JP2017064968A - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film having self-repairing capacity or moldability and achieving both durability and antifouling properties.SOLUTION: There is provided a laminated film having a surface layer on at least one surface of a support substrate, wherein the elastic modulus (Ez)(MPa) obtained by measurement of the surface of the surface layer by an atomic force microscope and in a cross section perpendicular to the support substrate of the surface layer, and the elastic modulus (E)(MPa) obtained by measurement of the position of 50% of the thickness of the surface layer by an atomic force microscope satisfy the following conditions 1 and 2. Condition 1 E>E, Condition 2 1 MPa≤E≤50 MPa.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated film that achieves both durability and antifouling properties in addition to excellent self-repairability and moldability.

  In recent years, a film provided with a surface layer made of a synthetic resin having scratch resistance, such as a battery cover of a display, an automobile, or a mobile phone, has been used. For these surface layers, scratch resistance is an important characteristic for surface protection. Generally, various polymer polymers such as organosilane polyfunctional acrylics described in Patent Document 1 are used. The surface hardness of the coating film has been increased by using a "high crosslink density material" that is coated with a composition containing, and dried, heat or UV cured, and an "organic-inorganic hybrid material" in which various fillers are combined. By using a so-called “hard coat material”, scratch resistance is imparted.

  On the other hand, the above hard coat film has high surface hardness and excellent scratch resistance, but once generated scratches cannot be recovered and cracks may occur during molding due to insufficient elongation following the molding. In extreme cases, the film may be broken or the surface layer may be peeled off, so that it is difficult to apply to a portion where a flexible display or three-dimensional processing is applied. In view of the above, Patent Documents 2 and 3 propose “self-healing material” or “self-healing material” that achieves scratch resistance by restoring the scratches generated on the surface by the elasticity of the material of the surface layer. ,Attention has been paid.

  Films using these materials as the surface layer can be used to protect notebook PCs, mobile phones, automobiles, etc., where there are scratches on their lives. It is superior to the hard coat material laminated film, and has an advantage that it can be applied to uneven portions.

  On the other hand, in a film using a self-healing material for the surface layer, the surface hardness is low, in other words, the cross-linking density of the coating film is generally low, so there is a problem of poor antifouling properties, blocking resistance, and water resistance. there were.

  In such a background, as a method for solving the above problems, Patent Documents 4 and 5 provide a self-healing material composition having a self-healing property by increasing the surface hardness by increasing the crosslinking density of the coating film. Furthermore, an invention in which an antifouling layer is provided on the surface of a laminate as in Patent Document 6 has been proposed.

JP 2009-184284 A International Publication No. 2011/136042 Pamphlet Japanese Patent Laid-Open No. 11-228905 JP 2012-180487 A JP2012-107101A JP 2008-62408 A

  However, although the laminated film using the “hard coat material” for the surface layer described above can be provided with functions such as antireflection properties and antifouling properties, from the viewpoint of moldability, there are problems as described above. In spite of its extremely high surface hardness, it is often scratched and detracts from its appearance in daily life.

  In Patent Document 4, by increasing the crosslink density, the curl is very small and self-healing property is excellent although the surface hardness and scratch resistance are excellent, but the crosslink density of the entire coating film is increased. Therefore, although it has a self-repairing property, the drawback that it takes time to recover the wound has been a problem in practical use.

  Similarly in Patent Document 5, the surface hardness can be increased by controlling the crosslinking density, and excellent stain resistance and water resistance can be expressed, but the crosslinking density of the entire coating film is increased. Therefore, there is a practical problem that it takes time to recover the wound.

  In Patent Document 6, in order to impart antifouling properties, a polyvinylidene chloride layer is laminated on the surface as a dye migration prevention layer. However, the polyvinylidene chloride layer is easily scratched, and is practically scratch resistant. There is a problem. In addition, none of Patent Documents 4 to 6 has been conceived of the structure of the present invention.

  Then, this invention is providing the laminated | multilayer film which balances durability and antifouling property in addition to the outstanding self-repairing property and moldability.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and completed the following invention. That is, the present invention is as follows.
1. In a laminated film having a surface layer on at least one surface of a support substrate, the elastic modulus (Ez) (MPa) obtained by measuring the surface of the surface layer with an atomic force microscope, and the support of the surface layer The elastic modulus ( _EX50 ) (MPa) obtained by measuring the position of 50% of the thickness of the surface layer with an atomic force microscope in the cross section perpendicular to the substrate satisfies the following conditions 1 and 2. A laminated film characterized by
Condition 1 E _Z > E _X50
Condition 2 1 MPa ≦ E _X50 ≦ 50 MPa
2. The elastic modulus (Ez) satisfies the following condition 3: 1. A laminated film according to 1.
Condition 3 100 MPa ≦ E _Z <1 GPa
3. The surface layer has two or more layers, and the thickness of each of the outermost layer (referred to as A layer) and the second layer from the outermost surface (referred to as B layer) is T _A (μm), T _{When B} (μm) is satisfied, the following condition 4 and condition 5 are satisfied: Or 2. A laminated film according to 1.
Condition _{4 2 ≦ T B / T A} ≦ 500
Condition 5 0.01 μm ≦ T _A ≦ 5 μm
4). The surface layer contains particles, and the particle concentration increases from the support substrate side toward the surface side. To 3. A laminated film according to any one of the above.
5. 2. A reflectance is 2.0% or less, and the refractive index (n _A ) of the A layer and the thickness (T _A ) of the A layer satisfy the following conditions 6 and 7. Or 4. A laminated film according to 1.
Condition 6 1.35 ≦ n _A ≦ 1.40
Conditions 7 50nm ≦ _{T A} ≦ 150nm
6). The surface layer satisfies the following condition 8: 1. ~ 5. A laminated film according to any one of the above.
Condition 8 A resin having at least one segment selected from the group consisting of a (poly) caprolactone segment, a (poly) carbonate segment, and a (poly) alkylene glycol segment is included.

  According to the present invention, it is possible to provide a laminated film having both excellent self-repairability, moldability, durability and antifouling properties.

It is sectional drawing which shows the structure of the laminated | multilayer film of this invention.

  In achieving the above-mentioned problems, the present inventors have examined the compatibility of “hard physical properties and flexible physical properties”. As a result, in the compatibility of two physical properties, (1) the elastic force of the outermost surface layer of the surface layer, (2 ) It came to the consideration that two elements of the distribution of elastic force in the surface layer influence.

  A laminated film using a material that exhibits self-healing properties for the surface layer and a general thermoplastic resin for the substrate controls self-healing properties, that is, by controlling the elastic force of the entire surface layer. Although it is possible to improve the scratch resistance, characteristics that require surface hardness such as antifouling properties that depend on the characteristics of the material that exhibits self-healing properties cannot be obtained. On the other hand, in order to impart antifouling properties, there is a method in which a hydrophobic polyfunctional acrylate or the like is contained in the entire surface layer having self-healing properties, but the entire surface layer laminated on the support substrate is hardened. For this reason, it was found that the self-repair speed is slow and the repeated wearability may be insufficient. In other words, in the surface layer where the elastic modulus is uniform, the elastic modulus according to the self-healing material and other additives constituting the surface layer governs the self-healing property of the laminated film in which the material is laminated on the support substrate. Therefore, it is thought that excellent self-repairability and moldability cannot be maintained.

  From the above consideration, the present inventors have found a laminated film having a surface layer having the following structure, which can achieve both excellent self-repairability, moldability and surface hardness by controlling the elastic modulus of the surface layer.

First, the laminated film of the present invention is a laminated film in which a surface layer (2 in FIG. 1) is formed on at least one surface of a support substrate (1 in FIG. 1) as shown in FIG. The elastic modulus (E _Z ) (MPa) (3 in FIG. 1) obtained by measuring the surface of the surface layer with an atomic force microscope, and the cross section perpendicular to the supporting substrate of the surface layer, The elastic modulus (E _X50 ) (MPa) (4 in FIG. 1) obtained by measuring the position of 50% of the thickness with an atomic force microscope preferably has the following relationship.
Condition 1 E _Z ≧ E _X50
Condition 2 1 MPa ≦ E _X50 ≦ 50 MPa.

