hydroxyl groups at the 2nd, 3rd and 6th positions are substituted with acyl groups, the degree of substitution (maximum degree of substitution) is 3.0. The method for measuring the substitution degree of the acyl group can be carried out in accordance with ASTM D-817-91.

The weight average molecular weight (Mw) of the cellulose ester is preferably 75,000 or more, more preferably 80,000 or more, from the viewpoint of improving the heat resistance and strength (resistance to tension and tearing) of the film. More preferably, it is 85,000 or more. On the other hand, the smaller the molecular weight, the more the deformation force of the film over time can be absorbed between the resin molecules, and wrinkles and peeling can be suppressed. Therefore, the weight average molecular weight (Mw) is preferably 300,000 or less, more preferably. Is 200,000 or less, more preferably 150,000 or less.

The value of the ratio Mw / Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose ester is preferably 2.0 to 3.5. The weight average molecular weight (Mw) and number average molecular weight (Mn) of these cellulose esters can be measured using gel permeation chromatography (GPC), for example, under the following conditions.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three products manufactured by Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1000000-500 calibration curves with 13 samples are used. Thirteen samples are used at approximately equal intervals.

(Hydrophilic layer (anti-fogging layer))
As described above, the surface of the cellulose ester film is hydrophilized by light irradiation or saponification. Usually, light irradiation is performed on one side of the film, while saponification is performed on both sides of the film. Thereby, some of the substituents in which carbon is substituted in the side chains existing on the film surface are substituted with oxygen-containing polar groups such as hydroxyl groups. By such a hydrophilic treatment, an appropriate water absorption is imparted to the film surface. Even if water drops adhere to the film surface to which water absorption is given, for example, when rain or moisture in the air is condensed, the surface is wet and spreads, and the haze is increased by forming a hydrated layer. Therefore, the anti-fogging property in terms of ensuring visibility is exhibited.

In this specification, the hydrophilization treatment refers to, for example, a treatment for substituting an acyloxy group in a cellulose ester described later with an oxygen-containing polar group such as a hydroxyl group, a carbonyl group, or a carboxylic acid group. Particularly preferred. By the hydrophilic treatment, a hydrophilic group is introduced into the antifogging layer, resulting in a layer excellent in hydrophilicity and water absorption, and antifogging properties are exhibited.

Examples of the light irradiation method include treatment using vacuum ultraviolet rays. For example, (1) Excimer UV irradiation with a light source (excimer UV lamp) using Ar, Kr, Xe or the like in a nitrogen environment ( Excimer UV irradiation method) and (2) a method using a low-pressure mercury lamp. Among these, excimer UV is irradiated from the viewpoint that it is excellent in hydrophilization in the depth direction of the film, can impart sufficient water absorption to the film surface, and can easily obtain a film with little change in performance over time. The method is preferred. Among these, it is particularly preferable to irradiate with a light source using Xe.

In the light irradiation using these light sources, the integrated light amount is preferably adjusted appropriately for each light source. This prevents the film from becoming excessively hydrophilic. Hereinafter, each method will be described.

(1) Method of irradiating excimer UV The method of irradiating excimer UV will be specifically described by way of example using a xenon (Xe) lamp. Xe used in a xenon lamp is a rare gas, and atoms of the rare gas are chemically bonded to form no molecule. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. For Xe,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer UV of 172 nm is emitted.

A method using dielectric barrier discharge is known for obtaining excimer UV. Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. It is a similar discharge called a very thin micro discharge.

In addition to the dielectric barrier discharge, electrodeless electric field discharge is also known as a method for efficiently obtaining excimer UV. The electrodeless field discharge is a discharge due to capacitive coupling, and is also called an RF discharge. The lamp and electrodes and their arrangement may be basically the same as in dielectric barrier discharge, but the high frequency applied between the two electrodes is several MHz. In the electrodeless field discharge, a spatially and temporally uniform discharge can be obtained in this way. The xenon lamp emits UV having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency.

Also, since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, the excimer lamp does not emit light having a long wavelength that causes a temperature increase due to light, and irradiates energy of a single wavelength in the ultraviolet region, so that an increase in the surface temperature of the irradiation object can be suppressed. Therefore, it is suitable for irradiation to a resin film that is easily affected by heat.

Excimer UV treatment is a treatment method in which light is irradiated with an excimer UV light source in a state where the oxygen concentration is lowered (generally lower than 1%) by nitrogen purging or vacuuming. An excimer irradiation device commercially available from USHIO INC. Or M.D. excimer can be used as appropriate.

When an excimer lamp having a peak wavelength of 165 nm to 175 nm using Xe as a discharge gas is used, the integrated light amount is preferably 50 mJ or more and 1000 mJ or less, more preferably 100 mJ or more and 900 mJ or less, and 300 mJ or more and 600 mJ or less. More preferably. By performing light irradiation so as to obtain such an integrated light amount, the surface of the film is well hydrophilized, and sufficient water absorption performance is exhibited. Further, such water absorption performance hardly changes over time.

(2) Method using a low-pressure mercury lamp As a specific example of a method using a low-pressure mercury lamp, for example, a low-pressure mercury lamp having a peak wavelength of 180 nm to 190 nm and a low-pressure mercury lamp having a peak wavelength of 250 nm to 260 nm are used. The method to use is mentioned. When using a low-pressure mercury lamp having a peak wavelength of 180 nm to 190 nm and a low-pressure mercury lamp having a peak wavelength of 250 nm to 260 nm, the integrated light quantity of the peak wavelength is preferably 1000 mJ to 10,000 mJ, and preferably 3000 mJ to 9000 mJ. More preferably, it is more preferably 5000 mJ or more and 8000 mJ or less. By performing light irradiation so as to obtain such an integrated light amount, the surface of the film is well hydrophilized, and sufficient water absorption performance is exhibited. Further, such water absorption performance hardly changes over time. Furthermore, a low-pressure mercury lamp can easily provide an antifogging function when irradiated under the atmosphere rather than under nitrogen and under vacuum. Moreover, yellowing of a film can be prevented by cutting a wavelength of 254 nm with a filter.

In the method using a low-pressure mercury lamp, for example, a low-pressure mercury lamp commercially available from USHIO INC. Can be used.

In addition to the above light irradiation, a corona discharge treatment or a plasma treatment may be performed. The corona discharge treatment is a treatment performed by applying a high voltage of 1 kV or higher between the electrodes under atmospheric pressure and discharging. By corona discharge treatment, oxygen-containing polar groups (hydroxyl group, carbonyl group, carboxylic acid group, etc.) are generated on the film surface, and the surface is hydrophilized. The corona discharge treatment can be performed using an apparatus commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. The plasma treatment is a treatment for irradiating the substrate surface with a plasma gas to modify the substrate surface, and examples thereof include glow discharge treatment and flame plasma treatment. For these treatments, for example, methods described in JP-A-6-123062, JP-A-11-293011, JP-A-11-005857, etc. can be used. By the plasma treatment, oxygen-containing polar groups (hydroxyl group, carbonyl group, carboxylic acid group, etc.) are generated on the film surface, and the surface is hydrophilized. In the glow discharge treatment, a film is placed between opposing electrodes, a plasma-excitable gas is introduced into the apparatus, and a high-frequency voltage is applied between the electrodes, thereby plasma-exciting the gas and causing a glow between the electrodes. It is what discharges. Thereby, the film surface is processed and hydrophilicity is improved.

[Method for producing cellulose ester film]
Next, the manufacturing method of the cellulose-ester film 14 which has anti-fogging property is demonstrated.

The cellulose ester film 14 includes: (a) a step of forming a cellulose ester by a solution casting method or a melt casting method (film forming step); and (b) a step of hydrophilizing the surface of the film formed. Can be manufactured. In addition, you may manufacture the cellulose-ester film 14 which has anti-fogging property by performing a hydrophilic treatment by the process of said (b) using a commercially available cellulose-ester film.

