JP4407099B2 - Laminated body - Google Patents

Description

【００４０】
【発明の効果】
上記の評価結果が示すように、積層体において硬質有機樹脂層に対して金属あるいはこれらの化合物を添加することで機能層の耐剥離性、耐摩耗性、耐擦傷性などの機械強度の耐久性を向上させることができ、低コストにて安定した品質の製品を供給することが可能となる。
【００４１】
【図面の簡単な説明】
【図１】本発明の積層体の構成を示す断面図である。
【符号の説明】
１ 支持基材
２ 硬質有機樹脂層
３ 機能層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a laminate that lasts for a long time the mechanical strength performance against peeling, rubbing, scratching, and the like of the functional layer when laminating the functional layer to provide various functions on a support substrate. In particular, the present invention relates to a laminate in which an inorganic compound is laminated as a functional layer using physical vapor deposition (PVD) or chemical vapor deposition (CVD) such as vapor deposition, sputtering, and ion plating.
[0002]
[Prior art]
Conventionally, an antireflection film applied to the surface of a display screen of a display has a hard organic resin layer formed on a plastic film such as polyethylene terephthalate (PET) or triacetyl cellulose (TAC), and is made of a highly refractive material. The reflectance is reduced by forming an inorganic compound such as a certain titanium oxide or silicon oxide which is a low refractive material as a multilayer thin film. In addition, conductive films in which conductive zinc oxide, indium oxide, tin oxide, etc. are laminated on plastic, electromagnetic wave shielding films and antistatic films, and the above transparent and conductive materials to provide both antireflection and conductive functions. Products such as anti-reflective films that have antistatic functions by forming multilayer thin films by using zinc oxide, indium oxide, tin oxide, etc., and gas barrier films laminated with silicon oxide and magnesium oxide It has become. Thus, the laminated body which provided the functional layer according to the intended purpose in various fields is used.
[0003]
Use and commercialize laminates to improve the mechanical strength and how to maintain the mechanical strength for a long time so that the functional layer meeting the purpose in the laminate does not peel off from the support substrate. It is an important point above. In such a laminate, an inorganic compound is laminated directly on the support substrate, or when the support substrate is an organic resin containing plastic, corona treatment, discharge treatment, ultraviolet irradiation treatment, flame treatment, plasma treatment, etc. The functional layer is laminated by surface modification. However, in such a surface modification treatment method, even if the mechanical strength is satisfied, the mechanical strength often does not last long. These causes are said to be caused by, for example, the base material, the organic resin, or the functional layer being denatured due to temperature and temperature change, and ultraviolet rays and visible light, and the functional layer is peeled off. Furthermore, it is recognized that the durability decreases as the number of functional layers or the thickness of the functional layers increases.
[0004]
In such a case, an intermediate layer called a glue layer or a primer layer is formed on the hard organic resin at an arbitrary thickness, and a functional layer is formed thereon to function as a hard organic resin layer. A method for improving the adhesion and light resistance of the layer is generally taken. For example, Japanese Patent Laid-Open No. 2000-86932 discloses that, by forming a water-based inorganic oxide as a primer layer on an organic resin layer, good adhesion and appearance can be obtained both in the initial stage and after the accelerated weathering test. Is disclosed. JP-A-2001-205729 discloses that a film containing a metal oxide as a primer layer is formed on a fluororesin film to develop the characteristics as designed in the functional layer, and long-term durability. It is disclosed that a laminate having excellent adhesion can be obtained. However, the following problems arise in producing such a laminate. First, producing the intermediate layer as described above is accompanied by an increase in the number of steps, resulting in poor production efficiency and consequently cost. Furthermore, since it is necessary to produce an intermediate layer without impairing the appearance of the functional layer and the performance of the functional layer, it must be made very thin. In such a case, it is difficult to confirm whether or not the intermediate layer is adhered during production, and such a thin film thickness is difficult to control.
[0005]
[Problems to be solved by the invention]
The present invention has been made for the purpose of providing a laminate having good production efficiency and capable of maintaining the mechanical strength immediately after production of the functional layer of the laminate for a long time.
[0006]
[Means for Solving the Problems]
The invention of claim 1 comprises a support substrate, a metal or a hard organic resin layer compound is added thereof is provided a laminate at least one layer of the functional layer to the hard organic resin layer are laminated The support base material is a polyethylene terephthalate film, the hard organic resin layer is a cured UV curable acrylic resin, and the functional layer is made of TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ . One layer selected from four layers, one composed of indium oxide, or one composed of four layers of ZnO / SiO ₂ / ZnO / SiO ₂ , wherein the metal is cobalt, chromium, copper, iron The additive ratio of the additive added to the hard organic resin layer is 0.05 to 1 mol in terms of metal based on the ultraviolet curable acrylic resin. % Of the laminate.