  The “surface layer” in the present invention refers to a layer formed on a supporting substrate. That is, when only one layer is formed on the support base material, the one layer becomes a “surface layer”. For example, when two or more layers are formed on a supporting base material, all the two or more layers excluding the supporting base material are referred to as one “surface layer”.

  Here, the “layer” refers to a portion having a finite thickness that can be distinguished by having a boundary surface and a portion adjacent to each other in the thickness direction from the surface side of the laminated film toward the thickness direction. More specifically, when the cross section of the laminated film is observed with an electron microscope (transmission type, scanning type) or an optical microscope, it indicates what is distinguished by the presence or absence of a discontinuous boundary surface.

  In addition, the elastic modulus measurement with an atomic force microscope is a compression test with a probe of a very small portion, and is a degree of deformation due to a pressing force. Therefore, using a cantilever with a known spring constant, the surface and the surface layer The elastic modulus in the cross section at the position of 50% of the thickness is measured. Specifically, the elastic modulus in the cross section at the position of 50% of the thickness of the surface layer is obtained by cutting the laminated film and measuring the elastic modulus in the cross section at the position of 50% of the thickness of the surface layer with an atomic force microscope. Details will be described in the Examples section, but using the atomic force microscope shown below, the tip of the cantilever tip is brought into contact with the cross section of the surface or surface layer, and the force curve is measured with a pressing force of 55 nN. The amount of bending of the cantilever can be measured. Details will be described later.

Atomic force microscope: MFP-3DSA-J manufactured by Asylum Technology
Cantilever: A cantilever “R150-NCL-10 manufactured by NANOSENSORS (material Si, spring constant 48 N / m, radius of curvature of the tip 150 nm).

The relationship between the elastic modulus E _z and the elastic modulus E _x50 shown in Condition 1 intends that the elastic modulus of the surface is preferably higher than the elastic modulus at the position of 50% of the thickness of the surface layer.

In Condition 1, when E _Z < _EX50 , the hardness of the surface layer is low and the crosslinking density is low, so that the scratch resistance may be low, or the self-repairing property may not be obtained. Moreover, antifouling property may not be obtained. When 1 MPa ≦ E _X50 ≦ 50 MPa shown in Condition 2 and E _X50 is 1 MPa or less, there is a possibility that the elastic force is low, the scratch recovery time is slow, or the original shape may not be restored. May not be compatible with surface hardness. If the elastic modulus of E _X50 is greater than 50MPa, the crosslinking density is high, scratches resilience is lowered for wounding by high pressure or high strength materials, that is, there are cases where self-repairing does not express fully functional.

Specifically, _EZ preferably satisfies the following conditions.
Condition 3 100 MPa ≦ E _Z ≦ 1 GPa.

As described above, _EZ is an elastic modulus obtained by measuring the surface layer with an atomic force microscope. When the surface elastic modulus Ez value is 100 MPa or less, the surface hardness is low and the crosslink density is low. Sexuality may not be obtained. On the other hand, if it is higher than 1 GPa, it means that the surface hardness is very high, and antifouling property is obtained, but self-repairing property may not be exhibited.

When the surface layer is formed of two or more layers, the surface side layer (5 in FIG. 1, ie, A layer) and the second layer from the surface (6, ie, B layer in FIG. 1) Each thickness (T _A (μm), T _B (μm)) preferably satisfies the following conditions.
Condition _{4 2 ≦ T B / T A} ≦ 500
Condition 5 0.01 μm ≦ T _A ≦ 5 μm.

In order to develop the self-repair function, the elastic modulus is important, and it can be said that the thickness of each layer is also an important factor that affects the elastic modulus. Condition 4 means that the B layer is thicker than the A layer.
In the present invention, when the surface layer is formed of two or more layers, A layer is a layer on the surface side is largely responsible elastic modulus E _Z shown in the condition 3.

A layer of surface A layer of a thickness _{T A} ([mu] m) is, in relation to the thickness _{T B} ([mu] m) of the B layer is a second layer from the _surface, if T B / _{T A} is less than 2, the surface The scratch resistance of the A layer is excellent, but the scratch recovery time may be delayed. Also, if T B _/ T _A is greater than 500 is excellent in the self-healing, it may scratch easily remains on the surface A layer.

Further, as described above, since the self-healing when the thickness _{T A} is too thick A layer is not easily expressed, the thickness _{T A} of the A layer is preferably satisfies the following conditions 5μm or 0.01 [mu] m. If the thickness T _A of the A layer is less than 0.01 [mu] m, there are cases where sufficient surface hardness can not be obtained, do not express antifouling property. Conversely, if T _A exceeds 5μm, which can express a sufficient antifouling property, high surface hardness of the A layer, the elastic modulus increases, self-healing may be lowered. The thickness _{T A} of the A layer is more preferably, 0.05 .mu.m or 5μm or less, more preferably 0.1μm or more 5μm or less. The upper limit of the thickness T _A of the A layer, the lower limit may be any of the above combinations.

  The thickness of each layer can be measured by cutting a cross section in the thickness direction and using an optical microscope or an electron microscope.

  The surface layer in the present invention preferably contains particles, and the particle concentration is preferably increased from the substrate side toward the surface side. The particle concentration mentioned here can be confirmed by performing cross-sectional observation with a TEM (transmission electron microscope) and counting the number of particles. Specifically, the laminated film of the present invention was embedded and cured with an epoxy resin for electron microscope (Queto 1812 manufactured by Nissin EM), and then a cross section of the surface layer of the laminated film with an ultramicrotome (Ultracut S manufactured by Leica). Is prepared as a measurement sample, the entire cross-sectional area from the substrate side to the surface is measured, and the number of particles is counted. Details of the measurement method will be performed later.

  As the particle concentration increases from the substrate side to the surface layer, the elastic modulus can be increased, and the outermost surface of the surface layer can be provided with slipperiness, anti-blocking properties, and repeated scratching properties. It is.

The laminated film in the present invention preferably has a reflectance of 2.0% or less, and the refractive index n _A and thickness T _{A of the} A layer satisfy the following conditions.
Condition 6 1.35 ≦ n _A ≦ 1.40
Conditions 7 50nm ≦ _{T A} ≦ 150nm.

  The reflectance here is a wavelength of 380 to 780 nm of light using a spectrophotometer (manufactured by Shimadzu Corporation; UV-3100) obtained by painting the side of the laminated film on which the surface layer is not laminated with a black paint. It refers to the lowest value obtained from the spectral reflectance obtained by measuring the reflection spectrum. Further, the refractive index refers to a value calculated using a reflection spectrum obtained by a reflection spectral film thickness meter and optical simulation software.

When the refractive index n _A of the A layer is less than 1.35 or greater than 1.40, the reflected light on the surface of the laminated film increases, so that external light may be reflected and visibility may be lowered.
Further, when the thickness T _A of the A layer is greater than 50nm less than or 150nm, the interference effect of light in the visual region can not be obtained, to feel strong and unwanted reflections of external light, a sufficient reflection characteristics It may not be obtained.

The surface layer in the present invention preferably satisfies the following conditions.
Condition 8: A resin having at least one segment selected from the group consisting of a (poly) caprolactone segment, a (poly) carbonate segment, and a (poly) alkylene glycol segment is included.

  About each segment which resin which comprises the said surface layer contains, it can confirm by TOF-SIMS, FT-IR, etc.

  The (poly) caprolactone segment refers to a chemical formula 1, the (poly) alkylene glycol segment refers to a chemical formula 2, and the (poly) carbonate segment refers to a chemical formula 3.

  Here, the polycaprolactone includes those having caprolactone repeating units of 1 (monomer), 2 (dimer), 3 (trimer), and oligomers having caprolactone repeating units of up to 35. The polyalkylene glycol also includes those having an alkylene glycol repeating unit of 2 (dimer) and 3 (trimer) and an oligomer having an alkylene glycol repeating unit of up to 11. Further, the polycarbonate also includes those having carbonate repeating units such as 2 (dimer) and 3 (trimer), and oligomers having up to 16 carbonate repeating units.

n is an integer of 1 to 35.

n is an integer of 2 to 4, and m is an integer of 2 to 11.

n is an integer of 2-16.
R ₄ represents an alkylene group or cycloalkylene group having 1 to 8 carbon atoms.

