JP6528681B2 - Laminated film, and method of manufacturing laminated film - Google Patents

Description

  The present invention relates to a laminated film having both abrasion resistance, in particular, repeated scratch resistance and moldability.

  In recent years, a plastic film provided with a surface layer made of a synthetic resin or the like has been used for the purpose of protecting an optical material such as a color filter or a flat panel display or surface of an automobile body There is.

  Since these surface layers are required to have scratch resistance as an important characteristic from the viewpoint of surface protection, various prepolymers such as organosilanes and polyfunctional acrylics described in Non-Patent Document 1 are generally used. , A coating composition containing an oligomer, etc., by coating-drying-heating or UV curing, a "highly crosslinked density material", or an "organic-inorganic hybrid material" combining various surface modification fillers, etc. The scratch resistance is imparted by using a so-called "hard coat material" having an increased surface hardness.

  On the other hand, the surface layer is required to have scratch resistance as an essential characteristic from the viewpoint of surface protection, and various properties such as chemical resistance, oil resistance and moldability are also required according to the application. In particular, since the moldability is likely to cause "cracks" or "peel" to deformation simply by hardening the coating, it is hard to be damaged but is flexible, and it is required to have both abrasion resistance and moldability. There is.

  As a laminate film having both abrasion resistance and moldability in a hard coat material, Patent Document 1 states that “It is a laminate film in which a hard coat layer is provided on at least one surface of a substrate film, and it is It is proposed that the maximum value of the surface hardness of the hard coat layer is 0.05 GPa or more and 4.0 GPa or less, and the crack elongation under 100 ° C. atmosphere is 15% or more and less than 250%. There is.

  On the other hand, films using a so-called "self-healing material" are proposed in Patent Documents 2 and 3 which repair scratches on the surface by deformation of the elastic recovery range of the material of the surface layer and achieve scratch resistance. Furthermore, as a material whose moldability is improved by improving the extensibility of the self-repairing material, Patent Document 4 states that “at least one resin (A) selected from epoxy resin, oxetane resin, vinyl ether resin A resin composition comprising a polyol (B) having a number average molecular weight of 400 or more and an active energy ray-sensitive catalyst (C), wherein the polyol (B) has a main chain consisting of carbon-carbon bonds (B1) , Polycarbonate polyol (B2), polyester polyol (B3), and polyether polyol (B4) The active energy ray-curable coating agent "is proposed, which is a Lumpur.

  Further, as another method of improving the moldability of the self-repairing material, as an invention focusing on the laminated structure, Patent Document 5 “In at least one surface of the resin substrate, a stress relaxation layer and a self-repairing layer The self-repairing layer is made of at least a soft synthetic resin, and the hardness H of the stress relaxation layer in contact with the self-repairing layer is the nanoindentation of the self-repairing layer. A laminate with a self-repairing layer, which is characterized by being equal to or lower than the hardness H according to

Plastic hard coat applied technology CMC publication 2004

JP, 2009-184284, A International Publication No. 2011/136042 JP-A-11-228905 JP 2007-284613 A JP, 2011-5766, A

  However, despite the extremely high surface hardness, molded articles using the above-mentioned "hard coat material" for the surface layer are often damaged in daily life and often impair the appearance, and the inventors of the present invention As a result, it was found that the "hard coat material" had a high surface hardness, but when repeatedly rubbed with a soft cloth or the like, it caused fine scratches on the surface and the surface became cloudy.

  On the other hand, when the present inventors confirmed the materials proposed in Patent Document 2 and Patent Document 3, it is hard to be scratched in daily life, and the scratch is recovered by the self-repairing function even after repeated rubbing. Thus, it was found that the abrasion resistance equal to or higher than that of the hard coat material was obtained.

  However, the self-healing material appears to be excellent in formability because it is a flexible material, but when it is actually formed, the surface layer and crack in the surface layer immediately after the formation, or at storage after the formation It has been found that (cracks) and the surface layer may peel from this as a starting point.