(A) Film-forming step First, a cellulose ester is formed by a solution casting method or a melt casting method. Hereinafter, the film forming method will be described by taking the case of using the solution pouring method as an example, but the melt pouring method can also be carried out with reference to a conventionally known method. In the case of film formation by the solution pouring method, the film formation step is preferably (i) a dope preparation step, (ii) a dope casting step, (iii) a drying step 1, (iv) a peeling step, and (v) a stretching step. (Vi) a drying step 2 and (vii) a film winding step.

(I) Dope preparation process A dope preparation process is a process which prepares dope by dissolving the cellulose ester and the additive mentioned later in a solvent as needed. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy is poor. Become. The concentration that achieves both of these is, for example, 10 to 35% by mass, and preferably 15 to 25% by mass.

The solvent used at the time of dope preparation may be used alone or in combination of two or more. From the viewpoint of production efficiency, it is preferable to use a solvent (good solvent) that dissolves cellulose ester alone and a solvent (poor solvent) that does not swell or dissolve cellulose ester alone. The good solvent is preferably methylene chloride or methyl acetate. As the poor solvent, for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used. A form in which water is contained in the dope in an amount of 0.01 to 2% by mass is also preferable.

As the solvent used for dissolving the cellulose ester, a solvent in which the solvent removed from the film by drying in the film forming step is recovered and reused can be used.

A general method can be used as a method of dissolving the cellulose ester when preparing the dope described above. Further, by combining heating and pressurization, it is possible to heat above the boiling point at normal pressure.

Subsequently, it is preferable to filter the dope obtained above using an appropriate filter medium such as filter paper. Thereby, impurities in the dope can be removed and reduced. As the filter medium, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is more preferable. It does not specifically limit as a filter medium, A well-known filter medium can be used.

(Ii) Dope Casting Step The dope casting step is a step of casting (casting) the dope onto an endless metal support. The metal support preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used. The cast width can be 1 to 4 m. The surface temperature of the metal support can be set to −50 ° C. or higher and lower than the boiling point of the solvent, preferably 0 to 40 ° C., and more preferably 5 to 30 ° C.

The method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When warm air is used, wind at a temperature higher than the target temperature may be used.

(Iii) Drying step 1
The drying step 1 is a step of drying the cast dope as a web. The surface temperature of the metal support is the same as in the dope casting process. A higher temperature is preferable because the web can be dried at a higher speed. However, if the temperature is too high, the web may foam or the flatness may deteriorate.

(Iv) Peeling process A peeling process is a process of peeling a web from a metal support body. In order for the film after film formation to exhibit good flatness, the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass. Alternatively, it is 60 to 130% by mass, and more preferably 20 to 30% by mass or 70 to 120% by mass.

In the present specification, the residual solvent amount is defined by the following formula.
Residual solvent amount (% by mass) = {(MN) / N} × 100
(Wherein, M is the mass of a sample taken at any time during or after production of the web or film, and N is 115 ° C. of the sample taken at any time during or after production of the web or film. Is the mass after heating for 1 hour)

(V) Stretching step The stretching step is a step of stretching the web immediately after peeling from the metal support in at least one direction. By performing the stretching treatment, the orientation of molecules in the film can be controlled. The stretched film may be a biaxially stretched film, but is preferably a uniaxially stretched film. However, the stretching step is not essential, and the cellulose ester film may be an unstretched film.

When stretching, it is preferable to stretch 1.05 to 1.50 times in the width direction (TD direction). By performing the stretching treatment based on such a stretching ratio, the resin molecules are oriented, expansion and contraction with time in the orientation direction is suppressed, and elasticity is imparted to the film. Therefore, even if the thickness of the film is small, excellent workability is imparted while suppressing the generation of wrinkles over time while maintaining high antifogging properties.

In addition to this, or alternatively, the film may be stretched at a stretching ratio of 1.01 to 1.50 times in the longitudinal direction (MD direction). Stretching in the width direction (TD direction) and the longitudinal direction (MD direction) can be performed sequentially or simultaneously.

The amount of residual solvent in the stretched film is preferably 1 to 50% by mass, more preferably 3 to 45% by mass. In the case of such an amount of residual solvent, it is easy to achieve both production efficiency and film transparency.

The stretching method is not particularly limited. As a stretching method, for example, a method is used in which a circumferential speed difference is applied to a plurality of rolls, and the roll circumferential speed difference is used to stretch in the MD direction. Examples include a method of spreading the film in the traveling direction and stretching it in the MD direction, a method of stretching the film in the horizontal direction and stretching in the TD direction, and a method of simultaneously stretching in the MD / TD direction and stretching in both the MD / TD directions.

Further, the stretching method may be oblique stretching. Diagonal stretching means crossing the film feeding direction and the winding direction, and transporting one end of the film in the width direction ahead of the other end, thereby causing the film to cross the width direction. This is a method of stretching in an oblique direction.

The stretching temperature is preferably 120 ° C. or higher and 200 ° C. or lower, more preferably 150 ° C. or higher and 200 ° C. or lower, and further preferably higher than 150 ° C. and 190 ° C. or lower.

The film is preferably heat-set after stretching. The heat setting is preferably performed at a temperature higher than the final stretching temperature in the TD direction and within a temperature range of Tg-20 ° C., usually for 0.5 to 300 seconds. At this time, it is preferable to perform heat fixing while sequentially raising the temperature in a range where the temperature difference is 1 to 100 ° C. in the region divided into two or more. In addition, Tg (glass transition temperature) of a film is controlled by the kind of material which comprises a film, and the ratio of the material which comprises, and can be calculated | required by the method of JISK7121: 1987.

(Vi) Drying step 2
Drying step 2 is a step of further drying the stretched film. In the drying step 2, the film is preferably dried so that the residual solvent amount is 1% by mass or less, more preferably 0.1% by mass or less, and further preferably 0 to 0.01% by mass or less. It is.

(Vii) Film winding process A film winding process is a process of winding up the web after drying (finished cellulose-ester film). When the film is wound, a film having good dimensional stability can be obtained by setting the residual solvent amount to 0.4% by mass or less.

(B) Hydrophilization treatment step This is a step of drawing out the formed cellulose ester film and imparting antifogging properties to the film surface by the hydrophilic treatment. Since the details of this process are as described above, the description thereof is omitted.

[Additives contained in cellulose ester film]
Next, the additive which the cellulose ester film used by this embodiment can contain is demonstrated. For the purpose of further improving the antifogging performance, the cellulose ester film used in the present embodiment includes, for example, the following (a) plasticizer, (b) ultraviolet absorber, (c) fine particles, (d) dye, ( e) A sugar ester compound and (f) an acrylic copolymer may be included. Among them, it is preferable to include at least one or more of (a) a plasticizer, (b) an ultraviolet absorber, and (c) fine particles, and (a) a plasticizer, (b) an ultraviolet absorber, and (c) all of the fine particles. It is more preferable to contain.

(A) Plasticizer The cellulose ester film preferably contains a plasticizer for the purpose of improving mechanical strength and water resistance. As the plasticizer, a polyester compound is preferable.

Although it does not specifically limit as a polyester compound, For example, the polymer (henceforth a "polyester polyol") obtained by the condensation reaction of dicarboxylic acid or these ester-forming derivatives, and glycol (henceforth "polyester polyol"), or the said A polymer in which the terminal hydroxyl group of the polyester polyol is sealed with a monocarboxylic acid (hereinafter referred to as “end-capped polyester”) can be used. In the present specification, the ester-forming derivative is an esterified product of dicarboxylic acid, dicarboxylic acid chloride, or anhydride of dicarboxylic acid.

The use of the polyester polyol or the end-capped polyester further suppresses peeling and wrinkling of the film over time. The reason why such an effect is obtained is not clear, but the above-mentioned compound is oriented in the surface direction during film formation, and the deformation stress at the time of moisture absorption is dispersed in the thickness direction. It is estimated that wrinkles can be suppressed.

Specific examples of the polyester compound include ester compounds represented by the following general formula (A).

B- (GA) n-GB (A)
Wherein B is a hydroxyl group, a benzene monocarboxylic acid residue or an aliphatic monocarboxylic acid residue, and G is an alkylene glycol residue having 2 to 18 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms or a carbon atom. An oxyalkylene glycol residue having 4 to 12 carbon atoms, A is an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 16 carbon atoms, and n is an integer of 1 or more .)

