JP2017105003A - Scattering prevention film and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a scattering prevention film which can prevent a small flying object from passing through a glass substrate even when the small flying object has collided with the glass substrate, can prevent scattering of a broken piece of the broken glass, and can suppress occurrence of rainbow unevenness.SOLUTION: In a scattering prevention film which has a transparent resin substrate, a protective layer arranged on one surface of the transparent resin substrate through an easily adhesive layer, and an adhesive layer arranged on the other surface of the transparent resin substrate, a thickness of the transparent resin substrate is 100 μm or more, a thickness ratio between the transparent resin substrate and the adhesive layer is in a range of 100:10 or more and 100:40 or less, only one layer of the transparent resin substrate is contained in the scattering prevention film, and the layer number of the easily adhesive layers is one layer or two layers.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an anti-scattering film for preventing broken glass fragments from scattering.

  Conventionally, glass substrates used as window materials for buildings, automobiles and the like are required to have anti-scattering properties that can prevent glass fragments from scattering when the glass substrate is broken. . As a method for imparting scattering prevention to a glass substrate, for example, a method of bonding a resin film having scattering prevention (hereinafter referred to as a scattering prevention film) to the surface of a glass substrate has been proposed.

  For example, Patent Document 1 proposes an anti-scattering film that is laminated in at least two layers in the thickness direction and has a tear strength, Young's modulus, and the like defined to predetermined values. Patent Document 2 proposes a scattering prevention film in which the peeling force of an adhesive layer disposed between two substrates is defined to a predetermined value.

JP-A-10-76620 JP 2014-26247 A

  By the way, in the case of the window material of a motor vehicle, there is a problem that small and hard flying objects such as pebbles (hereinafter also referred to as “small flying objects”) collide with each other during traveling, and the glass substrate is destroyed. Therefore, in the case of window materials for automobiles, even if a small flying object collides with the glass substrate, the small flying object can be suppressed from penetrating the glass substrate, and the broken glass It is desirable to use an anti-scattering film that can prevent the fragments from scattering. However, as in Patent Documents 1 and 2 described above, the conventionally proposed scattering prevention film is not assumed to be used for automobile window materials, and the scattering prevention property is not sufficient.

  In addition, as a method for suppressing small flying objects from penetrating the glass substrate and improving the scattering prevention property of the scattering prevention film, for example, in order to improve the mechanical strength of the scattering prevention film, a scattering prevention film is used. Examples thereof include a method of forming a multilayer structure and a method of disposing a protective layer on the surface of the scattering prevention film. In disposing the protective layer on the surface of the anti-scattering film, an easy adhesion layer is usually provided from the viewpoint of ensuring adhesion between the resin film constituting the anti-scattering film and the protective layer.

  Therefore, the inventors of the present invention have attempted to create a scattering prevention film that can exhibit sufficient scattering prevention properties even when used in a window material of an automobile, by using the method as described above. As a result, although the anti-scattering film having the desired anti-scattering property was obtained, a rainbow unevenness occurred, and a problem was found that the visibility when the anti-scattering film was used for a window material was reduced. did. Such a problem becomes conspicuous when the anti-scattering film is used for a glass substrate with low light transmittance, so-called smoked glass, or when it is used for a bent glass substrate.

  The present invention has been made in view of the above problems, and even when a small flying object collides with a glass substrate, the small flying object can be suppressed from penetrating the glass substrate, and can be destroyed. The main object of the present invention is to provide a scattering prevention film capable of suppressing the scattering of broken glass pieces and capable of suppressing the occurrence of rainbow unevenness.

  In order to solve the above problems, the present invention provides a transparent resin substrate, a protective layer disposed on one surface of the transparent resin substrate via an easy-adhesion layer, and the other of the transparent resin substrate. The thickness of the transparent resin substrate is 100 μm or more, and the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less. A scattering prevention film, wherein the transparent resin base material contained in the scattering prevention film is only one layer, and the number of the easy-adhesion layers is one or two. Providing a prevention film.

  According to the present invention, the thickness of the transparent resin substrate is 100 μm or more, and the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less. Even when a small flying object collides with the glass substrate when bonded to the glass substrate, the small flying object can be prevented from penetrating the glass substrate, and the broken glass substrate It is possible to prevent the fragments from scattering. In addition, since the transparent resin base material included in the anti-scattering film is only one layer and the number of easy-adhesion layers is one or two, anti-scattering that can suppress the occurrence of rainbow unevenness It can be a film.

  In this invention, it is preferable that the optical film thickness of the said easily bonding layer exists in the range of 95 nm or more and 195 nm or less. When the optical film thickness of the easy-adhesion layer is within a predetermined range, it is possible to more effectively suppress the occurrence of rainbow unevenness.

  The present invention is also a glass substrate and a laminate in which a scattering prevention film is laminated on one surface of the glass substrate, the scattering prevention film comprising a transparent resin substrate and the transparent resin substrate. Having a protective layer disposed on one surface of the adhesive layer and an adhesive layer disposed on the other surface of the transparent resin substrate, and the thickness of the transparent resin substrate is 100 μm or more. Yes, the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less, and the transparent resin substrate contained in the scattering prevention film is only one layer, and Provided is a laminate in which the number of the easy-adhesion layers is one or two.

