JP4566625B2 - Decorative film for glass - Google Patents

Description

  The present invention relates to a decorative film for glass. More specifically, the present invention is a laminated film of a base composed of a biaxially stretched polyethylene terephthalate film and a top composed of a soft polyester film embossed on the upper surface, where the glass is broken. The present invention relates to a decorative film for glass having excellent anti-scattering properties, good design and appearance, and curling is suppressed.

Conventionally, films having various functions have been developed and marketed as window glass films. For example, when it breaks due to a disaster such as an earthquake, a glass anti-scattering film that prevents glass fragments from scattering, an internal anti-glare film that makes the inside difficult to see from the outside, and blocks ultraviolet rays and infrared rays contained in sunlight An ultraviolet shielding film, an infrared shielding film, a composite functional film for glass having two or more of these functions, or a glass film having these functions and decorative properties are on the market.
Among these, the anti-scattering decorative film for glass has heretofore been mainly made of polyvinyl chloride (PVC) resin. However, in recent years, non-PVC is desired due to environmental problems. It has become like this.
Examples of the glass anti-scattering film using a non-PVC material include a biaxially stretched polyethylene terephthalate (PET) film or a glycol-modified polyethylene terephthalate resin (the dicarboxylic acid component is terephthalic acid and the glycol component is ethylene). Copolyester-based resin: PETG) film having a glycol of 40-80 mol% and 1,4-cyclohexanedimethanol 20-60 mol%, and a laminated film having a biaxially stretched PET film as a base and so on.
However, those using the above-mentioned biaxially stretched PET film have a problem that transferability and appearance during embossing are poor and it is difficult to exhibit excellent surface design. In addition, the film using a laminated film of PETG film and biaxially stretched PET film has insufficient emboss transferability of the PETG film on the top, and after laminating and integrating both films, There are problems such as being easy to occur.
In addition, a biaxially stretched polyethylene naphthalate film having a higher mechanical strength than the biaxially stretched PET film is used, and a laminated film that can more favorably prevent the scattering of glass at the time of breakage is disclosed (for example, Patent Document 1). However, this laminated film also has the same problem as the biaxially stretched PET film.
JP-A-9-76441

  The present invention uses a non-PVC material under such circumstances, has excellent anti-scattering properties when the glass is broken, has good design and appearance, and has a curling effect. It is made for the purpose of providing the decorative film for glass by which generation | occurrence | production was suppressed.

As a result of intensive research to develop the decorative film for glass having the above-mentioned excellent functions, the present inventors used a biaxially stretched PET film as a base and an embossing treatment on the upper surface as the top. The inventors have found that the purpose can be achieved by a laminated film using a soft polyester film having a specific composition, and have completed the present invention based on this finding.
That is, the present invention
In the laminated film (1) upper base and the base are stacked, the upper base is, (A) (a-1) of polyethylene terephthalate having a glass transition temperature of -10 to 40 ° C. Some of the other ethylene glycol units A modified polyethylene terephthalate resin substituted with a glycol unit and (a-2) an amorphous polyethylene terephthalate resin having a glass transition temperature of 50 to 120 ° C. in a weight ratio of 20:80 to 80:20, and (a -3) A resin component containing 1 to 40% by weight of a methacrylic acid ester / acrylic acid ester rubber graft copolymer and (B) 0.2 to 10 parts by weight of wax per 100 parts by weight, Glass film characterized by being an embossed film and having a biaxially stretched polyethylene terephthalate film as a base. Decoration film,
(2) (a-2) Amorphous polyethylene terephthalate resin having a glass transition temperature of 50 to 120 ° C., wherein the dicarboxylic acid component is terephthalic acid, the glycol component is ethylene glycol 40 to 80 mol%, and 1,4-cyclohexane The decorative film for glass according to item (1), which is a combination with 60 to 20 mol% of dimethanol,
(3) The decorative film for glass according to (1) or (2) above, wherein a top coat layer is provided on the embossed surface of the upper surface.
(4) The decorative film for glass according to (3), wherein the topcoat layer is a layer formed using a silicone-based topcoat agent,
(5) The decorative film for glass according to the above (3) or (4), wherein the topcoat layer contains an antibacterial agent,
(6) The decorative film for glass according to the above (5), wherein the antibacterial agent is a zinc antibacterial agent,
(7) The decorative film for glass according to any one of (1) to (6) above, wherein a printed layer is provided on the upper surface of the underlying biaxially stretched polyethylene terephthalate film.
(8) The decorative film for glass according to any one of (1) to (7) above, which has a pressure-sensitive adhesive layer on the back surface, and (9) the pressure-sensitive adhesive layer according to (8) above, wherein the pressure-sensitive adhesive layer contains a colorant. Decorative film for glass,
Is to provide.