[0008]
The invention according to claim 2 is the laminate according to claim 1 , wherein the metal compound is made of a metal oxide.
[0009]
The invention according to claim 3, wherein the metal or compound thereof is a laminate according to claim 1 or 2, characterized in that it consists of colloidal particles.
[0011]
The invention described in claim 4 is the laminate according to any one of claims 1 to 3 , wherein the functional layer has an antireflection function.
[0012]
The invention according to claim 5 is the laminate according to any one of claims 1 to 3 , wherein the functional layer has a transparent conductive function.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an embodiment of the present invention will be described.
As shown in FIG. 1, the present invention is a laminate in which a functional layer (3) is laminated on a support substrate (1) through a hard organic resin layer (2).
The supporting substrate (1) can be selected depending on what function is used for what purpose. For example, glass substrate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), polycarbonate (PC), polyacryl (PMMA), nylon (Ny), polyethersulfone (PES), polyvinyl chloride Plastic films, sheets, and plates such as (PVC), polypropylene (PP), and triacetyl cellulose (TAC) can be used.
[0016]
In the present invention, the hard organic resin layer (2) is provided as an undercoating layer between the supporting substrate (1) and the functional layer (3) in order to sufficiently exhibit the mechanical strength of the functional layer. This hard organic resin layer can be made of a cured resin or thermosetting resin by ionizing radiation or ultraviolet irradiation, and particularly UV curable acrylic esters, acrylamides, methacrylic esters, methacrylamides, etc. Acrylic and organic silicon resins and thermosetting polysiloxane resins are preferred. Further, the film thickness of the machine resin layer is sufficient if it is 3 μm or more, but is preferably in the range of 5 to 7 μm from the viewpoint of transparency, coating accuracy, and ease of handling. As long as these hard organic resin layers are uniformly coated, any coating method may be used.
[0017]
In the present invention, a metal or a compound thereof is added to the hard organic resin layer (2) in order to maintain the mechanical strength immediately after production in the laminate for a long time.
[0018]
Although it does not restrict | limit especially as said metal or those compounds, For example, metals, such as cobalt, chromium, copper, iron, tin, zinc, or those metal compounds can be used.
Examples of the metal compound include oxides, nitrides, oxynitrides, sulfides, and organometallic compounds such as metal alkoxides. The oxides of cobalt, chromium, copper, iron, tin, and zinc are CoO _x (X = 1 to 1.5), CrO _x (X = 1 to 3), CuO _x (X = 0.5 to 1). , FeO _x (X = 1 to 1.5), SnO _x (X = 2 to 4), compounds that can be represented by ZnO (X = 2), and the like.
In addition, one kind or two or more kinds of metals or compounds thereof may be added.
[0019]
Moreover, it is preferable that the metal to add or those compounds are colloidal particles.
The average particle diameter of the colloidal particles for maintaining the mechanical strength of the laminate is suitably 1 to 100 nm, but is preferably 10 to 50 nm when importance is placed on the optical property function. Moreover, the said alkoxide, salt, etc. may be applied to the metal compound of cobalt, chromium, copper, iron, tin, and zinc as long as the performance of the functional layer is not significantly impaired.
[0020]
The amount of the additive to the hard organic resin layer (2) may be as long as it does not hinder the function of the functional layer (3), and is suitably 10 mol% or less in terms of metal. The increase in the amount added does not maintain the mechanical strength, but conversely causes a functional deterioration of the functional layer as an optical thin film. In the case of providing an optical characteristic function such as antireflection, the range of 0.05 to 1 mol% is desirable.
[0021]
Further, the hard organic resin layer (2) is subjected to a light diffusive treatment generally called anti-glare by mixing and dispersing inorganic or organic fine particles having an average particle diameter of 0.01 to 3 μm or making the surface shape uneven. Can do. These fine particles are not particularly limited as long as they are transparent, but low refractive materials are preferable, and silicon oxide and magnesium fluoride are preferable in terms of stability and heat resistance.
[0022]
The functional layer (3) can have various functions depending on purposes such as antireflection, conductivity, antifouling, antistatic, electron wave blocking, gas barrier, and the like. These functional layers may be composed of a plurality of layers, and one layer may have a plurality of functions. In addition, two or more functional layers having different functions may be provided.
