JP6326780B2 - Window pasting film - Google Patents

Description

  The present invention relates to a window pasting film. More specifically, while having sufficient adhesive strength, it is difficult for bubbles to remain at the time of pasting, and there is little adhesive residue at the time of peeling, which can be easily pasted and peeled, and further suppresses the transmission of heat rays and ultraviolet rays. The present invention relates to an excellent film for window pasting.

  In general, a film for pasting a window has a strong adhesion to the window glass in order to have a function of preventing the window glass from scattering, and it is not easy to peel it off from the window glass. Even with a type of film that uses an adhesive, it is difficult to apply it without leaving any bubbles or to remove it without leaving any adhesive glue, because of its high adhesive strength for functions such as preventing window glass from scattering. It was.

  Further, when the window pasting film is scratched due to some external factor, the pasted film may be peeled off and the window pasting film may be pasted again. If the adhesive force between the adhesive and window pasting film is too weak or the cohesive force of the adhesive is too small, the adhesive will remain on the glass side when peeled off from the window pasting film, and later There is also a problem of affecting the pasting of the film.

  Patent Document 1 discloses a technique for a window pasting film provided with a silicone rubber adsorption layer, and Patent Document 2 discloses a technique for providing a through-hole in a silicone rubber adsorption layer, which makes it relatively easy to generate bubbles. It is a film for window pasting that can be applied without leaving any residue, and can be peeled off cleanly without adhesive residue. However, depending on the temperature and humidity conditions of the environment, it may peel off from the edge of the film if left for a long period of time. Yes, the adhesive strength was not sufficient.

JP 2011-183742 A JP2013-14012A

  The present invention has been made in view of the above-mentioned problems and situations, and the solution is to have a sufficient adhesive force, and it is difficult for air bubbles to remain at the time of application, and there is little adhesive residue at the time of peeling, which makes it easy to apply. Another object is to provide a window pasting film that can be attached and peeled and has an excellent effect of suppressing transmission of heat rays and ultraviolet rays.

In order to solve the above-mentioned problems, the present inventor is a window pasting film having an adhesive layer on the outermost layer in the process of examining the cause of the above-mentioned problem, and the adhesive layer is an acrylic adhesive and matting agent particles The average particle size of the matting agent particles and the average layer thickness of the adhesive layer satisfy a specific relationship, the average particle size M of the matting agent particles, and the monodispersity of the particle size of the matting agent particles And, if the average number per unit area (cm ² ) of the matting agent particles is a film for affixing a window within a specific range, air bubbles hardly remain at the time of application while having a sufficient adhesive force, Further, the present inventors have found that there can be provided a window pasting film that has little adhesive residue at the time of peeling, can be easily attached and peeled, and has an excellent effect of suppressing transmission of heat rays and ultraviolet rays.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A window pasting film having an adhesive layer on the outermost layer,
The pressure-sensitive adhesive layer contains acrylic pressure-sensitive adhesive and matting agent particles, and the value of the average particle diameter M of the matting agent particles and the value of the average layer thickness d of the pressure-sensitive adhesive layer satisfy the conditions specified by the following formula 1. ,
The average particle size M of the matting agent particles is in the range of 3 to 50 μm, the monodispersity of the particle size of the matting agent particles is 25% or less, and the unit area (cm ² ) A window pasting film, wherein the average number per window is in the range of 0.1 to 80.

Formula 1: d <M (μm)
2. 2. The window pasting film according to claim 1, wherein the value of the average particle diameter M of the matting agent particles and the value of the average layer thickness d of the adhesive layer satisfy a condition defined by the following formula 2.

Formula 2: 2d <M <10d (μm )

3 . The average film thickness d of the said adhesion layer exists in the range of 1-20 micrometers, The film for window sticking of Claim 1 or 2 characterized by the above-mentioned.

4 . The window pasting film according to any one of claims 1 to 3 , wherein the window pasting film is an optical reflection film.

5 . 5. The window sticking according to claim 4 , wherein the optical reflective film has an optical reflective layer in which a high refractive index layer and a low refractive index layer are alternately laminated on at least one surface of a support. the film.

6 . The optical reflection film has an infrared light reflection multilayer film layer in which layers containing a first polymer species and layers containing a second polymer species are alternately laminated on at least one surface of a support. The film for window pasting of Claim 4 characterized by these.

  The film for window pasting of the present invention has a sufficient adhesive force by means of putting a matting agent having a large particle size in the adhesive layer, and it is difficult for bubbles to remain at the time of application, and there is little adhesive residue at the time of peeling, and it is easy It is possible to provide a window pasting film that can be pasted and peeled and is excellent in the effect of suppressing the transmission of heat rays and ultraviolet rays.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  In a window pasting film, if the surface irregularity height of the matting agent added to the adhesive layer is small, the smooth glass and the adhesive layer are adsorbed so that they are not easily slid to each other. Moreover, if the height of the unevenness is too large, the adhesive strength is reduced. Therefore, if the unevenness of the surface of the matting agent is appropriately designed as a window pasting film, bubbles can easily escape from between the irregularities while maintaining sufficient adhesion, and adsorption with the glass is suppressed. It is thought that it is easy to stick on the window glass because it is slippery. Furthermore, when peeling off from the window glass, it is considered that there is little adhesive residue due to the unevenness, and it becomes easy to peel off.

  Moreover, as a factor other than the height of the surface unevenness due to the matting agent, the average number per unit area of the unevenness due to the matting agent also affects, and when the average number of the matting agent is too large, the adhesion point with the glass decreases. As a result, scattering of transmitted light increases optically, and transparency is deteriorated. In addition, it may gradually peel off when left for a long time after being applied. On the other hand, if the average number of matting agents is too small, bubbles are not easily removed when pasted on a window, and workability and wrinkles are more easily reduced. In addition, there is a problem that adhesive residue may occur when peeling off.

  Therefore, it is presumed that the excellent effect of the present invention can be obtained by designing the unevenness height of the matting agent and the average number of matting agents within the optimum height and number range.

The schematic sectional drawing which shows an example of a structure of the film for window pasting of this invention Schematic sectional view showing an example of another configuration of the film for window pasting of the present invention Schematic sectional view showing an example of another configuration of the film for window pasting of the present invention Schematic diagram showing an example of the adhesive layer of the present invention in which matting agent particles are encapsulated

The window pasting film of the present invention is a window pasting film having an adhesive layer on the outermost layer,
The pressure-sensitive adhesive layer contains acrylic pressure-sensitive adhesive and matting agent particles, and the value of the average particle diameter M of the matting agent particles and the value of the average layer thickness d of the pressure-sensitive adhesive layer satisfy the conditions specified by the following formula 1. The average particle diameter M of the matting agent particles is in the range of 3 to 50 μm, the monodispersity of the particle diameter of the matting agent particles is 25% or less, and the unit area of the matting agent particles ( The average number per cm ² ) is in the range of 0.1 to 80. This feature is a technical feature common to the inventions according to claims 1 to 6 .

As an embodiment of the present invention, the value of the average particle diameter M of the matting agent particles and the value of the layer thickness d of the adhesive layer satisfy the condition defined by the formula 2 from the viewpoint of manifesting the effects of the present invention. It is preferable. Further, the average number per unit area (cm ² ) of the matting agent is 0.1 to 80, and it is possible to remove bubbles or paste while maintaining adhesion without deteriorating the transparency of the film. Ru can rest improvement.

In addition, the average layer thickness d of the adhesive layer according to the present invention, it is within the scope of 1~20μm may be impart moderate unevenness (height) in the adhesive layer according to the present invention, maintaining the sliding property However, it is preferable from the viewpoint of improving bubble loss and adhesive residue.

  The window pasting film of the present invention is preferably an optical reflection film, which is a preferred embodiment for the effect of suppressing transmission of heat rays and ultraviolet rays. In addition, the optical reflective film has an optical reflective layer in which a high refractive index layer and a low refractive index layer are alternately laminated on at least one surface of the support, thereby suppressing the transmission of heat rays and ultraviolet rays. Since it becomes an excellent film for window pasting, it is preferable.

  Moreover, as another embodiment, the optical reflective film has an infrared layer in which layers containing a first polymer species and layers containing a second polymer species are alternately laminated on at least one surface of a support. It is preferable to have a light reflecting multilayer film layer because it becomes a window pasting film excellent in the effect of suppressing the transmission of heat rays and ultraviolet rays.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Film for Window Pasting of the Present Invention >>
The window pasting film of the present invention is a window pasting film having an adhesive layer as the outermost layer, the adhesive layer containing an acrylic adhesive and matting agent particles, and the average particle diameter M of the matting agent particles. The value of the adhesive layer and the value of the thickness d of the adhesive layer satisfy the condition defined by the following formula 1, the average particle diameter M of the matting agent particles is in the range of 3 to 50 μm, and the matting agent particle particles The monodispersity of the diameter is 25% or less, and the average number per unit area (cm ² ) of the matting agent particles is in the range of 0.1 to 80, and this configuration It has a sufficient adhesive force, it is hard to leave bubbles at the time of pasting, and there is little adhesive residue at the time of peeling, it can be easily pasted and peeled, and it has an excellent effect of suppressing the transmission of heat rays and ultraviolet rays Provide window-paste film The

Formula 1: d <M (μm)
<Composition of the film for window pasting of the present invention>
First, the basic structure of the window pasting film of the present invention (hereinafter sometimes simply referred to as a film) will be described with reference to the drawings. However, the present invention is not limited to this.

  1-3 is a schematic sectional drawing which shows an example of a structure of the film for window sticking of this invention.

  In FIG. 1, a window pasting film 1 has an optical reflection layer 3 composed of a plurality of refractive index layers having different refractive indexes on a transparent resin film 2, and further has an adhesive layer 4 thereon. A protective sheet (laminate sheet) that can be peeled off before being attached to a window glass (not shown) may be laminated on the adhesive layer 4, and an anti-curl layer or an anti-blocking layer is provided on the opposite side of the transparent resin film 2. It may be provided. Furthermore, a conductive layer, an antistatic layer, a gas barrier layer, an antifouling layer, a deodorizing layer, a droplet layer, a slippery layer, an abrasion resistant layer, an electromagnetic wave shielding layer, an ultraviolet absorbing layer, a printing layer, a fluorescent light emitting layer, You may have one or more of functional layers, such as a hologram layer and a colored layer.

  The optical reflection layer 3 is preferably composed of a laminated body composed of a low refractive index layer 3a and a high refractive index layer 3b, and the low refractive index layer 3a and the high refractive index layer 3b are laminated alternately. It is preferable to have two or more layers as a body.

  FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the window pasting film of the present invention.

  The optical reflection layer 3 is formed on both sides of the transparent resin film 2, the adhesive layer 4 is provided on the outermost layer on the side of the optical reflection layer 3 that is attached to the window, and the outermost layer of the optical reflection layer 3 on the opposite side. The hard coat layer 5 is provided.

  FIG. 3 is a schematic cross-sectional view showing another example of the configuration of the window pasting film of the present invention.

  The window pasting film is composed of an infrared light reflective multilayer film layer 6 in which layers 6a containing a first polymer species and layers 6b containing a second polymer species are alternately laminated, and further on the window. The pressure-sensitive adhesive layer 4 is provided on the surface to be attached, and the hard coat layer 5 is provided on the opposite surface.

  The total thickness of the window pasting film of the present invention is preferably in the range of 30 to 200 μm, more preferably in the range of 40 to 100 μm, and still more preferably 45 to 75 μm.

  As an optical characteristic of the window pasting film of the present invention, the visible light transmittance measured by JIS R 3106 (1998) is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more. It is.

  Hereinafter, each component of the film for window pasting of this invention is demonstrated.

<Adhesive layer>
The pressure-sensitive adhesive layer according to the present invention is the outermost layer of a window pasting film, the pressure-sensitive adhesive layer contains matting agent particles, the average particle diameter M of the matting agent particles, and the average layer thickness of the pressure-sensitive adhesive layer. The value of d satisfies the condition defined by the following formula 1. That is, the adhesive layer contains a matting agent having an average particle diameter larger than the average layer thickness of the adhesive layer, and is provided with irregularities on the surface of the adhesive layer, and the irregularities may be included in the adhesive layer. It may be exposed from the adhesive layer. It is preferable that the adhesive layer is included so that the matting agent does not fall off from the window pasting film.

Formula 1: d <M (μm)
FIG. 4 is a schematic view showing an example of the pressure-sensitive adhesive layer of the present invention in which matting agent particles are encapsulated.

  In FIG. 4, the matting agent particles 7 are included in the adhesive layer 4, and the relationship between the average particle diameter M of the matting agent particles and the average layer thickness d of the adhesive layer is shown. In the pressure-sensitive adhesive layer according to the present invention, the relationship between M and d satisfies the condition defined by Formula 1.

  The average particle size M of the matting agent particles can be obtained, for example, by taking a scanning micrograph (SEM image) of 100 matting agent particles, measuring the particle size, and obtaining an average value. The particle diameter referred to in the present invention is represented by the diameter when it is circular, and if it is an irregular shape other than circular, the projected area is converted into a circle equivalent and displayed as the diameter at that time. Next, the arithmetic average particle diameter (μm) of 100 matting agent particles is obtained and is defined as the average particle diameter M. The average particle diameter can be measured using an image processing measurement device (for example, Luzex AP; manufactured by Nireco Corporation).

  The average layer thickness of the pressure-sensitive adhesive layer is the average layer thickness when the pressure-sensitive adhesive layer is dried, and refers to the thickness of the layer in the region where the matting agent particles are not present as shown in FIG.

  Layer thickness measurement methods can be broadly divided into optical and contact methods. Contact methods have the advantage of being able to measure opaque films such as metals, but in general, optical measurement can be performed. preferable. There are two types of optical measurement methods: a method of measuring with an ellipsometer and a method of measuring with a reflectance spectroscopy (light interference method), both of which can be preferably used.

  The ellipsometer is a measurement method similar to reflectance spectroscopy except that the incident light is not perpendicular and uses two polarizations, which reflect light in a certain wavelength range perpendicular to the sample. The reflectance is measured from the thin film. In the present invention, it is preferable to measure the layer thickness by reflectance spectroscopy which can be measured relatively easily.

In reflectance spectroscopy, for example, while using a layer thickness measurement system F20 (manufactured by Filmetrics) as a device used and FILMeasure (manufactured by Filmetrics) as a software used, while moving the window pasting film on an XY stage, The thickness of the adhesive layer is measured every 1 mm ² . The measurement time per 1 mm ² is measured in about 1 second. For example, it is possible to arbitrarily select 100 places where the matting agent particles are not present and average the layer thicknesses obtained by the measurement to obtain an average layer thickness d.

  Furthermore, it is preferable that the value of the average particle diameter M of the matting agent particles and the value of the average layer thickness d of the adhesive layer satisfy the conditions defined by the following formula 2.

Formula 2: 2d <M <10d (μm)
By satisfying the condition defined by Formula 2, an adhesive layer that has a sufficient adhesive force, hardly leaves bubbles at the time of pasting, and has little adhesive residue at the time of peeling, which can be easily stuck or peeled off is formed. be able to.

  The average layer thickness d of the pressure-sensitive adhesive layer according to the present invention is preferably in the range of 1 to 20 μm. If it is 1 micrometer or more, there exists a tendency for adhesiveness to improve and sufficient adhesive force is acquired. Conversely, if it is 20 μm or less, the transparency of the window pasting film is not only improved, but also after the window pasting film is pasted on the window glass, when it is peeled off, cohesive failure does not occur between the adhesive layers, to the glass surface. There is a tendency for the remaining adhesive to disappear.

The average particle size M of the matting agent particles according to the present invention, Ru der range of 3 to 50 [mu] m. When the average particle diameter is within this range, it is possible to form an adhesive layer in which bubbles are hardly left at the time of pasting and less adhesive residue is left at the time of peeling. Furthermore, it can be included in the adhesive layer having the above layer thickness, so that the matting agent does not easily fall off and does not impair the transparency of the window pasting film.

  The matting agent particles according to the present invention may be primary particles or secondary particles in which primary particles are aggregated. The matting agent particles to be used may be one type or two or more types.

  Examples of matting agent particles include inorganic particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, silica Examples of the organic particles include silicone resin, fluorine resin, polystyrene resin, polyacrylate resin, polymethyl methacrylate resin, and polycarbonate resin, and the organic particles are appropriately selected from these. Is preferred.

  Among the matting agent particles, silicon dioxide is preferable as the inorganic particles, and polyacrylate resin and polymethyl methacrylate resin are preferable as the organic particles. Among them, it is preferable to use organic particles such as polyacrylate resin and polymethyl methacrylate resin for the adhesive layer according to the present invention.

  The silicon dioxide is preferably obtained by condensing a reactive silicon compound under hydrolysis conditions. This method is preferable because the relative standard deviation of the average particle diameter can be easily adjusted. Specifically, a method for producing an alkoxysilane compound by hydrolysis and condensation in the presence of water exceeding the hydrolysis equivalent in an organic solution described in JP-B 05-4325, Patent No. 3484611 The production method can be used by hydrolyzing and condensing an alkoxysilane compound in the gas phase in the presence of fine water droplets as described. In addition, a dispersion in glycol described in Japanese Patent Publication No. 06-57317 and a method described in Japanese Patent No. 3187592 can also be used.

  Examples of the fine particles of silicon dioxide include Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 manufactured by Nippon Aerosil Co., Ltd., preferably Aerosil 200V, R972. , R972V, R974, R202, R812. Two or more kinds of these fine particles may be used in combination. When using 2 or more types together, it can mix and use in arbitrary ratios. In this case, fine particles having different average particle sizes and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

  The matting agent particles of the polyacrylate resin and the polymethyl methacrylate resin are truly spherical and have very high transparency, there is no aggregation between the particles, and the average particle size can be arbitrarily adjusted between about 0.1 to 500 μm. Yes, commercially available products can be preferably used. Soken Chemical Co., Ltd. Chemisnow MX series, MR series, MP series, etc., Sekisui Plastics Co., Ltd. Techpolymer MBX series, SSX series, etc. are mentioned, and fine particles having a desired average particle size can be appropriately selected.

The amount of the matting agent according to the present invention, the particle size and degree of dispersion, the layer thickness of the layer a matting agent, but also on the smoothness of the support, generally window film film 1 m ² per 0.02 to 0 A range of .8 g is preferable, and a range of 0.04 to 0.5 g per 1 m ² is more preferable.

Further, the matting agent particles according to the present invention is to have a high monodispersity, preferably from the viewpoint of enhancing the transparency in addition to the effect of the present invention, monodispersity of particle size, Ru der than 25%.

  The monodispersity can be defined by the coefficient of variation of the particle size distribution that can be calculated using the particle size obtained from the particle size distribution measurement, and is determined by the following equation.

Coefficient of variation (%) = (standard deviation of particle size distribution / average particle size) × 100
In the particle size distribution measurement, for example, matting agent particles are dispersed in water, and an appropriate amount thereof is put into the apparatus. When a laser hits a particle in a dispersion medium, it is known from the light scattering theory that the particle type and the particle size are scattered with a specific refractive index and size. Using this principle, the average particle size is calculated. And it can prescribe | regulate by the variation coefficient of the particle diameter distribution which can be calculated using the particle diameter obtained from the particle size distribution measurement.

  The matting agent particles according to the present invention are preferably spherical (spherical) from the viewpoint of enhancing transparency in addition to the effects of the present invention. Whether it is spherical or not is defined based on a scanning electron micrograph (SEM image) of the matting agent particles.

  Specifically, a scanning electron micrograph is taken of the matting agent particles, and 100 matting agent particles are randomly selected. When the major axis of the selected matting agent particles is a and the minor axis is b, an average value of a / b values is obtained as an aspect ratio. In addition, when drawing a circumscribing rectangle for each particle (referred to as “the circumscribing rectangle”), the shortest short side of the circumscribed rectangle is the shortest length, and the longest long side is the length. Is the major axis.

  When the aspect ratio is in the range of 1.00 to 1.15, and more preferably in the range of 1.00 to 1.05, it is classified as a spherical shape. If it is outside the range of 1.00 to 1.15, it is classified as an indeterminate form. The closer the aspect ratio is to 1, the higher the sphericity.

  The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, polyvinyl butyral pressure-sensitive adhesives, and ethylene-vinyl acetate pressure-sensitive adhesives. Can do.

When pasting the window pasting film of the present invention on the window glass, water is sprayed on the window, and the pasting method for matching the adhesive layer of the present window pasting film to the wet glass surface, the so-called water pasting method is pasted again, It is preferably used from the viewpoint of repositioning and the like. Therefore, adhesive strength in humid water is present weak, are needed use acrylic adhesive.