In the above general formula (A), a compound in which B is a hydroxyl group corresponds to a polyester polyol, and a compound in which B is a benzene monocarboxylic acid residue or an aliphatic monocarboxylic acid residue corresponds to an end-capped polyester. The polyester compound represented by the general formula (A) is obtained by the same reaction as a normal polyester plasticizer.

As the aliphatic monocarboxylic acid component of the polyester compound represented by the general formula (A), for example, an aliphatic monocarboxylic acid having 3 or less carbon atoms is preferable, and examples include acetic acid, propionic acid, and butanoic acid (butyric acid). Each of these can be used as one kind or a mixture of two or more kinds.

Examples of the benzene monocarboxylic acid component of the polyester compound represented by the general formula (A) include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal There are propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid, aliphatic acid and the like, and these can be used as one kind or a mixture of two or more kinds, respectively. In particular, it is preferable to contain benzoic acid or p-toluic acid.

Examples of the alkylene glycol component having 2 to 18 carbon atoms of the polyester compound represented by the general formula (A) include ethylene glycol, 1,2-propanediol (1,2-propylene glycol), 1,3-propanediol (1 , 3-propylene glycol), 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 2,3-butane Diol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl 2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentane Diols, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, and the like. It is used as one kind or a mixture of two or more kinds. Of these, ethylene glycol, diethylene glycol, 1,2-propylene glycol, and 2-methyl 1,3-propanediol are preferable, and ethylene glycol, diethylene glycol, and 1,2-propylene glycol are more preferable. In particular, an alkylene glycol having 2 to 12 carbon atoms is preferable because of excellent compatibility with the resin constituting the film. More preferred are alkylene glycols having 2 to 6 carbon atoms, and still more preferred are alkylene glycols having 2 to 4 carbon atoms.

Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the polyester compound represented by the general formula (A) include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. Glycols can be used as one or a mixture of two or more.

Examples of the aryl glycol having 6 to 12 carbon atoms of the polyester compound represented by the general formula (A) include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, cyclohexanediethanol, and 1,4-benzenedimethanol. And these glycols can be used as one kind or a mixture of two or more kinds.

Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms of the polyester compound represented by the general formula (A) include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. There are acids and the like, and these are used as one kind or a mixture of two or more kinds, respectively.

Examples of the aryl dicarboxylic acid component having 6 to 16 carbon atoms of the polyester compound represented by the general formula (A) include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, There are 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,6-anthracenedicarboxylic acid and the like. The aryl dicarboxylic acid may have a substituent on the aromatic ring. Examples of the substituent include a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group, and an aryl group having 6 to 12 carbon atoms.

In the general formula (A), when B is a hydroxyl group, that is, when the polyester compound is a polyester polyol, A is preferably an aryl dicarboxylic acid residue having 10 to 16 carbon atoms. For example, a dicarboxylic acid having an aromatic cyclic structure such as a benzene ring structure, a naphthalene ring structure, or an anthracene ring structure can be used. Specific examples of the aryl dicarboxylic acid component include orthophthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. And acid, 1,8-naphthalenedicarboxylic acid, and 2,6-anthracene dicarboxylic acid. Preferred are 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, and more preferred is 2 1,3-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, particularly preferably 2,6-naphthalenedicarboxylic acid. These can be used alone or in combination of two or more.

The polyester polyol preferably has an average carbon number of 10 to 16 in the dicarboxylic acid used as a raw material. If the carbon number average of the dicarboxylic acid is 10 or more, the film has excellent dimensional stability, and if the carbon number average is 16 or less, it has excellent compatibility with the resin constituting the film, and the resulting film is transparent. The property is remarkably excellent. The dicarboxylic acid preferably has an average carbon number of 10 to 14, and more preferably has an average carbon number of 10 to 12.

The average carbon number of the dicarboxylic acid of the polyester polyol means the carbon number of the dicarboxylic acid when the polyester polyol is polymerized using a single dicarboxylic acid, but the polyester using two or more kinds of dicarboxylic acids. When polymerizing a polyol, it means the sum of the products of the carbon number of each dicarboxylic acid and the molar fraction of the dicarboxylic acid.

If the average carbon number is 10 to 16, the above-mentioned aryl dicarboxylic acid having 10 to 16 carbon atoms and other dicarboxylic acids can be used in combination. The dicarboxylic acid that can be used in combination is preferably a dicarboxylic acid having 4 to 9 carbon atoms. For example, succinic acid, glutaric acid, adipic acid, maleic acid, orthophthalic acid, isophthalic acid, terephthalic acid, esterified products thereof, acid A chloride and an acid anhydride can be mentioned.

Specific examples of the dicarboxylic acid in which the polyester polyol has 10 to 16 carbon atoms are shown below, but the present embodiment is not limited thereto.
(1) 2,6-naphthalenedicarboxylic acid (2) 2,3-naphthalenedicarboxylic acid (3) 2,6-anthracene dicarboxylic acid (4) 2,6-naphthalenedicarboxylic acid: succinic acid (75:25 to 99: 1 molar ratio)
(5) 2,6-Naphthalenedicarboxylic acid: terephthalic acid (50:50 to 99: 1 molar ratio)
(6) 2,3-naphthalenedicarboxylic acid: succinic acid (75:25 to 99: 1 molar ratio)
(7) 2,3-naphthalenedicarboxylic acid: terephthalic acid (50:50 to 99: 1 molar ratio)
(8) 2,6-anthracene dicarboxylic acid: succinic acid (50:50 to 99: 1 molar ratio)
(9) 2,6-anthracene dicarboxylic acid: terephthalic acid (25:75 to 99: 1 molar ratio)
(10) 2,6-Naphthalenedicarboxylic acid: Adipic acid (67:33 to 99: 1 molar ratio)
(11) 2,3-naphthalenedicarboxylic acid: adipic acid (67:33 to 99: 1 molar ratio)
(12) 2,6-anthracene dicarboxylic acid: adipic acid (40:60 to 99: 1 molar ratio)

Examples of the polyester compound that can be used in the present embodiment include compounds having an octanol-water partition coefficient (logP (B)) of 0 or more and less than 7 from the viewpoint of water solubility and orientation of the compound, in addition to the polyester polyol described above. It is also preferable to use it.

The polyester polyol is a dicarboxylic acid or an ester-forming derivative thereof (a component corresponding to A in the general formula (A)) and a glycol (a component corresponding to G in the general formula (A)). For example, it can be produced by an esterification reaction in a well-known and conventional manner for 10 to 25 hours in the temperature range of 180 to 250 ° C., for example.

In performing the esterification reaction, a solvent such as toluene or xylene may be used, but a method using no solvent or glycol used as a raw material as a solvent is preferable.

As the esterification catalyst, for example, tetraisopropyl titanate, tetrabutyl titanate, p-toluenesulfonic acid, dibutyltin oxide and the like can be used. The esterification catalyst is preferably used in an amount of 0.01 to 0.5 parts by mass based on 100 parts by mass of the total amount of dicarboxylic acids or their ester-forming derivatives.

The molar ratio in the reaction of the dicarboxylic acid or their ester-forming derivative with the glycol must be such that the terminal group of the polyester is a hydroxyl group, so that the molar ratio is 1 mol of the dicarboxylic acid or their ester-forming derivative. The glycol is 1.1 to 10 moles. Preferably, the glycol is 1.5 to 7 moles per mole of the dicarboxylic acid or their ester-forming derivatives, and more preferably, the glycol is moles per mole of the dicarboxylic acid or their ester-forming derivatives. 2 to 5 moles.

The terminal group of the polyester polyol is a hydroxyl group, but the polyester polyol may contain a carboxy group-terminated compound as a by-product. However, the carboxy group terminal in the polyester polyol lowers the humidity stability, so that the content is preferably low. Specifically, the acid value is preferably 5.0 mgKOH / g or less, more preferably 1.0 mgKOH / g or less, and still more preferably 0.5 mgKOH / g or less. Here, the “acid value” refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid (carboxy group present in the sample) contained in 1 g of the sample. The acid value can be measured according to JIS K0070: 1992.