When the functional layer (3) is intended for antireflection, titanium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide are used as the compounds forming the transparent thin film. And using a mixture selected from at least one or more of silicon oxide and magnesium fluoride so that the reflectivity is reduced based on the refractive index, the optical film thickness, and the stacking order optical theory of thin films Designed in combination. For example, when reducing the reflectance of light having a wavelength λ = 520 nm, indium oxide / tin oxide (refractive index 2.0 to 2.3, optical film thickness λ / 8) / silicon oxide (refractive index 1.45 to 1.48). Optical film thickness λ / 8) / indium oxide / tin oxide (refractive index 2.0 to 2.3 optical film thickness λ / 4) / silicon oxide (refractive index 1.45 to 1.48 optical film thickness λ / 4) With such a film thickness configuration, an antireflection function can be obtained.
[0024]
When the functional layer (3) is intended for antistatic, electron wave blocking, and conductivity, zinc oxide, indium oxide, tin oxide, or a mixture of the oxides forming the conductive thin film is used. A layer can be formed.
[0025]
Moreover, when a functional layer (3) aims at antifouling property, fluorocarbon, perfluorosilane, and these polymer layers can be provided.
[0026]
These functional layers are prepared by wet coating method (dip coating method, spin coating method, flow coating method, spray coating method, roll coating method, gravure coating method, etc.), PVD (Physical Vapor Deposition) method (vacuum deposition method, reactivity). It is formed by a known method such as a vapor deposition method, an ion beam assisted vapor deposition method, a sputtering method, an ion plating method, or the like, or a CVD (Chemical Vapor Deposition) method.
[0027]
【Example】
The present invention will be described in detail with reference to examples, but is not limited thereto.
<Example 1>
A 100 μm thick transparent polyethylene terephthalate (PET) film is coated with an ultraviolet curable acrylic resin containing 1% of cobalt acetate (Co (C ₂ H ₃ O ₂ ) ₂ .4H ₂ O) in terms of metal. A hard organic resin layer having a thickness of 5 μm was provided by being cured by irradiation. Thereafter, in order to impart an antireflection function to the hard organic resin layer, a functional layer composed of four layers of TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ is laminated by a plasma assisted vapor deposition method. A prevention film was prepared.
[0029]
<Example 2>
A transparent polyethylene terephthalate (PET) film having a thickness of 100 μm is coated with an ultraviolet curable acrylic resin containing 1% of colloidal particles of Cr having an average particle diameter of 100 nm in terms of metal, and cured by ultraviolet irradiation to have a thickness of 5 μm. A hard organic resin layer was provided. Thereafter, in order to impart an antireflection function to the hard organic resin layer, four layers of TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ are laminated by a plasma assisted vapor deposition method to produce an antireflection film of Example 2. did.
[0030]
<Example 3>
A transparent polyethylene terephthalate (PET) film having a thickness of 100 μm is coated with an ultraviolet curable acrylic resin containing 1% colloidal particles of cupric oxide CuO having an average particle diameter of 100 nm in terms of metal, and cured by ultraviolet irradiation. A hard organic resin layer having a thickness of 5 μm was provided. Thereafter, in order to impart an antireflection function to the hard organic resin layer, a functional layer composed of four layers of TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ was laminated by the plasma assist vapor deposition method, and the reflection of Example 3 was performed. A prevention film was prepared.
[0031]
<Example 4>
A transparent polyethylene terephthalate (PET) film with a thickness of 100 μm is coated with an ultraviolet curable acrylic resin containing 1% of Fe fine particles with an average particle diameter of 50 nm, and cured by ultraviolet irradiation to form a hard organic resin layer with a thickness of 5 μm. Provided. Thereafter, in order to impart an antireflection function to the hard organic resin layer, a functional layer was laminated with indium oxide by a plasma-assisted vapor deposition method to produce a transparent conductive film of Example 4.
[0032]
<Example 5>
A transparent polyethylene terephthalate (PET) film having a thickness of 100 μm is coated with an ultraviolet curable acrylic resin containing 1% of Fe (Oi-C ₃ H ₇ ) ₃ in terms of metal, and cured by irradiation with ultraviolet rays. A hard organic resin layer having a thickness of 5 μm was provided. Thereafter, in order to impart an antireflection function and a transparent conductive function to the hard organic resin layer, a functional layer composed of four layers of ZnO / SiO ₂ / ZnO / SiO ₂ was laminated by a plasma assisted deposition method. An antireflection and transparent conductive film 5 was prepared.