  The acrylic pressure-sensitive adhesive to be used may be either solvent-based or emulsion-based, but a solvent-based pressure-sensitive adhesive is preferable because it is easy to increase the adhesive strength and the like, and among them, those obtained by solution polymerization are preferable. As a raw material when producing such a solvent-based acrylic pressure-sensitive adhesive by solution polymerization, for example, as a main monomer serving as a skeleton, an acrylic ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acryl acrylate, As a comonomer to improve cohesive strength, vinyl acetate, acrylonitrile, styrene, methyl methacrylate, etc., to further promote crosslinking, to give stable adhesive strength, and to maintain a certain level of adhesive strength even in the presence of water Examples of the functional group-containing monomer include methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, and glycidyl methacrylate. Since the adhesive layer of the laminated film requires a particularly high tack property as the main polymer, those having a low glass transition temperature (Tg) such as butyl acrylate are particularly useful.

  This adhesive layer contains additives such as stabilizers, surfactants, UV absorbers, flame retardants, antistatic agents, antioxidants, thermal stabilizers, lubricants, fillers, coloring, adhesion modifiers, etc. It can also be made. In particular, when used for window sticking as in the present invention, the addition of an ultraviolet absorber is also effective for suppressing deterioration of the window sticking film due to ultraviolet rays.

(Crosslinking agent)
Moreover, in this invention, when water-soluble resin is used for the optical reflection layer mentioned later, it is also preferable to add the crosslinking agent which can react with the said water-soluble resin to the adhesion layer.

  As a method for bonding the window pasting film of the present invention to a window glass, a water pasting method is preferably used. The water pasting method referred to in the present invention means that after applying water to the adhesive layer surface or the substrate surface of the window pasting film of the present invention, it is pasted under pressure with the window pasting film of the present invention and the substrate, for example, a window glass. It is a method to match.

  Adhesion between the adhesive layer and the optical reflective layer by spreading the adhesive to the adjacent optical reflective layer and causing a curing reaction with the water-soluble resin of the optical reflective layer by wetting the adhesive layer when water is applied Will improve dramatically. Therefore, when peeling off the window pasting film, an excellent window pasting film in which no adhesive residue such as an adhesive is generated on the window glass surface side can be provided.

  The cross-linking agent suitable for the adhesive layer according to the present invention is not particularly limited as long as it causes a cross-linking reaction with the reactive group of the water-soluble resin. For example, when the water-soluble resin is gelatin, Aldehyde-based curing agents, active halogen-based curing agents, active vinyl-based compounds and the like are preferable, and when the water-soluble resin is polyvinyl alcohol, boric acid and its salts are preferable, but other known ones can be used, In general, it is a compound capable of reacting with a reactive group possessed by a water-soluble resin, and is appropriately selected depending on the type of the water-soluble resin.

  Specific examples of the crosslinking agent include, for example, epoxy curing agents (diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidyl cyclohexane, N, N-diglycidyl- 4-glycidyloxyaniline, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, etc.), aldehyde curing agents (formaldehyde, glioxal, etc.), active halogen curing agents (2,4-dichloro-4-hydroxy-1,3,5) -S-triazine, etc.), active vinyl compounds (1,3,5-trisacryloyl-hexahydro-s-triazine, bisvinylsulfonylmethyl ether, etc.), aluminum alum, and the like. Even if used together It does not.

  In the present invention, the above-mentioned crosslinking agent can also be used in the optical reflection layer in order to cure the water-soluble resin as a binder.

In the present invention, the content of the water-soluble resin content per unit area of the cross-linking agent (g / m ^2), containing a layer constituting the optical reflective layer in contact with the adhesive layer in the pressure-sensitive adhesive layer (g / m ² ) To 0.01 times or more and 0.30 times or less. If the content (g / m ² ) per unit area of the cross-linking agent in the adhesive layer is 0.01 times or more, the effect of suppressing adhesive residue when peeling the window pasting film from the window glass is large, 0.30. If it is 2 times or less, it is effective for suppressing a decrease in reflectance of the optical reflection layer.

  The method for forming the pressure-sensitive adhesive layer according to the present invention includes, as appropriate, adding the matting agent particles and other additives according to the present invention to the solvent containing the pressure-sensitive adhesive and dispersing the matting agent particles to obtain a coating solution. , Roller coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, etc., then layered by heating and then solidified by drying It is preferable to do.

  When applying, the lower layer of the pressure-sensitive adhesive layer, for example, a transparent resin film, can be surface-treated, and can be appropriately selected from corona discharge treatment, plasma discharge treatment, alkali treatment and the like. The adhesion between the adhesive layer and the lower layer can be improved by the surface treatment.

  The concentration of the pressure-sensitive adhesive in the coating solution may be appropriately determined depending on the layer thickness after forming the pressure-sensitive adhesive layer, a coating machine, coating conditions, and the like, and is usually 0.1 to 50% by mass.

  In consideration of productivity and prevention of aggregation of the matting agent in the coating solution, the coating solution preferably contains the matting agent in an amount of 0.01 to 20% by mass, preferably 0.02 to 10% by mass. More preferably, it is most preferable to contain 0.05-5 mass%.

The average number per unit area (cm ² ) of the matting agent in the pressure-sensitive adhesive layer according to the present invention is in the range of 0.1 to 80. It is possible to obtain a pressure-sensitive adhesive layer that is less likely to remain and has little adhesive residue at the time of peeling, and can be easily applied and peeled off. Preferably 80 0.5, and more preferably 1-50.

The average number per unit area (cm ² ) of the matting agent is present in a 10 cm square area of the film for window pasting by sampling about 10 locations by scanning micrograph (SEM image). It can be determined by counting the number of matting agents, converting the value per unit area (cm ² ) and averaging the number of samples.

In order for the average number per unit area (cm ² ) of the matting agent to fall within the range of 0.1 to 500, it is preferable to adjust by the amount of the matting agent added to the coating solution.

<Transparent resin film>
A transparent resin film is preferably used as the support for the window pasting film of the present invention.

  The thickness of the transparent resin film used in the present invention is preferably in the range of 30 to 200 μm, more preferably in the range of 30 to 70 μm, and most preferably in the range of 35 to 70 μm. If the thickness is 30 μm or more, wrinkles during handling are less likely to occur, and if the thickness is 200 μm or less, the ability to follow a curved glass surface is improved when bonded to glass, and wrinkles are less likely to occur. Become.

  The transparent resin film used in the present invention is preferably a biaxially oriented polyester film. However, unless the obtained film deviates from the gist of the present invention, an unstretched or at least one stretched polyester film is used. You can also. A stretched film is preferable from the viewpoint of strength improvement and thermal expansion suppression.

  The transparent resin film used in the present invention preferably has a thermal shrinkage within a range of 0.1 to 3% at a temperature of 150 ° C. from the viewpoint of preventing generation of wrinkles of the film and cracking of the reflective layer. The content is more preferably in the range of 1.5 to 3%, and further preferably in the range of 1.9 to 2.7%.

  The transparent resin film used in the present invention is not particularly limited as long as it is transparent, and various resin films can be used. Polyolefin films (polyethylene, polypropylene, etc.), polyester films (polyethylene terephthalate, polyethylene naphthalate). Phthalate, etc.), polyvinyl chloride, cellulose acetate, etc. can be used, and a polyester film is preferred. Although it does not specifically limit as a polyester film (henceforth polyester), It is preferable that it is polyester which has the film formation property which has a dicarboxylic acid component and a diol component as main structural components. The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethanedicarboxylic acid, Examples thereof include cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis ( 4-Hydroxyphenyl) sulfone, bisphenol fluorene hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like. Among the polyesters having these as main constituent components, from the viewpoint of transparency, mechanical strength, dimensional stability, etc., dicarboxylic acid components such as terephthalic acid, 2,6-naphthalenedicarboxylic acid, diol components such as ethylene glycol and 1 Polyester having 1,4-cyclohexanedimethanol as the main constituent is preferred. Among these, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.

  The transparent resin film used in the present invention may contain particles under conditions that do not impair transparency in order to facilitate handling. Examples of particles used in the present invention include inorganic particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and crosslinked polymers. Examples thereof include organic particles such as particles and calcium oxalate. Examples of the method of adding particles include a method of adding particles in a polyester as a raw material, a method of adding directly to an extruder, and the like. Well, you may use two methods together. In the present invention, additives may be added in addition to the above particles as necessary. Examples of such additives include stabilizers, lubricants, cross-linking agents, anti-blocking agents, antioxidants, dyes, pigments, and ultraviolet absorbers.

  The transparent resin film can be produced by a conventionally known general method. For example, an unstretched transparent resin film that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and rapidly cooling it. The unstretched transparent resin film is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, and other known methods such as transparent resin film flow (vertical axis) direction. Alternatively, a stretched transparent resin film can be produced by stretching in the direction perpendicular to the flow direction of the transparent resin film (horizontal axis). Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the transparent resin film, it is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

  In addition, the transparent resin film may be subjected to relaxation treatment or off-line heat treatment in terms of dimensional stability. The relaxation treatment is preferably carried out in the process from the heat setting in the stretching process of the polyester film to the winding in the transversely stretched tenter or after exiting the tenter. The relaxation treatment is preferably performed at a treatment temperature in the range of 80 to 200 ° C, and more preferably at a treatment temperature in the range of 100 to 180 ° C. Moreover, it is preferable that the relaxation rate is within a range of 0.1 to 10% in both the longitudinal direction and the width direction, and more preferably, the relaxation rate is within a range of 2 to 6%. The relaxed base material is subjected to the following off-line heat treatment to improve heat resistance and to improve dimensional stability.

The transparent resin film is preferably coated with the undercoat layer coating solution in-line on one or both sides during the film forming process. In the present invention, undercoating during the film forming process is referred to as in-line undercoating. Examples of resins used in the undercoat layer coating solution useful in the present invention include polyester resins, acrylic-modified polyester resins, polyurethane resins, acrylic resins, vinyl resins, vinylidene chloride resins, polyethyleneimine vinylidene resins, polyethyleneimine resins, and polyvinyl alcohol resins. , Modified polyvinyl alcohol resin, gelatin and the like, and any of them can be preferably used. A conventionally well-known additive can also be added to these undercoat layers. The undercoat layer can be coated by a known method such as roll coating, gravure coating, knife coating, dip coating or spray coating. The coating amount of the undercoat layer is preferably in the range of 0.01 to ² g / m ² (dry state).

<< First Embodiment of Optical Reflective Film >>
The window pasting film of the present invention is preferably an optical reflecting film, and as a first embodiment, the optical reflecting film has a high refractive index layer and a low refractive index layer on at least one surface of a support. It is preferable to have an optical reflection layer in which are alternately laminated.