  The details of the polycaprolactone segment, the polyalkylene glycol segment, and the polycarbonate segment will be described later. The resin constituting the surface layer has these segments, so that the surface layer exhibits self-repairing properties and is excellent in molding. Showing gender.

  In the case where the surface layer of the laminated film in the present invention is a surface layer formed of two or more layers, the polycaprolactone segment, the polyalkylene glycol segment, and the polycarbonate segment may be included in any layer, From the viewpoint of self-repairability and moldability, it is preferably contained in any layer.

  Hereinafter, embodiments of the present invention will be described in detail.

[Laminated film and surface layer]
The laminated film of the present invention may be in a planar state or a three-dimensional shape after being molded as long as it has a surface layer exhibiting the above-described physical properties. Here, the “surface layer” in the present invention may be formed of one “layer” or may be formed of a plurality of “layers”. Here, the “layer” can be distinguished from the surface of the laminated film in the thickness direction by having a boundary surface adjacent to the thickness direction and the element composition, inclusion shape, and physical properties are discontinuous and finite. The site | part which has the thickness of. On the other hand, when the physical properties and elemental composition in the surface layer are continuously changing, it is handled as one layer.

  The surface layer, which is the subject of the present invention, has functions for achieving both self-healing properties and moldability, such as antifouling properties, antireflection properties, antistatic properties, electrical conductivity, heat ray reflectivity, near infrared absorptivity, and electromagnetic wave shielding. It may have other functions such as property and easy adhesion.

  The thickness of the surface layer is not particularly limited, but is preferably 1 μm or more and 100 μm or less, and more preferably 1 μm or more and 50 μm or less.

  Although the details will be described later as a method for producing the laminated film for forming the surface layer, the following two methods are preferable. The first method is a method in which two or more kinds of coating compositions are formed by “sequentially” coating, drying and curing on a supporting substrate. Here, “sequentially apply” means to form a surface layer by applying-drying-curing one type of coating composition and then applying-drying-curing different types of coating composition. Means.

  Another production method is a method in which two or more kinds of coating compositions are formed by applying, drying and curing “simultaneously” on a supporting substrate. There are no particular restrictions as long as the number of types of coating compositions is two or more. Here, “coating at the same time” means drying and curing after forming two or more types of liquid films on a supporting substrate in the production process.

[Supporting substrate]
The material constituting the support substrate used in the laminated film of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, may be a copolymer or a blend of two or more types. Good. More preferably, the resin constituting the support base material is preferably a thermoplastic resin because of good moldability.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins, and polyarylate resins. Fluorine resins such as polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-6 fluoropropylene copolymer, vinylidene fluoride resin, acrylic Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin, or a methacrylic resin from the viewpoint of strength, heat resistance, and transparency, and a polyester resin is particularly preferable.

  The polyester resin in the present invention is a general term for polymers having an ester bond as a main bond chain, and is obtained by polycondensation of an acid component and its ester and a diol component. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and the like. These may be copolymerized with other dicarboxylic acids and their esters or diol components as acid components or diol components. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in terms of transparency, dimensional stability, heat resistance and the like.

  In addition, for the support substrate, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant for adjusting the refractive index may be added. The support substrate may be either a single layer configuration or a laminated configuration.

  Various surface treatments can be applied to the surface of the support substrate before the surface layer is formed. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

  In addition to the surface layer of the present invention, a functional layer such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorption layer can be provided in advance on the surface of the support substrate. It is preferable to provide a layer.

[Coating composition]
The laminated film of the present invention can form a surface layer having a structure capable of achieving the aforementioned physical properties by applying, drying, and curing a coating composition on a supporting substrate by using a laminated film manufacturing method described later. . Here, the “coating composition” is a liquid composed of a solvent and a solute, and is a material capable of forming a surface layer by volatilizing, removing and curing in the step of applying the solvent onto the support substrate and drying the solvent. Point to. Here, the “type” of the coating composition refers to liquids that are different in part even in the type of solute constituting the coating composition. This solute is a resin or a material that can form them in the coating process (hereinafter referred to as a precursor), particles, and polymerization initiators, curing agents, catalysts, leveling agents, ultraviolet absorbers, antioxidants, etc. Consists of various additives.

  The laminated film of the present invention is formed by using two types of coating compositions (hereinafter referred to as “coating composition A” and “coating composition B”) and sequentially or simultaneously applying the same on a supporting substrate. Is preferred. Here, the coating composition A is a liquid capable of forming a material having a high elastic modulus and high surface hardness by coating, drying, and curing on a supporting substrate, and is suitable for forming the A layer on the surface side. Resin or precursor. The coating composition B is a liquid capable of forming a material having a low elastic modulus and excellent self-healing properties by coating, drying and curing on the support substrate, and forms a layer other than the surface layer A. A suitable resin or precursor.

  In the method for producing a laminated film, when three or more kinds of coating compositions are used, the coating composition A and the coating composition B can be prepared by appropriately mixing them according to the physical properties of the coating film. Details of these coating compositions will be described below.

[Coating composition A]
The coating composition A is a liquid containing a material suitable for forming the surface-side A layer or a precursor that can be formed, and the above-mentioned (poly) caprolactone segment, (poly) carbonate segment, ( A resin or a precursor containing a segment selected from the group consisting of poly) alkylene glycol segments may be included. In addition, the resin containing a segment selected from the previous segment group has antifouling property, antireflection property, antistatic property, antifouling property, conductivity, heat ray reflectivity, near infrared absorption property, electromagnetic wave shielding property, easy adhesion Various materials that impart properties may also be included. Examples of materials that impart antifouling properties include materials containing fluorine compound segments, polyfunctional acrylates, and butadiene-based materials. The material imparting antireflection properties refers to a material in which the refractive index nA of the surface layer A layer can be in the range of 1.35 to 1.45.

[Coating composition B]
The coating composition B is a liquid that can form a material having a low elastic modulus and excellent self-healing properties by coating, drying and curing on a supporting substrate. A resin suitable for forming a layer containing, or a precursor, a resin containing a segment selected from the group consisting of the aforementioned (poly) caprolactone segment, (poly) carbonate segment, (poly) alkylene glycol segment as a solute, or A precursor may be included. Hereinafter, the details of each segment will be described.

[Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]
First, the polycaprolactone segment refers to the segment represented by Formula 1 above.
The resin containing the polycaprolactone segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the polycaprolactone segment.

  The resin containing a polycaprolactone segment is particularly preferably a polycaprolactone having 2 to 3 functional hydroxyl groups. Specifically, polycaprolactone diol represented by Chemical Formula 4,

Here, m + n is an integer from 4 to 35, m and n are each an integer from 1 to 34, R is C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ , C (CH ₃ ) ₃ (CH ₂ ) ₂ Or a polycaprolactone triol represented by Chemical Formula 5,

Here, l + m + n is an integer of 3 to 30, l, m, and n are integers of 1 to 28, R is CH ₂ CHCH ₂ , CH ₃ C (CH ₂ ) ₃ , CH ₃ CH ₂ C (CH ₂ ). ₃ or the like and polycaprolactone-modified hydroxyethyl (meth) acrylate represented by Chemical Formula 6

Here, n is an integer of 1 to 25, and R can be active energy ray-polymerizable caprolactone such as H or CH ₃ . Examples of other active energy ray-polymerizable caprolactone include polycaprolactone-modified hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxybutyl (meth) acrylate, and the like.

  Furthermore, in the present invention, the resin containing the polycaprolactone segment may contain (or copolymerize) other segments and monomers in addition to the polycaprolactone segment. For example, a polydimethylsiloxane segment, a polysiloxane segment, or a compound containing an isocyanate compound described later may be contained (or copolymerized).

  In the present invention, the weight average molecular weight of the polycaprolactone segment in the resin containing the polycaprolactone segment is preferably 500 to 2,500, and more preferably 1,000 to 1,500. . When the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, the self-repairing effect is more exhibited, and the repeated scratching property is further improved, which is preferable.

  Next, the polyalkylene glycol segment refers to the segment represented by Formula 2 above. The resin containing the polyalkylene glycol segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the polyalkylene glycol segment.