The polyester polyol preferably has a hydroxy (hydroxyl group) value (OHV) in the range of 35 mg / g to 220 mg / g. The hydroxy (hydroxyl group) value here means the number of milligrams of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when the hydroxyl group contained in 1 g of a sample is acetylated. The hydroxy (hydroxyl group) value is obtained by acetylating a hydroxyl group in a sample with acetic anhydride, titrating acetic acid not used with a potassium hydroxide solution, and obtaining a difference from the initial titration value of acetic anhydride.

The hydroxyl content of the polyester polyol is preferably 70% or more. When the hydroxyl group content is low, the compatibility between the polyester polyol and the resin constituting the film tends to decrease. For this reason, the hydroxyl group content is preferably 70% or more, more preferably 90% or more, and still more preferably 99% or more. In the present embodiment, a compound having a hydroxyl group content of 50% or less is not included in the polyester polyol because one of the end groups is substituted with a group other than the hydroxyl group.

The hydroxyl group content can be determined by the following formula (B).
Y / X × 100 = hydroxyl group content (%) (B)
X: Hydroxyl value (OHV) of the polyester polyol
Y: 1 / (number average molecular weight (Mn)) × 56 × 2 × 1000

The polyester polyol preferably has a number average molecular weight within a range of 300 to 3,000, and more preferably a number average molecular weight of 350 to 2,000.

Further, the degree of dispersion of the molecular weight of the polyester polyol of this embodiment is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. If the degree of dispersion is within the above range, a polyester polyol excellent in compatibility with the resin constituting the film can be easily obtained.

Further, the polyester polyol preferably contains 50% or more of a component having a molecular weight of 300 to 1800. By setting the number average molecular weight within the above range, the compatibility can be greatly improved.

The end-capped polyester may be such that at least one of the two end groups B is a monocarboxylic acid residue. That is, one of the two end groups B may be a hydroxyl group and the other may be a monocarboxylic acid residue. However, it is preferable that both of the two terminal groups B are monocarboxylic acid residues.

As the terminal group B, the above-mentioned benzene monocarboxylic acid residue and aliphatic monocarboxylic acid residue can be used, and preferably a benzene monocarboxylic acid residue can be used. That is, the terminal group B is preferably an aromatic terminal polyester.

The end-capped polyester is composed of glycol (a component corresponding to G in the general formula (A)), a dicarboxylic acid or an ester-forming derivative thereof (a component corresponding to A in the general formula (A)) and a monocarboxylic acid or These ester-forming derivatives (components corresponding to B in the general formula (A)) can be obtained by an esterification reaction. For example, JP 2011-52205 A, JP 2008-69225 A, It can be synthesized with reference to Kaikai 2008-88292, JP-A-2008-115221 and the like.

The ester compound of the present embodiment is a mixture having a distribution in molecular weight and molecular structure at the time of its synthesis. Among them, preferred components for the present embodiment, for example, phthalic acid residues as A in the general formula (A) and It is preferable to contain at least one polyester compound having an adipic acid residue.

The end-capped polyester has a number average molecular weight of preferably 300-1500, more preferably 400-1000. The acid value is 0.5 mg KOH / g or less, the hydroxy (hydroxyl group) value is 25 mg KOH / g or less, more preferably the acid value is 0.3 mg KOH / g or less, and the hydroxy (hydroxyl group) value is 15 mg KOH / g or less.

Hereinafter, specific compounds of the ester compound represented by the general formula (A) that can be used in the present embodiment are shown, but the present embodiment is not limited thereto.

The film of this embodiment preferably contains the polyester compound in an amount of 0.1 to 30% by mass, particularly 0.5 to 10% by mass, based on the entire film (100% by mass). As other plasticizers, materials described in [0102] to [0155] of International Publication No. 10/026832, etc. can be appropriately used.

(B) Ultraviolet absorber The film of this embodiment can contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of improving the durability of the film by absorbing ultraviolet rays of 400 nm or less. The ultraviolet absorber is added so that the transmittance at a wavelength of 370 nm is 10% or less, preferably 5% or less, more preferably 2% or less.

The ultraviolet absorber is not particularly limited, and examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders, and the like. Can be mentioned. Among these, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and triazine ultraviolet absorbers are preferably used, and benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers are more preferably used. Specifically, for example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxyphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (Straight and side chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone and the like are listed, and commercially available products are Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 928 and the like are preferably used. In addition, a discotic compound such as a compound having a 1,3,5-triazine ring is also preferably used as the ultraviolet absorber.

The cellulose ester solution in the present embodiment preferably contains two or more ultraviolet absorbers. As the UV absorber, a polymer UV absorber can also be preferably used. In particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.

As a method for adding the ultraviolet absorber, the ultraviolet absorber is dissolved in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof, and then added to the dope. The method of adding directly into the dope composition can be employed. At that time, it is preferable to use a dissolver or a sand mill in an organic solvent and a cellulose ester for those that do not dissolve in an organic solvent, such as inorganic powder, and then add to the dope after dispersion.

The amount of the UV absorber used is not uniform depending on the type of UV absorber, usage conditions, etc., but when the dry film thickness is 30 to 200 μm, it is 0.5 to 10% by mass relative to the film. Is preferable, and 0.6 to 4% by mass is more preferable.

(C) Fine particles The film preferably contains fine particles from the viewpoint of slipperiness and storage stability. As fine particles, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples thereof include magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

As for silicon dioxide, a hydrophobized one is preferable for achieving both slipperiness and haze. Of the four silanol groups, those in which two or more are substituted with a hydrophobic substituent are preferred, and those in which three or more are substituted are more preferred. The hydrophobic substituent is preferably a methyl group.

The average primary particle diameter of silicon dioxide is preferably 20 nm or less, and more preferably 10 nm or less. The average primary particle size of the fine particles is determined by observing the particles with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), observing 100 particles, measuring the particle size, and using the average value as the primary value. The average particle diameter can be set.

As the fine particles of silicon dioxide, for example, those commercially available under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above, manufactured by Nippon Aerosil Co., Ltd.) are used. be able to.

Examples of polymer fine particles include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (manufactured by Toshiba Silicone Co., Ltd.) What is marketed with a brand name can be used.

Among these, Aerosil 200V, Aerosil R972V, and Aerosil R812 are preferable because they have a large effect of reducing the friction coefficient while keeping the film haze low, and Aerosil R812 is more preferably used.

The amount of fine particles added is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the cellulose ester. The larger the added amount, the better the dynamic friction coefficient, and the smaller the added amount, the fewer the aggregates.

In the film of this embodiment, it is preferable that the dynamic friction coefficient of at least one surface is 0.2 to 1.0.

(D) Dye A dye can be added to the film for adjusting the color within a range not impairing the effects of the present embodiment. For example, a blue dye may be added to the film in order to suppress the yellowness of the film. Preferred examples of the dye include anthraquinone dyes.

(E) Sugar ester compound Examples of the sugar ester compound used in the present embodiment include glucose, galactose, mannose, fructose, xylose, or arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol. , Lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose or kestose. In addition, gentiobiose, gentiotriose, gentiotetraose, xylotriose, galactosyl sucrose, and the like are also included.

Among these compounds, compounds having both a pyranose structure and a furanose structure are particularly preferable. Specifically, sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable.

The monocarboxylic acid used for esterifying all or part of the hydroxyl groups in the pyranose structure or furanose structure is not particularly limited, and is known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid. An acid or the like can be used. One kind of carboxylic acid may be used, or two or more kinds may be mixed.

Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, Examples thereof include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and octenoic acid.

Preferred examples of the alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.

Preferred aromatic monocarboxylic acids include, for example, aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, and naphthalene. Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as carboxylic acid and tetralincarboxylic acid, or derivatives thereof. Specifically, xylic acid, hemelitic acid, mesitylene acid, prenicylic acid, γ-isoduric acid, duric acid, mesitonic acid, α-isoduric acid, cumic acid, α-toluic acid, hydroatropic acid, atropic acid, hydrocinnamic acid , Salicylic acid, o-anisic acid, m-anisic acid, p-anisic acid, creosote acid, o-homosalicylic acid, m-homosalicylic acid, p-homosalicylic acid, o-pyrocatechuic acid, β-resorcylic acid, vanillic acid, Examples thereof include isovanillic acid, veratrumic acid, o-veratrumic acid, gallic acid, asaronic acid, mandelic acid, homoanisic acid, homovanillic acid, homoveratrumic acid, o-homoveratric acid, phthalonic acid, and p-coumaric acid. Of these, benzoic acid and naphthylic acid are particularly preferable.