  Further, Patent Documents 4 and 5 propose that one of the problems is to achieve both self-repairing property and moldability, but the present inventors confirmed that in any case, the effect is a crack during molding Or was not sufficient in terms of repeated abrasion. Further, none of Patent Documents 1 to 5 has been conceived about the structure of the present invention. Therefore, an object of the present invention is to provide a laminated film having both abrasion resistance, in particular, repeated abrasion resistance and moldability.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of repeating earnest research, the present inventors completed the following invention. That is, the present invention is as follows.
(1) A laminated film having a surface layer including an A layer and a B layer on at least one surface of a supporting substrate, the B layer and the A layer being in contact in this order from the supporting substrate side, A Storage elastic modulus (hereinafter referred to as E _A25 , E _B25 , E _C25 ) measured by a microhardness tester of the layer, B layer, and the supporting substrate (hereinafter referred to as E ₁₂₀ , E _{B 120} , etc.) E _C120 ) A laminated film characterized by satisfying the following conditions.
Condition 1 E A ₂₅ <E _{B 25} ≦ E _{C 25}
Condition 2 E _B120 ≦ E A ₁₂₀ <E _{C 120}
Condition 3 E A ₂₅ ≦ 100 MPa
(2) The laminated film according to (1), wherein the layer A, the layer B, and the supporting substrate satisfy the following conditions.
Condition 4 0 <E _C25 −E _B25 <5 GPa
Condition 5 0 <E _A120 -E _B120 <50 MPa
(3) The laminated film according to (1) or (2), wherein the glass transition temperature (hereinafter, Tg _B ) of the layer _B satisfies the following conditions.
Condition 6 60 ° C. ≦ Tg _B ≦ 130 ° C.
(4) The laminated film according to any one of (1) to (3), wherein the thickness (hereinafter referred to as TB) of the layer _B satisfies the following condition.
Condition 7 0.1 μm ≦ T _B ≦ 5 μm
(5) In a cross section perpendicular to the base material of the surface layer, the position of 10% of the surface layer thickness (hereinafter referred to as position 1), 50% (hereinafter referred to as position 2), 99 from the surface of the surface layer The elastic modulus E1, E2 or E3 by atomic force microscope at each position of% (hereinafter referred to as position 3) is characterized by the following condition (1) to (4) Laminated film.
Condition 8 E1 ≦ E2 <E3
Condition 9 E1 ≦ 100 MPa
Condition 10 E3 1 1 GPa
(6) The method for producing a laminated film according to any one of (1) to (5), wherein the surface layer is formed by sequentially applying two or more types of coating compositions onto a supporting substrate, and A method of producing a laminated film characterized by being cured.
(7) The method for producing a laminated film according to any one of (1) to (5), wherein the surface layer simultaneously applies two or more types of coating compositions onto a supporting substrate, and then dried A method of producing a laminated film characterized by being cured.

According to the present invention, it is possible to provide a laminated film having both abrasion resistance, in particular, repeated scratch resistance and moldability.

It is an example of sectional drawing which shows the structure of the laminated | multilayer film of this invention. It is an example of sectional drawing which shows the structure of the laminated | multilayer film of this invention. It is sectional drawing which shows an example of the formation method of the surface layer in this invention. It is sectional drawing which shows an example of the formation method of the surface layer in this invention. It is sectional drawing which shows an example of the formation method of the surface layer in this invention.

  In achieving the above problems, the present inventors (1) why the self-healing material is superior in abrasion resistance to the hard coat material in a practical use environment, (2) the soft self-healing material immediately after molding, or The reason why the surface layer is cracked in the later storage and the reason why the surface layer is peeled off starting from the crack was examined in detail, and the following discussion was reached.

  First, the above (1) will be described. The formation of flaws on the plastic surface is affected by three factors: "pressure", "hardness of abrading" and "number of times of rubbing". The reason why hardcoat materials are easily scratched in the actual use environment is that the scratching mechanism in the actual use environment, that is, "in the actual use environment, the surface is scratched but the contact frequency is very high while the surface hardness is low". caused by. With hard-coat materials, internal hardness does not lead to scratches on the surface of the material, even under conditions where the hardness of the abrasive is low or the pressure at the time of abrasion is low and the surface is not scratched by one abrasion, This is accumulated as distortion as the "number of times of abrasion" increases. As a result, it is considered that the hard coat material having high hardness and small strain range capable of elastic deformation is finally scratched beyond the strain tolerance. On the other hand, the self-repairing material is strong in the actual use environment and effective for repeated abrasions because the elastic recovery range of the material is large, so that the strain can be released even under the above-mentioned conditions and no scratch is formed it is conceivable that.

