JP2005343113A - Sunshine shielding film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sunshine shielding film which is a film having a vapor deposition layer of aluminum that has a function of reflecting near infrared rays contained in the sunshine and glued on windowpanes/windowshields of buildings/automobiles for the purpose of shielding the sunshine, which has a low haze value, in which that the aluminum vapor deposition layer becomes transparent after the gluing is suppressed, and which shows good winding suitability as for the intermediate film in the manufacturing process. <P>SOLUTION: The sunshine shielding film is formed by laying, on one surface of a polyester film, an aluminum vapor deposition layer having a visible light transmittance of 15-75% and a hard coat layer in the order and providing an adhesive agent layer on its opposite surface. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a solar radiation shielding film and a method for producing the same. More specifically, the present invention is a film having an aluminum vapor-deposited layer having a function of reflecting near infrared rays contained in solar radiation, and is attached to a window glass of a building or an automobile for the purpose of shielding solar radiation, and has a haze value. The present invention relates to a solar shading film that is small in size and that suppresses the transparency of an aluminum vapor-deposited layer after sticking and has good winding-up properties of an intermediate film processed product in the production process, and a method for producing the same.

Conventionally, a plastic film is used for pasting a window glass or a window plastic board for various purposes.
For example, sunlight entering a room through a window glass includes ultraviolet rays and infrared rays in addition to visible rays. Ultraviolet rays contained in sunlight cause sunburn, and adverse effects on the human body have recently been pointed out, and it is well known that the contents of the sun are altered by ultraviolet rays. On the other hand, infrared rays contained in sunlight also have problems such as causing an increase in indoor temperature due to direct sunlight and reducing the cooling effect in summer. Therefore, in order to avoid such an unfavorable situation, an ultraviolet shielding film or an infrared shielding film is used for attaching a window glass or a plastic board for windows.
These window glass and window plastic board film are usually ionizing radiation curable resins such as polyester acrylates, epoxy acrylates, urethane acrylates, polyol acrylates to impart scratch resistance to the surface. A hard coat layer formed by applying resin and curing the resin is provided.
By the way, in order to reduce heat and save energy in building windows, vehicle windows, refrigerated and frozen showcase windows, etc., they are attached to these windows to reflect heat rays (especially near infrared rays) or Members that provide absorbing performance have been proposed. For example, a heat ray reflective film for windows formed by forming a metal thin film such as aluminum, silver, or gold on the surface of a transparent film substrate by sputtering or vapor deposition is disclosed (for example, see Patent Document 1 and Patent Document 2). .
In such a heat ray reflective solar shading film, conventionally, an aluminum thin film that is inexpensive and lightweight and easy to deposit is often used as the gold layer thin film, and generally has the structure and production shown in FIG. The process is taken. FIG. 1 is an explanatory view showing the structure and manufacturing process of a conventional solar shading film.
That is, an aluminum vapor deposition layer (Al vapor deposition layer) is provided on one surface of the polyester film in the first step, an aluminum protective layer (Al protective layer) is provided thereon in the second step, and then the third step. In the process, a hard coat layer is provided on the back side of the polyester film. Thereafter, in the fourth step, a solar radiation shielding film is produced by providing an adhesive layer on the aluminum protective layer and bonding the release film.
However, the solar radiation shielding film having such a configuration has the following two problems.
The first problem is that when the solar radiation shielding film having this configuration is attached to the window glass of an automobile, after a few days, it becomes a circular shape having a diameter of several millimeters to several centimeters, or linearly along a heat ray print. The aluminum vapor deposition layer may become transparent.