<Optical reflection layer>
The optical reflection layer expresses a function of blocking sunlight, particularly an infrared component, and is composed of a plurality of refractive index layers having different refractive indexes. Specifically, a high refractive index layer and a low refractive index layer are laminated. The optical reflection layer according to the present invention may have any structure including at least one laminate (unit) composed of a high refractive index layer and a low refractive index layer. It is preferable to have a configuration in which two or more of the above laminates composed of a rate layer are laminated. In this case, the uppermost layer and the lowermost layer of the optical reflection layer may be either a high refractive index layer or a low refractive index layer, but it is preferable that both the uppermost layer and the lowermost layer are low refractive index layers. When the uppermost layer is a low refractive index layer, the coating property is improved, and when the lowermost layer is a low refractive index layer, it is preferable from the viewpoint of improving adhesion.

  Here, whether an arbitrary refractive index layer of the optical reflection layer is a high refractive index layer or a low refractive index layer is determined by comparing the refractive index with an adjacent refractive index layer. Specifically, when a refractive index layer is used as a reference layer, if the refractive index layer adjacent to the reference layer has a lower refractive index than the reference layer, the reference layer is a high refractive index layer (the adjacent layer is a low refractive index layer). It is judged to be a rate layer.) On the other hand, if the refractive index of the adjacent layer is higher than that of the reference layer, it is determined that the reference layer is a low refractive index layer (the adjacent layer is a high refractive index layer). Therefore, whether the refractive index layer is a high refractive index layer or a low refractive index layer is a relative one determined by the relationship with the refractive index of the adjacent layer. Depending on the relationship, it can be a high refractive index layer or a low refractive index layer.

  Here, there are two components constituting the high refractive index layer (hereinafter also referred to as “high refractive index layer component”) and components constituting the low refractive index layer (hereinafter also referred to as “low refractive index layer component”). In some cases, a layer (mixed layer) containing the high refractive index layer component and the low refractive index layer component is mixed at the interface of the two layers. In this case, in the mixed layer, a set of portions where the high refractive index layer component is 50% by mass or more is defined as a high refractive index layer, and a set of portions where the low refractive index layer component exceeds 50% by mass is defined as a low refractive index layer. . Specifically, when the low refractive index layer includes, for example, different metal oxide particles in the low refractive index layer and the high refractive index layer, the concentration profile of the metal oxide particles in the layer thickness direction in these laminated films , And the composition can determine whether the mixed layer that can be formed is a high refractive index layer or a low refractive index layer. The concentration profile of the metal oxide particles in the laminated film is sputtered at a rate of 0.5 nm / min using the XPS surface analyzer, etching from the surface to the depth direction, with the outermost surface being 0 nm. It can be observed by measuring the atomic composition ratio. Further, even when the metal oxide particles are not contained in the low refractive index component or the high refractive index component and are formed only from the water-soluble resin, similarly, in the concentration profile of the water-soluble resin, for example, It was confirmed that the mixed region was present by measuring the carbon concentration in the layer thickness direction, and further, its composition was measured by EDX (energy dispersive X-ray spectroscopy), and was etched by sputtering. Each layer can be regarded as a high refractive index layer or a low refractive index layer.

  There is no particular limitation on the XPS surface analyzer, and any model can be used, but ESCALAB-200R manufactured by VG Scientific Fix Co. was used. Mg is used for the X-ray anode, and measurement is performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA).

  In general, in a window pasting film, it is preferable to design a large difference in refractive index between a low refractive index layer and a high refractive index layer from the viewpoint that infrared reflectance can be increased with a small number of layers. . In this embodiment, in at least one of the laminates (units) composed of the low refractive index layer and the high refractive index layer, the difference in refractive index between the adjacent low refractive index layer and high refractive index layer is 0.1 or more. Preferably, it is 0.3 or more, more preferably 0.35 or more, and particularly preferably more than 0.4. When the window pasting film has two or more laminates (units) of a high refractive index layer and a low refractive index layer, the refraction of the high refractive index layer and the low refractive index layer in all the laminates (units). It is preferable that the rate difference is within the preferable range. However, even in this case, the refractive index layer constituting the uppermost layer or the lowermost layer of the optical reflection layer may have a configuration outside the above preferred range.

  From the above viewpoint, the number of refractive index layers of the optical reflection layer (units of high refractive index layer and low refractive index layer) is preferably 100 layers or less, that is, 50 units or less, and 40 layers (20 units). ) Or less, more preferably 20 layers (10 units) or less.

<Refractive index layer: high refractive index layer and low refractive index layer>
It is preferable that at least the high refractive index layer or the low refractive index layer in contact with the adhesive layer contains a water-soluble resin. The high refractive index layer and the low refractive index layer may further contain metal oxide particles, a protective agent, a curing agent, and other additives as necessary.

(Water-soluble resin)
The water-soluble resin is not particularly limited, and polyvinyl alcohol resins, gelatin, celluloses, thickening polysaccharides, and resins having reactive functional groups can be used. Of these, it is preferable to use a polyvinyl alcohol-based resin. The water-soluble in the present invention means a compound in which 1% by mass or more, preferably 3% by mass or more dissolves in an aqueous medium.

  Polyvinyl alcohol resins preferably used in the present invention include, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate (unmodified polyvinyl alcohol), cation-modified polyvinyl alcohol having a terminal cation-modified, anionic group Also included are anion-modified polyvinyl alcohol having a modified nature, modified polyvinyl alcohol modified with acrylic, reactive polyvinyl alcohol (for example, “Gosefimer Z” manufactured by Nippon Gosei Co., Ltd.), and vinyl acetate resin (for example, “Exeval” manufactured by Kuraray). . These polyvinyl alcohol resins can be used in combination of two or more, such as the degree of polymerization and the type of modification. Further, silanol-modified polyvinyl alcohol having a silanol group (for example, “R-1130” manufactured by Kuraray Co., Ltd.) can be used in combination.

  Examples of the cation-modified polyvinyl alcohol include 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-61-110483. It is obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

  Anion-modified polyvinyl alcohol is described in, for example, polyvinyl alcohol having an anionic group as described in JP-A-1-206088, 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 alcohol includes, for example, a polyvinyl alcohol derivative in which a polyalkylene oxide group as described in JP-A-7-9758 is added to a part of vinyl alcohol, and JP-A-8-25795. The block copolymer of the vinyl compound and vinyl alcohol which have the described hydrophobic group is mentioned. Polyvinyl alcohol can be used in combination of two or more, such as the degree of polymerization and the type of modification.

  Examples of the vinyl acetate resin include EXEVAL (trade name: manufactured by Kuraray Co., Ltd.) and Nichigo G polymer (trade name: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

  The degree of polymerization of the polyvinyl alcohol-based resin is preferably in the range of 1500 to 7000, and more preferably in the range of 2000 to 5000. A polymerization degree of 1500 or more is preferable because crack resistance of the coating film during formation of the refractive index layer is improved. On the other hand, when the degree of polymerization is 7000 or less, the coating liquid at the time of forming the refractive index layer is preferable.

  In the present invention, “degree of polymerization” refers to a viscosity average degree of polymerization, and a value measured according to JIS-K6726 (1994) is adopted. Specifically, after the polyvinyl alcohol-based resin is completely re-saponified and purified, the intrinsic viscosity [η] (dl / g) measured in water at 30 ° C. can be obtained by the following formula (P).

Formula (P)
P = ([η] × 10 ³ /8.29) ^{(1 / 0.62)}
In the above formula, P represents the degree of polymerization, and η represents the intrinsic viscosity.

  The high refractive index layer and the low refractive index layer constituting the optical reflection layer preferably contain polyvinyl alcohol resins having different saponification degrees. Thereby, mixing of the interface is suppressed, the infrared light reflectance (infrared light shielding rate) becomes better, and the haze is lowered. At this time, the saponification value of the polyvinyl alcohol resin of either the high refractive index layer or the low refractive index layer may be high, but the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer is higher. It is preferable. When the metal oxide particles are included in the high refractive index layer, the polyvinyl alcohol resin having a high degree of saponification can protect the metal oxide particles. The difference in the absolute value of the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer and the low refractive index layer is preferably 3 mol% or more, more preferably 5 mol% or more. It is preferable that the difference in the absolute value of the saponification degree is 3 mol% or more because the intermixed state of the high refractive index layer and the low refractive index layer is set to a preferable level. The difference in absolute value of the saponification degree is preferably as large as possible, but from the viewpoint of solubility of polyvinyl alcohol in water, the difference in absolute value of the saponification degree is preferably 20 mol% or less. .

  The saponification degree of the polyvinyl alcohol-based resin contained in the high refractive index layer and the low refractive index layer is preferably 75 mol% or more from the viewpoint of solubility in water. The saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer and the low refractive index layer is 90 mol% or more for one refractive index layer and 90 mol% for the other refractive index layer. The saponification of one refractive index layer is preferably 90 mol% or less, and the saponification degree of the refractive index layer is more preferably 95 mol% or more. In particular, the saponification degree of the polyvinyl alcohol resin contained in the low refractive index layer is more preferably 90 mol% or less, and the saponification degree of the polyvinyl alcohol resin contained in the high refractive index layer is more preferably 95 mol% or more. It is preferable that the degree of saponification of the polyvinyl alcohol-based resin in the low refractive index layer and the high refractive index layer is in the above relationship since the interlayer mixing state of the high refractive index layer and the low refractive index layer can be set to a preferable level. The upper limit of the degree of saponification of the polyvinyl alcohol-based resin is not particularly limited, but is usually less than 100 mol%, preferably 99.9 mol% or less.

  In the present invention, the content of the polyvinyl alcohol-based resin (total polyvinyl alcohol-based resin) is in the range of 5 to 50% by mass with respect to 100% by mass of the total mass (solid content) of each refractive index layer. Preferably, it is in the range of 10 to 40% by mass, and more preferably in the range of 14 to 30% by mass. When the content of the polyvinyl alcohol resin is 5% by mass or more, the film surface becomes uniform and the transparency can be improved when the coating film formed during the formation of the refractive index layer is dried. On the other hand, when the content of the polyvinyl alcohol-based resin is 50% by mass or less, when the metal oxide particles are included in the refractive index layer, the content is appropriate, and the refractive index of the high refractive index layer and the low refractive index layer. This is preferable because the difference can be increased. In the present specification, “film surface” (also referred to as “surface”) means the surface of the coating film obtained when the refractive index layer is formed. The “all polyvinyl alcohol-based resin” means the total amount of polyvinyl alcohol-based resin contained in each refractive index layer.