  According to the present invention, it is a laminated film of a base composed of a biaxially stretched polyethylene terephthalate film and a top composed of a soft polyester film having an embossed treatment on the upper surface, and prevents scattering when the glass is broken. It is possible to provide a decorative film for glass having excellent design properties, good design and appearance, and curling is suppressed.

The decorative film for glass of the present invention is a laminated film obtained by laminating an upper film having an upper surface subjected to an embossing process and a base film.
The upper film includes (A) (a-1) a modified polyethylene terephthalate resin having a glass transition temperature of −10 to 40 ° C. and (a-2) an amorphous polyethylene terephthalate resin having a glass transition temperature of 50 to 120 ° C. the weight ratio of 20: 80 to 80: see contains a ratio of 20, and further (a-3) a methacrylic acid ester / acrylic acid ester rubber graft copolymer 1 to 40% by weight including the resin component, the 100 weight A film containing 0.2 to 10 parts by weight of (B) wax is used per part.
In this overlying film, (a-1) modified polyethylene terephthalate resin having a glass transition temperature of −10 to 40 ° C. used as one of the resin components is mainly composed of terephthalic acid as a dicarboxylic acid component, for example. In some cases, those containing isophthalic acid, naphthalenedicarboxylic acid, etc., while ethylene glycol is included as the glycol component, tetramethylene glycol, polyethylene glycol, polytetramethylene glycol, neopentyl glycol, cyclohexanedimethanol, bisphenol compounds Examples thereof include a modified polyethylene terephthalate resin obtained by copolymerization using an ethylene oxide adduct. Among these, a polyethylene terephthalate resin in which the dicarboxylic acid component is terephthalic acid and the glycol component is mainly copolymerized with ethylene glycol, polytetramethylene glycol, and 1,4-cyclohexanedimethanol can be particularly preferably used. .
This modified polyethylene terephthalate-based resin may be used alone or in combination of two or more. When using 2 or more types together, the glass transition temperature of the mixture should just exist in the range of -10-40 degreeC.

In the case of (a-2) an amorphous polyethylene terephthalate resin having a glass transition temperature of 50 to 120 ° C., which is another component in the resin component (A), for example, as a dicarboxylic acid component, mainly terephthalic acid. In the meantime, those containing other dicarboxylic acids such as isophthalic acid are used, and on the other hand, ethylene glycol is used as the glycol component and one containing 1,4-cyclohexanedimethanol or neopentyl glycol is copolymerized. Non-crystalline polyethylene terephthalate resin can be used. Among these, the dicarboxylic acid component is terephthalic acid, and the glycol component is ethylene glycol 40 to 80 mol% and 1,4-cyclohexanedimethanol 20 to 60 mol%, a copolymerized polyethylene terephthalate or a dicarboxylic acid component However, it is terephthalic acid, and copolymer polyethylene terephthalate mainly composed of ethylene glycol and neopentyl glycol as the glycol component can be preferably used, and the former copolymer polyethylene terephthalate is particularly preferable. Examples of copolymer polyethylene terephthalate in which the dicarboxylic acid component is terephthalic acid and the glycol component is ethylene glycol 40 to 80 mol% and 1,4-cyclohexanedimethanol 20 to 60 mol% include, for example, “PETG6763” of Eastman Chemical Co. Or the like. Examples of copolymer polyethylene terephthalate in which the dicarboxylic acid component is terephthalic acid and the glycol component is mainly composed of ethylene glycol and neopentyl glycol include, for example, “E-01” of Kanebo Gosei Co., Ltd., Toyobo Co., Ltd. “SR173CA” and the like.
This amorphous polyethylene terephthalate resin may be used alone or in combination of two or more. When using 2 or more types together, the glass transition temperature of the mixture should just exist in the range of 50-120 degreeC.