  According to the present invention, the thickness of the transparent resin substrate is 100 μm or more, and the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less. Even when a small flying object collides, the small flying object can be prevented from penetrating the glass substrate, and a broken piece of broken glass can be prevented from scattering. Moreover, the transparent resin base material contained in a scattering prevention film is only one layer, and the laminated body which can suppress generation | occurrence | production of a rainbow nonuniformity because the number of layers of an easily bonding layer is one layer or two layers It can be.

  In this invention, while having the outstanding scattering prevention property, there exists an effect that the scattering prevention film which can suppress generation | occurrence | production of a rainbow nonuniformity can be provided.

It is a schematic sectional drawing which shows an example of the scattering prevention film of this invention. It is a schematic sectional drawing which shows the other example of the scattering prevention film of this invention. It is a schematic sectional drawing which shows an example of the laminated body of this invention. It is a schematic sectional drawing which shows an example of the scattering prevention film of the comparative example 2. It is a schematic diagram which shows an example of the falling ball test machine used for a falling ball test.

  Hereinafter, the scattering prevention film and laminated body of this invention are demonstrated in detail.

A. Anti-scattering film The anti-scattering film of the present invention comprises a transparent resin substrate, a protective layer disposed on one surface of the transparent resin substrate via an easy adhesion layer, and the other surface of the transparent resin substrate. The thickness of the transparent resin substrate is 100 μm or more, and the thickness ratio of the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less. A scattering prevention film, wherein the transparent resin base material included in the scattering prevention film has only one layer, and the number of the easy-adhesion layers is one or two. is there.

The scattering prevention film of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of the anti-scattering film of the present invention. As illustrated in FIG. 1, the anti-scattering film 10 of the present invention includes a transparent resin base material 1, a protective layer 3 disposed on one surface of the transparent resin base material 1 via an easy adhesion layer 2, And an adhesive layer 4 disposed on the other surface of the transparent resin substrate 1. In the present invention, the thickness _{T 1} of the transparent resin substrate 1 is 100μm or more, the thickness ratio of the transparent resin substrate 1 and the adhesive layer 4 _(T 1: T ₂₎ is 100: 10 to 100: 40 Within the following range. Furthermore, in this invention, the transparent resin base material 1 contained in the scattering prevention film 10 is only 1 layer, and the number of layers of the easily bonding layer 2 is 1 layer or 2 layers, It is characterized by the above-mentioned.

According to the present invention, the thickness of the transparent resin substrate is 100 μm or more, and the mechanical strength of the anti-scattering film can be improved by having the protective layer on the surface. Therefore, when the anti-scattering film of the present invention is bonded to a glass substrate used as a window material for automobiles or the like, even if the small flying object collides with the glass substrate, the small flying object is a glass substrate. It is possible to suppress penetration of the material. That is, penetration resistance can be obtained.
Moreover, according to the present invention, when the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less, the scattering prevention film of the present invention is used as a window material for automobiles or the like. When it bonds to the glass base material used, it can suppress that the fragment of the broken glass base material scatters, and can obtain scattering prevention property.
Furthermore, according to this invention, the said transparent resin base material contained in a scattering prevention film is only 1 layer, and an easily bonding layer is 1 layer or 2 layers, By the upper layer or lower layer of an easily bonding layer, Since reflection of light at the boundary surface can be suppressed to the minimum, the occurrence of rainbow unevenness due to the reflection light strengthening interference can be suppressed.

  Hereinafter, each structure in the scattering prevention film of this invention is demonstrated.

1. Easy adhesion layer The easy adhesion layer in this invention is arrange | positioned at one surface of the transparent resin base material contained only in one layer in a scattering prevention film, and the number of layers is 1 layer or 2 layers, It is characterized by the above-mentioned.

  In this invention, the number of layers of the easily bonding layer provided in a scattering prevention film is 1 layer or 2 layers. When the number of layers of the easy adhesion layer is one, for example, as shown in FIG. 1, the easy adhesion layer 2 is disposed between the transparent resin substrate 1 and the protective layer 3. On the other hand, when the number of easy-adhesion layers is two, for example, as shown in FIG. 2, the first easy-adhesion layer 2a is disposed between the transparent resin substrate 1 and the protective layer 3, and the transparent resin A second easy-adhesion layer 2 b is disposed between the base material 1 and the pressure-sensitive adhesive layer 4. Thus, the number of layers of the easy-adhesion layer provided on the anti-scattering film is one layer or two, so that the easy-adhesion layer and the easy-adhesion layer are compared with the anti-scattering film having a plurality of easy-adhesion layers. It is possible to suppress the occurrence of rainbow unevenness due to the difference in refractive index with other layers in contact with the surface, and the occurrence of rainbow unevenness due to variations in the thickness of the easily adhesive layer.