(gelatin)
Examples of gelatin used include various gelatins that have been widely used in the field of silver halide photographic light-sensitive materials. More specifically, acid-treated gelatin, alkali-treated gelatin, enzyme-treated gelatin, and derivatives thereof can be mentioned.

(Cellulose)
The cellulose to be used is not particularly limited, but a water-soluble cellulose derivative can be preferably used. Examples of the water-soluble cellulose derivative include water-soluble cellulose derivatives such as carboxymethyl cellulose (cellulose carboxymethyl ether), methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose; carboxymethyl cellulose (cellulose that is a carboxylic acid group-containing cellulose) Carboxymethyl ether) and carboxyethyl cellulose.

(Thickening polysaccharide)
The thickening polysaccharide that can be used is not particularly limited, and includes generally known natural simple polysaccharides, natural complex polysaccharides, synthetic simple polysaccharides, and synthetic complex polysaccharides. Specifically, pectin, galactan (eg, agarose, agaropectin, etc.), galactomannoglycan (eg, locust bean gum, guaran, etc.), xyloglucan (eg, tamarind gum, tamarind seed gum, etc.), glucomannoglycan (Eg, salmon mannan, wood-derived glucomannan, xanthan gum, etc.), galactoglucomannoglycan (eg, softwood-derived glycan), arabinogalactoglycan (eg, soybean-derived glycan, microorganism-derived glycan, etc.) (Eg, gellan gum), glycosaminoglycans (eg, hyaluronic acid, keratan sulfate, etc.), alginic acid and alginates, agar, κ-carrageenan, λ-carrageenan, ι-carrageenan, naturals derived from red algae Molecular polysaccharides, and the like.

(Resin having a reactive functional group)
Examples of the resin having a reactive functional group used include polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic resin. Acrylic resin such as acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid Copolymer, styrene-acrylic acid resin such as styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-sodium styrenesulfonate copolymer, styrene-2-hydroxyethyl acrylate copolymer, styrene- 2-hydroxyethyla Chryrate-potassium styrenesulfonate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer, vinyl acetate-maleic acid Examples thereof include vinyl acetate copolymers such as ester copolymers, vinyl acetate-crotonic acid copolymers, vinyl acetate-acrylic acid copolymers, and salts thereof.

  The above water-soluble resins may be used alone or in combination of two or more.

<Metal oxide particles>
The metal oxide particles are an optional component that can be contained in the refractive index layer. By including the metal oxide particles, the refractive index difference between the low refractive index layer and the high refractive index layer can be increased.

  As described above, whether the layer is a high refractive index layer or a low refractive index layer is a relative one that is determined by the relationship with the adjacent refractive index layer, but can be included in the low refractive index layer. The metal oxide particles will be described as “first metal oxide particles”, and typical metal oxide particles that can be contained as a high refractive index layer will be described as “second metal oxide particles”.

(First metal oxide particles)
Examples of the first metal oxide particles include, but are not limited to, silicon dioxide such as zinc oxide, synthetic amorphous silica, and colloidal silica, alumina, and colloidal alumina. Of these, silicon dioxide is preferably used, and colloidal silica is particularly preferably used. The first metal oxide may be used alone or in combination of two or more.

  Colloidal silica is obtained by heating and aging a silica sol obtained by metathesis using an acid of sodium silicate or the like and passing through an ion exchange resin layer.

  As such colloidal silica, a synthetic product or a commercially available product may be used. Examples of commercially available products include Snowtex series (Snowtex OS, OXS, S, OS, 20, 30, 40, O, N, C, manufactured by Nissan Chemical Industries, Ltd.).

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

  The average particle diameter of the first metal oxide particles (preferably silicon dioxide) is preferably in the range of 3 to 100 nm, and more preferably in the range of 3 to 50 nm. In the present specification, the “average particle diameter (number average)” of the metal oxide particles is determined by observing the particles themselves or any 1000 particles appearing on the cross section or surface of the refractive index layer with an electron microscope. The diameter is measured, and the value obtained as the simple average value (number average) is adopted. At this time, the particle diameter of the particle is expressed by a diameter assuming a circle equal to the projected area.

  The content of the first metal oxide particles in the low refractive index layer is preferably in the range of 20 to 75 mass% with respect to 100 mass% of the total solid content of the low refractive index layer, and is preferably 30 to 70. It is more preferably in the range of mass%, more preferably in the range of 35 to 69 mass%, and particularly preferably in the range of 40 to 68 mass%. It is preferable that the content of the first metal oxide particles is 20% by mass or more because a desired refractive index can be obtained. On the other hand, when the content of the first metal oxide particles is 75% by mass or less, the coating property of the coating solution that can be used when forming the low refractive index layer can be improved.

(Second metal oxide particles)
Although it does not restrict | limit especially as a 2nd metal oxide particle, It is preferable that it is different from a 1st metal oxide particle. Specific examples include titanium oxide, zirconium oxide, zinc oxide, alumina, colloidal alumina, niobium oxide, and europium oxide. Among these, from the viewpoint of forming a transparent and high refractive index layer having a higher refractive index, it is preferable to use titanium oxide or zirconium oxide, and more preferably to contain rutile (tetragonal) titanium oxide particles. In addition, a 2nd metal oxide may be used independently, or 2 or more types may be mixed and used for it.

  As the titanium oxide, it is preferable to use a titanium oxide sol whose surface is modified so as to be dispersible in water or an organic solvent. Examples of the preparation method of the aqueous titanium oxide sol include, for example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, JP-A-63-3. Reference can be made to the matters described in Japanese Patent No. 17221.

  When titanium oxide particles are used as the second metal oxide particles, for example, “Titanium oxide—physical properties and applied technology” Manabu Seino p255-258 (2000) Gihodo Publishing Co., Ltd. Alternatively, the method of step (2) described in paragraphs “0011” to “0023” of International Publication No. 2007/039953 can be referred to. The production method according to the above step (2) is a step of treating titanium oxide hydrate with at least one basic compound selected from the group consisting of alkali metal hydroxides or alkaline earth metal hydroxides. After (1), it comprises a step (2) of treating the obtained titanium oxide dispersion with a carboxylic acid group-containing compound and an inorganic acid.

  The titanium oxide particles may be in the form of core-shell particles coated with a silicon-containing hydrated oxide. The core-shell particles have a structure in which the surface of the titanium oxide particles is coated with a shell made of a silicon-containing hydrated oxide on a titanium oxide serving as a core. In this case, the volume average particle diameter of the titanium oxide particles serving as the core portion is preferably in the range of 1 to 30 nm, and more preferably in the range of 4 to 30 nm. By including such core-shell particles, intermixing of the high refractive index layer and the low refractive index layer can be suppressed by the interaction between the silicon-containing hydrated oxide of the shell layer and the water-soluble resin.

  The silicon-containing hydrated oxide may be any of a hydrate of an inorganic silicon compound, a hydrolyzate and / or a condensate of an organosilicon compound, and preferably has a silanol group. Therefore, the core-shell particles are preferably silica-modified (silanol-modified) titanium oxide particles in which titanium oxide particles are silica-modified.

  The coating amount of the silicon-containing hydrated compound of titanium oxide is preferably in the range of 3 to 30% by mass and more preferably in the range of 3 to 10% by mass with respect to 100% by mass of titanium oxide. Preferably, it is in the range of 3 to 8% by mass. A coating amount of 3% or more is preferable because the core-shell particles can be formed stably. On the other hand, when the coating amount is 30% by mass or less, it is preferable because the high refractive index layer has a desired refractive index value.

  The average particle diameter (number average) of the second metal oxide particles is preferably in the range of 3 to 100 nm, and more preferably in the range of 3 to 50 nm.

  The second metal oxide particles preferably have a volume average particle diameter of 50 nm or less, more preferably in the range of 1 to 45 nm, and still more preferably in the range of 5 to 40 nm. A volume average particle size of 50 nm or less is preferable because it has less haze and is excellent in visible light transmittance. In addition, the volume average particle diameter referred to in the present invention means the volume average particle diameter of primary particles or secondary particles dispersed in a medium. As the volume average particle diameter, a value measured by the following method is adopted. Specifically, arbitrary 1000 particles appearing on the cross section and the surface of the refractive index layer are observed with an electron microscope to measure the particle diameter, and the particle diameters of d1, d2,. In a group of metal oxide particles in which n1, n2,..., Ni, and nk particles are present, when the volume per particle is vi, the volume average particle diameter mv according to the following formula (M): Is calculated.

Formula (M)
mv = {Σ (vi · di)} / {Σ (vi)}
The content of the second metal oxide particles is preferably in the range of 15 to 85% by mass and preferably in the range of 20 to 80% by mass with respect to 100% by mass of the total solid content of the high refractive index layer. It is more preferable that it is in the range of 30 to 75% by mass. By setting it as the said range, it can be set as a favorable infrared-light shielding property.

  The first metal oxide particles and the second metal oxide particles are preferably monodispersed. In addition, the monodispersion as used in the field of this invention means that the monodispersity calculated | required by following formula (D) is 40% or less, More preferably, it is 30% or less, Most preferably, it is 0.1-20%. It is.

Formula (D) Monodispersity (%) = (Standard deviation of particle diameter) / (Average value of particle diameter) × 100
It is preferable that the first metal oxide particles and the second metal oxide particles are in an ionic state (that is, the charges have the same sign). For example, when forming a refractive index layer, when simultaneous multilayer coating is applied, if the ionicity is the same, formation of aggregates at the interface can be prevented, and good haze can be obtained. As a means for aligning ionicity, for example, when silicon dioxide (anion) is used for the low refractive index layer and titanium oxide (cation) is used for the high refractive index layer, the silicon dioxide is treated with aluminum or the like to be cationized. Alternatively, as described above, there is a method in which titanium oxide is treated with a silicon-containing hydrated oxide to be anionized.

(Protective agent)
In this invention, it is preferable to contain water-soluble resin which coat | covers (protects) a metal oxide particle in a refractive index layer. Hereinafter, a water-soluble resin (hereinafter also referred to as “protective agent”) for coating (protecting) the metal oxide particles will be described. In addition, the said protective agent has a role for making it easy to disperse | distribute a metal oxide particle in a solvent.