  The resin containing a polyalkylene glycol segment is preferably a polyalkylene glycol (meth) acrylate having an acrylate group at the terminal in order to impart elasticity. The number of acrylate functional groups (or methacrylate functional groups) of the polyalkylene glycol (meth) acrylate is not limited, but is most preferably monofunctional from the viewpoint of self-healing properties of the cured product.

  Examples of the polyalkylene glycol (meth) acrylate contained in the coating composition used for forming the surface layer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polybutylene glycol (meth) acrylate. . The structures are represented by the following chemical formula 7, chemical formula 8, and chemical formula 9, respectively.

  Polyethylene glycol (meth) acrylate:

  Polypropylene glycol (meth) acrylate:

  Polybutylene glycol (meth) acrylate:

In Chemical Formula 7, Chemical Formula 8, and Chemical Formula 9, R is hydrogen (H) or a methyl group (—CH ₃ ), and m is an integer from 2 to 11.

  In the present invention, the resin constituting the surface layer is preferably formed by reacting a compound containing an isocyanate group, which will be described later, with the hydroxyl group of (poly) alkylene glycol (meth) acrylate and using it as the urethane (meth) acrylate in the surface layer. However, (2) It can have a urethane bond and (3) (poly) alkylene glycol segment, and as a result, it can improve the toughness of the surface layer and improve self-repairability, which is preferable.

  Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl as the hydroxyalkyl (meth) acrylate compounded at the same time as the urethanization reaction between the compound containing an isocyanate group and the polyalkylene glycol (meth) acrylate Examples include (meth) acrylate.

  Next, the polycarbonate segment refers to the segment represented by Formula 3 above.

  The resin containing the polycarbonate segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the polycarbonate segment.

As the resin containing a polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferable. Specifically, it is represented by Chemical Formula 10.
Polycarbonate diol:

n is an integer of 2-16.
R represents an alkylene group having 1 to 8 carbon atoms or a cycloalkylene group.

  The polycarbonate diol may have any number of repeating carbonate units, but if the number of repeating carbonate units is too large, the strength of the cured urethane (meth) acrylate will decrease, so the number of repeating units should be 10 or less. Is preferred. The polycarbonate diol may be a mixture of two or more types of polycarbonate diols having different repeating numbers of carbonate units.

  The polycarbonate diol preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is less than 500, suitable flexibility may be difficult to obtain, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated. It is.

  Moreover, as polycarbonate diol used by this invention, PACCEL CD-PL of UH-CARB, UD-CARB, UC-CARB (Ube Industries, Ltd.), PLACEL CD-H (Daicel Chemical Industries, Ltd.), Kuraray polyol C A product such as a series (Kuraray Co., Ltd.) or a duranol series (Asahi Kasei Chemicals Co., Ltd.) can be suitably exemplified. These polycarbonate diols can be used alone or in combination of two or more.

[Compound containing urethane bond and isocyanate group]
In the present invention, the “urethane bond” refers to a bond represented by Chemical Formula 11.

When the coating composition A contains a commercially available urethane-modified resin, the resin constituting the surface side of the surface layer can have a urethane bond. Moreover, when forming the surface side of the surface layer, a urethane bond is generated by applying, drying and curing a coating composition A containing a compound containing an isocyanate group and a compound containing a hydroxyl group as a precursor. A urethane bond can also be contained on the surface side of the surface layer.

  In this invention, it is preferable to introduce | transduce a urethane bond into resin which comprises the surface side of a surface layer by making an isocyanate group and a hydroxyl group react, and producing | generating a urethane bond. By repeating the isocyanate group and the hydroxyl group to generate a urethane bond, the toughness of the surface layer is improved and the self-repairing property is improved, whereby the repeated scratching property can be improved.

  In addition, if a resin containing the above-mentioned polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment or a hydroxyl group is present, a urethane bond is formed between these resin and a compound containing an isocyanate group as a precursor by heat or the like. It is also possible to make it.

  When a surface layer is formed using a compound containing an isocyanate group and a resin containing a polysiloxane segment having a hydroxyl group, which will be described later, or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the toughness of the surface layer and self-healing In addition to the property, the surface slipperiness can be increased, which is more preferable from the viewpoint of repeated scratching.

  In the present invention, the compound containing an isocyanate group refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Examples include isocyanurate bodies, isocyanurate bodies of hexamethylene diisocyanate, (poly) isocyanates such as a burette body of hexamethylene isocyanate, and block bodies of the above isocyanates.

  Of these isocyanate group-containing compounds, aliphatic isocyanates are preferred because of their high self-healing properties compared to alicyclic and aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. The isocyanate group-containing compound is particularly preferably an isocyanate having an isocyanurate ring from the viewpoint of heat resistance, and most preferably an isocyanurate of hexamethylene diisocyanate. Isocyanates having an isocyanurate ring form a surface layer having both self-healing properties and heat resistance.

[Fluorine compound segment, polysiloxane segment, polydimethylsiloxane segment]
First, the fluorine compound segment refers to a segment including at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group.

  Here, a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are alkyl groups, oxyalkyl groups, alkenyl groups, alkanediyl groups, and oxyalkanediyl groups. A part or all of the substituents are replaced by fluorine, both of which are mainly composed of fluorine atoms and carbon atoms, and there may be branching in the structure. A plurality of linked dimers, trimers, oligomers, and polymer structures may be formed.

  The fluorine compound segment is preferably a fluoropolyether segment, which is a site comprising a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., more preferably represented by Chemical Formula 12 and Chemical Formula 13. It is a fluoropolyether segment.

  In order for the resin contained in the surface layer to contain a fluorine compound segment, the coating composition A described above preferably contains the following fluorine compound D. This fluorine compound D is a compound represented by Chemical Formula 14.

Here, R ^f1 represents a fluorine compound segment, R ₇ represents an alkanediyl group, alkanetriyl group, and an ester structure, urethane structure, ether structure, or triazine structure derived therefrom, and D ¹ represents a reactive site. Indicates.

  This reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such reactive sites include alkoxysilyl groups and silanol groups in which alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. Can be mentioned. Of these, vinyl groups, allyl groups, alkoxysilyl groups, silyl ether groups, silanol groups, epoxy groups, and acryloyl (methacryloyl) groups are preferred from the viewpoints of reactivity and handling properties.

  An example of the fluorine compound D is a compound shown below. 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltri Chlorosilane, 2-perfluorooctyl isocyanate silane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluoro Butyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- Perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro -5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate Octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-par Fluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro- 3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methyl Hexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoro Examples include pentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol.

The fluorine compound D may have a plurality of fluoropolyether moieties per molecule.
Examples of commercially available fluorine compounds D include RS-75 (DIC Corporation), OPTOOL DAC-HP (Daikin Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Co., Ltd.), and the like. Can be used.

  Next, the polysiloxane segment will be described. In the present invention, the polysiloxane segment refers to a segment represented by Chemical Formula 15.

In the present invention, a partially hydrolyzed product of a silane compound containing a hydrolyzable silyl group, an organosilica sol or a coating composition obtained by adding a hydrolyzable silane compound having a radical polymer to the organosilica sol, a polysiloxane segment It can be used as a resin to contain.

  Resins containing polysiloxane segments are tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrimethyl. A hydrolyzable silyl group on the surface of an organosilica sol dispersed in a complete or partial hydrolyzate of a silane compound having a hydrolyzable silyl group such as alkoxysilane or γ-methacryloxypropylalkyldialkoxysilane or an organic solvent. The thing etc. which added the hydrolysis silane compound of this can be illustrated.

  In the present invention, the resin containing a polysiloxane segment may contain (copolymerize) other segments in addition to the polysiloxane segment. For example, a monomer component having a polycaprolactone segment and a polydimethylsiloxane segment may be contained (copolymerized).

  When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, the surface using a coating composition containing a resin (copolymer) containing a polysiloxane segment having a hydroxyl group and a compound containing an isocyanate group When the layer is formed, the surface layer having a polysiloxane segment and a urethane bond can be efficiently formed.

  Next, the polydimethylsiloxane segment will be described. In the present invention, the polydimethylsiloxane segment refers to a segment represented by Chemical Formula 16.

  When the resin constituting the surface side of the surface layer has a polydimethylsiloxane segment, the polydimethylsiloxane segment is coordinated to the surface of the surface layer. By coordinating the polydimethylsiloxane segment to the surface of the surface layer, the lubricity of the surface layer surface can be improved and the frictional resistance can be reduced. As a result, it is possible to improve the repeated rubbing property.