  The easily adhesive layer in the present invention preferably has an optical film thickness within a predetermined range. By setting the optical film thickness of the easy-adhesion layer within a predetermined range, it is possible to more effectively suppress the occurrence of rainbow unevenness when the scattering prevention film of the present invention is used for a window material. The reason for this is as follows. That is, first, the optical film thickness (nd) is a product of the refractive index (n) and the physical film thickness (d). Therefore, by adjusting the optical film thickness of the easy-adhesion layer within a predetermined range, when light enters the easy-adhesion layer, the boundary surface with the upper layer of the easy-adhesion layer and the boundary with the lower layer of the easy-adhesion layer It can be designed such that the light reflected from the surface causes a phase shift. Then, destructive interference occurs between the light reflected at the interface with the upper layer of the easy-adhesion layer and the light reflected at the interface with the lower layer of the easy-adhesion layer, before being emitted from the anti-scattering film. It becomes possible to cancel each other. Accordingly, it is possible to more effectively suppress the occurrence of rainbow unevenness.

The optical film thickness of such an easy adhesion layer preferably satisfies, for example, 1 / 4λ. Here, “λ” preferably represents a wavelength region centered on a wavelength of 580 nm. The wavelength region centered on the wavelength of 580 nm corresponds to, for example, a visible light region within a wavelength range of 580 nm ± 200 nm, that is, a wavelength range of 380 nm to 780 nm. Therefore, the optical film thickness of the easy adhesion layer in the present invention is, for example, 380 nm / 4 or more and 780 nm / 4 or less, that is, 95 nm or more and 195 nm or less. The occurrence of rainbow unevenness can be effectively suppressed. Among them, the optical film thickness of the easy-adhesion layer in the present invention is preferably such that the wavelength in the visible light region is more in the range centered on the wavelength 580 nm, for example, the wavelength 580 nm ± 120 nm of 460 nm to 700 nm. Based on the range, it is preferably 460 nm / 4 or more and 700 nm / 4 or less, that is, 115 nm or more and 175 nm or less. Particularly, based on the range of 510 nm or more and 650 nm or less, which is the wavelength of 580 ± 70 nm, 510 nm / 4 or more and 650 nm / 4 or less, that is, 128 nm or more and 163 nm or less is preferable.
In addition, the optical film thickness of the easily bonding layer in this invention can be adjusted by changing the thickness of an easily bonding layer, for example.

  Although the physical film thickness of the easily bonding layer in this invention should just be a grade which can fully adhere | attach the member used as the upper layer and lower layer of an easily bonding layer, it is not specifically limited. In the present invention, a physical film thickness that satisfies the optical film thickness described above is preferable, and can be adjusted as appropriate according to the refractive index of the easy-adhesion layer described above. Specifically, it is preferably in the range of 10 nm to 300 nm, more preferably in the range of 25 nm to 200 nm, and particularly preferably in the range of 50 nm to 150 nm.

Moreover, it is preferable that the easily bonding layer in this invention has a refractive index in a predetermined range. The refractive index of the easy adhesion layer is mainly determined according to the material and physical film thickness of the easy adhesion layer. In the present invention, from the viewpoint of suppressing the reflection of light at the interface with the upper layer of the easy-adhesion layer or the interface with the lower layer, it is appropriately adjusted according to the refractive index of the member that is the upper layer or the lower layer of the easy-adhesion layer. It is preferable to do. For example, when the anti-scattering film of the present invention is laminated in the order of a transparent resin substrate, an easy adhesion layer, and a protective layer, the refractive index of the easy adhesion layer is the refractive index of the transparent resin substrate and the refractive index of the protective layer. It is preferable that the refractive index of each member increases or decreases stepwise depending on the stacking order. Moreover, it is preferable that the difference with the refractive index of the member used as the upper layer or lower layer of an easily bonding layer is small, and as a specific refractive index difference, it is preferable that it is 0.15 or less, and it is 0.10 or less especially. In particular, 0.08 or less. The refractive index of such an easily adhesive layer is preferably 1.50 or more and 1.65 or less, and more preferably 1.51 or more and 1.63 or less. Reflection of light at the boundary surface with the upper layer of the easy-adhesion layer or the boundary surface with the lower layer can be suppressed, and the occurrence of rainbow unevenness can be effectively suppressed.
In addition, the refractive index of an easily bonding layer should be measured using a multi-wavelength Abbe refractometer (manufactured by Atago Co., Ltd.) or an optical non-contact film thickness measuring device (manufactured by Filmetrics) of reflectance spectroscopy. Can do.

  The easy-adhesion layer in the present invention preferably contains a resin material as a main component. For example, the resin material is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more with respect to 100% by mass of the total solid content of the easy adhesion layer. It is preferable to contain 80% by mass or more. Moreover, in this invention, it is preferable to contain 99 mass% or less of resin materials with respect to 100 mass% of solid content total amount of an easily bonding layer, it is preferable to contain 98 mass% or less especially, and 95 mass% or less is included especially. Is preferred. When the easy-adhesion layer contains a resin material as a main component, a desired adhesive force can be exhibited.

  Examples of the resin material contained in the easy-adhesion layer include polyester resins, acrylic resins, and urethane resins, among which polyester resins are preferable, and polyester resins having a naphthalene ring in the molecule are particularly preferable.