This is because the aluminum in the aluminum vapor deposition layer is hydroxylated by the used construction liquid (surfactant aqueous solution of about 0.1% by weight) when the solar radiation shielding film is attached to glass. When sticking an adhesive film to glass, in order to prevent air bubbles from entering between the glass and the adhesive layer, the construction liquid is generally sprayed onto the adhesive layer surface and the glass surface, and the film is temporarily placed in place. After fixing, a method of pressure-bonding while scraping the construction liquid with a squeegee is used.
The construction liquid remaining between the glass and the pressure-sensitive adhesive layer sequentially penetrates into the pressure-sensitive adhesive layer and the aluminum protective layer, and eventually reaches the aluminum vapor deposition layer. Since this aluminum vapor deposition layer has low moisture permeability, the construction liquid stays in the aluminum protective layer for several days. Then, with the passage of time, the construction liquid aggregates due to surface tension, swells the aluminum protective layer, and forms blisters due to a pool of water with a diameter of several mm to several cm.
The swelling due to the water pool promotes the hydroxylation of aluminum when the temperature rises due to solar radiation, and the aluminum deposited layer in that portion becomes transparent.
The aluminum protective layer is generally applied with a gravure coater or the like after dissolving a polyester resin or the like in a solvent. These resins can prevent hydroxylation of aluminum due to moisture in the air, but cannot prevent penetration of the construction liquid remaining during construction.
The second problem is that the winding property in the manufacturing process is poor.
The conventional solar shading film having the configuration of FIG. 1 is generally produced by performing the first step, the second step, the third step, and the fourth step described above. However, when a hard coat layer is provided on the back surface A side of the polyester film in the third step and wound in a roll shape, the slipperiness between the hard coat layer and the aluminum protective layer is poor (dynamic friction coefficient and static friction coefficient are large). For this purpose, fine particles and a lubricant are added to the aluminum protective layer. As a result, since visible light is refracted and scattered when passing through the fine particles, there arises a problem that the haze value is unavoidable.
As a means for coping with the above problem, there is a means for producing the solar shading film having the configuration of FIG. 1 by partially changing the order of the manufacturing steps. FIG. 2 is an explanatory diagram showing the configuration and manufacturing process of the solar shading film having the configuration shown in FIG. 1 and different manufacturing processes.
That is, the first step and the second step are the same as those in FIG. 1, but after the adhesive layer is provided on the aluminum protective layer in the third step and the release film is bonded, the polyester step is performed in the fourth step. A hard coat layer is provided on the back A side of the film to produce a solar shading film. In this method, if fine particles are added to the release film, the winding property can be improved without increasing the haze value of the solar shading film.
However, in this case, since the silicone resin as a release agent is set off on the back surface B side of the release film, after the third step, when the roll is wound into a roll, the silicone resin becomes the back surface B. When the transition is made from the side to the back surface A side of the polyester-based film and the hard coat layer is formed in the fourth step, the problem arises that repelling occurs and it is difficult to form a good hard coat layer.
On the other hand, as near-infrared absorbing light transmissive materials, organic materials such as anthraquinone derivatives and amino compounds, and complex materials such as chromium and cobalt complex thiol nickel complexes are known. However, in the solar radiation shielding film provided with a layer containing these materials, those using the organic material have poor durability, and the initial performance deteriorates with changes in environmental conditions and the passage of time. There is a drawback of going. In addition, although those using complex materials are durable, they have absorption not only in the near infrared region but also in the visible region, and many of the compounds themselves are strongly colored, limiting their use. There is a disadvantage that it cannot escape.
JP 57-59748 A JP-A-57-59749