  The protective agent is preferably a polyvinyl alcohol resin from the viewpoint of adsorptivity, and more preferably a modified polyvinyl alcohol from the viewpoint of transparency and stabilization. At this time, the degree of polymerization of the protective agent is preferably in the range of 100 to 700, and more preferably in the range of 200 to 500. When the degree of polymerization is in the above range, the metal oxide particles can be stabilized, which is preferable. When polyvinyl alcohol is used as the protective agent, the saponification degree is preferably 95% mol or more from the viewpoint of adsorptivity to the metal oxide particles, and is in the range of 98 to 99.5 mol%. It is more preferable that

  In this invention, it is preferable that content of the protective agent in a refractive index layer exists in the range of 0.1-30 mass% with respect to 100 mass% of metal oxide particles, and 0.5-20 mass% More preferably, it is in the range of 1 to 10% by mass. It is preferable for the content of the protective agent to be in the above range since the liquid stability of the coating liquid that can be used when forming the refractive index layer is excellent and the coating property is stable.

(Curing agent)
The refractive index layer may further contain a curing agent. The curing agent can react with a water-soluble resin (preferably a polyvinyl alcohol resin) contained in the refractive index layer to form a hydrogen bond network.

  The curing agent that can be used together with the polyvinyl alcohol-based resin is not particularly limited as long as it causes a curing reaction with the polyvinyl alcohol-based resin, and examples thereof include boric acid, borate, and borax.

Boric acid or borate refers to oxygen acid having a boron atom as a central atom and a salt thereof. Specifically, orthoboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, Examples include boric acid and salts thereof. Borax is a mineral represented by Na ₂ B ₄ O ₅ (OH) ₄ · 8H ₂ O (sodium tetraborate (Na ₂ B ₄ O ₇ ) decahydrate).

  Boric acid, boric acid salt, and borax are usually used by adding them in the form of an aqueous solution to a coating solution that can be used in forming the refractive index layer.

  Moreover, a well-known thing can be used besides the said hardening | curing agent. For example, the compound which has a functional group which can react with a polyvinyl alcohol-type resin, and the compound which accelerates | stimulates the reaction of the functional groups which a polyvinyl alcohol-type resin has are mentioned. Specific examples include diglycidyl ethyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-diglycidylcyclohexane, N, N-diglycidyl-4-glycidyloxyaniline, sorbitol polyglycidyl ether. , Epoxy curing agents such as glycerol polyglycidyl ether; aldehyde curing agents such as formaldehyde and glyoxal; active halogen curing agents such as 2,4-dichloro-4-hydroxy-1,3,5, -s-triazine; Active vinyl compounds such as 1,3,5-trisacryloyl-hexahydro-s-triazine and bisvinylsulfonylmethyl ether; aluminum alum, titanium-based crosslinking agent (TC-300; manufactured by Matsumoto Fine Chemical Co., Ltd.), zirconi Beam based crosslinking agent (ZIRCOSOL AC-20, ZIRCOSOL ZA-30; manufactured by Daiichi Kigenso Ltd., etc.) and the like.

  Of the above curing agents, boric acid and its salts and / or borax are preferably used in the present invention. When boric acid and its salt and / or borax are used, the metal oxide particles and the hydroxy group of the polyvinyl alcohol resin can form a hydrogen bond network. As a result, interlayer mixing between the high refractive index layer and the low refractive index layer is suppressed, and preferable infrared light shielding characteristics can be achieved. In particular, after a multilayer coating of a high refractive index layer and a low refractive index layer is performed by a coater, the film surface temperature of the coating film is once cooled to about 15 ° C., and then the film surface is dried by a so-called set coating process. When forming, the said effect can be expressed more preferably.

  The content of the curing agent is preferably in the range of 1 to 600 mg, more preferably in the range of 100 to 600 mg, per 1 g of water-soluble resin (preferably polyvinyl alcohol resin).

(Other additives)
The refractive index layer may further contain various additives as necessary.

  In the present invention, various additives applicable to the high refractive index layer and the low refractive index layer are listed below. For example, ultraviolet absorbers described in JP-A-57-74193, JP-A-57-87988, and JP-A-62-261476, JP-A-57-74192, and JP-A-57-87989. , JP-A-60-27285, JP-A-61-14659, JP-A-1-95091, JP-A-3-13376, etc. Or various nonionic surfactants, JP-A-59-42993, JP-A-59-52689, JP-A-62-280069, JP-A-61-228771, and JP-A-4-219266. Optical brighteners, sulfuric acid, phosphoric acid, acetic acid, citric acid, sodium hydroxide, potassium hydroxide, potassium carbonate, etc. Lubricants such as tylene glycol, antiseptics, antifungal agents, antistatic agents, matting agents, heat stabilizers, antioxidants, flame retardants, crystal nucleating agents, inorganic particles, organic particles, thickeners, lubricants, infrared absorption Examples include various known additives such as agents, dyes, and pigments.

  As described above, whether the refractive index layer is a high refractive index layer or a low refractive index layer is a relative one determined by the relationship with the adjacent refractive index layer, but the refractive index of the low refractive index layer. (NL) is preferably in the range of 1.10 to 1.60, more preferably in the range of 1.30 to 1.50. On the other hand, the refractive index (nH) of the high refractive index layer is preferably in the range of 1.80 to 2.50, more preferably in the range of 1.90 to 2.20. In addition, the value measured as follows shall be employ | adopted for the value of the refractive index of each refractive index layer. Specifically, a sample is prepared by cutting a coating film obtained by applying a refractive index layer to be measured as a single layer on a support to a size of 10 cm × 10 cm. In order to prevent reflection of light on the back surface of the sample, a surface (back surface) opposite to the measurement surface is roughened, and light absorption processing is performed with a black spray. Using the spectrophotometer U-4000 type (manufactured by Hitachi, Ltd.), 25 samples of the reflectance in the visible region (400 nm to 700 nm) were measured using the spectrophotometer U-4000 type (manufactured by Hitachi, Ltd.). An average value is obtained, and an average refractive index is obtained from the measurement result.

  The reflectance in the specific wavelength region is determined by the difference in refractive index between two adjacent layers and the number of stacked 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 light reflectance of 90% or more, if the refractive index difference is smaller than 0.1, it is necessary to stack 200 layers or more. In such a case, the productivity may decrease, the scattering at the laminated interface increases, the transparency may decrease, and a manufacturing failure may occur. From the standpoint of improving reflectivity and reducing the number of layers, there is no upper limit to the difference in refractive index.

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

  The optical reflection layer may be provided only on one side of the substrate or on both sides of the substrate, but is preferably provided on both sides of the substrate. As described above, the optical reflective layer may have a large number of refractive index layers in some cases. When such a large number of stacked layers is provided on one side, the optical reflection layer may be curled. However, by providing optical reflecting layers on both sides of the substrate, the curl balance is improved, and as a result, curling can be suppressed.

<Method for forming optical reflection layer>
The method for forming an optical reflective layer according to the present invention is not particularly limited, but a coating solution for a high refractive index layer containing a water-soluble binder resin and metal oxide particles, a water-soluble binder resin and a metal oxide on a substrate. The manufacturing method including the process of apply | coating the coating liquid for low refractive index layers containing particle | grains is preferable.

  The coating method is not particularly limited, and for example, roller coating method, rod bar coating method, air knife coating method, spray coating method, slide curtain coating method, US Pat. No. 2,761,419, US Pat. No. 2,761791 And a slide hopper coating method and an extrusion coating method described in the above. In addition, as a method of applying a plurality of layers in a multilayer manner, sequential multilayer coating or simultaneous multilayer coating may be used.

<< Second Embodiment of Optical Reflective Film >>
As a second embodiment of the window pasting film of the present invention, the optical reflective film is formed by applying the high refractive index layer and the low refractive index layer on the substrate as described above, and drying it. It is preferable to have an infrared light reflecting multilayer film layer in which layers containing a first polymer species and layers containing a second polymer species are alternately laminated on at least one surface of the support.

<Infrared light reflecting multilayer film layer>
In general, by laminating a plurality of films having different refractive index characteristics so as to be reflected at the interface between adjacent layers, the film reflected by the interference reflected by the plurality of interfaces is strengthened or weakened. It is known to provide desired reflection or transmission characteristics.

  The infrared light reflecting multilayer film layer (hereinafter also referred to as a multilayer film) according to the present invention is formed by alternately laminating films produced from polymer species, which will be described later, having a refractive index difference of 0.05 at least. It has a characteristic of selectively increasing the reflectance of light in the outer region.

  As for these multilayer films, for example, US Pat. No. 3,610,724, US Pat. No. 3,771,176, US Pat. No. 4,446,305, US Pat. No. 4,540,623, US Pat. No. 5,448,404, US Pat. No. 5,882,774, U.S. Pat. No. 6,045,894, U.S. Pat. No. 6,653,230, WO 99/39224, and U.S. Patent Application Publication No. 2001 / 0022982A1.

  The layer containing the polymer species can be formed by any combination, but it is preferable that at least one of the alternately laminated layers is birefringent and oriented. In a preferred embodiment, it is preferred that one of the alternately stacked layers is birefringent and oriented, and the other alternately stacked layer is isotropic.

  In one embodiment, the infrared light reflecting multilayer film layer comprises a layer containing a first polymer species comprising polyethylene terephthalate (PET) or a copolymer of polyethylene terephthalate (coPET), and poly (methyl methacrylate) (PMMA) or poly ( It is formed from layers (also referred to as alternating layers) alternately laminated with layers containing a second polymer species including a copolymer of methyl methacrylate) (coPMMA). In another embodiment, it is formed from alternating layers of a first polymer species comprising polyethylene terephthalate and a second polymer species comprising a copolymer of poly (methyl methacrylate and ethyl acrylate). In another embodiment, a first polymer species comprising cyclohexanedimethanol (PETG) or a copolymer of cyclohexanedimethanol (coPETG) and a second polymer comprising polyethylene naphthalate (PEN) or a copolymer of polyethylene naphthalate (coPEN). Formed from alternating layers with polymer species. In another embodiment, formed from alternating layers of a first polymer species comprising polyethylene naphthalate or a copolymer of polyethylene naphthalate and a second polymer species comprising a copolymer of poly (methyl methacrylate) or poly (methyl methacrylate). Is done.

  For useful combinations of alternating polymer species layers, reference may be made to the technique disclosed in US Pat. No. 6,352,761.

  The infrared light reflecting film layer has an average visible light transmittance (400 to 780 nm) of at least 45% and less than 10% for light of 780 nm to 2500 nm, in combination with the effect of the infrared light absorbing nanoparticle layer described later, or And an average infrared light transmittance of less than 15%. In another embodiment, the infrared light reflective film layer has an average visible light transmission of at least 60% and an infrared light transmission of 20% or less for substantially all wavelengths between 950 nm and 2500 nm. .