  Next, the above-mentioned (2) will be described. The laminated film using a material that develops self-repairing property by elastic recovery as a surface layer and a general thermoplastic resin as a base material described in Patent Documents 2 to 3 has a surface layer “entropy elastic body = rubber elasticity It can be said that the body and the supporting base material are "energy elastic bodies", and therefore they are formed of materials whose mechanical behavior to heat is largely different. When such a film is heated and molded, the supporting base material is plastically deformed and fixed, but the self-repairing layer is deformed in the elastic deformation range, and thus becomes stretched by the supporting base material, and the surface Residual stress occurs in the layer. When the surface layer is an entropy elastic body when subjected to further heating in a post-process, for example, injection molding, or reaches a high temperature in the use environment, the elastic modulus is higher than at the time of molding, and at the time of molding It is considered that when the elongation of E is large, the fracture limit is reached and a crack occurs.

  Therefore, as the surface layer of the laminated film, the present inventors have a surface having the following structure, which has both the excellent scratch resistance as described above, in particular sufficient moldability while having repeated scratch resistance in a practical use environment. A laminated film having a layer was found.

  First, the laminated film of the present invention has a surface layer including A layer and B layer on at least one surface of the supporting substrate 3 as shown in FIG. 1, and B layer and A layer from the supporting substrate side Are in contact in this order.

The layer which is the second layer from the side of the supporting substrate in the surface layer (1 in FIG. 1, ie A layer), the layer in contact with the supporting substrate (2 in FIG. 1 ie B layer), the supporting substrate Storage modulus of elasticity at 25 ° C. (hereinafter referred to as E ₂₅ , E _{B 25} , E _{C 25} ) measured by a microhardness tester (3 in FIG. 1, hereinafter referred to as C layer), storage modulus of 120 ° C. (hereinafter, It is preferable that E _A120 , E _B120 , E _C120 ) satisfy the following conditions.
Condition 1 E A ₂₅ <E _{B 25} ≦ E _{C 25}
Condition 2 E _B120 ≦ E A ₁₂₀ <E _{C 120}
Condition 3 E A ₂₅ ≦ 100 MPa.

Here, condition 1 is the elastic modulus at 25 ° C., that is, the layer A (layer in contact with the layer B in the surface layer) at the temperature at which the laminated film is used in actual use, the layer B in contact with the support substrate in the surface layer And C) (support base material). The C layer has the highest storage modulus, the B layer has a higher storage modulus than the A layer, and the same as or lower than the C layer, meaning that the A layer has the lowest storage modulus. More preferably, E _A25 <E _B25 <E _C25 .

  With such a configuration, the layer B has sufficient cohesion, and the surface layer has sufficient adhesion to the layer C, and peeling does not easily occur even in repeated use in practical use. preferable.

  The surface layer may include other layers as long as it includes an A layer and a B layer. That is, the constitution of the surface layer may be composed of three or more layers as shown in FIG. 3. In this case, the elastic modulus of the layer (referred to as Z layer) on the surface side of layer A is not particularly limited. The Z layer preferably has an elastic modulus close to that of the A layer. Here, the Z layer may have other functions such as antifouling property, fingerprint resistance, anti-dyeing property, antireflective property, antiglare property, antistatic property, and the like.

  The storage elastic modulus measured by the above-described microhardness tester means a value measured by using a microhardness tester by preparing an ultrathin section of the cross section of the surface layer of the laminated film. Details of the specific measurement method and calculation method will be described later.

If the order of the elastic modulus is reversed, that is, E A ₂₅ > E _{B 25} > E _{C 25} , strain release due to elastic recovery of the surface layer can not be released, and therefore, it may be weak to repeated abrasion. In addition, when the order changes, that is, E _B25 > E _A25 > E _B25, etc., a stress concentration portion may be formed in the layer, and peeling may occur in the vicinity thereof.

Condition 2 shows the elastic modulus at 120 ° C., that is, the elastic modulus of layer A, layer B and layer C near the molding temperature of the laminated film, and layer B has the lowest elastic modulus or layer A. Likewise, layer A has a lower modulus than layer C, meaning layer C has the highest modulus. More preferably, E _B120 <E _A120 <E _C120 .