  Under such circumstances, the present invention is a film that has an aluminum vapor deposition layer having a function of reflecting near infrared rays contained in solar radiation, and is attached to a window glass of a building or an automobile for the purpose of shielding solar radiation. The purpose of the present invention is to provide a solar shading film that has a low haze value and suppresses the transparency of the aluminum vapor-deposited layer after sticking, and has good winding-up properties for intermediate film processed products in the manufacturing process. Is.

As a result of intensive studies to develop a solar radiation shielding film having the above-mentioned preferable properties, the inventors have changed the configuration and manufacturing process of the conventional solar radiation shielding film as shown in FIG. For this reason, it was found that the purpose can be achieved.
FIG. 3 is an explanatory view showing an example of the structure and manufacturing process of the solar shading film of the present invention, and an aluminum vapor-deposited layer having a visible light transmittance in a specific range and a hard surface on one surface of a polyester film. A structure is shown in which a coat layer is laminated in order and an adhesive layer and a release film are provided on the opposite side.
In the solar shading film having such a structure, the construction liquid remaining between the glass and the pressure-sensitive adhesive layer at the time of application penetrates into the pressure-sensitive adhesive layer, but does not penetrate into the polyester film, and thus reaches the aluminum vapor deposition layer. In other words, the aluminum in the aluminum deposited layer is not hydroxylated to make it transparent. This is because the polyester film is generally biaxially stretched, and thus has a higher crystallinity and lower water absorption and moisture permeability than the polyester resin used in conventional aluminum protective layers.
On the other hand, by making the dynamic friction coefficient of the back surface C of the polyester film within a certain range, in the winding after providing the aluminum vapor deposition layer in the first step and in the winding after providing the hard coat layer in the second step It has good slipperiness, and even if it is wound up in a roll shape, generation of wrinkles, creases, protrusions, etc. is suppressed.
Generally, a filler is added for the purpose of reducing the dynamic friction coefficient. However, in the case of internal addition, the haze value is increased. Therefore, by adding the filler only to the surface layer, the friction coefficient is reduced and the haze value is also reduced. can do.
For the aluminum vapor deposition layer, the visible light transmittance is selected in consideration of the effect of shielding solar radiation and the balance of water vapor transmission rate. If the visible light transmittance is too high, the solar radiation shielding effect will be insufficient, while if the visible light transmittance is too low, the water vapor transmission rate will be small, so the drying of the construction liquid will be slow, and swelling due to puddles will occur. Cheap.
The present invention has been completed based on such findings.
That is, the present invention
(1) An aluminum vapor-deposited layer having a visible light transmittance of 15 to 75% and a hard coat layer are sequentially laminated on one surface of a polyester film, and an adhesive layer is provided on the opposite surface. A solar shading film,
(2) The solar radiation shielding film according to (1) above, wherein the polyester film has a dynamic friction coefficient of 0.3 to 0.8 and a haze value of 0.4 to 1.6%,
(3) The solar radiation shielding film according to the above (1) or (2), wherein the aluminum vapor deposition layer has a thickness of 5 to 40 nm,
(4) The solar radiation shielding film according to (1), (2) or (3) above, wherein the hard coat layer is a cured resin layer by ionizing radiation,
(5) The solar radiation shielding film according to any one of (1) to (4) above, wherein the thickness of the hard coat layer is 0.5 to 30 μm,
(6) An aluminum vapor deposition layer having a visible light transmittance of 15 to 75% is provided on one surface of the polyester film, and then a hard coat layer is formed thereon, and then an adhesive layer is formed on the opposite surface. Item (6) above, wherein the method for producing a solar shading film, and (7) the polyester film has a dynamic friction coefficient of 0.3 to 0.8 and a haze value of 0.4 to 1.6%. A method for producing a solar shading film according to claim 1,
Is to provide.

  According to the present invention, the film has an aluminum vapor deposition layer having a function of reflecting near infrared rays contained in solar radiation, and is attached to a window glass of a building or an automobile for the purpose of shielding solar radiation, and has a small haze value. And the transparency of the aluminum vapor deposition layer after sticking is suppressed, and the solar radiation shielding film with favorable winding-up property of the intermediate film processed goods in a manufacturing process, and its manufacturing method can be provided.

In the solar shading film of the present invention, an aluminum vapor deposition layer having a visible light transmittance of 15 to 75% and a hard coat layer are sequentially laminated on one surface of a polyester film, and an adhesive layer is provided on the opposite surface. Have a structure.
In the present invention, the polyester film used as the base film includes, for example, polyethylene terephthalate and its copolymer, polyethylene naphthalate and its copolymer, polybutylene terephthalate and its copolymer, polycyclohexylene methylene terephthalate and its The film obtained using the copolymer and the mixed resin which combined 2 or more types of these can be mentioned. Among these, a polyethylene terephthalate film is preferable in terms of performance and price, and a biaxially stretched polyethylene terephthalate film is particularly preferable.
In the present invention, it is preferable to use a polyester film having a dynamic friction coefficient of 0.3 to 0.8 and a haze value of 0.4 to 1.6% on the opposite surface on which at least the aluminum vapor deposition layer is provided. . If the dynamic friction coefficient of the polyester film is within the above range, the winding property is good in the winding operation after forming the aluminum vapor deposition layer and the winding operation after forming the hard coat layer, and it is wound into a roll. Even so, the generation of wrinkles, creases, and protrusions is suppressed.
The dynamic friction coefficient is important as an index of winding ability. However, since the film that has been wound and stopped is further subjected to a shearing force as the winding proceeds, it is also required that the static friction coefficient is small. In the present invention, it is preferable to use a polyester film having a static friction coefficient in the range of 0.3 to 0.8. The dynamic friction coefficient and the static friction coefficient are values measured according to “JIS K 7125: 1999 Plastic-film and sheet-friction coefficient test method”.
On the other hand, when the haze value is less than 0.4, the dynamic friction coefficient and the static friction coefficient are large and the winding property is poor and the production is difficult. On the other hand, when the haze value exceeds 1.6%, the film becomes cloudy and is transparent. Becomes worse. A preferred haze value is in the range of 0.4 to 1.2%. In addition, the said haze value is a value measured according to "JIS K 7136: 2000 Plastics-Determination of haze of transparent material".
As a method for adjusting the dynamic friction coefficient, static friction coefficient, and haze value of the polyester film to the above ranges, a method of adding a filler or the like only to the surface layer portion is generally used.
In the present invention, the thickness of the polyester film is not particularly limited, but is usually about 5 to 200 μm, preferably 10 to 100 μm.
For the purpose of improving the adhesion to the layer provided on the surface of this polyester film, one or both surfaces can be subjected to a surface treatment by an oxidation method, a concavo-convex method or the like as desired. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and examples of the unevenness method include a sand blast method, a solvent, and the like. Treatment methods and the like. These surface treatment methods are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, primer treatment can also be performed.