[0033]
<Comparative Example 1>
A transparent polyethylene terephthalate (PET) film having a thickness of 100 μm was coated with an ultraviolet curable resin and cured by irradiating with ultraviolet rays to provide a hard organic resin layer having a thickness of 5 μm. Thereafter, in order to impart an antireflection function to the hard organic resin layer, a functional layer composed of four layers of TiO ₂ / SiO ₂ / TiO ₂ / SiO ₂ was laminated by the plasma assist deposition method, and the reflection of Comparative Example 1 was performed. A prevention film was prepared.
[0034]
<Comparative example 2>
A transparent polyethylene terephthalate (PET) film having a thickness of 100 μm was coated with an ultraviolet curable resin and cured by irradiating with ultraviolet rays to provide a hard organic resin layer having a thickness of 5 μm. Thereafter, in order to impart a transparent conductive function to the hard organic resin layer, indium oxide was laminated as a functional layer by a plasma assisted vapor deposition method to produce a transparent conductive film of Comparative Example 2.
[0035]
<Comparative Example 3>
A transparent polyethylene terephthalate (PET) film having a thickness of 100 μm was coated with an ultraviolet curable resin and cured by irradiating with ultraviolet rays to provide a hard organic resin layer having a thickness of 5 μm. Thereafter, in order to impart an antireflection function and a transparent conductive function to the hard organic resin layer, a functional layer composed of four layers of ZnO / SiO ₂ / ZnO / SiO ₂ was laminated by a plasma assisted deposition method, and a comparative example 3 antireflection and transparent conductive film was produced.
[0036]
The mechanical strength of surface peeling, scratching, and abrasion of these laminates was evaluated by the following evaluation methods.
[0037]
<Surface peeling>
(Tape peeling test applying JIS K 5400)
Make 100 squares of 1 mm in a grid pattern with a cutter, count the number of squares that are not peeled off by sticking tape on it. For example, 60/100 indicates that 40 squares were peeled off.
<Scratched>
(Pencil test applying JIS K 5400)
When 5 lines are drawn with a 1 kg load with a pencil of hardness 3H, the number of scratches is counted. For example, 3/5 indicates that there were three lines that were not damaged.
<Wear>
(Steel wool test)
The steel wool (# 0000) is reciprocated by 50 mm at a load of 1 kg / cm ² to examine how many times it was damaged. For example, 5 times indicates that the 5th time it was damaged.
The following method was used as a durability test for evaluating the durability of the mechanical strength.
<Durability test (1) (light resistance)>
(Light resistance test applying JIS B 7751)
The film was exposed to ultraviolet rays for 240 hours using an ultraviolet long life fade meter FAL-5 (light source; ultraviolet carbon arc) manufactured by Suga Test Instruments Co., Ltd., and then the surface peeling test was performed.
<Durability test (2) (moisture and heat resistance)>
The film was allowed to stand for 1000 hours in an environment with a temperature of 65 ° C. and a humidity of 95%, and then allowed to stand for 24 hours in an environment with a temperature of 25 ° C. and a humidity of 65%.
[0038]
The evaluation results are shown in Table 1.
[0039]
[Table 1]

[0040]
【The invention's effect】
As the above evaluation results show, durability of mechanical strength such as peeling resistance, abrasion resistance, and scratch resistance of the functional layer can be obtained by adding metal or these compounds to the hard organic resin layer in the laminate. This makes it possible to supply products of stable quality at low cost.
[0041]
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a configuration of a laminate according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Support base material 2 Hard organic resin layer 3 Functional layer

Claims (5)

On a supporting substrate, a metal or a hard organic resin layer compound is added thereof is provided, at least one layer of the functional layer is a laminate that is laminated on the hard organic resin layer,
The support substrate is a polyethylene terephthalate film;
The hard organic resin layer is obtained by curing an ultraviolet curable acrylic resin,
That the functional layer consists of four layers of _{TiO 2 / SiO 2 / TiO 2} / SiO 2, made of indium oxide, or _is selected from those consisting of four layers of ZnO / SiO 2 / ZnO / SiO 2 1 Layer of
The metal is one or more selected from cobalt, chromium, copper, and iron;
The laminate according to claim 1, wherein an additive ratio of the additive added to the hard organic resin layer is in a range of 0.05 to 1 mol% in terms of metal based on the ultraviolet curable acrylic resin .   The laminate according to claim 1, wherein the metal compound is made of a metal oxide.   The laminate according to claim 1 or 2, wherein the metal or a compound thereof comprises colloidal particles.   The laminate according to any one of claims 1 to 3, wherein the functional layer has an antireflection function.   The laminate according to any one of claims 1 to 3, wherein the functional layer has a transparent conductive function.

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