Oligosaccharide ester compounds can be applied as “compounds having 1 to 12 at least one pyranose structure or furanose structure” described later.

The oligosaccharide is produced by allowing an enzyme such as amylase to act on starch, sucrose, etc., and examples of the oligosaccharide applicable to this embodiment include malto-oligosaccharide, isomalt-oligosaccharide, fructo-oligosaccharide, and galactooligosaccharide. And xylooligosaccharides.

Moreover, the said ester compound is a compound which condensed 1 or more and 12 or less of at least 1 sort (s) of the pyranose structure or furanose structure represented with the following general formula (B). In the general formula (B), R ₁₁ to R ₁₅ and R ₂₁ to R ₂₅ are each an acyl group having 2 to 22 carbon atoms or a hydrogen atom, m and n are each an integer of 0 to 12, and m + n is 1 to 12. Represents an integer.

R ₁₁ to R ₁₅ and R ₂₁ to R ₂₅ are preferably a benzoyl group or a hydrogen atom. The benzoyl group may further have a substituent R ₂₆ , and examples of R ₂₆ include an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group. Further, these alkyl groups, alkenyl groups, and phenyl groups are substituted. It may have a group. Oligosaccharides can also be produced in the same manner as ester compounds.

More specific examples of sugar ester compounds include compounds represented by general formula (1).

In the formula, R ₁ to R ₈ represent a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 2 to 22 carbon atoms. R ₁ to R ₈ may be the same or different.

The compounds represented by the general formula (1) are specifically shown below (Compound 1-1 to Compound 1-23), but are not limited thereto. In the table below, when the average substitution degree is less than 8.0, any one of R ₁ to R ₈ represents a hydrogen atom.

(F) Acrylic copolymer The film of this embodiment can contain the acrylic polymer whose weight average molecular weight is 500-30000. Above all, the weight obtained by copolymerizing ethylenically unsaturated monomer Xa having no aromatic ring and hydrophilic group in the molecule and ethylenically unsaturated monomer Xb having no aromatic ring and having a hydrophilic group in the molecule. Polymer X having an average molecular weight of 5,000 to 30,000, more preferably, an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule and an ethylenically unsaturated group having no aromatic ring and a hydrophilic group in the molecule. A weight average molecular weight of 500 to 3,000 obtained by polymerizing a polymer X having a weight average molecular weight of 5,000 to 30,000 obtained by copolymerization with a saturated monomer Xb and an ethylenically unsaturated monomer Ya having no aromatic ring. The polymer Y is preferably contained.

The acrylic copolymer can be added in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the cellulose ester.

(Hard coat layer)
<Hard coat resin>
The hard coat resin forming the hard coat layer is preferably an actinic radiation curable resin from the viewpoint of excellent mechanical film strength (abrasion resistance, pencil hardness). That is, it is a layer mainly composed of a resin that is cured through a crosslinking reaction upon irradiation with active rays (also called active energy rays) such as ultraviolet rays and electron beams. As the actinic radiation curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams. The Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin curable by ultraviolet irradiation is particularly excellent in mechanical film strength (abrasion resistance, pencil hardness). It is preferable from the point. Examples of the ultraviolet curable resin include an ultraviolet curable acrylate resin, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable resin. A curable epoxy resin or the like is preferably used, and among them, an ultraviolet curable acrylate resin or an ultraviolet curable urethane acrylate resin is preferable.

As the ultraviolet curable acrylate resin, polyfunctional acrylate is preferable. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule. Examples of the polyfunctional acrylate monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. , Tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tri / tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, glycerol triacrylate relay , Dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol di Methacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pen Pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, etc. isocyanurate derivatives of the active energy ray-curable are preferably exemplified.

Examples of the ultraviolet curable urethane acrylate resin include, for example, a polyurethane obtained by reacting an alcohol, a polyol, and / or a hydroxyl group-containing compound such as a hydroxyl group-containing acrylate and an isocyanate or, if necessary, these reactions. It is obtained by esterifying a compound with (meth) acrylic acid. More specifically, it is an addition reaction product of polyisocyanate and an acrylate having one hydroxy group and one or more (meth) acryloyl groups in one molecule. Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4 ′. A compound having two isocyanate groups bonded to an alicyclic hydrocarbon such as aromatic isocyanate such as diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, 1,4-cyclohexane diisocyanate (hereinafter referred to as alicyclic diisocyanate and A compound having two isocyanate groups bonded to an aliphatic hydrocarbon such as trimethylene diisocyanate and hexamethylene diisocyanate (hereinafter referred to as aliphatic diisocyanate). Abbreviated as sulphonate.) Phenylene diisocyanate, aromatic diisocyanates such as toluene diisocyanate, and aromatic aliphatic diisocyanates such as xylylene diisocyanate. These polyisocyanates can be used alone or in combination of two or more, preferably aliphatic diisocyanates and alicyclic diisocyanates. Of these, isophorone diisocyanate, norbornane diisocyanate, toluene diisocyanate and hexamethylene diisocyanate are preferred. Examples of the acrylate having one hydroxy group and one or more (meth) acryloyl groups in one molecule include trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). Examples include polyacrylates of polyvalent hydroxy group-containing compounds such as acrylates, adducts of these polyacrylates and ε-caprolactone, adducts of these polyacrylates and alkylene oxides, and epoxy acrylates. It is done. The acrylate having one hydroxy group and one or more (meth) acryloyl groups in one molecule can be used alone or in combination of two or more.

Further, among acrylates having one hydroxy group and one or more (meth) acryloyl groups in one molecule, acrylates having one hydroxy group and 3 to 5 (meth) acryloyl groups in one molecule are preferable. Examples of such acrylates include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

Specific products of the UV curable urethane acrylate resin include: Nippon Synthetic Chemical Industry Co., Ltd., Shikou UV-1700B, UV-6300B, UV-7600B, UV-7630B, UV-7630B, UV-7640B, Kyoeisha Chemical Co., Ltd. Company-made, UA-306H, UA-306T, UA-306I, UA-510H, Shin-Nakamura Chemical Co., Ltd., NK Oligo UA-1100H, NK Oligo UA-53H, NK Oligo UA-33H, NK Oligo UA-15HA Etc.

The viscosity of the actinic radiation curable resin can be measured using a B-type viscometer under the condition of 25 ° C. after stirring and mixing the resin with a disper. A monofunctional acrylate may also be used.

Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples thereof include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate. Such monofunctional acrylates can be obtained from Nippon Kasei Kogyo Co., Ltd., Shin-Nakamura Chemical Co., Ltd., Osaka Organic Chemical Co., Ltd., etc.

When a monofunctional acrylate is used, it is preferably contained in the range of polyfunctional acrylate: monofunctional acrylate = 80: 20 to 98: 2 in terms of the mass ratio of polyfunctional acrylate to monofunctional acrylate.

<Photopolymerization initiator>
The hard coat layer preferably contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin. The amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: active ray curable resin = 20: 100 to 0.01: 100. Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. It is not something.

Commercially available products may be used as such photopolymerization initiators, and preferred examples include Irgacure 184, Irgacure 907, and Irgacure 651 manufactured by BASF Japan.

<Conductive agent>
The hard coat layer may contain a conductive agent in order to impart antistatic properties. Preferred conductive agents include metal oxide particles or π-conjugated conductive polymers. An ionic liquid is also preferably used as the conductive compound.

<Leveling agent>
The hard coat layer may contain a leveling agent in order to smooth the surface. As the leveling agent, silicone surfactants, fluorine surfactants, anionic surfactants, fluorine-siloxane graft compounds, fluorine compounds, acrylic copolymers, and the like can be used.