In the solar shading film of the present invention, there is no particular limitation on the method of forming the aluminum vapor deposition layer provided on one surface of the polyester film, and the conventional method used to form the aluminum vapor deposition layer on the plastic film. Any method can be appropriately selected and used. Examples of the method for forming the aluminum vapor deposition layer include vacuum vapor deposition, sputtering, and ion plating. Here, in vacuum deposition, the vapor deposition material is heated and evaporated by a method such as resistance heating, electron beam heating, laser beam heating, arc discharge in a vacuum of about 10 ⁻² to 10 ⁻⁵ Pa, and is applied to the surface of the polyester film. A vapor deposition layer is formed. In sputtering, cations such as Ar ⁺ accelerated by glow discharge are bombarded on a target (deposition material) in a vacuum of about ¹ to 10 ⁻¹ Pa where an inert gas such as argon is present. Then, the vapor deposition material is sputter evaporated to form a vapor deposition layer on the surface of the polyester film. Examples of the evaporation method include DC (direct current) sputtering, RF (radio frequency) sputtering, magnetron sputtering, and bias sputtering. Ion plating is a vapor deposition method that combines the above vacuum vapor deposition and sputtering. In this method, in a vacuum of about 1 to 10 ⁻¹ Pa, the evaporated atoms released by heating are ionized and accelerated in an electric field to adhere to the polyester film surface in a high energy state to form a vapor deposition layer. Let

In the present invention, the aluminum vapor deposition layer formed in this way needs to have a visible light transmittance of 15 to 75%. If the visible light transmittance is less than 15%, the water vapor transmission rate is small, so that the drying of the construction liquid remaining between the pressure-sensitive adhesive layer and the glass is slow, and swelling due to a water pool tends to occur. On the other hand, when the visible light transmittance exceeds 75%, the near-infrared reflection effect (sunlight shielding effect) becomes insufficient, and the object of the present invention cannot be achieved. A preferable visible light transmittance is in the range of 30 to 70%. The visible light transmittance is a value measured according to “JIS A 5759: 1998 film for architectural window glass”.
The thickness of the aluminum vapor deposition layer is not particularly limited, but is preferably selected in the range of 5 to 40 nm, more preferably 10 to 30 nm, from the viewpoint of the balance between the effect of blocking solar radiation and the visible light transmittance.
In the solar shading film of the present invention, the hard coat layer formed on the aluminum vapor-deposited layer is not particularly limited as long as it has transparency and has an abrasion resistance function, and is a conventional window glass film. Of those used as the hard coat layer, it can be appropriately selected and used, but a cured resin layer by ionizing radiation is particularly preferred. The cured resin layer by ionizing radiation refers to a resin layer that has an energy quantum in an electromagnetic wave or a charged particle beam, that is, a resin layer that has been crosslinked and cured by irradiation with ultraviolet rays or an electron beam.
In order to form a cured resin layer by ionizing radiation, an ionizing radiation sensitive resin composition containing an ionizing radiation curable compound and a photopolymerization initiator used as necessary is coated on the above-described aluminum vapor deposition layer. The coating film can be formed by irradiating with ionizing radiation and curing the coating film.

In the ionizing radiation sensitive resin composition, as the ionizing radiation curable compound, for example, a photopolymerizable prepolymer and / or a photopolymerizable monomer can be used. The photopolymerizable prepolymer includes a radical polymerization type and a cationic polymerization type, and examples of the radical polymerization type photopolymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, polyol acrylate, and the like. It is done. Here, as the polyester acrylate-based prepolymer, for example, by esterifying the hydroxyl group of a polyester oligomer having a hydroxyl group at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth) acrylic acid. The epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. The urethane acrylate-based prepolymer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Furthermore, the polyol acrylate-based prepolymer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. These photopolymerizable prepolymers may be used alone or in combination of two or more.
On the other hand, as a cationic polymerization type photopolymerizable prepolymer, an epoxy resin is usually used. Examples of the epoxy resins include compounds obtained by epoxidizing polyphenols such as bisphenol resins and novolac resins with epichlorohydrin, etc., and compounds obtained by oxidizing a linear olefin compound or a cyclic olefin compound with a peroxide or the like. Etc.

Examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. , Hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate phosphate, allylated cyclohexyl di (meta) ) Acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipenta Polyfunctional acrylates such as erythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate are preferably used. These photopolymerizable monomers may be used alone or in combination of two or more thereof, or may be used in combination with the photopolymerizable prepolymer.
On the other hand, as a photopolymerization initiator, for radical polymerization type photopolymerizable prepolymers and photopolymerizable monomers, known ones conventionally used, such as acetophenones, benzophenones, alkylaminobenzophenones, benzyl , Benzoins, benzoin ethers, benzyldimethylacetals, benzoylbenzoates, α-acyloxime esters and other aryl ketone photopolymerization initiators, sulfides, thioxanthones and other sulfur-containing photopolymerization initiators, acyl Any one or more of acylphosphine oxides such as diarylphosphine oxide, anthraquinones, and other photopolymerization initiators can be appropriately selected and used. Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions, aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, hexafluoro The compound which consists of anions, such as antimonate and hexafluoroarsenate, is mentioned. These may be used alone or in combination of two or more. Moreover, the compounding quantity of a photoinitiator is chosen in the range of 0.2-10 weight part normally with respect to 100 weight part of all the photocurable components, Preferably it is 0.5-7 weight part.
In the case of the electron beam curable type, the photopolymerization initiator may not be used.

The ionizing radiation-sensitive resin composition in the present invention may further include a monofunctional acrylate monomer, a photosensitizer, a polymerization inhibitor, a crosslinking agent, an antioxidant, an ultraviolet ray, as long as the object of the present invention is not impaired. Various additive components such as an absorbent, a light stabilizer, a leveling agent, and an antifoaming agent can be contained.
Here, examples of the monofunctional acrylate monomer include n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth). At least one selected from acrylate and the like can be used. These monofunctional acrylate monomers are photocuring components.
As photosensitizers, for example, tertiary amines, p-dimethylaminobenzoic acid esters, thiol sensitizers, and the like can be used. In the case of the electron beam curable type, this photosensitizer may not be used.
The compounding quantity of a photosensitizer is normally selected in the range of 1-20 weight part with respect to 100 weight part of all the photocurable components, Preferably it is 2-10 weight part.
Further, as the antioxidant, the ultraviolet absorber, and the light stabilizer, it can be appropriately selected from conventionally known ones, and in particular, a reactive antioxidant having a (meth) acryloyl group in the molecule. It is advantageous to use an ultraviolet absorber or a light stabilizer. In this case, an antioxidant component, an ultraviolet absorber component, and a light stabilizer component are bonded to polymer chains formed by irradiation with ionizing radiation. Accordingly, the escape of each component from the cured layer over time is suppressed, so that each function is exhibited over a long period of time.
The ionizing radiation-sensitive resin composition in the present invention contains the above-mentioned ionizing radiation curable compound, a photopolymerization initiator used as necessary, and various additive components in a suitable solvent as required. It can be prepared by adding in proportion and dissolving or dispersing.
Examples of the solvent used in this case include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, Alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolve solvents such as ethyl cellosolve are used.
The concentration and viscosity of the resin composition thus prepared are not particularly limited as long as they can be coated, and can be appropriately selected according to the situation.

Next, the resin composition is coated on the aluminum vapor deposition layer by using a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. Then, a coating film is formed, and after drying, the hard coating layer is formed by irradiating this with ionizing radiation to cure the coating film.
As ionizing radiation, for example, ultraviolet rays or electron beams are used. The ultraviolet rays are obtained with a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like, and the irradiation amount is usually 100 to 500 mJ / cm ² , while the electron beam is obtained with an electron beam accelerator or the like, Usually 150 to 350 kV. Among these ionizing radiations, ultraviolet rays are particularly preferable. In addition, when using an electron beam, a cured film can be obtained, without adding a polymerization initiator.
The thickness of the hard coat layer thus formed is preferably in the range of 0.5 to 30 μm. If the thickness is less than 0.5 μm, the surface hardness of the solar radiation shielding film is insufficient, and the scratch resistance may not be sufficiently exhibited. If the thickness exceeds 30 μm, the curing shrinkage rate and the heat and humidity shrinkage rate increase. The solar shading film is likely to curl or crack, and is disadvantageous in terms of production. Therefore, the thickness of the hard coat layer is more preferably 1 to 20 μm, and particularly preferably in the range of 1.5 to 15 μm.