In the present invention, the content ratio of the component (a-1) and the component (a-2) is selected in the range of 20:80 to 80:20 by weight ratio. When the content ratio of the component (a-1) and the component (a-2) is in the above range, a flexible polyester material is obtained, and the resulting film has an easy embossing property capable of expressing excellent design properties. When the base biaxially stretched polyethylene terephthalate film is laminated, curling is suppressed. A preferable content ratio of the component (a-1) and the component (a-2) is 30:70 to 70:30 by weight ratio, and particularly preferably in the range of 35:65 to 65:35.
In the present invention, the (A) resin component is used as the component (a-3) as the component (a-1) in order to improve other physical properties of the film to be obtained, such as film-forming properties. Resins other than the component and the component (a-2) can be contained. As the component (a-3), methacrylic acid ester-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / ethylene-propylene rubber graft copolymer, acrylonitrile-styrene / Acrylic acid ester graft copolymer, methacrylic acid ester / acrylic acid ester rubber graft copolymer, methacrylic acid ester-acrylonitrile / acrylic acid ester rubber graft copolymer, thermoplastic polyester elastomer and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the component (a-3) in the resin component (A) is preferably 1 to 40% by weight. If content of this (a-3) component exists in the said range, the film in which film forming property etc. improved could be given, without impairing the said various characteristics requested | required as an upper film. The more preferable content of the component (a-3) is 1 to 30% by weight, and particularly preferably 3 to 20% by weight.

Examples of the methacrylic acid ester-styrene / butadiene rubber graft copolymer include an elastomer obtained by graft copolymerization of methyl methacrylate and styrene on polybutadiene. Examples of the acrylonitrile-styrene / butadiene rubber graft copolymer include an elastomer obtained by graft copolymerization of acrylonitrile and styrene with polybutadiene. Examples of the acrylonitrile-styrene / ethylene-propylene rubber graft copolymer include an elastomer obtained by graft copolymerization of acrylonitrile and styrene with an ethylene-propylene rubber. Examples of the acrylonitrile-styrene / acrylic ester graft copolymer include an elastomer obtained by graft copolymerization of acrylonitrile and styrene with a polyacrylic ester.
Examples of the methacrylic acid ester / acrylic acid ester rubber graft copolymer include an elastomer obtained by graft copolymerization of methyl methacrylate with a polyacrylic acid ester. Examples of the methacrylic acid ester-acrylonitrile / acrylic acid ester rubber graft copolymer include elastomers obtained by graft copolymerization of methyl acrylate and acrylonitrile on polyacrylic acid ester.
Examples of the thermoplastic polyester elastomer include an elastomer having a hard segment composed of a terephthalic acid component and a glycol component and a soft segment composed of a polyalkylene glycol. Among these, a methacrylic acid ester / acrylic acid ester rubber graft copolymer can be particularly preferably used.
Moreover, polybutylene terephthalate and copolymer polybutylene terephthalate can also be used as needed.