  In the present invention, as the resin containing a polydimethylsiloxane segment, it is preferable to use a copolymer obtained by copolymerizing a vinyl monomer with a polydimethylsiloxane segment.

  For the purpose of improving the toughness of the surface layer, the resin containing polydimethylsiloxane segments is preferably copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group.

  When the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, a coating composition containing a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group is used. When the surface layer is formed, the surface layer having a polydimethylsiloxane segment and a urethane bond can be efficiently formed.

  When the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, any of a block copolymer, a graft copolymer, and a random copolymer may be used. When the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, this is referred to as a polydimethylsiloxane copolymer. Polydimethylsiloxane copolymer can be produced by living polymerization method, polymer initiator method, polymer chain transfer method, etc., but considering the productivity, polymer initiator method, polymer chain transfer method can be used. It is preferable to use it.

  When the polymer initiator method is used, it can be copolymerized with other vinyl monomers using a polymer azo radical polymerization initiator represented by Chemical Formula 17. In addition, a two-stage polymerization is carried out by synthesizing a prepolymer in which a peroxide group is introduced into the side chain by copolymerizing a peroxy monomer and polydimethylsiloxane having an unsaturated group at a low temperature, and then copolymerizing the prepolymer with a vinyl monomer. Can also be done.

m is an integer of 10 to 300, and n is an integer of 1 to 50.

When the polymer chain transfer method is used, for example, HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH is added to the silicone oil represented by Chemical Formula 18 to form a compound having an SH group, and then the SH group A block copolymer can be synthesized by copolymerizing the silicone compound and vinyl monomer using chain transfer.

m is an integer of 10 to 300.

  In order to synthesize a polydimethylsiloxane graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound represented by Chemical Formula 19, that is, a methacrylic ester of polydimethylsiloxane and a vinyl monomer. it can.

m is an integer of 10 to 300.

  Examples of vinyl monomers used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride , Vinyl fluoride, vinylidene fluoride, glycidyl acrylate Glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethyl Examples thereof include methacrylate, N, N-diethylaminoethyl methacrylate, diaceton acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and allyl alcohol.

  Polydimethylsiloxane copolymers include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, isopropyl alcohol, etc. It is preferable that the alcoholic solvent is produced by a solution polymerization method alone or in a mixed solvent.

  If necessary, a polymerization initiator such as benzoyl peroxide or azobisisobutylnitrile is used in combination. The polymerization reaction is preferably performed at 50 to 150 ° C. for 3 to 12 hours.

  The amount of the polydimethylsiloxane segment in the polydimethylsiloxane copolymer in the present invention is 1 to 100 mass% of all components of the polydimethylsiloxane copolymer in terms of lubricity and antifouling property of the surface layer. It is preferably 30% by mass. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

  In the present invention, when a resin containing a polydimethylsiloxane segment is used as the coating composition used for forming the surface layer, other segments are contained (copolymerized) in addition to the polydimethylsiloxane segment. May be. For example, a polycaprolactone segment or a polysiloxane segment may be contained (copolymerized).

  The coating composition used to form the surface layer includes a copolymer of a polycaprolactone segment and a polydimethylsiloxane segment, a copolymer of a polycaprolactone segment and a polysiloxane segment, a polycaprolactone segment, a polydimethylsiloxane segment, and a polymer. A copolymer with a siloxane segment can be used. The surface layer obtained using such a coating composition can have a polycaprolactone segment and a polydimethylsiloxane segment and / or a polysiloxane segment.

  The reaction of polydimethylsiloxane copolymer, polycaprolactone, and polysiloxane in a coating composition used to form a surface layer having a polycaprolactone segment, a polysiloxane segment, and a polydimethylsiloxane segment is a polydimethylsiloxane When synthesizing the copolymer, a polycaprolactone segment and a polysiloxane segment can be appropriately added and copolymerized.

[Particle component]
The particles contained in the surface layer of the laminated film of the present invention may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of durability.

  Here, “inorganic particles” include those subjected to surface treatment. This surface treatment means introducing a compound onto the particle surface by chemical bonds (including covalent bonds, hydrogen bonds, ionic bonds, van der Waals bonds, hydrophobic bonds, etc.) and adsorption (including physical adsorption and chemical adsorption). Even if the compound introduced by the surface treatment is an organic compound, it is an inorganic particle if the underlying particle is an inorganic particle.

The type of inorganic particles contained is preferably 1 or more and 20 or less. As for the kind of inorganic particle, 1 type or more and 10 types or less are more preferable, and 2 or more types and 4 types or less are especially preferable. Here, the kind of inorganic particles is determined by the kind of elements constituting the inorganic particles, and when any surface treatment is performed, it is decided by the kind of elements constituting the particles before the surface treatment. For example, since titanium oxide (TiO ₂ ) and nitrogen-doped titanium oxide (TiO _2−x N _x ) in which part of oxygen in titanium oxide is replaced with nitrogen as an anion, the elements constituting the inorganic particles are different, Suppose that they are different types of inorganic particles. Further, if particles (ZnO) consisting only of the same element, for example, Zn, O, even if there are a plurality of particles having different number average particle diameters, and the composition ratio of Zn and O is different, These are the same type of particles. Even if there are a plurality of Zn particles having different oxidation numbers, as long as the elements constituting the particles are the same (in this example, all elements other than Zn are the same), these are the same kind of particles. And

  In addition, the particles contained in the coating composition of the present invention are contained in the surface layer in a form in which the surface state has been changed by heat, ionizing radiation, or the like in a process such as coating, drying, curing or vapor deposition. There is also.

  The inorganic particles are not particularly limited, but are preferably metal or metalloid oxides, nitrides, borides, chlorides, carbonates, sulfates, composite oxides containing two metals, metalloids, Different elements may be introduced between the lattices, lattice points may be replaced with different elements, or lattice defects may be introduced.

  The inorganic particles are oxide particles in which at least one metal or semimetal selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba, and Ce is oxidized. More preferably.

Specifically, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide It is preferably at least one metal oxide or semimetal oxide selected from the group consisting of (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ .SnO ₂ ). Particularly preferred is silica (SiO ₂ ).

  Here, the number average particle diameter of the inorganic particles means the number-based arithmetic average length diameter described in JIS Z8819-2: 2001, using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like. The primary particles are observed, and the diameter of the circumscribed circle of each primary particle is defined as the equivalent particle diameter, and the value obtained from the number-based average value is indicated. In the case of a molding material, the number average particle diameter can be determined by observing the surface or cross section. In the case of a coating composition, the coating composition diluted with a solvent is dropped and dried. Thus, it is possible to prepare and observe a sample.

[solvent]
The coating composition A and the coating composition B preferably contain a solvent. The number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less. Here, the “solvent” refers to a substance that is liquid at room temperature and normal pressure, and can be removed from the coating film by evaporating almost the whole amount in the drying step after coating.

  Here, the kind of solvent is determined by the molecular structure constituting the solvent. That is, the same elemental composition and the same type and number of functional groups have different bond relationships (structural isomers), which are not structural isomers, but what conformations are in three-dimensional space Those that do not overlap exactly even if they are removed (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are handled as different solvents.

[Other additives]
The coating composition A and the coating composition B preferably contain a polymerization initiator, a curing agent, and a catalyst. A polymerization initiator and a catalyst are used to accelerate the curing of the surface layer. As the polymerization initiator, those capable of initiating or accelerating polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization reaction or the like of components contained in the coating composition are preferable.

  Various polymerization initiators, curing agents and catalysts can be used. In addition, the polymerization initiator, the curing agent, and the catalyst may be used alone, or a plurality of polymerization initiators, curing agents, and catalysts may be used simultaneously. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like.

  As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropane-1-o , 1- [4- (2-Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and materials thereof And the like having a high molecular weight.

  In addition, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, etc. may be added to the coating composition A and the coating composition B used for forming the surface layer as long as the effects of the present invention are not impaired. . Thereby, the surface layer can contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like. Examples of the leveling agent include acrylic copolymers, silicone-based and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalic acid anilide-based, triazine-based and hindered amine-based ultraviolet absorbers. Examples of the antistatic agent include metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt and calcium salt, and conductive polymers such as polythiophene and polypyrrole.