In the solar shading film of the present invention, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer provided on the surface opposite to the hard coat layer of the polyester film as the base film is not particularly limited, and is a conventionally known pressure-sensitive adhesive, For example, it can be appropriately selected from rubber-based, acrylic-based, silicone-based, polyurethane-based and polyester-based pressure-sensitive adhesives. Of these, acrylic and silicone pressure-sensitive adhesives are particularly suitable. These pressure-sensitive adhesives may be used alone or in combination of two or more.
As the acrylic pressure-sensitive adhesive, those containing a crosslinking agent together with a (meth) acrylic acid ester copolymer having a weight average molecular weight of 300,000 or more as a resin component are preferable.
The (meth) acrylic acid ester-based copolymer includes (meth) acrylic acid ester having 1 to 20 carbon atoms in the alkyl group of the ester portion, a monomer having a functional group having active hydrogen, and, if desired, Preferred examples include copolymers with other monomers used.
Here, examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms of the alkyl group in the ester portion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
On the other hand, examples of the monomer having a functional group having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) (Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; acrylamide, methacrylamide, N-methylacrylamide, N-methyl Acrylamides such as methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide; monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, (meth) acrylic Acids such as monoethylaminopropyl ( Data) acrylate monoalkyl aminoalkyl, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, ethylenically unsaturated carboxylic acids such as citraconic acid. These monomers may be used independently and may be used in combination of 2 or more type.

Examples of other monomers used as desired include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; styrene Styrene monomers such as α-methylstyrene; diene monomers such as butadiene, isoprene and chloroprene; nitrile monomers such as acrylonitrile and methacrylonitrile; N, N-dimethylacrylamide, N, N— And N, N-dialkyl-substituted acrylamides such as dimethylmethacrylamide. These may be used alone or in combination of two or more.
In the acrylic pressure-sensitive adhesive, the (meth) acrylic acid ester copolymer used as a resin component is not particularly limited with respect to the copolymerization form, and may be any of random, block, and graft copolymers. . The molecular weight is preferably 300,000 or more in terms of weight average molecular weight, more preferably 350,000 to 2.5 million. If the weight average molecular weight is less than 300,000, the adhesive force to the adherend may be insufficient.
In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

In the present invention, this (meth) acrylic acid ester copolymer may be used alone or in combination of two or more.
There is no restriction | limiting in particular as a crosslinking agent in this acrylic adhesive, Arbitrary things can be suitably selected from what was conventionally used as a crosslinking agent in an acrylic adhesive. Examples of such crosslinking agents include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, metal chelate compounds, metal alkoxides, metal salts, and the like, but polyisocyanate compounds are preferably used. It is done.
Examples of polyisocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Polyisocyanates, etc., and biurets, isocyanurates, and adducts that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. Can be mentioned.
In this invention, this crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. The amount used depends on the type of the crosslinking agent, but is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester copolymer. It is selected in the range of the part.
In addition, a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a silane coupling agent, a filler, and the like can be added to the acrylic pressure-sensitive adhesive as desired.