Examples of the silicone surfactant include polyether-modified silicone, and the KF series manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Examples of the acrylic copolymer include commercially available compounds such as BYK-350 and BYK-352 manufactured by BYK Japan. Examples of the fluorosurfactant include MegaFuck RS series and MegaFuck F-444 MegaFuck F-556 manufactured by DIC Corporation. The fluorine-siloxane graft compound refers to a copolymer compound obtained by grafting polysiloxane and / or organopolysiloxane containing siloxane and / or organosiloxane alone to at least a fluorine-based resin. Such a fluorine-siloxane graft compound can be prepared by a method as described in Examples described later. Alternatively, examples of commercially available products include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Chemical Industry Co., Ltd. Moreover, as a fluorine-type compound, Daikin Industries Ltd. OPTOOL DSX, OPTOOL DAC, etc. can be mentioned. These components are preferably added in the range of 0.005 parts by mass or more and 5 parts by mass or less with respect to the solid component in the hard coat composition.

<Ultraviolet absorber>
The hard coat layer may further contain an ultraviolet absorber. The content of the ultraviolet absorber is preferably in a mass ratio of ultraviolet absorber: hard coat resin = 0.01: 100 to 10: 100. Since the ultraviolet absorber absorbs ultraviolet rays of 400 nm or less, durability can be improved. In particular, the ultraviolet absorber preferably has a transmittance of 10% or less at a wavelength of 370 nm, more preferably 5% or less, and still more preferably 2% or less. Specific examples of the ultraviolet absorber are not particularly limited. For example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex salts, inorganic powders. Examples include the body.

More specifically, for example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6 -(Linear and side chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, and the like can be used. Commercially available products may be used. For example, TINUVIN such as TINUVIN 109, TINUVIN 171, TINUVIN 234, TINUVIN 326, TINUVIN 327, and TINUVIN 328 manufactured by BASF Japan Ltd. can be preferably used.

Preferably used ultraviolet absorbers are benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and triazine ultraviolet absorbers, and particularly preferably benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.

In addition, a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as an ultraviolet absorber. As the UV absorber, a polymer UV absorber can be preferably used, and a polymer type UV absorber is particularly preferably used.

As the benzotriazole ultraviolet absorber, TINUVIN 109 (octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-) manufactured by BASF Japan Ltd., which is a commercial product, is available. Yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate), TINUVIN 928 (2 -(2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol) and the like can be used. As the triazine-based ultraviolet absorber, commercially available TINUVIN 400 (2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -manufactured by BASF Japan Ltd.- Reaction product of 5-hydroxyphenyl and oxirane), TINUVIN 460 (2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5 Triazine), TINUVIN 405 (2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester Reaction products) and the like.

<solvent>
The hard coat layer is a component that forms the above-described hard coat layer, diluted with a solvent that swells or partially dissolves the film as a base material, and is applied onto the film by the following method as a hard coat layer composition. It is preferable to provide a hard coat layer by drying and curing.

As the solvent, ketones (methyl ethyl ketone, acetone, etc.) and / or acetate esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (ethanol, methanol), propylene glycol monomethyl ether, cyclohexanone, methyl isobutyl ketone, etc. are preferable. The coating amount of the hard coat layer is suitably in the range of 0.1 to 40 μm as wet film thickness, and preferably in the range of 0.5 to 30 μm. The dry film thickness is in the range of an average film thickness of 0.01 to 20 μm, preferably in the range of 0.5 to 10 μm. More preferably, it is in the range of 0.5 to 5 μm.

As a method for applying the hard coat layer, known methods such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method can be used.

[Method of forming hard coat layer]
After applying the hard coat layer composition, it may be dried and cured by irradiation with active rays (also referred to as UV curing treatment), and if necessary, heat treatment may be performed after the UV curing treatment. The heat treatment temperature after the UV curing treatment is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. By performing the heat treatment after the UV curing treatment at such a high temperature, a hard coat layer having excellent film strength can be obtained.

Drying is preferably performed by high-temperature treatment at a temperature of 90 ° C. or higher in the rate of drying section. More preferably, the temperature in the decreasing rate drying section is 90 ° C. or higher and 125 ° C. or lower.

In general, it is known that the drying process changes from a constant state to a gradually decreasing state when drying starts. The decreasing section is called the decreasing rate drying section. In the constant rate drying section, the amount of heat flowing in is all consumed for solvent evaporation on the coating film surface, and when the solvent on the coating film surface decreases, the evaporation surface moves from the surface to the inside and enters the decreasing rate drying section. Thereafter, the temperature of the coating film surface rises and approaches the hot air temperature, so that the temperature of the actinic radiation curable resin composition rises, the resin viscosity decreases, and the fluidity increases.

As a light source for UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually in the range of 50 to 1000 mJ / cm ² , preferably in the range of 50 to 300 mJ / cm ² . In the UV curing treatment, oxygen removal (for example, replacement with an inert gas such as nitrogen purge) can be performed to prevent reaction inhibition by oxygen. The cured state of the surface can be controlled by adjusting the removal amount of the oxygen concentration. When irradiating actinic radiation, it is preferably performed while applying tension in the film transport direction, and more preferably while applying tension in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the transport direction on the back roller, or the tension may be applied in the width direction or the biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.

[Method for producing glass laminate]
In the method for producing a glass laminate of the present embodiment, both sides or one side of the cellulose ester film are subjected to a hydrophilic treatment by light irradiation or saponification to form an antifogging layer, and any surface is formed when the antifogging layer is formed on both sides. When the anti-fogging layer is formed on one side, the heat ray reflecting layer is laminated on the surface opposite to the anti-fogging layer. In addition, after laminating | stacking a heat ray reflective layer on one surface of a cellulose-ester film, you may hydrophilize the other surface by light irradiation light irradiation, and form an anti-fogging layer. Thereafter, if necessary, a hard coat layer is laminated on the antifogging layer. Then, the adhesive for water sticking is apply | coated on a heat ray reflective layer or glass, glass and a heat ray reflective layer surface are stuck, and a glass laminated body is obtained. Alternatively, the water sticking adhesive may be applied onto the heat ray reflective layer and dried, and when applied to a window glass of a building or a vehicle, water sticking may be applied to the water sticking adhesive.

[Performance measurement method for heat and light]
Insulation performance and solar heat shielding performance of glass laminates or thermal barrier / antifogging films are generally JIS R 3209 (multi-layer glass), JIS R 3106 (obtain transmittance, reflectance, emissivity, and solar heat of plate glass) Rate test method) and JIS R 3107 (calculation method of thermal resistance of plate glass and heat transmissivity in architecture).

Measure solar transmittance, solar reflectance, emissivity, and visible light transmittance. (1) Using a spectrophotometer with a wavelength (300 to 2500 nm), measure the spectral transmittance and spectral reflectance of various single glass plates. The emissivity is measured using a spectrophotometer having a wavelength of 5.5 to 50 μm. In addition, a predetermined value is used for the emissivity of float plate glass, polished plate glass, mold plate glass, and heat ray absorbing plate glass. (2) The solar transmittance, solar reflectance, solar absorption rate, and modified emissivity are calculated according to JIS R 3106 by calculating the solar transmittance, solar reflectance, solar absorption rate, and vertical emissivity. The corrected emissivity is obtained by multiplying the vertical emissivity by the coefficient shown in JIS R 3107. The heat insulation and solar heat shielding properties are calculated by (1) calculating the thermal resistance of the multilayer glass according to JIS R 3209 using the measured thickness value and the corrected emissivity. However, when the hollow layer exceeds 2 mm, the gas thermal conductance of the hollow layer is determined according to JIS R 3107. (2) The heat insulation is obtained by adding a heat transfer resistance to the heat resistance of the double-glazed glass and calculating the heat flow resistance. (3) The solar heat shielding property is calculated by obtaining the solar heat acquisition rate according to JIS R 3106 and subtracting it from 1.

〔Example〕
Hereinafter, specific examples of the present invention will be described as examples. For comparison with the present invention, comparative examples will also be described. The present invention is not limited to the following examples. In the following description, “parts” or “%” indicates “parts by mass” or “mass%” unless otherwise specified.