In the present invention, the wax of the component (B) in the upper film is not particularly limited, and examples thereof include hydrocarbon waxes such as paraffin wax, polyethylene wax and polypropylene wax, stearic acid, hydroxystearic acid, composite stearic acid, Fatty acid waxes such as oleic acid, aliphatic amide waxes such as stearic acid amide, oxystearic acid amide, oleic acid amide, erucyl amide, ricinoleic acid amide, behenic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, Examples thereof include aliphatic ester waxes such as n-butyl stearate and montanic acid ester wax, aliphatic metal soap waxes, urea-formaldehyde waxes and the like. Among these, the aliphatic ester waxes have good compatibility with the amorphous polyethylene terephthalate resin and can improve the moldability without impairing the transparency of the resulting film. It can be used suitably. These may be used individually by 1 type and may be used in combination of 2 or more type.
In the present invention, the wax of component (B) is contained in the range of 0.2 to 10 parts by weight per 100 parts by weight of the resin component (A). When the wax of component (B) is in the above range, the moldability and the like can be improved without impairing the transparency of the film obtained and other required properties. The content of the component (B) is preferably 0.5 to 5 parts by weight, particularly preferably in the range of 1 to 4 parts by weight.

The upper film in the present invention may appropriately contain various additives as long as the object of the present invention is not impaired. Examples of the additive to be included include an antioxidant, a weather resistance stabilizer, an antistatic agent, a heat stabilizer, a flame retardant, a release agent, a colorant, a surfactant, and a filler.
There is no restriction | limiting in particular in the thickness of the upper film in this invention, Usually, about 20-400 micrometers, Preferably it is 40-150 micrometers.
In the upper film in the present invention, an embossing treatment is performed on the upper surface in order to impart design properties. There is no restriction | limiting in particular in the preparation methods of such an upper film, For example, it can produce as follows.
First, a resin composition containing the (A) resin component, (B) wax, and various additives used as necessary at a predetermined ratio is prepared. Next, this resin composition is formed into a film by a conventionally known film forming method, for example, a casting method (solution casting method, extraction method (melt extrusion method; T-die method, inflation method, etc.), calendar method, or the like.
There is no particular limitation on the embossing treatment method applied to the upper surface of the film thus formed, for example, a method of embossing at the same time as the film formation online, or a drum heating embosser offline, A method of embossing using a multi-cylinder type embosser or the like can be used. The arithmetic average roughness Ra of the embossed surface is not particularly limited, but is usually about 0.1 to 25 μm, preferably 0.3 to 15 μm.

On the other hand, in the present invention, the biaxially stretched polyethylene terephthalate film used as the base film can be produced, for example, as follows.
Polyethylene terephthalate resin mainly composed of terephthalic acid as the dicarboxylic acid component and ethylene glycol as the glycol component, and various additives used as necessary, such as antioxidants, weathering stabilizers, antistatic agents, heat stabilizers It is produced by forming a resin composition containing a flame retardant, a release agent, a colorant, a surfactant, a filler, and the like by a tenter method, a tube method, or the like.
In the tenter method, the resin composition is put into an extruder, heated and melted, extruded into a sheet form from a die, cooled and solidified on a casting drum, and first a thick film is produced. Biaxial stretching and two-stage sequential stretching of the transverse stretching after longitudinal stretching are performed, and the latter two-stage sequential stretching is preferable. In this case, the film is first stretched in the longitudinal direction by a heated roll group between the slow (front) drive roll and the fast (rear) drive roll, then introduced into the tenter, heated while holding both ends of the film, and stretched in the lateral direction. Is done. Thereafter, heat fixing is performed in the tenter rear chamber in order to fix the plane orientation.
On the other hand, in the tube method, it is the same as the extrusion inflation method, the molten polymer is extruded from a ring die (annular die), biaxially stretched with compressed air after cooling, and the tube-shaped film is heated, Fix crystallization and molecular orientation.
The film is wound in the form of a tube, or cut into two to form two films.
In these methods, the film forming conditions are such that the extrusion temperature is usually about 250 to 300 ° C., and the stretching treatment is usually about 80 to 130 ° C., and is performed about 2 to 5 times in length and width, and heat setting. The temperature is usually about 150 to 240 ° C.