[Production method of laminated film]
As described above, the production method for forming the surface layer in the present invention is a method of forming two or more types of coating compositions by “sequentially” coating, drying and curing on a supporting substrate, and two types of methods. A method of forming the above coating composition by coating, drying and curing “simultaneously” on a supporting substrate is preferable. The method of “coating at the same time” is not particularly limited, but as a typical example, “multilayer slide die coating” in which two or more coating compositions are sequentially laminated and applied in a state before application. "Multi-layer slot die coat" which is laminated on the substrate simultaneously with application, "Wet-on-wet coat" in which one layer of liquid film is formed on the supporting substrate and then another layer is laminated in an undried state. Etc.

Type of coating composition used in the present production method, the number, and the supporting substrate by appropriately selecting, it is possible to control the modulus of elasticity E _X50 50% position of the thickness of the elastic modulus Ez and the surface layer of the surface Furthermore, the continuity of the form of the elastic modulus distribution in the surface layer can be controlled by appropriately selecting the type, composition, drying conditions, and curing conditions of the coating composition.

  The production method of the laminated film of the present invention uses a production method in which at least the coating composition A and the coating composition B are formed by applying, drying, and curing sequentially or simultaneously on the supporting substrate. More preferred.

  Next, the liquid film applied on the support substrate or the like is dried. In addition to completely removing the solvent from the resulting laminated film, the drying process preferably involves heating the liquid film.

  Examples of the drying method include heat transfer drying (adherence to a high-temperature object), convection heat transfer (hot air), radiant heat transfer (infrared ray), and others (microwave, induction heating). Among these, in the manufacturing method of the present invention, a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to make the drying speed uniform even in the width direction.

  Furthermore, you may perform the further hardening operation (hardening process) by irradiating a heat | fever or an energy ray. In the curing step, when curing with heat, it is preferably from room temperature to 200 ° C., more preferably from 100 ° C. to 200 ° C. from the viewpoint of the activation energy of the curing reaction, and from 130 ° C. to 200 ° C. More preferably it is.

  Moreover, when hardening with an active energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. In the case of curing with ultraviolet rays, the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable. When the oxygen concentration is high, the hardening of the outermost surface is inhibited, and the surface hardening may be insufficient.

Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. Case of UV cured using a high pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays 100~3,000mW / cm ^2, preferably 200~2,000mW / cm ^2, more preferably 300~1,500mW / cm ² performing the ultraviolet irradiation is preferred, the accumulated light quantity of ultraviolet 100~3,000mJ / cm ^2, preferably 200~2,000mJ / cm ^2, more preferably a 300~1,500mJ / cm ² under the condition that the It is more preferable to perform ultraviolet irradiation under conditions. Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

[Application example]
Since the laminated film of the present invention has both functions such as antireflection and antifouling properties and self-repairing properties, it can be widely used for, for example, electrical appliances, automobile interior members, and building members.

  For example, glasses, sunglasses, cosmetics boxes, plastic molded products such as food containers, smartphone housings, touch panels, keyboards, home appliances such as TVs and air conditioners, buildings, dashboards, car navigation systems, touch panels, rooms It can be suitably used for vehicle interior parts such as mirrors, and the surfaces of various printed materials.

  Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.

[Urethane (meth) acrylate A]
[Synthesis of Urethane (Meth) acrylate A1]
50 parts by mass of toluene, isocyanurate modified type of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals), polycaprolactone modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.) 76 parts by mass, 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate A1 having a solid content concentration of 50% by mass.

[Urethane (meth) acrylate B]
[Synthesis of urethane (meth) acrylate B1]
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanatohexanoate (LDI manufactured by Kyowa Hakko Kirin Co., Ltd.) and 119 parts by mass of polycarbonate diol (“Placcel” (registered trademark) CD-210HL manufactured by Daicel Chemical Industries, Ltd.) The parts were mixed, heated to 40 ° C. and held for 8 hours. Then, 28 parts by mass of 2-hydroxyethyl acrylate (Kyoeisha Chemical Co., Ltd., light ester HOA), 5 parts by mass of dipentaerystole hexaacrylate (M-400 manufactured by Toagosei Co., Ltd.), 0.02 parts by mass of hydroquinone monomethyl ether In addition, after maintaining at 70 ° C. for 30 minutes, 0.02 part by mass of dibutyltin laurate was added and maintained at 80 ° C. for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate B1 having a solid content concentration of 50% by mass.

[Urethane (meth) acrylate C]
[Synthesis of urethane (meth) acrylate C1]
Isocyanurate modified form of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc., isocyanate group content: 20.9% by mass), 50 parts by mass, polyethylene glycol monoacrylate (manufactured by NOF Corporation) "Blemmer" (registered trademark) AE-150, hydroxyl value: 264 (mgKOH / g)) 53 parts by mass, dibutyltin laurate 0.02 parts by mass and hydroquinone monomethyl ether 0.02 parts by mass were charged. And it reacted by hold | maintaining at 70 degreeC for 5 hours. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter sometimes referred to as MEK) was added to the reaction solution to obtain urethane (meth) acrylate C1 having a solid content concentration of 50% by mass.

[Siloxane compound]
[Siloxane compound 1]
As the siloxane compound 1, a silicon diacrylate compound (“EBECRYL” (registered trademark) 350 manufactured by Daicel Cytec Co., Ltd., solid content concentration: 100 mass%) was used.

[Fluorine compounds]
[Fluorine compound 1]
As the fluorine compound 1, an acrylate compound containing a fluoropolyether segment (“Megafac” (registered trademark) RS-75 manufactured by DIC Corporation, solid content concentration: 40 mass%, solvent (toluene and methyl ethyl ketone), 60 mass%)) was used.

[Photo radical polymerization initiator]
[Photoradical polymerization initiator 1]
As the photoradical polymerization initiator 1, “Irgacure” (registered trademark) 184 (manufactured by BASF Japan Ltd., solid content concentration: 100% by mass) was used.

[Multifunctional acrylate]
[Polyfunctional acrylate 1]
As the polyfunctional acrylate 1, a urethane acrylate oligomer (“SHIKOH” (registered trademark) UV-3310B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration: 100 mass%) was used.

[Multifunctional acrylate 2]
As the polyfunctional acrylate 2, “KAYARAD” (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., solid content concentration: 100 mass%), which is dipentaerythritol hexaacrylate, was used.

[Hollow silica]
[Hollow silica 1]
As the hollow silica 1, a hollow silica dispersion (“low refractive index hard coat” A-2502LR, manufactured by Pernox Co., Ltd., solid content concentration 10% by mass) was used.

[Preparation of coating composition A]
[Coating composition A1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 having a solid concentration of 30% by mass.
・ 45 parts by mass of urethane (meth) acrylate A1 solution (solid content concentration: 50 mass%) ・ 45 mass parts of urethane (meth) acrylate C1 solution (solid content concentration: 50 mass%) ・ 3 mass parts of siloxane compound 1 ・ 1 solution of fluorine compound (Solid content concentration: 40% by mass) 3.8 parts by mass, photoradical polymerization initiator 1 1.5 parts by mass, ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content: 50 mass%) 40 mass parts ・ Urethane (meth) acrylate C1 solution (solid content: 50 mass%) 40 mass parts ・ Polyfunctional acrylate 1 10 mass parts ・ Siloxane compound 1 3 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass-Radical radical polymerization initiator 1 1.5 parts by mass-Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A3]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration 50 mass%) 60 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration 50 mass%) 20 mass parts ・ Polyfunctional acrylate 1 10 mass parts ・ siloxane compound 1 3 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass-Radical radical polymerization initiator 1 1.5 parts by mass-Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A4]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid content of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration 50 mass%) 20 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration 50 mass%) 60 mass parts ・ Polyfunctional acrylate 1 10 mass parts ・ siloxane compound 1 3 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass-Radical radical polymerization initiator 1 1.5 parts by mass-Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration 50 mass%) 40 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration 50 mass%) 40 mass parts ・ Polyfunctional acrylate 2 10 mass parts ・ siloxane compound 1 3 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass-Radical radical polymerization initiator 1 1.5 parts by mass-Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A6]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration: 50 mass%) 20 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration: 50 mass%) 20 mass parts ・ Fluorine compound 1 solution (solid content concentration: 40 mass%) 3.8 parts by mass · Hollow silica 1 40 parts by mass · Photoradical polymerization initiator 1 1.5 parts by mass · Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A7]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 having a solid concentration of 30% by mass.
・ 90 parts by mass of urethane (meth) acrylate C1 solution (solid content concentration: 50 mass%) ・ 3 mass parts of siloxane compound 1 ・ 3.8 mass parts of fluorine compound 1 solution (solid content concentration: 40 mass%) ・ Photoradical polymerization initiator 1 1.5 parts by mass / ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A8]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration: 50 mass%) 45 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration: 50 mass%) 45 mass parts ・ Radical radical polymerization initiator 1 1.5 mass parts -10 parts by mass of ethylene glycol monobutyl ether.