Moreover, it is preferable that the easily bonding layer in this invention contains a crosslinking agent as needed from a viewpoint of providing an easily bonding function other than the resin material mentioned above. Examples of the crosslinking agent include a melanin crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and an epoxy crosslinking agent. Especially, it is preferable that a melanin crosslinking agent, an oxazoline crosslinking agent, and a carbodiimide crosslinking agent are included.
When the easy-adhesion layer contains a crosslinking agent, the content of the crosslinking agent is, for example, in the range of 1% by mass to 40% by mass with respect to 100% by mass of the total solid content of the easy-adhesion layer. Preferably, it is preferably in the range of 3% by mass to 35% by mass, particularly preferably in the range of 5% by mass to 30% by mass.

Furthermore, it is preferable that the easily bonding layer in this invention contains an organic or inorganic particle | grain from a viewpoint of improving slipperiness and blocking resistance other than the resin material mentioned above. Such particles are not particularly limited. For example, inorganic particles include colloidal silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, carbon black, zeolite particles and the like, and organic particles include acrylic particles. , Silicone particles, polyimide particles, Teflon (registered trademark) particles, crosslinked polyester particles, crosslinked polystyrene particles, crosslinked polymer particles, and core-shell particles. In the present invention, it is preferable to include colloidal silica.
When the easy-adhesion layer contains particles, the content of the particles is, for example, in the range of 0.05% by mass or more and 8% by mass or less with respect to 100% by mass of the total solid content of the easy-adhesion layer. Among them, it is preferable that the content be in the range of 0.1% by mass to 5% by mass.

The method for forming an easy-adhesion layer in the present invention is not particularly limited as long as it is a method capable of forming a desired easy-adhesion layer. For example, an easy-adhesion layer is formed on a transparent resin substrate using a wet coating method. Is preferably formed. Examples of the wet coating method include coating methods such as a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, a spin coating method, and an extrusion coating method.
In the present invention, it is particularly preferable that the easy-adhesion layer is formed by a so-called in-line coating method in which the transparent resin base material is produced.
Furthermore, when applying the easy-adhesion layer composition constituting the easy-adhesion layer on the transparent resin base material, from the viewpoint of improving the applicability and adhesion, a corona discharge treatment, flame is applied to the surface of the transparent resin base material. Pretreatment such as treatment or plasma treatment is preferably performed.

2. Protective layer The protective layer in this invention is a member arrange | positioned through the easily bonding layer in one surface of a transparent resin base material.

  The protective layer in the present invention can suppress the sticking of the transparent resin base material by glass fragments when the anti-scattering film of the present invention is bonded to a glass base material, and can withstand the impact of small flying objects that collide. The penetrability can be further improved. That is, it becomes possible to improve the scattering prevention property as a scattering prevention film.

  The protective layer in the present invention preferably has a refractive index within a predetermined range. Specifically, as described in the above-mentioned section “1. Easy-adhesion layer”, for example, the refractive index of the protective layer is preferably in the range of 1.40 to 1.60, Especially, it is preferable that it exists in the range of 1.42 or more and 1.57 or less.

  As a material used for the protective layer in the present invention, a material used for a general protective layer can be used. Examples thereof include ionizing radiation curable resins that are cured by ionizing radiation. Here, “ionizing radiation” means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually an ultraviolet ray or an electron beam is used. Electromagnetic waves such as γ rays, and charged particle beams such as α rays and ion rays can also be used.

  Examples of the ionizing radiation curable resin include acrylate resins, oxetane resins, silicone resins, and the like. In the present invention, in addition to the ionizing radiation curable resin, other materials may be added as necessary. As other materials, for example, a silicone compound or a fluorine compound may be added to improve the stain resistance, and an electron conduction type such as PEDOT-PSS, lithium, etc. An ion conductive type antistatic agent such as a salt-based material may be added. Furthermore, a fluorine-based compound or the like may be added to improve water repellency.

As the thickness of the protective layer in the present invention, by having the protective layer, when the anti-scattering film of the present invention is bonded to a glass substrate, it is more effective to pierce the transparent resin substrate with glass fragments. It is preferable that the thickness be such that the effect of further improving the penetration resistance of the colliding small flying object can be obtained. Specifically, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 15 μm or less, and particularly preferably 2 μm or more and 10 μm or less.
In addition, the thickness of a protective layer can be measured by observing a cross section, for example using a scanning electron microscope (SEM).

  The protective layer in the present invention preferably has a predetermined surface hardness. Specifically, it is preferably higher than the surface hardness of the transparent resin substrate described above, for example, the pencil hardness of JIS K5600-5-4 (1999) on the surface of the protective layer is preferably F or more, Above all, it is preferably H or more.

As a method for forming a protective layer in the present invention, any method can be used as long as it can form a protective layer on the surface of a transparent resin substrate, and a general method for forming a protective layer can be used. For example, the method of apply | coating and hardening the protective layer composition which a protective layer comprises on a transparent resin base material is mentioned.
Examples of the method for applying the protective layer composition include spin coating, dipping, spraying, die coating, bar coating, roll coater, meniscus coater, flexographic printing, screen printing, and pea coater. There are known methods.
Moreover, as a method of hardening a protective layer composition, the method of irradiating ionizing radiation is mentioned, for example. Examples of the light source used at this time include an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp.

3. Adhesive layer The adhesive layer in this invention is a member arrange | positioned on the surface on the opposite side to the side by which the protective layer of the transparent resin base material was arrange | positioned. The thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less.