The thickness of the biaxially stretched polyethylene terephthalate film thus obtained is not particularly limited, but is usually about 25 to 220 μm, preferably 40 to 190 μm. If the thickness is less than 25 μm, the scattering prevention property is inferior, and the glass may be easily broken. The thickness of the biaxially stretched polyethylene terephthalate film is 220 μm or less and has a sufficient performance as a decorative film for glass. Usually, the thickness does not need to exceed 220 μm.
In the present invention, physical or chemical methods such as an oxidation method and a concavo-convex method are optionally used for the purpose of improving the adhesion with the layer provided on one side or both sides of each of the above-mentioned base film and base film. Surface treatment can be performed. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. As these surface treatment methods, generally, a corona discharge treatment method is preferably used in terms of effects and operability. Hot melt coating and primer treatment can also be performed.
In the decorative film for glass of the present invention, the base film and the lower surface side (the side opposite to the embossed surface) of the upper film are faced to be laminated and integrated to produce a laminated film. In this case, as a lamination method, a thermal lamination method, a dry lamination method using an adhesive, or the like can be employed. Although there is no restriction | limiting in particular in the adhesive agent to be used, A polyester-type adhesive agent can be used suitably.
Further, in the present invention, the biaxially stretched polyethylene terephthalate film, which is the base film, can be laminated after the printing is performed on the upper surface of the biaxially stretched polyethylene terephthalate film, if desired. There is no particular limitation on this printing method, and any of a relief printing plate, a flat plate, an intaglio printing plate, and a stencil printing plate can be used. Of these, gravure printing, which is one type of intaglio printing, and flexographic printing, which is a type of relief printing, can be suitably used.

In the decorative film for glass of the present invention, a top coat layer can be provided on the embossed surface of the upper surface of the laminated film. There is no restriction | limiting in particular in the kind of this topcoat layer, What is necessary is just to select suitably according to a desired function.
Specifically, when a topcoat layer having antifouling performance is desired, a cured silicone resin layer is preferably provided using a reactive silicone resin. As said reactive silicone resin, what has a functional group bridge | crosslinked with a polyisocyanate compound can be used in a molecule | numerator, for example. A silicone resin cured layer can be formed by applying a coating liquid containing this reactive silicone resin and a polyisocyanate compound as a curing agent to the upper surface of the upper film and subjecting it to a heat drying treatment.
Moreover, an ultraviolet curable silicone resin can also be used. Examples of the ultraviolet curable silicone resin include a radical addition type having an alkenyl group and a mercapto group, a hydrosilylation reaction type having an alkenyl group and a hydrogen atom, a cationic polymerization type having an epoxy group, and a (meth) acryl group. A radical polymerization type silicone resin having Among these, a cationic polymerization type having an epoxy group and a radical polymerization type having a (meth) acryl group are preferable.
Examples of silicone resins having an epoxy group or (meth) acryl group in the molecule include epoxypropoxypropyl-terminated polydimethylsiloxane, (epoxycyclohexylethyl) methylsiloxane-dimethylsiloxane copolymer, methacryloxypropyl-terminated polydimethylsiloxane, and acryloxy. And propyl-terminated polydimethylsiloxane.
Examples of the silicone resin having a vinyl group in the molecule include terminal vinyl polydimethylsiloxane and vinylmethylsiloxane homopolymer.
A coating liquid containing the ultraviolet curable silicone resin and, if desired, a photopolymerization initiator is applied to the upper surface of the upper film, and after drying, the coating film is irradiated with ultraviolet rays to form a cured silicone resin layer. Can be formed.

On the other hand, when a hard coat function having excellent scratch resistance is desired for the top coat layer, a resin layer such as an acrylic resin, polyurethane, or polyamide can be provided. Among these, a polyurethane cured layer formed using a two-component polyurethane composed of a polyol component and a polyisocyanate component is preferable.
In addition, a coating liquid containing an acrylic UV curable resin is applied to the upper surface of the upper film, and after drying, the coating film is irradiated with UV light to form a cured resin layer with even better scratch resistance. It can also be formed.
Although there is no restriction | limiting in particular in the thickness of the topcoat layer formed in this way, Usually, about 1-10 micrometers, Preferably it is 2-5 micrometers.
In the decorative film for glass of the present invention, the top coat layer can contain an antibacterial agent as desired. There is no particular limitation on the type of the antibacterial agent, and it can be appropriately selected and used from conventionally known inorganic antibacterial agents and organic antibacterial agents, but inorganic antibacterial agents are preferred from the viewpoint of weather resistance and the like. It is.
Examples of inorganic antibacterial agents include zinc-based, silver-based, and titanium oxide-based materials. Among these, zinc-based antibacterial agents are preferable in terms of balance between color resistance, discoloration resistance, weather resistance, and antibacterial activity. Agents are preferred.
In the present invention, when the zinc-based antibacterial agent is used, the content of the antibacterial agent in the topcoat layer is usually 0.05 to 1.5% by weight, preferably 0.1 to 0.7% by weight. is there.