[Coating composition A9]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration: 50 mass%) 20 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration: 50 mass%) 20 mass parts ・ Polyfunctional acrylate 1 10 mass parts ・ Fluorine compound 1 Solution (solid content concentration: 40% by mass) 3.8 parts by mass, 40 parts by mass of hollow silica 1, 1.5 parts by mass of radical photopolymerization initiator 1, 10 parts by mass of ethylene glycol monobutyl ether.

[Coating composition A10]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A10 having a solid concentration of 30% by mass.
-90 parts by mass of urethane (meth) acrylate C1 solution (solid concentration 50% by mass)-1.5 parts by mass of radical photopolymerization initiator 1-10 parts by mass of ethylene glycol monobutyl ether.

[Coating composition A11]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A11 having a solid concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration: 50 mass%) 45 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration: 50 mass%) 45 mass parts ・ Radical radical polymerization initiator 1 1.5 mass parts -10 parts by mass of ethylene glycol monobutyl ether.

[Coating composition A12]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A12 having a solid concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration 50 mass%) 60 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration 50 mass%) 20 mass parts ・ Polyfunctional acrylate 1 30 mass parts ・ Siloxane compound 1 3 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass-Radical radical polymerization initiator 1 1.5 parts by mass-Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A13]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A13 having a solid content concentration of 30% by mass.
-Urethane (meth) acrylate C1 solution (solid content concentration 50 mass%) 40 mass parts-Hollow silica 1 40 mass parts-Photoradical polymerization initiator 1 1.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts.

[Preparation of coating composition B]
[Coating composition B1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B1 having a solid concentration of 30% by mass.
・ 60 parts by mass of urethane (meth) acrylate A1 solution (solid content concentration 50 mass%) ・ 20 mass parts of urethane (meth) acrylate C1 solution (solid content concentration 50 mass%) ・ 3 mass parts of siloxane compound 1 ・ Initiation of radical photopolymerization Agent 1 1.5 parts by mass / Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition B2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B2 having a solid content concentration of 30% by mass.
-20 parts by mass of urethane (meth) acrylate A1 solution (solid content concentration 50% by mass)-60 parts by mass of urethane (meth) acrylate C1 solution (solid content concentration 50% by mass)-3 parts by mass of siloxane compound 1-Start of radical photopolymerization Agent 1 1.5 parts by mass / Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition B3]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B3 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate A1 solution (solid content concentration: 50 mass%) 40 mass parts ・ Urethane (meth) acrylate C1 solution (solid content concentration: 50 mass%) 40 mass parts ・ Siloxane compound 1 3 mass parts ・ Radical radical polymerization initiation Agent 1 1.5 parts by mass / Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition B4]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B4 having a solid content concentration of 30% by mass.
-80 parts by mass of urethane (meth) acrylate A1 solution (solid content concentration 50% by mass)-3 parts by mass of siloxane compound 1-1.5 parts by mass of radical photopolymerization initiator 1-10 parts by mass of ethylene glycol monobutyl ether.

[Coating composition B5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B5 having a solid concentration of 30% by mass.
-80 parts by mass of urethane (meth) acrylate B1 solution (solid content: 50% by mass)-3 parts by mass of siloxane compound 1-1.5 parts by mass of radical photopolymerization initiator 1-10 parts by mass of ethylene glycol monobutyl ether.

<Method for producing laminated film>
[Method 1 for creating laminated film by sequential application (two-layer structure)]
As a supporting substrate, “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm in which an easy-adhesive paint is applied on a PET resin film was used. Apply the coating composition of the lowermost layer using a continuous application device with a slot die coater, adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes the specified film thickness, then under the following conditions A drying step and a curing step were performed to form a lowermost layer.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 2 "Curing process" for minutes
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: Atmospheric atmosphere.

Furthermore, using the same device, change the coating composition to the outermost layer, apply it by adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes the specified film thickness, then under the following conditions A drying process and a curing process were performed to obtain a laminated film.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 2 "Curing process" for minutes
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 200 ppm or less in volume ratio.

[Method 2 for creating laminated film by simultaneous multi-layer application (application by multi-layer slot die coater)]
As a supporting substrate, “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm in which an easy-adhesive paint is applied on a PET resin film was used. Using a multi-layer slot die coater, the coating composition B is discharged from the slot on the upstream side in the conveying direction of the supporting substrate of the apparatus, and the coating composition A is discharged from the slot on the downstream side in the conveying direction of the supporting substrate. The discharge flow rate was adjusted so that the amount ratio was applied, and then the drying process and the curing process were performed under the following conditions to obtain a laminated film.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 2 "Curing process" for minutes
Irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 200 ppm or less in volume ratio.

  The laminated film of Examples 1-15 and Comparative Examples 1-10 was created by the above method. Table 1 shows the method for producing the laminated film corresponding to each example and comparative example, and the coating composition used.

<Evaluation of laminated film>
About the produced laminated film, the following performance evaluation was implemented and the obtained result is shown in Table 2. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

[Measurement of elastic modulus by atomic force microscope]
Cross sections of the laminated films of Examples 1 to 15 and Comparative Examples 1 to 10 were cut out by the freezing microtome method, and the cross section was used as a measurement surface for the elastic modulus _EX 50 at a position of 50% of the thickness of the surface layer. To the surface layer using an AFM “MFP-3DSA-J” manufactured by Asylum Technology and a cantilever “R150-NCL-10 (material Si, spring constant 48 N / m, radius of curvature of the tip 150 nm)” manufactured by NANOSENSORS. A force curve (cantilever moving speed 2 μm / s, maximum indentation load 2 μN) was measured in a contact mode perpendicular to the thickness direction of the surface layer at a position of 50% of the thickness.

  Moreover, the elastic modulus (Ez) of the surface layer was also measured. Specifically, it was fixed to a dedicated sample table so that the surface of the surface layer of the laminated film was a measurement surface, and measured in a direction perpendicular to the surface.

[Crack elongation of surface layer]
The laminated film was cut into a length of 10 mm × 200 mm, held with a chuck in the longitudinal direction, and stretched with an Instron type tensile tester (ultra precision material tester MODEL 5848 manufactured by Instron) at a pulling rate of 100 mm / min. The measurement temperature was 23 ° C. When stretching, the sample during stretching was observed, and stopped when a crack (crack) occurred visually (the amount of strain when stopping was adjusted to be an integer of 5). Samples to be measured from the next were sequentially sampled with the strain amount lowered by 5% from the strain amount at the time of stopping, and finally the strain amount until cracks were not visually observed.

Note that the strain amount x (%) was calculated by the following equation, where the distance between the initial tensile chucks was 50 mm and the distance between the tensile chucks was a (mm).
Strain amount: x = ((a-50) / 50) × 100.

  Cut out the thin film cross section of the cracked portion of the sample collected, observe the surface layer at a magnification such that the thickness of the surface layer to be observed is 30 mm or more on the observation screen of the transmission electron microscope, and determine the average thickness of the surface layer. When cracks of 50% or more have occurred, cracks are present (the surface layer is broken), and among the samples with cracks, the strain value of the sample with the lowest strain is defined as the crack elongation. . And the same measurement was performed 3 times in total and the average value of those crack elongation was made into the crack elongation of a surface layer.