Examples of the silicone-based pressure-sensitive adhesive include those containing polymethylsiloxane or polyphenylsiloxane as a main component and optionally containing a crosslinking agent such as a peroxide, a tackifier, a plasticizer, or a filler. .
In the present invention, among these pressure-sensitive adhesives, an acrylic pressure-sensitive adhesive containing an acrylic resin having a weight average molecular weight of 300,000 or more is particularly preferable as a resin component because of excellent weather resistance.
In the solar shading film of the present invention, these pressure-sensitive adhesives may be directly applied to a base film to provide a pressure-sensitive adhesive layer, and a release film may be further bonded, or a pressure-sensitive adhesive may be applied on the release film. After providing the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer may be transferred by sticking it to a substrate film. In this case, the release film may be adhered as it is without being peeled off if desired, and may be peeled off when the solar radiation shielding film is used. The thickness of the pressure-sensitive adhesive layer provided on the base film is usually 5 to 100 μm, preferably about 10 to 60 μm.
Examples of the release film include paper substrates such as glassine paper, coated paper, cast coated paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates, or polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate. Examples thereof include a polyester film such as phthalate or a plastic film such as a polyolefin film such as polypropylene or polyethylene and a release agent such as a silicone resin applied thereto. Although there is no restriction | limiting in particular about the thickness of this peeling film, Usually, it is about 20-150 micrometers.
According to the method of the present invention, the solar radiation shielding film of the present invention having such a configuration can be produced as follows.
According to the method of the present invention, an aluminum vapor deposition layer having a visible light transmittance of 15 to 75% is provided on one surface of a polyester film, and then a hard coat layer is formed on the aluminum vapor deposition layer. A solar shading film is produced by forming a layer. At this time, as the polyester film, a film having a dynamic friction coefficient of 0.3 to 0.8 and a haze value of 0.4 to 1.6% is preferably used. By passing through such a process, in the winding operation after aluminum deposition and the winding operation after forming the hard coat layer, the winding property is good, and even if it is wound into a roll, wrinkles, creases, protrusions, etc. Occurrence is suppressed.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.
In addition, each physical property was calculated | required according to the method shown below.
(1) Dynamic friction coefficient and static friction coefficient of base film Measured using a tensile tester “Autograph AGS-1000D” manufactured by Shimadzu Corporation according to “JIS K 7125: 1999 Plastic-film and sheet-friction coefficient test method”. did.
(2) Haze value The haze value was measured using “Haze Meter NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd. according to “JIS K 7136: 2000 Determination of haze of plastic-transparent material”.
(3) Winding suitability 500 nm of the solar radiation shielding film of Examples and Comparative Examples prepared using a polyester film having a width of 1550 mm is wound up, and visually observed for wrinkles, breaks and deformation at the winding part. And evaluated according to the following criteria.
○: Wrinkles, breakage, and deformation are not recognized.
(Triangle | delta): Any one of a wrinkle, bending, and a deformation | transformation is recognized.
X: Wrinkles, creases, and deformations are all recognized.
(4) Visible light transmittance and solar radiation transmittance Measured using a spectral transmittance meter “UV-3101PC” manufactured by Shimadzu Corporation according to “JIS A 5759: 1998 Film for architectural window glass”.
(5) Swelling due to puddle A 300 mm square sample film is attached to a 3 mm thick glass plate by the following method. After spraying 0.1% by weight neutral detergent aqueous solution onto the glass plate surface and the adhesive layer surface of the film, the glass plate surface and the adhesive layer surface of the film are overlapped, and a squeegee for screen printing with a width of 100 mm from the center of the film. The aqueous solution is scraped out by applying a load of 5 to 10 N toward the end. After being left for 3 hours in an environment of 23 ° C. and 50% RH, the presence or absence of swelling due to water accumulation was visually observed.
(6) Clarification of aluminum In the same manner as in (5) above, a sample obtained by scraping the aqueous solution under a load of 5 to 10 N was left in an environment of 60 ° C. and 85% RH for 2 weeks, and the aluminum deposited layer was transparent. The presence or absence of crystallization was visually observed.

Example 1
Polyester film having a thickness of 23 μm as a base film [Toray Plastics, Inc. “Lumirror U60”, double-sided slippery transparent PET # 23, dynamic friction coefficient 0.5, static friction coefficient 0.6, haze value 0.8%] on one side, a vacuum evaporation machine [“high vacuum web made by Leybold” coater "], an aluminum vapor deposition layer having a film thickness of 15 nm and a visible light transmittance of 35% was provided.
Next, 100 parts by weight of a difunctional monomer dipentaerythritol pentaacrylate [“Sartomer SR399E” manufactured by Nippon Kayaku Co., Ltd.], 5 parts by weight of an acetophenone photopolymerization initiator [“Irgacure 651” manufactured by Ciba Specialty Chemicals, Ltd.] After preparing a coating solution containing 150 parts by weight of toluene, it was coated on the aluminum vapor deposition layer with a Mayer bar # 4 so that the dry thickness was 2 μm. A hard coat layer was formed by curing by irradiating with / cm ² of ultraviolet rays.
Subsequently, an acrylic pressure-sensitive adhesive ["PU-V" manufactured by Lintec Co., Ltd.] was applied to the back surface (surface without the hard coat layer) of the polyester film as the base film so that the dry thickness was 20 μm. Subsequently, a release film [“SP-PL251011” manufactured by Lintec Corporation] in which a silicone resin was applied to the polyester film was bonded to prepare a solar shading film. The physical property evaluation results are shown in Table 1.
Example 2
In Example 1, it carried out similarly to Example 1 except having set the film thickness to 5 nm so that the visible light transmittance | permeability of an aluminum vapor deposition layer might be 70%, and produced the solar radiation shielding film. The physical property evaluation results are shown in Table 1.