In the decorative film for glass of the present invention, an adhesive layer can be provided on the back surface. As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, acrylic, urethane and silicone pressure-sensitive adhesives are preferable from the viewpoint of weather resistance and the like, and acrylic pressure-sensitive adhesive is particularly preferable.
There is no particular limitation on the method for forming the pressure-sensitive adhesive layer. For example, a solvent-type acrylic pressure-sensitive adhesive, a non-aqueous emulsion-type acrylic pressure-sensitive adhesive, and a water-based emulsion-type acrylic pressure-sensitive adhesive on a release paper having a silicone coating on a paper substrate. Then, a water-soluble acrylic adhesive is applied and dried to form an adhesive layer. It is also possible to use an ultraviolet curable adhesive. It is preferable to laminate so that the pressure-sensitive adhesive layer formed on the release paper is in contact with the back surface of the decorative film. In the pressure-sensitive adhesive layer, a colorant, a tackifier resin, a crosslinking agent, an antioxidant, a weathering agent, and the like can be blended as necessary. The colorant is preferably a pigment from the viewpoint of weather resistance.
FIG. 1 is a schematic cross-sectional view of an example of a decorative film for glass according to the present invention, in which a decorative film for glass 10 includes a base film made of a biaxially stretched polyethylene terephthalate film 1 provided with a printing layer 2, An upper film having an embossed layer (not shown) on the upper surface and a top film made of a soft polyester film 3 provided with a topcoat layer 4 is laminated thereon, and an adhesive layer 5 is provided on the rear surface. Has the structure.
Such a decorative film for glass of the present invention is a laminated film made of non-PVC and has excellent anti-scattering properties when the glass is broken, and has good design and appearance, and curl It has the feature that generation | occurrence | production of was suppressed.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples and comparative examples, the following materials were used.
(1) (a-1) Modified PET system: Modified polyethylene terephthalate resin, manufactured by Mitsubishi Rayon Co., Ltd., trade name “DN124”, terephthalic acid / ethylene glycol / polytetramethylene glycol / 1,4-cyclohexanedimethanol Polymer, glass transition temperature 10 ° C.
(2) (a-2) Amorphous PET series: Amorphous polyethylene terephthalate resin, manufactured by Eastman Chemical Japan, trade name “PETG6763”, terephthalic acid / ethylene glycol / 1,4-cyclohexanedimethanol Copolymer, glass transition temperature 81 ° C.
(3) (a-3) FM21: Methacrylate / Acrylate rubber graft copolymer, manufactured by Kaneka Chemical Co., Ltd., trade name “Kane Ace FM21”, average particle size 0.05 to 0.3 μm.
(4) (B) Lubricant: Montanate ester wax, manufactured by Client Japan Co., Ltd., trade name “Licowax OP”, calcium saponified montanate ester wax.
(5) Biaxially stretched polyethylene terephthalate (PET) film: 50 μm in thickness and 75 μm in thickness are manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., using the product name “T600E”, and 20 μm in thickness is manufactured by Teijin DuPont Films, Ltd. The brand name "Teijin Tetron Film G2" is used.
(6) Adhesive: Acrylic adhesive, manufactured by Toyo Ink Manufacturing Co., Ltd., trade name “BPS-5296”
(7) Urethane-based coating agent: Toyo Ink Manufacturing Co., Ltd., trade name “URV283 mat base” (acrylic resin) and “UR130B varnish” (isocyanate-based) two-component curable urethane paint (8) silicone-based Coating agent: Toyo Ink Mfg. Co., Ltd., trade name “SUR200 mat varnish” (silicone resin) and “SUR200 Kokazai” (isocyanate type) two-component curable silicone urethane paint (9) Silver antibacterial agent: Toa Product name “AG300”, manufactured by Gosei Co., Ltd., average particle size 0.9 μm
(10) Zinc-based antibacterial agent: manufactured by Toa Gosei Co., Ltd., trade name “NOVALON VZF101”, average particle size 1.0 μm