[Surface layer self-healing]
After leaving the laminated film at a temperature of 20 ° C. for 12 hours, in the same environment, the surface layer was scratched horizontally 5 times with a brass brush (manufactured by TRUSCO) and left for 5 minutes. The state of the scratch was determined visually according to the following criteria. Evaluation was performed 5 times for each sample, and the average score was rounded to the first decimal place.
10 points: No scratches left at 1 kg load 7 Scratches remain at 1 kg load, but no scratches left at 700 g 4 points: No scratches left at 700 g load, but no scratches left at 500 g 1 point: At 500 g load The wound remains.

[Durability against scratches on the surface layer]
After the laminated film is left at a temperature of 20 ° C. for 12 hours, the surface of the surface layer is rubbed 10 times with steel wool # 000 at a load of 200 g in the same environment, and the surface condition after being left for 5 minutes is classified as follows. went. The evaluation was performed 5 times for each sample, and the average score was rounded off to the first decimal place.
10 points: No scratch 7 points: 1 to 10 scratches 4 points: 11 to 20 scratches 1 point: The surface layer of the test part was completely peeled off.

[Contamination resistance]
Jeans (containing a dye) wetted with water of 6 cm × 6 cm was brought into close contact with the surface layer of the laminated film cut out to a size of 9 cm × 6 cm, and sandwiched between 6 cm × 6 cm glass plates. It was wrapped in a polyethylene film so that the water did not evaporate, and a 3 kg weight was placed on the glass plate and left in an oven at 70 ° C. After 24 hours, the laminated film was placed on a white paper equivalent to the white part of the contamination gray scale described later, and the contamination degree of the surface layer surface was changed to 1 to 5 on the contamination gray scale (JIS L0805 (2005)). Grade 1 (Grade 1 is dirty gray scale No. 1 or more than that level (dirt remains dark), Grade 2 is gray scale No. 2 for stain (significantly dirty), 3 The grade is for gray scale No. 3 for contamination (slightly remains), the grade 4 is for gray scale No. 4 for contamination (almost no dirt is left), and the grade 5 is for gray stain for contamination Judgment was made with a scale of No. 5 (no dirt remained). In addition, in accordance with the notation of JIS L0805 (2005), when it is between each class, for example, between the first class and the second class, it is set to “1-2”. Furthermore, the determination was made according to the following criteria.
10 points: Dye transfer resistance of surface layer is grade 5 7 points: Dye transfer resistance of surface layer is grade 4 or more and less than grade 5 4 points: Dye migration resistance of surface layer is grade 3 or more and less than grade 4 1 point: Dye resistance of surface layer is less than 3rd grade.

[Measurement of reflectance of laminated film]
A spectrophotometer (manufactured by Shimadzu Corporation; UV-3100) is used to measure the reflection spectrum of the light having a wavelength of 380 to 780 nm when the surface of the laminated film on which the surface layer is not laminated is painted with a black paint. The lowest value of the obtained spectral reflectance was obtained, and the lowest value was taken as the reflectance of the laminated film. Moreover, the following classification was performed for the minimum value. In addition, evaluation was performed 5 times about each sample and the value which rounded off the average score to the first decimal place was employ | adopted.
10 points: Minimum reflectance of less than 1 7 points: Minimum reflectance of 1 to less than 2 4 points: Minimum reflectance of 2 to less than 3 1 point: Minimum reflectance of 3 or more.

[Measurement of Ta and Tb]
By observing a cross section using an electron microscope (SEM), the thicknesses of the A layer and the B layer on the support substrate were measured. The thickness of each layer was measured according to the following method. The thickness of each layer was read by software (image processing software ImageJ) from an image obtained by photographing a cross section of the laminated film at a magnification of 3,000 with an SEM. The average value obtained by measuring the layer thickness of 30 points in total was defined as Ta and Tb.

[Measurement of refractive index of layer _A (n _A )]
The refractive index (n _A ) of the A layer is measured with respect to the laminated film by a reflectance spectral film thickness meter (trade name [FE-3000], manufactured by Otsuka Electronics Co., Ltd.), Using the software [FE-Analysis] attached to the apparatus, the refractive index at 550 nm is obtained according to the method described in [Film thickness measuring apparatus general catalog P6 (nonlinear least squares method)] manufactured by Otsuka Electronics Co., Ltd., and the refractive index at 550 nm. Was the refractive index (n _A ) of the A layer.

The optical constants (C ₁ , C ₂ , C ₃ ) are calculated by the least square method (curve fitting method) using the Cauchy dispersion formula (Formula 1) as an approximate expression of the chromatic dispersion of the refractive index, and the refraction at 550 nm. The rate was measured.

[Particle concentration in the surface layer]
The particle concentration of the surface layer can be confirmed by observing a cross section using a transmission electron microscope (TEM) and counting the number of particles. Specifically, the procedure was as follows. An image obtained by photographing an ultra-thin section of a laminated film at a magnification of 100,000 times with a TEM is applied every 100 nm from the surface side over the width of the same length as the thickness of the surface layer by software (image processing software ImageJ). Trimming was performed. Trimming is performed on the entire cross-sectional area from the surface side to the base material side. Next, the white balance of the image was adjusted so that the brightest part and the darkest part fit within an 8-bit tone curve, and the contrast was adjusted so that the particles could be clearly distinguished, and then the number of particles in the image was counted. In addition, particles that are cut at the edge of the image are not counted. By counting the number of particles in each image, it was confirmed whether or not the particle concentration increased from the substrate side to the surface side. Here, the particle concentration increases from the substrate side to the surface side when the distance from the substrate side is plotted on the horizontal axis and the number of particles is plotted on the vertical axis, the slope of the approximate straight line obtained by the least square method Is positive.

DESCRIPTION OF SYMBOLS 1 Support base material 2 Surface layer 3 The surface of a surface layer (elastic modulus ( _EZ ) measurement position)
4 Position of 50% of the thickness of the surface layer (elastic modulus ( _EX50 ) measurement position)
5 Surface layer of the surface layer (A layer)
6 Second layer from the surface layer (B layer)

  The laminated film according to the present invention takes advantage of self-repairability, moldability, durability, antifouling properties, plastic molded products such as glasses / sunglasses, cosmetic boxes, food containers, smartphone housings, touch panels, keyboards, It can be suitably used for home appliances such as TV / air conditioner remote controls, buildings, dashboards, car navigation / touch panels, vehicle interiors such as room mirrors, and various printed materials.

Claims (6)

In a laminated film having a surface layer on at least one surface of a support substrate, the elastic modulus (Ez) (MPa) obtained by measuring the surface of the surface layer with an atomic force microscope, and the support of the surface layer The elastic modulus ( _EX50 ) (MPa) obtained by measuring the position of 50% of the thickness of the surface layer with an atomic force microscope in the cross section perpendicular to the substrate satisfies the following conditions 1 and 2. A laminated film characterized by
Condition 1 E _Z > E _X50
Condition 2 1 MPa ≦ E _X50 ≦ 50 MPa The laminated film according to claim 1, wherein the elastic modulus (Ez) satisfies the following condition 3.
Condition 3 100 MPa ≦ E _Z <1 GPa The surface layer has two or more layers, and the thickness of each of the outermost layer (referred to as A layer) and the second layer from the outermost surface (referred to as B layer) is T _A (μm), T The laminated film according to claim 1, wherein the following condition 4 and condition 5 are satisfied when _B (μm) is satisfied.
Condition _{4 2 ≦ T B / T A} ≦ 500
Condition 5 0.01 μm ≦ T _A ≦ 5 μm The laminated film according to any one of claims 1 to 3, wherein the surface layer contains particles, and the particle concentration increases from the support substrate side toward the surface side. The reflectance is 2.0% or less, and the refractive index (n _A ) of the A layer and the thickness (T _A ) of the A layer satisfy the following conditions 6 and 7. The laminated film according to 3 or 4.
Condition 6 1.35 ≦ n _A ≦ 1.40
Conditions 7 50nm ≦ _{T A} ≦ 150nm The laminated film according to claim 1, wherein the surface layer satisfies the following condition 8.
Condition 8 A resin having at least one segment selected from the group consisting of a (poly) caprolactone segment, a (poly) carbonate segment, and a (poly) alkylene glycol segment is included.

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