  With such a configuration, the modulus of elasticity of the B layer becomes lower than that of the A layer during molding, so no residual stress is left in the A layer, and cracking occurs even at high temperatures in heating and use environments in the subsequent steps. It is preferable because it is difficult.

If the order of the elastic modulus is _reversed , that is, E A ₁₂₀ ≦ E _{B 120} <E _{C 120} , residual stress may build up during molding by the above-mentioned mechanism, and cracking may occur at a high temperature in the heating and use environment in the subsequent steps. .

Here, the condition 3 indicates a preferable range of the elastic modulus (E _A25 ) at 25 ° C. of the layer A. The value of E _A25 is preferably at most 100 MPa, more preferably at most 50 MPa, and particularly preferably 20 MPa. When the value of E A ₂₅ exceeds 100 MPa, release of strain due to elastic recovery may be insufficient at repeated abrasion. The small value of E _A does not cause any problem in achieving this subject, but when it is 1 MPa or less, the surface may be tacky and may not be practical from the viewpoint of surface protection. is there.

Furthermore, it is preferable to satisfy the following condition 4 and condition 5.
Condition 4 0 <E _C25 −E _B25 <5 GPa
Condition 50 <E _A120 -E _B120 <50 MPa.

Here, the condition 4 indicates the range of the difference in preferable storage elastic modulus of the layer B and the layer C at the temperature in the practical use environment of the laminated film, and more preferably 100 MPa <EC ₂₅ −EB ₂₅ <3 GPa .

When E _C25 -E _B25 is 5 GPa or more, the adhesion of the surface layer to the supporting substrate may be insufficient, and thus the repeated abrasion resistance may be reduced. When E _C25 -E _B25 becomes zero, the difference in elastic modulus between the A layer and the B layer becomes large as a result, stress concentration at the interface between the A layer and the B layer becomes large, and a scratch remains due to abrasion by a hard material It may be easier.

Condition 5 indicates the range of the difference in storage modulus between layers A and B at the molding temperature, more preferably 0 < _{EA120- EB120} <30 MPa, still more preferably 0 < _EA120- E. _B120 <10 MPa.

When E _A120 -E _B120 is 50 MPa or more, the adhesion between the surface layer and the supporting substrate may be insufficient in the molding process, which may cause wrinkles. Further, when the direction of E _{B 120} is larger than E _{A 120,} residual stress occurs at the interface between the A layer and the B layer during molding, which may easily crack or peel.

Furthermore, the surface layer preferably satisfies the following condition 6.
Condition 6 60 ° C. ≦ Tg _B ≦ 130 ° C.
Here, the condition 6 indicates a preferable range of the glass transition temperature of the layer (B layer) in contact with the support base in the surface layer, and more preferably 60 ° C. ≦ Tg _B ≦ 100 ° C.

  The said glass transition temperature shows the value calculated | required from the maximum value of the temperature dispersion of ratio (loss tangent) of the storage elastic modulus and loss elastic modulus which were measured by the above-mentioned micro hardness meter. Details of the measurement method will be described later.

  When the glass transition temperature of the layer B is lower than 60 ° C., the adhesion between the surface layer and the supporting substrate is reduced, so that the scratch may be easily left by peeling at room temperature or abrasion with a hard material. In addition, when the glass transition temperature of the layer B is higher than 130 ° C., depending on the conditions, cracking and peeling may occur easily during molding.

Furthermore, the surface layer preferably satisfies the following condition 7:
Condition 7 0.1 μm ≦ T _B ≦ 5 μm.

Here, Condition 7 indicates a preferable range of the thickness (T _B ) of the layer (B layer) in contact with the supporting substrate in the surface layer, and more preferably 0.5 μm ≦ T _B ≦ 3 μm. If the thickness of the layer B is smaller than 0.1 μm, the ability to absorb residual stress generated between the surface layer and the support base during molding may become slightly weak, and if the thickness is more than 5 μm, the surface layer and the support base Adhesion between materials may be slightly weak.