Moreover, evaluation of the decorative film for glass obtained by the Example and the comparative example was performed by the following method.
(1) Embossed transfer appearance In a doubling device [Kawakami Iron Works Co., Ltd.], between a heating drum having a temperature of 140 ° C and a cooling drum, a metal engraving roll having a temperature of 140 ° C and a pressure roll coated with semi-rigid rubber Install an embossing roll. A pear-textured surface having an arithmetic average roughness Ra of 4 μm was used with the film obtained by the 8-inch inverted L-type calender machine film shown in Table 1 as the top, and the biaxially stretched PET film shown in Table 1 as the base. Embossing is performed under conditions of an embossing pressure of 2.9 N and a line speed of 10 m / min. About the laminated film obtained by embossing, arithmetic mean roughness Ra, emboss transferability, and appearance were evaluated according to the following reference steps.
○: Deep embossing with arithmetic average roughness Ra of 2 μm or more is included, and it is possible to show a calm appearance with almost no reflection of light. Δ: Embossing with arithmetic average roughness Ra of 0.3 μm to less than 2 μm Weak and slightly reflected in light and inferior in appearance as a decorative film ×: Arithmetic average roughness Ra is less than 0.3 μm, strong in reflected light and greatly inferior in appearance as a decorative film (2) Curl property The film was cut into a size of 10 cm x 10 cm, placed on a horizontal plate, the curled state of the test piece was observed, and the curl property was evaluated in the next evaluation stage.
◎: No curling is observed and good ○: Slight curling is observed, but there is no practical problem ×: Clearly curled and practically problematic level (3) Contamination prevention surface of test piece Is stained with magic ink (Magic Ink Blue No500, manufactured by Uchida Yoko) in a circular shape with a diameter of 2 cm, left for 2 hours, and then wiped off with a cloth soaked in ethanol. The color residue on the surface of the test piece at this time was visually evaluated.
○: Contamination can be removed almost completely. Δ: Color residue can be seen. ×: Contamination can hardly be removed. (4) Antibacterial properties Based on the antibacterial evaluation film adhesion method specified in JIS Z 2801, a test bacterial solution ( Escherichia coli) was dropped and adhered to the entire surface of the test piece with a film. After storage for 24 hours at a temperature of 35 ° C. and a relative humidity of 90% or more, the difference in increase / decrease in the number of viable bacteria was measured and evaluated in the next evaluation stage.
◎: A large antibacterial effect is obtained with an increase / decrease value difference of 2 or more in antibacterial evaluation (film adhesion method) ○: An antibacterial effect with an increase / decrease value difference of 0.1 or more and less than 2.0 in antibacterial evaluation (film adhesion method) Slightly inferior Δ: Can withstand use, but has almost no antibacterial effect ×: No antibacterial effect at all, and withstands use (5) Anti-scattering property A method (impact destruction test) defined in JIS A 5759 The test was conducted based on the B method (interlaminar displacement fracture test). In Method A, an impact fracture test was conducted at a drop height of 30 cm, and the total weight of 10 large pieces was 0.78 N or less, and the mass of one dropped piece was 0.54 N or less as a pass. It was judged. In the method B, a glass scattering prevention rate A of 95% or more was judged as acceptable. Those that passed both of these tests were evaluated as ○, those that passed only one as Δ, and those that failed both as ×.
(6) Scratch resistance A pencil hardness test was carried out under a load of 1.96 N based on JIS K 5400, and the evaluation was performed in the next evaluation stage.
○: 3B or more Δ: Less than 3B 6B or more ×: Less than 6B