<Example 1>
(Formation of anti-fogging layer)
One side of a cellulose ester film (6UA (manufactured by Konica Minolta Co., Ltd.)) was irradiated with excimer light at an intensity of 500 mJ / cm ² to hydrophilize the surface, thereby producing an antifogging film. The reforming apparatus provided with the excimer light source and the reforming process conditions are as follows.

<Modification processing equipment>
Excimer irradiation device MODEL: MECL-M-1-200 manufactured by M.D.Com
Wavelength: 172nm
Lamp filled gas: Xe
<Reforming treatment conditions>
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Oxygen concentration in the irradiation device: 0.3%

(Formation of heat ray reflective layer)
Next, a high-refractive index layer coating solution and a low-refractive index layer coating solution were alternately applied to the surface opposite to the hydrophilic surface of the cellulose ester film (6UA) to form a heat ray reflective layer. . A specific forming method is as follows.

<Preparation of titanium oxide particle sol>
An aqueous sodium hydroxide solution (concentration 10 mol / L) was added to 10 L (liter) of an aqueous suspension (TiO ₂ concentration 100 g / L) in which titanium dioxide hydrate was suspended in water, with stirring, 30 L, 90 The mixture was heated to 0 ° C. and aged for 5 hours, and then neutralized with hydrochloric acid, filtered, and washed with water. In the above reaction (treatment), titanium dioxide hydrate was obtained by thermal hydrolysis of an aqueous titanium sulfate solution according to a known method.

The base-treated titanium compound was suspended in pure water so as to have a TiO ₂ concentration of 20 g / L, and citric acid was added in an amount of 0.4 mol% with respect to the amount of TiO ₂ with stirring, and the temperature was raised. When the liquid temperature reached 95 ° C., concentrated hydrochloric acid was added to a hydrochloric acid concentration of 30 g / L, and the mixture was stirred for 3 hours while maintaining the liquid temperature to oxidize the titanium oxide particles to 20% by mass. A titanium particle sol solution was prepared.

When the pH and zeta potential of the obtained titanium oxide particle sol solution were measured, the pH at 25 ° C. was 1.4, and the zeta potential was +40 mV. Furthermore, when the particle size was measured by Zetasizer Nano manufactured by Malvern, the volume average particle size was 35 nm, and the monodispersity was 16%. In addition, the titanium oxide particle sol solution was dried at 105 ° C. for 3 hours to obtain a particle powder, and X-ray diffraction measurement was performed using JDX-3530 type manufactured by JEOL Datum Co., Ltd. to obtain rutile type titanium oxide particles. It was confirmed.

<Colloidal silica sol>
Silica Dole 20P manufactured by Nippon Chemical Industry Co., Ltd. was used.

<Preparation of coating solution for high refractive index layer>
Titanium oxide particle sol solution prepared above, poval aqueous solution (Kuraray Co., Ltd., PVA217 5 wt% solution), thermal gelling agent aqueous solution (Shin-Etsu Chemical Co., Ltd., 60SH-50 2 wt% solution), low temperature gelation An aqueous agent solution (5% by weight pork skin gelatin solution) and pure water were appropriately blended while maintaining at 45 ° C. to prepare a coating solution for a high refractive index layer.

<Preparation of coating solution for low refractive index layer>
Colloidal silica sol solution, PVA aqueous solution (Kuraray Co., Ltd., PVA217 5 wt% solution), thermal gelling agent aqueous solution (Shin-Etsu Chemical Co., Ltd., 60SH-50 2 wt% solution), low temperature gelling agent aqueous solution (pig A 5% by weight solution of skin gelatin) and pure water were appropriately blended while maintaining at 45 ° C. to prepare a coating solution for a low refractive index layer.

<Film formation>
Using the above coating solution for the high refractive index layer and the coating solution for the low refractive index layer, the flow rate of each layer is adjusted by a simultaneous multi-layer slide coater, and the dry thickness of each layer is set to 200 nm. Simultaneous multi-layer coating was performed on the surface of the cellulose ester film (6UA) opposite to the surface subjected to the hydrophilic treatment so that seven rate layers were alternately laminated (coating step). Then, following the coating step, a cooling zone with cold air at 5 ° C. is passed in 20 seconds to gel the low-temperature gelling agent (cooling gelation step), and then the hot air drying zone with hot air at 50 ° C. is set for 20 seconds. In order to gel the thermal gelling agent (heating gelation step). Thereby, a heat ray reflective layer was formed.

(Formation of glass laminate)
And the glass laminated body of Example 1 is obtained by apply | coating the adhesive for water sticking (The Toagosei Co., Ltd. product, Aron Tack M-300) to the glass plate of thickness 3mm, and sticking with the surface at the side of a heat ray reflective layer. It was.

<Example 2>
In Example 1, both sides of the cellulose ester film (6UA) were hydrophilized by saponification instead of light irradiation to form an antifogging layer. Other than that was carried out similarly to Example 1, and obtained the glass laminated body of Example 2. FIG.

<Saponification conditions>
A 2N (2N) aqueous NaOH solution was set at 55 ° C., and the cellulose ester film (6UA) produced in this aqueous solution was immersed for 1 hour, washed with water and dried to produce an antifogging film.

<Example 3>
In Example 1, a hard coat layer composition mainly composed of ATM35-E (polyethoxylated tetramethylolmethane tetraacrylate: manufactured by Shin-Nakamura Chemical Co., Ltd.) was applied to the outer surface of the antifogging layer using an extrusion coater, and the constant rate After drying at a drying zone temperature of 50 ° C. and a reduced rate drying zone temperature of 50 ° C., the irradiance of the irradiated part is 100 mW / cm using an ultraviolet lamp while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. ² , the applied layer was cured with an irradiation dose of 0.2 J / cm ² to form a hard coat layer having a dry film thickness of 2 μm. Other than that was carried out similarly to Example 1, and obtained the glass laminated body of Example 3. FIG.

<Comparative Example 1>
In Example 1, a PMMA (polymethyl methacrylate) film having the same thickness was used instead of 6UA. Other than that was carried out similarly to Example 1, and obtained the glass laminated body of the comparative example 1. FIG.

<Comparative example 2>
In Example 2, a PET (polyethylene terephthalate) film having the same thickness was used instead of 6UA. Other than that was carried out similarly to Example 2, and obtained the glass laminated body of the comparative example 2. FIG.

<Comparative Example 3>
In Example 1, the glass laminate of Comparative Example 3 was obtained by omitting the antifogging layer.

<Comparative example 4>
In Example 1, mica whose surface was coated with titanium oxide according to Patent Document 1 was laminated on a cellulose ester film (6UA) as a heat ray reflective layer, and an antifogging drop agent was laminated as an antifogging layer according to Patent Document 1. A glass laminate of Comparative Example 4 was obtained.

<Adjustment of antifogging drop>
The following materials were mixed to prepare an antifogging drop.
Water 100 parts by weight Spherical silica colloid 5 parts by weight Polyethylene oxide 2 parts by weight

<Evaluation method>
(Transmittance)
About the produced glass laminated body, the transmittance | permeability was measured with the haze meter (NDH2000 (made by Nippon Denshoku)), and it evaluated based on the following evaluation criteria.
<Evaluation criteria>
○: The transmittance is 80% or more Δ: The transmittance is 70% or more and less than 80% ×: The transmittance is less than 70%

(Applicability to water application with adhesive for water application)
The period from the time when the glass plate and the surface on the heat ray reflective layer side were pasted with the water sticking adhesive to the time when the moisture of the water sticking adhesive evaporated was measured and evaluated based on the following evaluation criteria.
<Evaluation criteria>
○: Water evaporates within 1 day after sticking Δ: Water evaporates within 1 week and 1 week after sticking ×: Water remains for over 1 week after sticking

(Applicability to heat ray reflective layer application)
The wettability, uniformity, and adhesion when the coating solution for the high refractive index layer and the coating solution for the low refractive index layer were applied to the film were measured and evaluated based on the following evaluation criteria.
<Evaluation criteria>
◎: Good wettability, ensuring uniformity and adhesion ○: Applying uniformly, ensuring adhesion △: Applying uniformly, but not ensuring adhesion X: Unable to ensure uniformity and adhesion

(Visibility after vapor irradiation)
The rear visibility was examined while irradiating steam at 40 ° C. under conditions of 23 ° C. and 55% RH on the produced glass laminate, and evaluated based on the following evaluation criteria.
<Evaluation criteria>
○: The back is clearly visible even after irradiation for 20 seconds or longer. Δ: The rear is visible even after irradiation for 7 seconds or longer but less than 20 seconds.