Example 3
In Example 1, a polyester film having a thickness of 25 μm [“Lumirror # 25T70” manufactured by Toray Industries Inc., a dynamic friction coefficient of 0.4, a static friction coefficient of 0.5, and a haze value of 1.2%] was used as the base film. A solar shading film was produced in the same manner as in Example 1. The physical property evaluation results are shown in Table 1.
Comparative Example 1
A solar radiation shielding film having the structure shown in FIG. 1 was produced.
“Lumirror U60” (supra) is used as the polyester film, the aluminum vapor-deposited layer has a film thickness of 15 nm and a visible light transmittance of 35%, and a polyester resin [“Byron UR-8200” 20 manufactured by Toyobo Co., Ltd. A mixture of parts by weight and 80 parts by weight of “UR-8300”] was dissolved in 50 parts by weight of methyl ethyl ketone, applied with Meyer bar # 6, and then dried at 80 ° C. for 1 minute, resulting in a dry thickness of 1.5 μm. Thus, an aluminum protective layer was formed. Next, a hard coat layer was formed in the same manner as in Example 1, and then a pressure-sensitive adhesive layer was formed and a release film was bonded thereto to produce a solar radiation shielding film. The physical property evaluation results are shown in Table 1. In addition, a wrinkle and a crease | fold occurred at the time of winding up in roll shape after hard coat layer formation.
Comparative Example 2
In the structure of Comparative Example 1, in order to improve the winding property, except that 7 parts by weight of silica ["NIPGEL AY-200" manufactured by Nippon Silica Industry Co., Ltd.] per 100 parts by weight of the polyester resin was added to the aluminum protective layer, A solar shading film was produced in the same manner as in Comparative Example 1. The physical property evaluation results are shown in Table 1.

  As can be seen from Table 1, Examples 1 to 3 have good winding properties, do not swell due to water accumulation, and do not have aluminum transparency. In Comparative Example 1, the winding property is poor and there is swelling due to water accumulation, so that the aluminum is transparent. Although the comparative example 2 has good winding-up property, there is a swelling due to water accumulation, and the aluminum is transparent.

  The solar shading film of the present invention has an aluminum vapor deposition layer having a function of reflecting near infrared rays contained in solar radiation, has a small haze value, and suppresses the transparency of the aluminum vapor deposition layer after being applied, and a manufacturing process. The intermediate film processed product has a good winding property, and is attached to a window glass of a building or a car for the purpose of blocking solar radiation, for example.

It is explanatory drawing which shows the structure and manufacturing process of the conventional solar radiation shielding film. It is the structure shown in FIG. 1, Comprising: It is explanatory drawing which shows the structure and manufacturing process of a solar radiation shielding film from which a manufacturing process differs. It is explanatory drawing of an example which shows the structure and manufacturing process of the solar radiation shielding film of this invention.

Claims (7)

  Solar radiation characterized in that an aluminum vapor-deposited layer having a visible light transmittance of 15 to 75% and a hard coat layer are sequentially laminated on one surface of the polyester film, and an adhesive layer is provided on the opposite surface. Shielding film.   The solar radiation shielding film according to claim 1, wherein the polyester film has a dynamic friction coefficient of 0.3 to 0.8 and a haze value of 0.4 to 1.6%.   The solar radiation shielding film according to claim 1 or 2, wherein the aluminum vapor deposition layer has a thickness of 5 to 40 nm.   The solar radiation shielding film according to claim 1, wherein the hard coat layer is a cured resin layer formed by ionizing radiation.   The solar radiation shielding film according to claim 1, wherein the hard coat layer has a thickness of 0.5 to 30 μm.   An aluminum vapor deposition layer having a visible light transmittance of 15 to 75% is provided on one surface of a polyester film, and then a hard coat layer is formed thereon, and then an adhesive layer is formed on the opposite surface. A method for producing a solar shading film.   The method for producing a solar radiation shielding film according to claim 6, wherein the polyester film has a dynamic friction coefficient of 0.3 to 0.8 and a haze value of 0.4 to 1.6%.

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