Examples 1-6 and Comparative Examples 1-4
Each component of the type and amount for the upper film shown in Table 1 is kneaded with a Banbury mixer, and a roll temperature of roll No. 1 to 4 is set to 180 to 195 using an inverted L-type calender machine having a calendar roll diameter of 8 inches. An upper film having a thickness shown in Table 1 was formed at a temperature of ° C.
Next, the biaxially stretched PET film having the thickness shown in Table 1 and the above upper film are brought into close contact with a heating drum of a doubling apparatus [Kawakami Iron Works Co., Ltd.] and embossed on the upper ground by an embossing roll. And laminated by thermal lamination to produce a laminated film that was embossed. The arithmetic average roughness Ra of the embossed surface of each film was in the range of 0.2 to 2.4 μm.
In Example 3 and Comparative Examples 2 to 4, a topcoat layer having a thickness of 3 μm was formed on the upper surface of the upper film in the laminated film using a urethane coating agent. In Examples 4 and 5, a silicone coating agent containing 0.3% by weight of a silver-based antibacterial agent and a zinc-based antibacterial agent at a ratio of 0.3% by weight based on the total solid content was used. A coat layer was formed.
An acrylic pressure-sensitive adhesive layer having a thickness of 30 μm formed on the release paper was bonded to the back surface of each laminated film to form a glass decorative film. The evaluation results of each glass decorative film are shown in Table 1.

  The decorative film for glass of the present invention has excellent anti-scattering properties when glass is broken, has good design and appearance, and curling is suppressed, and is suitably used as an anti-scattering film for glass. .

It is typical sectional drawing of one example of the decorative film for glass of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Biaxially-stretched polyethylene terephthalate film 2 Printing layer 3 Soft polyester film 4 Topcoat layer 5 Adhesive layer 10 Decorative film for glass

Claims (9)

In the laminated film of the upper base and the base are stacked, the upper base is, (A) (a-1 ) a portion of the ethylene glycol units of a polyethylene terephthalate having a glass transition temperature of -10 to 40 ° C. In other glycol units The substituted modified polyethylene terephthalate resin and (a-2) an amorphous polyethylene terephthalate resin having a glass transition temperature of 50 to 120 ° C. in a weight ratio of 20:80 to 80:20, and (a-3) A resin component containing 1 to 40% by weight of a methacrylic acid ester / acrylic acid ester rubber graft copolymer and (B) 0.2 to 10 parts by weight of a wax per 100 parts by weight thereof, and an embossing treatment on the upper surface A decorative film for glass, characterized in that the film is a biaxially stretched polyethylene terephthalate film. Rum.   (a-2) An amorphous polyethylene terephthalate resin having a glass transition temperature of 50 to 120 ° C., wherein the dicarboxylic acid component is terephthalic acid, the glycol component is ethylene glycol 40 to 80 mol%, and 1,4-cyclohexanedimethanol 60 The decorative film for glass according to claim 1, which is a combination with ˜20 mol%.   The decorative film for glass according to claim 1 or 2, wherein a top coat layer is provided on an embossed surface of the upper surface.   The decorative film for glass according to claim 3, wherein the topcoat layer is a layer formed using a silicone-based topcoat agent.   The decorative film for glass according to claim 3 or 4, wherein the top coat layer contains an antibacterial agent.   The decorative film for glass according to claim 5, wherein the antibacterial agent is a zinc-based antibacterial agent.   The decorative film for glass according to any one of claims 1 to 6, wherein a printed layer is provided on the upper surface of the base biaxially stretched polyethylene terephthalate film.   The decorative film for glass according to any one of claims 1 to 7, further comprising an adhesive layer on the back surface. The decorative film for glass according to claim 8, wherein the pressure-sensitive adhesive layer contains a colorant.

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