  In the present invention, when the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less, the anti-scattering film of the present invention is bonded to a glass substrate. When this occurs, the glass fragments are wrapped in the adhesive layer, and good anti-scattering properties can be exhibited. Moreover, the puncture of the transparent resin base material by a glass piece can be suppressed, and the penetration resistance of the small flying object which collided can be improved. Furthermore, it becomes possible to ensure the flatness of the scattering prevention film. In the present invention, the thickness ratio between the transparent resin substrate and the adhesive layer is preferably in the range of 100: 10 or more and 100: 35 or less, particularly in the range of 100: 10 or more and 100: 30 or less. Preferably there is.

The thickness of such an adhesive layer is preferably 25 μm or more, for example, preferably 30 μm or more, and particularly preferably 35 μm or more. The thickness of the pressure-sensitive adhesive layer in the present invention is preferably 100 μm or less, for example, preferably 95 μm or less, and particularly preferably 90 μm or less.
In addition, the thickness of the adhesion layer can be measured by, for example, observing a cross section using a scanning electron microscope (SEM).

  It is preferable that the adhesive layer in this invention has adhesiveness of the grade which can maintain predetermined | prescribed adhesive strength between the glass base material used as window materials, such as a motor vehicle, and a transparent resin base material. Here, the predetermined adhesive strength is, for example, that the peel strength of the adhesive layer with respect to the glass substrate by the 180 degree peel test specified in JIS K6854-2 is preferably 10 N / 25 mm width or more, and in particular, 15 N / The width is preferably 25 mm or more, and particularly preferably 20 N / 25 mm width or more. Moreover, in this invention, it is preferable that the peeling strength of the adhesion layer is 50 N / 25mm width or less, for example, it is preferable that it is 45 N / 25mm width or less especially, and it is 40 N / 25mm width or less especially. Is preferred. When the adhesive strength of the adhesive layer is within the above range, it is possible to wrap more glass fragments that are damaged by the collision of small flying objects. Therefore, the piercing of the transparent resin base material by the glass fragments can be suppressed, and the penetration resistance of the colliding small flying object can be further improved.

  Examples of the material for the pressure-sensitive adhesive layer in the present invention include structural units derived from methacrylic acid esters, and acrylic resins derived from acrylic acid esters and / or other unsaturated monomers as necessary. Here, examples of the methacrylic acid ester include alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and pentyl methacrylate. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and pentyl acrylate.

  The pressure-sensitive adhesive layer in the present invention may have other materials as necessary in addition to the above-described materials. Other materials include, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slip properties, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, For the purpose of improving and modifying others, for example, lubricants, plasticizers, fillers, fillers, antistatic agents, antiblocking agents, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, dyes, pigments, etc. It may contain a coloring agent.

  The method for forming the pressure-sensitive adhesive layer in the present invention may be any method that can be formed on a transparent resin substrate, which will be described later, and can be the same as a general method for forming a pressure-sensitive adhesive layer. For example, the method of apply | coating and drying the adhesion layer composition which comprises an adhesion layer on a transparent resin base material is mentioned. Examples of coating methods used at this time include roll coating, reverse roll coating, transfer roll coating, gravure coating, gravure reverse coating, comma coating, rod coating, blade coating, bar coating, wire bar coating, die coating, and lip coating. And dip coat.

4). Transparent resin base material The transparent resin base material in this invention is a member which supports the easily bonding layer mentioned above, a protective layer, and the adhesion layer, and is a member characterized by the thickness being 100 micrometers or more. Further, the thickness ratio of the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less, and only one layer is included in the scattering prevention film.

  In the present invention, the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less. In addition, about the said thickness ratio, since it can be made to be the same as that of the content described in the item of "3. Adhesion layer" mentioned above, description here is abbreviate | omitted.

The thickness of the transparent resin substrate in the present invention is not particularly limited as long as it is 100 μm or more, but among them, it is preferably 125 μm or more, and particularly preferably 150 μm or more. Moreover, the thickness of the transparent resin base material in this invention can be 400 micrometers or less. When the thickness of the transparent resin base material is within the above range, when the anti-scattering film of the present invention is bonded to a glass base material, the piercing of the transparent resin base material by glass fragments can be suppressed. Further, the penetration resistance of the colliding small flying object can be further improved. That is, it is possible to sufficiently exhibit the characteristics as a scattering prevention film.
In addition, the thickness of a transparent resin base material can be measured by observing a cross section, for example using a scanning electron microscope (SEM).

The transparent resin substrate in the present invention preferably has a predetermined rigidity. For example, the Young's modulus of the transparent resin base material is preferably, for example, 1000 MPa or more and 7000 MPa or less, more preferably 1200 MPa or more and 6500 MPa or less, and particularly preferably 1400 MPa or more and 6000 MPa or less. When the Young's modulus of the transparent resin substrate is within the above range, the function as the anti-scattering film of the present invention can be sufficiently exerted, and the penetration resistance can be further improved.
The Young's modulus of the transparent resin base material can be measured using an SV-200 type tensile / compression tester manufactured by Imada Seisakusho in accordance with JIS-K-6301.