  In another embodiment, the infrared light reflecting film layer has an average light reflectance of 50% or more between 780 and 1200 nm and an average light transmittance of 50% or less between 1400 and 2500 nm. In a further embodiment, the infrared light reflecting film layer has an average light reflectance of 80% or more between 780 and 1200 nm and an average light transmittance of 20% or less between 1400 and 2500 nm. In yet another embodiment, the infrared light reflecting film layer has an average light reflectance of 90% or more between 780 and 1200 nm and an average light transmittance of 5% or less between 1400 and 2500 nm.

<Support>
In this embodiment, when a support is required, the above-mentioned transparent resin film can be preferably used as the support. Moreover, the structure which combines the said infrared light reflection film layer as a support body is also preferable.

<Other constituent layers of film for window pasting>
In the window pasting film according to the present invention, a conductive layer, an antistatic layer, a gas barrier layer, an easy adhesion layer (adhesion layer), an antifouling layer, an antifouling layer are added on the transparent resin film for the purpose of adding further functions. Functional layers such as odor layer, droplet layer, slippery layer, hard coat layer, wear-resistant layer, electromagnetic wave shielding layer, ultraviolet ray absorbing layer, printing layer, fluorescent light emitting layer, hologram layer, colored layer (visible light absorbing layer) You may have.

  Below, a hard-coat layer is demonstrated as a typical example.

(Hard coat layer)
The hard coat layer has a function of preventing scratches on the window pasting film. The hard coat layer contains a hard coat agent, and may further contain other additives as necessary.

  An active energy ray curable resin is used as the hard coating agent. In addition, you may use thermosetting resin etc. with the said active energy ray hardening resin as needed. In the present specification, the “active energy ray” represents an active ray such as an ultraviolet ray or an electron beam, and preferably means an ultraviolet ray.

  The active energy ray curable resin is not particularly limited, but preferably contains a monomer having an ethylenically unsaturated double bond, and more preferably an ultraviolet curable resin. The ultraviolet curable resin is not particularly limited, but is an ultraviolet curable urethane (meth) acrylate resin, an ultraviolet curable polyester (meth) acrylate resin, an ultraviolet curable epoxy (meth) acrylate resin, an ultraviolet curable polyol (meth) acrylate. Examples thereof include resins. Among these, it is preferable to use an ultraviolet curable (meth) acrylate resin.

  The ultraviolet curable urethane (meth) acrylate resin is obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 It can be easily obtained by reacting a (meth) acrylate monomer having a hydroxy group such as hydroxypropyl (meth) acrylate. For example, a mixture of 100 parts of Unidic 17-806 (manufactured by DIC Corporation) and 1 part of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) described in JP-A-59-151110 is preferably used.

  UV curable polyester (meth) acrylate resin is easy by reacting monomers such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylic acid to the hydroxyl or carboxy group at the end of the polyester. (For example, JP-A-59-151112).

  The ultraviolet curable epoxy (meth) acrylate resin can be obtained by reacting a terminal hydroxyl group of the epoxy resin with a monomer such as (meth) acrylic acid, (meth) acrylic acid chloride, or glycidyl (meth) acrylate. . For example, Unidic V-5500 (manufactured by DIC Corporation) can be used.

  The ultraviolet curable polyol (meth) acrylate resin is not particularly limited, but ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol. Examples include tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and alkyl-modified dipentaerythritol penta (meth) acrylate.

  The thermosetting resin is not particularly limited, and examples thereof include inorganic materials such as polysiloxane.

  The above resins may be used alone or in admixture of two or more.

  The hard coat agent can be obtained by curing the resin. Examples of the curing method include heat and active energy ray irradiation, but active energy ray irradiation is preferable from the viewpoint of curing temperature, curing time, cost, and the like.

  By irradiating the active energy ray-curable resin with active energy rays, the active energy ray-curable resin is cured through a crosslinking reaction or the like, and becomes a hard coat agent.

  A known additive can be used in the hard coat layer as necessary. Preferable additives include matting agents and dyes or pigments that can absorb or reflect infrared rays.

  The thickness of the hard coat is preferably 1 to 10 μm, and more preferably 2 to 5 μm.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Example 1
<Preparation of film 1 for window pasting>
[Preparation of transparent resin film]
As a transparent resin film, a polyethylene terephthalate film (A4300, double-sided easy-adhesion layer, thickness: 50 μm, length 200 m × width 210 mm, manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET film) was prepared.

(Preparation of adhesive layer side optical reflective layer)
(Preparation of coating solution 1 for low refractive index layer)
The following constituent materials were added and mixed in this order at 45 ° C., and then finished with 1000 parts of pure water to prepare a coating solution 1 for a low refractive index layer.

10 mass% colloidal silica (Snowtex OXS, average primary particle size: 4-6 nm, manufactured by Nissan Chemical Industries, Ltd.) 430 parts 3 mass% boric acid aqueous solution 85 parts pure water 182 parts 4 mass% polyvinyl alcohol (4 Mass% aqueous solution, PVA-235; Degree of polymerization: 3500; Degree of saponification: 88 mol%; manufactured by Kuraray Co., Ltd. 300 parts 5% by mass of surfactant (5 mass% aqueous solution, Amphital 20HD; manufactured by Kao Corporation)
3.0 parts (Preparation of coating solution 1 for high refractive index layer)
A coating solution 1 for a high refractive index layer was prepared according to the following procedure.

<Preparation of silica-modified titanium oxide particle dispersion>
First, a dispersion of silica-modified titanium oxide particles was prepared according to the following method, and a solvent or the like was added thereto.

  A dispersion of silica-modified titanium oxide particles was prepared as follows.

The titanium sulfate aqueous solution was thermally hydrolyzed by a known method to obtain titanium oxide hydrate. The obtained titanium oxide hydrate was suspended in water to obtain 10 L of an aqueous suspension of titanium oxide hydrate (TiO ₂ concentration: 100 g / L). To this, 30 L of an aqueous sodium hydroxide solution (concentration 10 mol / L) was added with stirring, the temperature was raised to 90 ° C., and the mixture was aged for 5 hours. The obtained solution was neutralized with hydrochloric acid, filtered and washed with water to obtain a base-treated titanium compound.

Next, the base-treated titanium compound was suspended in pure water and stirred so that the TiO ₂ concentration was 20 g / L. Under stirring, it was added citric acid in an amount of 0.4 mol% with respect to TiO ₂ weight. The temperature was raised to 95 ° C., concentrated hydrochloric acid was added so that the hydrochloric acid concentration was 30 g / L, and the solution temperature was maintained, followed by stirring for 3 hours. Here, when the pH and zeta potential of the obtained mixed liquid were measured, the pH at 25 ° C. was 1.4, and the zeta potential was +40 mV. Further, 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%.

  1 kg of pure water was added to 1 kg of a 20.0 mass% titanium oxide sol aqueous dispersion containing rutile-type titanium oxide particles to prepare a 10.0 mass% titanium oxide sol aqueous dispersion.

2 kg of pure water was added to 0.5 kg of the 10.0 mass% titanium oxide sol aqueous dispersion, followed by heating to 90 ° C. Thereafter, 1.3 kg of an aqueous silicic acid solution having a SiO ₂ concentration of 2.0 mass% was gradually added. The obtained dispersion is subjected to a heat treatment at 175 ° C. for 18 hours in an autoclave, and further concentrated to thereby contain 20% by mass of silica-modified titanium oxide particles containing titanium oxide having a rutile structure coated with SiO _2. A dispersion (sol aqueous dispersion) was obtained.

<Preparation of coating solution>
The following constituent materials were sequentially added at 45 ° C. to the sol dispersion of silica-modified titanium oxide particles prepared above, and finally finished with 1000 parts of pure water to prepare a coating solution 1 for a high refractive index layer.

Sol dispersion of 20.0% by mass of silica-modified titanium oxide particles 320 parts 1.92% by mass of citric acid aqueous solution 120 parts 10% by mass of polyvinyl alcohol (PVA-103, polymerization degree: 300, saponification degree: 99 mol) 20 parts 4 mass% polyvinyl alcohol (PVA-124, degree of polymerization: 2400, saponification degree: 99 mol%, manufactured by Kuraray Co., Ltd.) 350 parts 5 mass% surfactant aqueous solution (Amphithal HD) 1.0 part 9 layers Multi-layered slide hopper type wet coating apparatus is used, and the above-prepared coating liquid 1 for the low refractive index layer and coating liquid 1 for the high refractive index layer are kept at 45 ° C. On the other hand, nine layers were applied on a PET film, which was a transparent resin film heated to 45 ° C. Immediately after coating each refractive index layer coating solution, cold air of 5 ° C. was blown and set. At this time, even if the surface was touched with a finger, the time (set time) until nothing was attached to the finger was 5 minutes. After completion of the setting, warm air of 80 ° C. was blown and dried to prepare an optical reflection layer having 9 layers and a total thickness of 1.3 μm.

  At this time, in the nine-layer optical reflection layer, the lowermost layer and the uppermost layer were low refractive index layers. In the structure of the window pasting film 1, a low refractive index layer and a high refractive index layer were alternately laminated.

The coating amount was adjusted so that the layer thickness during drying was 150 nm for each of the low refractive index layer and the resin adhesive layer and 130 nm for each layer of the high refractive index layer. Each layer thickness was confirmed by cutting the produced window pasting film 1 and observing the cut surface with an electron microscope. At this time, when the interface between the two layers could not be clearly observed, the interface was determined by the XPS depth profile in the thickness direction of TiO ₂ contained in the layer obtained by the XPS surface analyzer.

(Formation of adhesive layer)
(Preparation of adhesive layer forming coating solution 1)
100 parts by mass of an acrylic resin having a hydroxy group, 50 parts by mass of MKC methyl silicate MS-56 (Mitsubishi Chemical's tetramethyl silicate partial hydrolyzate condensate, n average value = 10), 1 part by mass of dibutyltin laurate, xylene 700 parts by mass and 150 parts by mass of isopropyl alcohol were mixed and stirred to prepare a resin mixture having a solid content of 10% by mass.