The laminated film of the present invention is a laminated film having a surface layer including an A layer and a B layer on at least one surface of a supporting substrate as shown in FIG. 2, which is perpendicular to the substrate of the surface layer. In the cross section, the position of 10% of the surface layer thickness from the surface of the surface layer (hereinafter referred to as position 1; position of 5 in FIG. 2); 50% (hereinafter referred to as position 2). Elastic modulus E1, E2 and E3 by atomic force microscope at each position of 99% (hereinafter referred to as position 3) of position 3 and position 7) are the following condition 8, condition 9, condition 10 It is preferable to satisfy
Condition 8 E1 ≦ E2 <E3
Condition 9 E1 ≦ 100 MPa
Condition 10 E3 1 1 GPa
Condition 8 is intended to preferably increase the elastic modulus in the thickness direction of the surface layer from the surface side toward the substrate side, and preferably E1 ≦ E2 <E3, E1 <E2 <E3. It is more preferable that

  If this order is reversed, that is, E1> E2> E3, strain release due to elastic recovery can not be performed on the outermost surface, so it is vulnerable to repeated abrasion, and the outermost surface is strained because the elastic modulus of the lower portion is low even if the hardness is high. In the case of abrasion with a material having high pressure or high hardness, the abrasion resistance may be reduced.

  Condition 9 indicates a preferable range of the elastic modulus (E1) on the surface side of the surface layer. 100 MPa or less is preferable, 50 MPa or less is more preferable, and 20 MPa or less is especially preferable. If the value of E1 exceeds 100 MPa, release of strain due to elastic recovery may be insufficient at repeated rubbing. In addition, although the value of E1 is not particularly limited in achieving this subject because it is small, the surface may become tacky at 1 MPa or less, which may not be practical from the viewpoint of surface protection. .

  Condition 10 indicates a preferable range of the elastic modulus (E3) of the surface layer on the support substrate side. The value of E3 is preferably 1 GPa or more, more preferably 2 GPa or more, and particularly preferably 3 GPa or more. If the value of E3 is less than 1 GPa, the surface hardness may be insufficient, and the durability against abrasion by a hard material may be insufficient. The value of E3 is preferably as high as possible for scratch resistance, but the limit is about 100 GPa as a material that can be used as a surface layer on a laminated film from the viewpoint of practically bending resistance and processability.

  Here, measurement of the storage elastic modulus, loss elastic modulus, and glass transition temperature of the surface layer will be described. These measurements can be performed by obtaining a modulus mapping image [storage elastic modulus (E ') image / loss elastic modulus (E' ') image] using an ultra-microhardness tester (Tribo Indenter manufactured by Hysitron) it can.

For example, the laminated film is embedded and cured with an epoxy resin for electron microscopy (Quetol 812 manufactured by Nisshin EM Co., Ltd.), and then an ultra-thin section of the cross section of the surface layer of the laminated film is prepared with an ultramicrotome (Ultracut S manufactured by Leica Co.) Measure the sample under the following conditions and calculate the elastic modulus using Hertz's contact theory.
Measuring device: Tribo Indenter manufactured by Hysitron
Working indenter: Diamond Cubecorner indenter (curvature radius of 50 nm)
Measuring field of view: Approximately 30 mm square Measuring frequency: 200 Hz
Measurement atmosphere: room temperature and atmospheric contact load: 0.3μN
The measurement principle by the ultra-microhardness tester is explained below.

It is known that the stiffness (K) of the measurement system when the axisymmetric indenter is pressed into the sample is represented by equation (1).

Here, A is the projected area of the indentation formed by the contact of the sample with the indenter, and E ^* is the combined elastic modulus of the indenter system and the sample system.

  On the other hand, when the indenter comes in contact with the very surface of the sample, it is considered that the indenter tip can be regarded as a spherical shape, and the Hertzian contact theory for the contact between the spherical and the semi-infinite plate can be applied. In Hertz's contact theory, the radius a of the indentation projection surface when the indenter and the sample are in contact is represented by equation (2).

  Here, P is a load, and R is a radius of curvature of the indenter tip.

Therefore, the projected area A of the indentation formed by the contact of the sample and the indenter is represented by the equation (3), and E ^* can be calculated using the equations (1) to (3).