  The material used for the transparent resin substrate of the present invention is preferably a resin material having transparency. Here, “transparent” means that it is transparent to the extent that visual recognition from the inside of the vehicle is not hindered when the anti-scattering film of the present invention is used for an automobile curved glass unless otherwise specified. Therefore, “transparent” includes colorless and transparent, and colored transparency to the extent that visibility is not hindered. Strictly, it is not defined by transmittance, and depends on the transparency of the curved automobile glass using the anti-scattering film of the present invention. Can be adjusted accordingly.

  Examples of the material used for the transparent resin substrate in the present invention include cellulose (fiber) resins such as triacetyl cellulose (TAC), acrylic resins such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), and the like. A polyester resin, a polyolefin resin such as polypropylene (PP), a vinyl resin such as polyvinyl chloride (PVC), and a transparent resin film such as polycarbonate (PC) can be applied.

5). Others The anti-scattering film of the present invention usually has a separator film bonded on the surface of the adhesive layer opposite to the side in contact with the transparent resin substrate in the storage state before being bonded to a glass substrate. Has been. The separator film is a member for protecting the adhesive surface of the adhesive layer, and is peeled off when the adhesive surface is bonded to the glass substrate. In addition, since the separator film used in this invention can be made to be the same as that used for a general adhesion layer, description here is abbreviate | omitted.

B. Laminate The laminate of the present invention is a laminate in which a scattering prevention film is laminated on one surface of a glass substrate and the glass substrate, and the scattering prevention film comprises a transparent resin substrate and the transparent It has a protective layer disposed on one surface of the resin substrate via an easy-adhesion layer and an adhesive layer disposed on the other surface of the transparent resin substrate, and the thickness of the transparent resin substrate is 100 μm or more, the thickness ratio of the transparent resin substrate to the adhesive layer is in the range of 100: 10 or more and 100: 40 or less, and the transparent resin substrate contained in the scattering prevention film is only one layer. And the number of layers of the easy-adhesion layer is one or two.
Hereinafter, the laminate of the present invention will be described with reference to the drawings.

FIG. 3 is a schematic cross-sectional view showing an example of the laminate of the present invention. As shown in FIG. 3, the laminate 100 of the present invention has a structure in which a glass substrate 5 and a scattering prevention film 10 are laminated on one surface of the glass substrate 5. Moreover, the scattering prevention film 10 in this invention is the transparent resin base material 1, the protective layer 3 arrange | positioned through the easily bonding layer 2 on one surface of the transparent resin base material 1, and the transparent resin base material 1 And an adhesive layer 4 disposed on the other surface. In the present invention, the thickness _{T 1} of the transparent resin substrate 1 is 100μm or more, the thickness ratio of the transparent resin substrate 1 and the adhesive layer 4 _(T 1: T ₂₎ is 100: 10 to 100: 40 It is as follows. Furthermore, in this invention, the transparent resin base material 1 contained in the scattering prevention film 10 is only 1 layer, and the number of layers of the easily bonding layer 2 is 1 layer or 2 layers, It is characterized by the above-mentioned.

According to the present invention, the thickness of the transparent resin substrate is 100 μm or more, and the thickness ratio between the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less. Even when a small flying object collides, the small flying object can be prevented from penetrating the glass substrate, and the broken glass fragments can be prevented from scattering. Moreover, the transparent resin base material contained in a scattering prevention film is only one layer, and the laminated body which can suppress generation | occurrence | production of a rainbow nonuniformity because the number of layers of an easily bonding layer is one layer or two layers. It can be.
In addition, about a specific reason, since it can be made to be the same as that of the content described in the term of the above-mentioned "A. scattering prevention film", description here is abbreviate | omitted.

  The laminate of the present invention will be described separately for the scattering prevention film and the glass substrate.

1. Anti-scattering film The anti-scattering film in the present invention is disposed on the transparent resin base material, the protective resin layer disposed on one surface of the transparent resin base material via the easy adhesion layer, and the other surface of the transparent resin base material. The thickness of the transparent resin substrate is 100 μm or more, and the thickness ratio between the transparent resin substrate and the adhesion layer is in the range of 100: 10 or more and 100: 40 or less. The transparent resin substrate contained in is a member having only one layer, and the number of easy adhesion layers is one or two.

  In addition, since description about the scattering prevention film in this invention can be made to be the same as that of the content described in the term of the above-mentioned "A. scattering prevention film", description here is abbreviate | omitted.

2. Glass substrate The glass substrate in the present invention is not particularly limited as long as at least a scattering prevention film can be laminated. In this invention, it is preferable that it is a glass base material used as a window material of a motor vehicle from the point that it has the outstanding scattering prevention property.