In the obtained resin mixture, 0.025 parts by mass of Chemisnow MR-10HG (cross-linked acrylic fine particles manufactured by Soken Chemical Co., Ltd.) having an average particle diameter of 10 μm as a matting agent, 2.0 masses of tinuvin (UV absorber manufactured by BASF Japan) Part, Irganox (an antioxidant manufactured by BASF Japan) 0.5 part by mass and 1.0 part by mass of sanol (Sankyo Co., Ltd. light stabilizer) were mixed to prepare a coating solution 1 for forming an adhesive layer.
Using the prepared coating solution 1 for forming an adhesive layer, a wire bar is applied onto the low refractive index layer so that the amount of matting agent applied is 0.2 mg / m ² and dried. did. The thickness of the adhesive layer after drying was 8 μm. A 25 μm thick polyester film (Therapel, manufactured by Toyo Metallizing Co., Ltd.) was bonded as a separator film to the surface of the pressure-sensitive adhesive layer of the film with the pressure-sensitive adhesive layer using a bonding machine.

[Preparation of hard coat layer side optical reflective layer]
Using the prepared low-refractive-index layer coating solution 1 and high-refractive-index layer coating solution 1 on the PET film, which is the transparent resin film on the side opposite to the surface on which the adhesive layer-side optical reflective layer is formed, is the same. Nine layers of coating were applied.

[Formation of hard coat layer]
(Preparation of hard coat solution 1)
An AZO dispersion (product name: Celnax CX-Z610M-F2, average particle size 15 nm, manufactured by Nissan Chemical Industries, Ltd.) is diluted with methanol to an AZO concentration of 40% by mass, and an ultraviolet curable hard coat agent. KRM8495 (manufactured by Daicel-Cytec, a mixture of an acrylate-based cured resin and a polymerization initiator) is added, the total solid content is 30% by mass, the AZO concentration is 50% by mass, and the cured resin is 50% by mass. % (Including a polymerization initiator) to prepare a hard coat solution 1.

(Preparation of primer solution 1)
A polyvinyl acetal resin aqueous solution was prepared so that a polyvinyl acetal resin (product name: Eslek KW-1, acetalization degree 9 mol%, manufactured by Sekisui Chemical Co., Ltd.) was 10% by mass with respect to 90% by mass of water, and a primer solution 1 was produced.

  Using a micro gravure coater, primer solution 1 was applied onto the low refractive index layer, and a primer layer was formed so that the dry layer thickness was 1 μm.

Similarly, using a gravure coater, the hard coat solution 1 is applied onto the primer layer, dried at a constant rate drying zone temperature of 50 ° C. and a reduced rate drying zone temperature of 90 ° C., and then the illuminance of the irradiated part is 100 mW using an ultraviolet lamp. / in cm ^2, thereby curing the coated layer to irradiation dose as 0.2 J / cm ^2, so that the dry layer thickness is 4μm to form a hard coat layer, to prepare a window film film 1 shown in FIG.

<Preparation of film 2-20 for window pasting>
In the production of the window pasting film 1, the window pasting film was prepared in the same manner except that the average particle diameter of the matting agent added to the adhesive layer, the thickness of the adhesive layer, and the amount with the matting agent were changed as shown in Table 1. 2-20 were produced.

In addition, the average number of matting agent particles is the number of matting agents present in a 10 cm square area of the produced window pasting film by sampling about 10 locations by scanning micrograph (SEM image) photographing. It counted and calculated | required by converting the value per unit area (cm < ² >) and averaging with the number of samples.

<Preparation of films 21 and 22 for window pasting>
(Preparation of infrared light reflective multilayer film layer)
With reference to the examples of JP-T-2008-528313, an infrared light reflective multilayer film having about 446 layers was produced by a coextrusion method. An infrared light reflective multilayer film composed of this multilayer polymer was made from coPEN and PETG ((PET copolymerized, copolyester: Eastman Chemicals), which comprises 90% PEN and Polymerized with 10% PET starting monomer About 223 layers using feed block method (described in US Pat. No. 3,801,429) and having a nearly linear layer thickness gradient from layer to layer through the extrudate. The optical layer of was formed.

  In the same manner as in Example 1, the adhesive layer described in Table 1 was provided on one side of the multilayer film, and the hard coat layer was similarly provided on the opposite side where the adhesive layer was provided. 21 and 22 were obtained.

  The matting agent average particle diameter, the adhesion layer thickness, the amount with matting agent and the average number of matting agent particles in the adhesive layer were all adjusted as shown in Table 1. The thickness of each layer was 6 μm for the transparent resin film, and the total thickness was 36 μm including the infrared light reflecting multilayer film layer.

<Preparation of Films 23 to 26 for Window Pasting: Comparative Example>
The transparent resin film, the low refractive index layer coating liquid 1, the high refractive index layer coating liquid 1, the adhesive layer forming coating liquid 1, the hard coating liquid 1, and the primer liquid 1 used in the production of the window pasting film 1 were used. Using, the window pasting films 23-25 which have the layer structure of FIG. 2 were produced. The average particle size of the matting agent, the thickness of the adhesive layer, and the amount with the matting agent were all adjusted as shown in Table 1.

  Moreover, the window pasting film 26 which has the layer structure of FIG. 3 was produced using the transparent resin film and infrared light reflection multilayer film layer which were used in preparation of the film 21 for window pasting. The average thickness of the adhesive layer was adjusted as shown in Table 1.

<Preparation of Film 27 for Window Pasting: Comparative Example>
In producing the window pasting film 21, instead of using the coating solution 1 for forming the adhesive layer, the same procedure was carried out except that a silicone rubber layer was formed as an adhesive layer by the method described in Example paragraph [0076] of JP2013-14012A. Thus, a film 27 for pasting a window was produced.

  The following evaluation was performed using the window pasting films 1 to 27 produced as described above.

<< Evaluation of Film for Window Pasting >>
[Bubble removal]
After cutting each window pasting film produced above to a width of 20 cm and a length of 100 cm, the adhesive layer side is a 1.3 mm thick glass plate (manufactured by Matsunami Glass Kogyo Co., Ltd., “slide glass white edge polish”). After water is applied to the glass plate surface and pasted together by the water pasting method, a steel roller covered with a 6 mm thick rubber on a roll having a diameter of 15.2 cm (6 inches) and a width of 45 mm is used. The film and the glass were pressure-bonded with the roller so that only the weight of the roller was applied to the window pasting film surface.

A: Bubbles generated at the interface between the film and the glass can be easily removed by one ironing process. B: Bubbles generated at the interface between the film and the glass can be removed by three ironing processes. Bubbles need to be squeezed 4 to 10 times, but can be removed D: Bubbles generated at the interface between the film and the glass remain slightly even after squeezing four times or more E: Bubbles generated at the interface between the film and the glass Can hardly be removed [aging peeling]
After being pasted as described above for 8 days in an atmosphere at a temperature of 60 ° C., the state of peeling was evaluated by visual observation.

A: No change B: Slightly peeled off between the glass and film at the end of the sticking C: About 1 to 10% of the sticking area peels off D: A range exceeding 10% of the sticking area peels off [Remaining glue]
The separator film (25 μm thick polyester film) is peeled off, and the laminated film is directly attached to the cleaned glass plate with a thickness of 1.3 mm with a rubber roller (light load). Adhere closely. After pasting, leave it at a temperature of 70 ° C. for 1 week. Thereafter, the laminated film is peeled off at a speed of 5 m / min, the remaining amount of glue on the glass plate is observed, and evaluated according to the following criteria.
5: Remaining pressure-sensitive adhesive cannot be visually observed. 4: Remaining pressure-sensitive adhesive has a size of 1 mm square or more of 0.01 to less than 0.1 / 100 cm ^2.
3: Less than 0.1-1 piece / 100 cm ^{2 in} which the remaining adhesive has a size of 1 mm square or more
2: Less than 1-10 pieces / 100 cm ^{2 in} which the remaining adhesive has a size of 1 mm square or more
1: The remaining adhesive has a size of 1 mm square or more and more than 10 pieces / 100 cm ^{2 In} addition, the rank that can withstand practical use is 3 to 5.

〔transparency〕
For each of the film samples 1 to 17 for window pasting produced above, the light transmittance at 550 nm of the sample after being attached to glass using a spectrophotometer (using an integrating sphere, manufactured by Hitachi, Ltd., U-4000 type) It was measured.

[Near-infrared light reflectance]
The reflectivity in the region of 850 to 1150 nm was measured using a spectrophotometer (integral sphere use, V-670 type, manufactured by JASCO Corporation) for the window pasting film pasted on a 3 mm thick float plate glass. The sample was installed so that the light intrusion at the time of measurement came from the glass surface. The measurement was performed 3 times, the average value was calculated | required, and it was set as the infrared light reflectance.

  The results obtained as described above are shown in Table 1.

As is clear from the results shown in Table 1, the window pasting films 1-6, 8-10, 14, 16, 18, 20, and 21 that satisfy the conditions specified in the present invention are air bubbles relative to the comparative example. It can be seen that it is excellent in punching, peeling with time, adhesive residue, transparency, and near infrared light reflectance.

DESCRIPTION OF SYMBOLS 1 Film for window pasting 2 Transparent resin film 3 Optical reflection layer 3a Low refractive index layer 3b High refractive index layer 4 Adhesive layer 5 Hard coat layer 6 Infrared light reflection multilayer film layer 6a Layer containing 1st polymer seed 6b Second Layer containing polymer species of 7 matting agent particles

Claims (6)

A window pasting film having an adhesive layer on the outermost layer,
The pressure-sensitive adhesive layer contains acrylic pressure-sensitive adhesive and matting agent particles, and the value of the average particle diameter M of the matting agent particles and the value of the average layer thickness d of the pressure-sensitive adhesive layer satisfy the conditions specified by the following formula 1. ,
The average particle size M of the matting agent particles is in the range of 3 to 50 μm, the monodispersity of the particle size of the matting agent particles is 25% or less, and the unit area (cm ² ) A window pasting film, wherein the average number per window is in the range of 0.1 to 80.
Formula 1: d <M (μm) The window pasting film according to claim 1, wherein a value of an average particle diameter M of the matting agent particles and a value of an average layer thickness d of the adhesive layer satisfy a condition defined by the following formula 2.
Formula 2: 2d <M <10d (μm) The film for window pasting according to claim 1 or 2 whose average layer thickness d of said adhesion layer is in the range of 1-20 micrometers. The window pasting film according to any one of claims 1 to 3 , wherein the window pasting film is an optical reflection film. 5. The window pasting according to claim 4 , wherein the optical reflective film has an optical reflective layer in which a high refractive index layer and a low refractive index layer are alternately laminated on at least one surface of a support. the film. The optical reflection film has an infrared light reflection multilayer film layer in which layers containing a first polymer species and layers containing a second polymer species are alternately laminated on at least one surface of a support. The film for window pasting of Claim 4 characterized by these.

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