  Modulus mapping is based on the Hertz's contact theory. The indenter is brought into contact with the very surface of the sample, the indenter is micro-oscillated during the test, and the response amplitude to vibration, the phase difference as a function of time is obtained. It is a method of determining system stiffness) and D (sample damping).

  If this vibration is a simple harmonic oscillator, the sum (detection load component) F (t) of the force in the direction in which the indenter intrudes into the sample is expressed by equation (4).

  Here, the first term of the equation (4) is the force derived from the indenter axis (m: the mass of the indenter axis), the second term of the equation (4) is the force derived from the viscous component of the sample, the equation (4) the third term Represents the stiffness of the sample system and t represents time. Since F (t) of Formula (4) is dependent on time, it is represented like Formula (5).

Here, F ₀ is a constant, and ω is an angular frequency. By substituting the equation (5) into the equation (4), substituting the equation (6) which is a special solution of the ordinary differential equation, and solving the equation, the relational equations of the equations (7) to (10) can be obtained it can.

Here, φ is a phase difference. Since m is known at the time of measurement, the equation (7) to equation can be obtained by measuring the vibration amplitude (h ₀ ), the phase difference (φ) and the excitation vibration amplitude (F ₀ ) of the displacement at the time of measurement of the specimen. From (10), K and D can be calculated.

Formula (1)-Formula (10) are put together, E ^* is regarded as storage elastic modulus (E '), and formula (11) is used using Ks (= K-mω ² ) which is a sample origin among measurement system stiffness The storage modulus was calculated from

  The loss elastic modulus in the present invention can also be measured in the same manner as the measurement of the storage elastic modulus described above, and among the measurement system stiffnesses in the above equation (8), using Ks derived from the sample and summarized together with the equation (11) The loss elastic modulus was calculated from equation (12).

  The glass transition temperature in the present invention can also be measured in the same manner as the measurement of the storage elastic modulus described above, and the loss tangent (tan δ) is determined from the ratio of the storage elastic modulus and loss elastic modulus calculated earlier. The temperature of the peak value of) was taken as the glass transition temperature (Tg).

  The measurement of elastic modulus with an atomic force microscope in the present invention is a compression test with a probe of an extremely small portion, and is a degree of deformation due to a pressing force, so using a cantilever with a known spring constant Measure the elastic modulus at the cross section of each position. Specifically, the laminated film is cut, and the elastic modulus in the cross section at each position in the thickness direction of the surface layer is measured by an atomic force microscope. The details will be described in the section of the example, but using an atomic force microscope shown below, the probe at the tip of the cantilever was brought into contact with the cross section of the surface layer, and the force curve was measured by pressing load of 2 μN at maximum. It can be measured from the amount of deflection of the cantilever. Details will be described later.

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

  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 either in a flat state or in a three-dimensional shape after being formed, as long as it has a surface layer exhibiting the aforementioned physical properties. Here, the “surface layer” in the present invention is preferably formed of at least two or more layers.

  The thickness of the entire surface layer is not particularly limited, but is preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less.

  As the two or more layers described above, at least the surface layer, a layer (A layer) in contact with the B layer, a layer (B layer) in contact with the support base, the A layer, the B layer, the support base, It is preferable to satisfy the above relationship.

  The surface layer has anti-scratch properties, anti-reflecting properties, anti-static properties, conductivity, heat ray reflectivity, near-infrared absorptivity, in addition to the scratch resistance, which is the object of the present invention, and in particular the compatibility between repeated scratch resistance and moldability. , And may have other functions such as electromagnetic wave shielding and easy adhesion.

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

  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 , Polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochlorinated ethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride resin, and the like, acrylic resin Resin, methacrylic resin, polyacetal resin, polyglycolic acid resin, polylactic acid resin, etc. can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. From the viewpoint of strength, heat resistance and transparency, the thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin or a methacrylic resin, and a polyester resin is particularly preferable.

  The polyester resin in the present invention is a general term for a polymer having an ester bond as the main bond chain of the main chain, and is obtained by polycondensation of an acid component and its ester and diol component. Specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate. Moreover, what co-polymerized other dicarboxylic acid and its ester and diol component as an acid component and a diol component may be used for these. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in view of transparency, dimensional stability, heat resistance and the like.