Moreover, it is preferable that the glass base material in this invention is what is called smoked glass which suppressed light transmittance. When smoked glass is used, there is a problem that rainbow unevenness is easily seen as compared with the case of using a normal glass substrate having optical transparency. Therefore, when smoked glass is used, the effect of suppressing the occurrence of rainbow unevenness can be made more remarkable by using the anti-scattering film of the present invention.
When the glass substrate is smoked glass, the light transmittance of the glass substrate is preferably, for example, a total light transmittance of 50% or less, more preferably 40% or less, especially 30% or less. It is preferable that

  Furthermore, it is preferable that the glass substrate in the present invention has a bent surface that contacts the anti-scattering film, and it is particularly preferable that the glass substrate bend three-dimensionally. When using a glass substrate having flexibility, there is a problem that rainbow unevenness is easily seen as compared with the case of using a glass substrate having flatness. Therefore, when the glass base material which has flexibility is used, the effect that generation | occurrence | production of a rainbow nonuniformity can be suppressed can be made more remarkable by using the scattering prevention film in this invention. Specifically, for example, an automobile sunroof, a side window, a rear window, or the like is preferable, and an automobile sunroof is particularly preferable.

  The material of the glass substrate in the present invention can be appropriately selected depending on the application. For example, when the glass substrate is a sunroof or the like of an automobile, a material used as a general automobile window material is used. Can be mentioned. In addition, description about the specific material of a glass base material is abbreviate | omitted.

  Moreover, the thickness of the glass base material in this invention can be suitably adjusted according to the use etc. of the glass base material of this invention, and is not specifically limited. For example, when a glass substrate is used as a window material for an automobile, the thickness can be the same as that of a general automobile window material, and thus description thereof is omitted here.

3. Manufacturing method As a method of manufacturing the laminated body of this invention, the method of bonding a scattering prevention film to one surface of a glass base material is mentioned, for example. In addition, about the manufacturing method of a scattering prevention film, since it can be made to be the same as that of the content described in the term of the said "A. scattering prevention film", description here is abbreviate | omitted.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

  Hereinafter, the present invention will be specifically described with reference to examples.

[Example 1]
An easy-adhesion layer composition (thickness (physical film thickness): 65 nm) was applied on both surfaces of a transparent resin base material (material: polyethylene terephthalate, thickness: 188 μm, refractive index: 1.65) as shown below. , Refractive index: 1.52).
<Adhesive layer composition A>
The easy-adhesion layer composition A is an aqueous dispersion containing the recording material.
・ Acrylic resin: 100 parts by mass ・ Melamine cross-linking agent (Methylol-type melamine cross-linking agent (Nikarak M W12LF, manufactured by Sanwa Chemical Co., Ltd.)): 5 parts by mass Tex OL) ・ ・ ・ 1 part by mass

Next, on the easy-adhesion layer formed on one surface of the transparent resin substrate, a protective layer composition (material: acrylic ultraviolet curable resin (Seika Beam PET-HC301 manufactured by Dainichi Seika Kogyo Co., Ltd.), solid 50%) was applied using a wire bar coater # 10, dried at 80 ° C. for 5 minutes, and then cured by UV irradiation (450 mJ / cm ² ) to form a protective layer (thickness: 5 μm, refractive) Ratio: 1.50).

Next, an adhesive layer composition (material: acrylic adhesive (manufactured by Nitto Denko Corporation, CS-9821)) is applied by roll lamination on the easy-adhesion layer formed on the other surface of the transparent resin substrate. And dried to form an adhesive layer (thickness: 25 μm).
In this way, for example, a scattering prevention film having a configuration as shown in FIG. 2 was obtained.

[Example 2]
An anti-scattering film was obtained in the same manner as in Example 1 except that the easy adhesion layer composition B shown below was applied to form an easy adhesion layer (thickness: 100 nm, refractive index: 1.58).
<Adhesive layer composition B>
The easy-adhesion layer composition B is an aqueous dispersion containing the recording material.
-Naphthalene ring-containing polyester resin: 100 parts by mass-Melamine cross-linking agent (Methylol-type melamine cross-linking agent (Nikarak M W12LF, manufactured by Sanwa Chemical Co., Ltd.))-5 parts by mass-Colloidal silica (Nissan Chemical Industries ( Snowtex OL) ... 1 part by mass

[Example 3]
A scattering prevention film was obtained in the same manner as in Example 2 except that the thickness of the easy adhesion layer was 120 nm.

[Example 4]
A scattering prevention film was obtained in the same manner as in Example 1 except that the thickness of the transparent resin substrate was 100 μm.

[Example 5]
A commercially available polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., A4300) was used as the film with an easy adhesion layer. The said film with an easily bonding layer has a PET film (thickness: 188 micrometers) and an easily bonding layer (thickness (physical film thickness): 60 nm, refractive index: 1.53) as a transparent resin base material.

Next, a protective layer composition (material: acrylic ultraviolet curable resin (Seika Beam PET-HC301, manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 50%)) on the easy-adhesion layer is wire bar coater # 10. The coating layer was applied, dried at 80 ° C. for 5 minutes, and then cured by UV irradiation (450 mJ / cm ² ) to form a protective layer (thickness: 5 μm, refractive index: 1.50).

Next, an adhesive layer composition (material: acrylic adhesive (manufactured by Nitto Denko Corporation, CS-9821)) is applied by roll lamination on the easy-adhesion layer formed on the other surface of the transparent resin substrate. And dried to form an adhesive layer (thickness: 25 μm).
In this way, for example, a scattering prevention film having a configuration as shown in FIG. 2 was obtained.