(Abrasion resistance)
A steel wool test was performed on the glass laminates of Examples 1 and 3. The steel wool test uses a load variation type frictional wear test system HHS2000 manufactured by Haydon Co., Ltd., the surface of the antifogging layer for the glass laminate of Example 1, and the surface of the hard coat layer for the glass laminate of Example 3. Were reciprocated 10 times with steel wool applied with a load of 200 g / cm ² (manufactured by Nippon Steel Wool Co., Ltd., # 0000), and the occurrence of scratches was visually observed. The speed of steel wool was 500 mm / min, and the one-way travel distance of steel wool was 50 mm.

Table 1 and Table 2 show the evaluation results of Examples and Comparative Examples.

From the results in Table 1, it can be said that the transmittance is only x in Comparative Example 4, and the rear visibility is poor and inappropriate. For the other examples and comparative examples, it can be said that there is no problem in the transmittance. This is because the glass laminate of Comparative Example 4 contains mica that causes a decrease in transmittance.

Next, as for water sticking suitability by the water sticking adhesive, Comparative Example 1 is Δ, Comparative Examples 2 and 4 are ×, and it takes time for the water sticking adhesive to drain, that is, time for construction. Is undesirable. On the other hand, Examples 1 and 2 and Comparative Example 3 are ◯, which means that the time until the moisture of the water sticking adhesive is removed is short, that is, it can be applied in a short time. This is because a PMMA film is used in Comparative Example 1, a PET film is used in Comparative Example 2, and a film mainly composed of polyethylene is used in Comparative Example 4, and the moisture content of the adhesive for water application is low because the moisture permeability of these films is low. It is thought that it takes time to escape. On the other hand, in Examples 1 and 2 and Comparative Example 3, since the cellulose ester film having a high moisture permeability is used, it is considered that the moisture of the adhesive for water sticking was quickly removed.

Next, with regard to the suitability for applying the heat ray reflective layer, Comparative Example 1 is x, and it can be said that it is not practical. On the other hand, Example 1 is (double-circle), Example 2, and Comparative Examples 2 and 3 are (circle), and it can be said that there is no problem practically. In Example 1 and Comparative Example 3, it is considered that the film surface on which the heat ray reflective layer is laminated is also hydrophilized by saponification, so that it is excellent in coating suitability. Moreover, in Example 1 and Comparative Example 1, since the film surface on which the heat ray reflective layer is laminated is not hydrophilized, it is considered that the coating suitability inherent to each film is reflected.

Next, regarding the visibility after vapor irradiation, Comparative Examples 1 to 3 are x, and it can be said that the rear visibility is poor under high humidity and is not practical. Further, Comparative Example 4 is Δ, and it can be said that rear visibility is likely to deteriorate under high humidity, which is not preferable in practice. On the other hand, Example 1 and 2 is (circle), and it can be said that there is no problem in practical use with good backward visibility under high humidity. This is presumably because the antifogging treatment was not performed in Comparative Example 3, and the PMMA film of Comparative Example 1 and the PET film of Comparative Example 2 were not imparted with antifogging properties by light irradiation or saponification. Further, in Comparative Example 4, the antifogging property is imparted by the antifogging drop agent, but it is considered that there is not enough performance to cope with a rapid humidity change. On the other hand, in Examples 1 and 2, since the surface of the cellulose ester film is sufficiently hydrophilicized by light irradiation or saponification, it is considered that the cellulose ester film has good antifogging performance.

From the results in Table 2, with respect to scratch resistance, Example 3 having a hard coat layer is less likely to be scratched than Example 1 having no hard coat layer. Moreover, although the moisture permeability did not change so much in Examples 1 and 3, this is because a hard coat resin having a high moisture permeability (300 g / m ² · 24 hr or more) is used as the hard coat layer of Example 3. is there. Thereby, since a hard-coat layer does not prevent evaporation of the water | moisture content of the adhesive for water sticking, the water sticking property by the adhesive for water sticking is also favorable. And in Example 3, there is no problem in the visibility after vapor irradiation. This means that the hard coat layer does not interfere with the antifogging function.

From the above, the glass laminates of Examples 1 to 3 having no evaluation result have a heat shielding function and can be adhered to the glass in a short time with a water sticking adhesive, and are anti-fogged against sudden humidity changes. It can be said that it has characteristics. Furthermore, the glass laminate of Example 3 also has scratch resistance, and is more effective in usage forms that require scratch resistance, such as vehicle window glass.

The heat-shielding and anti-fogging film and glass laminate of the present embodiment described above can be expressed as follows.

1. A heat and anti-fogging film having a heat and anti-fogging function,
A cellulose ester film;
A hydrophilic heat ray reflective layer laminated on one surface of the cellulose ester film;
An antifogging film comprising: an antifogging layer formed by hydrophilizing the other surface of the cellulose ester film.

2. 2. The heat-shielding anti-fogging film as described in 1 above, further comprising a water sticking pressure-sensitive adhesive layered on the opposite side of the heat ray reflective layer from the cellulose ester film.

3. A surface of the anti-fogging layer is provided with a hard coat layer containing a hard coat resin having a moisture permeability of 300 g / m ² · 24 hr or more at 40 ° C. and 90% RH measured in accordance with JIS Z 0208. The heat shielding and antifogging film as described in 1 or 2 above.

4. 4. The heat-shielding antifogging film as described in any one of 1 to 3 above, wherein the heat ray reflective layer contains metal oxide particles.

5. 5. The thermal barrier and antifogging film as described in any one of 1 to 4 above, wherein a phosphoric acid plasticizer is not added to the cellulose ester film.

6. 6. The heat-shielding and anti-fogging layer according to any one of 1 to 5, wherein the anti-fogging layer is formed by irradiating the surface of the cellulose ester film with light having a photon energy of 155 kcal / mol or more. the film.

7. 7. A glass laminate, wherein the heat ray-reflecting antifogging film according to any one of 1 to 6 above and the glass are adhered to the heat ray reflective layer side with a water sticking adhesive.

The heat-shielding and anti-fogging film of the present invention can be used as a glass laminate by being bonded to a window glass of a building or a vehicle.

DESCRIPTION OF SYMBOLS 10 Glass laminated body 11 Glass 12 Adhesive for water sticking 13 Heat ray reflective layer 14 Cellulose ester film 14a Anti-fogging layer 15 Hard coat layer

Claims

A heat and anti-fogging film having a heat and anti-fogging function,
A cellulose ester film;
A hydrophilic heat ray reflective layer laminated on one surface of the cellulose ester film;
An antifogging film comprising: an antifogging layer formed by hydrophilizing the other surface of the cellulose ester film.
The heat-shielding anti-fogging film according to claim 1, further comprising a water sticking adhesive laminated on the opposite side of the heat ray reflective layer from the cellulose ester film.
A surface of the anti-fogging layer is provided with a hard coat layer containing a hard coat resin having a moisture permeability of 300 g / m 2 · 24 hr or more at 40 ° C. and 90% RH measured in accordance with JIS Z 0208. The heat-shielding anti-fogging film according to claim 1 or 2.
The heat shielding and antifogging film according to any one of claims 1 to 3, wherein the heat ray reflective layer contains metal oxide particles.
The heat-shielding and anti-fogging film according to any one of claims 1 to 4, wherein a phosphoric acid plasticizer is not added to the cellulose ester film.
The heat shield layer according to any one of claims 1 to 5, wherein the antifogging layer is formed by irradiating the surface of the cellulose ester film with light having a photon energy of 155 kcal / mol or more. Fog film.
7. A glass laminate comprising the heat-shielding and anti-fogging film according to claim 1 and the glass layer adhered to the heat ray reflective layer side with a water sticking adhesive.