[Example 6]
An anti-scattering film was prepared in the same manner as in Example 5 except that U426 (thickness of the easy adhesion layer: 140 nm, refractive index of the easy adhesion layer: 1.63) manufactured by Toray Industries, Inc. was used as the film with the easy adhesion layer. Obtained.

[Comparative Example 1]
An anti-scattering film was prepared in the same manner as in Example 5 except that U34 manufactured by Toray Industries, Inc. (thickness of the easy adhesive layer: 60 nm, refractive index of the easy adhesive layer: 1.56) was used as the film with the easy adhesive layer. Obtained.

[Comparative Example 2]
A film with an easy adhesion layer (U34 manufactured by Toray Industries, Inc.) is laminated on the adhesive layer of the anti-scattering film obtained in Comparative Example 1, and an adhesive layer composition (material: acrylic adhesive (Nitto Denko) Co., Ltd., CS-9821)) was applied by roll lamination and dried to form an adhesive layer (thickness: 25 μm).
Thus, for example, as shown in FIG. 4, the adhesive layers 4a and 4b, the easy adhesion layers 2a to 2d, and the transparent resin substrates 1a and 1b are laminated, and the protective layer is formed on the outermost easy adhesion layer 2a. Thus, an anti-scattering film 10 ′ having a configuration in which 3 is arranged was obtained.

[Evaluation]
(Spattering prevention)
The anti-scattering property was evaluated by performing a falling ball test on the anti-scattering films obtained in Examples 1 to 6 and Comparative Examples 1 and 2.

  FIG. 5 is a schematic diagram showing an example of a falling ball tester used for evaluation of scattering prevention. As shown in FIG. 5, the falling ball tester 200 includes a test body support unit 201 and a steel ball dropping unit 202. The test body support portion 201 is a portion that horizontally holds a test body 203 described later. The steel ball dropping part 202 is a part that holds the steel ball 204 at a predetermined height and drops the steel ball 204 from the position where the steel ball 204 is held toward the test body 203.

  A falling ball tester 200 shown in FIG. 5 is configured as a test apparatus that satisfies the conditions defined in the test item (4) of JIS R3212: 1998. In this test, the scattering prevention films obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were cut into 100 mm × 100 mm squares and attached to tempered glass having a size of 100 mm × 100 mm × 3 mm (thickness). did. It fixed to the test body support part 201 shown in FIG. 5 so that the glass surface of such a test body 203 might face upward. Then, a steel ball 102 having a weight of 227 g and a diameter of about 38 mm was dropped from a height of 3.5 m three times to evaluate whether or not the steel ball 204 penetrates the test body 203. The drop of the steel ball 204 with respect to one test body 203 was limited to once. Therefore, in Examples 1 to 6 and Comparative Examples 1 and 2, three identical specimens 203 were prepared, and the scattering prevention property was evaluated.

The anti-scattering property was evaluated as follows.
○: The steel ball did not penetrate the specimen. ×: The steel ball penetrated the specimen.

(Rainbow unevenness)
The tempered glass in the test body described above was used as a test glass as smoke glass (total light transmittance: 20%) of 100 mm × 100 mm × 3 mm (thickness). With the protective layer side of the test body as the top surface, a three-wavelength daylight white (National Palook, F.L15EX-N15W) is used as the light source, and the position where the reflection is most intense when viewed from obliquely above (distance 40 cm to 60 cm from the light source) Within the range, an angle of 15 ° to 45 ° with respect to the vertical of the film surface was observed and evaluated.
○: Rainbow unevenness did not occur at all angles Δ: Depending on the angle, rainbow unevenness occurred ×: Rainbow unevenness occurred at all angles

DESCRIPTION OF SYMBOLS 1 ... Transparent resin base material 2 ... Easy-adhesion layer 3 ... Protective layer 4 ... Adhesion layer 5 ... Glass base material 10 ... Anti-scattering film 100 ... Laminate

Claims (3)

A transparent resin substrate, a protective layer disposed on one surface of the transparent resin substrate via an easy-adhesion layer, and an adhesive layer disposed on the other surface of the transparent resin substrate;
The thickness of the transparent resin substrate is 100 μm or more,
A scattering prevention film having a thickness ratio between the transparent resin substrate and the adhesive layer in a range of 100: 10 or more and 100: 40 or less,
The said transparent resin base material contained in the said scattering prevention film is only one layer, and the number of layers of the said easily bonding layer is one layer or two layers, The scattering prevention film characterized by the above-mentioned.   The scattering prevention film according to claim 1, wherein an optical film thickness of the easy adhesion layer is in a range of 95 nm to 195 nm. A glass substrate, and a laminate in which a scattering prevention film is laminated on one surface of the glass substrate,
The scattering prevention film includes a transparent resin substrate, a protective layer disposed on one surface of the transparent resin substrate via an easy-adhesion layer, and an adhesive disposed on the other surface of the transparent resin substrate. The thickness of the transparent resin substrate is 100 μm or more, the thickness ratio of the transparent resin substrate and the adhesive layer is in the range of 100: 10 or more and 100: 40 or less, and the scattering prevention The said transparent resin base material contained in a film is only one layer, and the number of layers of the said easily bonding layer is 1 layer or 2 layers, The laminated body characterized by the above-mentioned.