  In addition, the supporting substrate includes various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, an inorganic particle, an organic particle, a viscosity reducing agent, a heat stabilizer, a lubricant, an infrared ray absorbent, an ultraviolet ray absorbent, A dopant for adjusting the refractive index may be added. The supporting substrate may have either a single-layer structure or a laminated structure.

  It is also possible to apply various surface treatments to the surface of the supporting substrate before forming the surface layer. Examples of 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 preferable, and glow discharge treatment and ultraviolet treatment are more preferable.

  In addition to the surface layer of the present invention, functional layers such as an adhesive layer, an antistatic layer, an undercoat layer, and an ultraviolet ray absorbing layer can be provided in advance on the surface of the supporting substrate, and in particular, adhesion is easy 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 above-mentioned physical properties by applying, drying and curing the coating composition on the supporting substrate using the method for manufacturing the laminated film described later. . Here, “coating composition” is a liquid comprising a solvent and a solute, which is applied on the above-mentioned supporting substrate, and a material which can form a surface layer by volatilizing, removing and curing the solvent in a drying step is used. Point to. Here, the “type” of the coating composition refers to a liquid in which the types of solutes constituting the coating composition are partially different. The solute is a resin or a material capable of forming them in a coating process (hereinafter referred to as a precursor), particles, and a polymerization initiator, a curing agent, a catalyst, a leveling agent, an ultraviolet absorber, an antioxidant, etc. It consists of various additives.

  The laminated film of the present invention is applied sequentially or simultaneously on a supporting substrate using at least two types of coating compositions (hereinafter referred to as coating composition A and coating composition B) as described above. It is preferable to form.

  Here, the coating composition A is a second layer from the supporting substrate side of the surface layer, that is, a resin suitable for forming the aforementioned A layer, or a liquid containing a precursor, and the B layer is formed in advance. A layer can be formed on the support substrate by coating, drying, curing, or simultaneously forming, coating, drying and curing the layer B on the support substrate.

  The coating composition B is a layer in contact with the support substrate of the surface layer, that is, a resin suitable for forming the B layer described above, or a liquid containing a precursor, and is applied onto the support substrate, dried, A layer B can be formed by curing or coating, drying and curing on the surface side simultaneously with layer A.

[Coating composition A]
The coating composition A is a liquid containing a material suitable for forming the layer A in the surface layer, or containing a precursor that can be formed, and a resin containing the following segments (1) to (3) as a solute: Or preferably contains a precursor.
(1) Segment containing at least one selected from the group consisting of polycaprolactone segment, polycarbonate segment and polyalkylene glycol segment (2) Urethane bond (3) Fluorine compound segment, polysiloxane segment and polydimethylsiloxane segment A segment containing at least one selected.

  About each segment which resin which comprises A layer in the surface of this surface layer contains, TOF-SIMS, FT-IR, etc. can confirm.

  Moreover, the mass part of said (1), (2), (3) contained in the coating composition A is (1) / (2) / (3) = 95/5/1-50/50/15. (1) / (2) / (3) = 90/10/1 to 60/40/10 are more preferable. The details of (1), (2) and (3) will be described below.

  Although the details of the (1) polycaprolactone segment, the polycarbonate segment and the polyalkylene glycol segment will be described later, the resin constituting the A layer on the surface of the surface layer has these segments, so that the self-repairing property of the surface layer Can improve the repetitive abrasion.

  Although the detail of the said urethane bond is mentioned later, when the resin which comprises A layer in the surface of the said surface layer has this coupling | bond, the toughness of the whole surface layer can be improved.

  Although the details of the fluoropolyether segment will be described later, when the resin constituting the surface layer contains these, molecules exhibiting low surface energy can be present at a high density on the outermost surface, and the repetitive abrasion of the surface is improves.

[Polycaprolactone Segment, Polycarbonate Segment, Polyalkylene Glycol Segment]
First, a polycaprolactone segment refers to a segment represented by Chemical Formula 1. The polycaprolactone also includes caprolactone having repeating units of 1 (monomer), 2 (dimer), 3 (trimer) and oligomers having caprolactone having up to 35 repeating units.

n is an integer of 1 to 35.

  It is preferable that the resin containing a polycaprolactone segment has at least one or more hydroxyl groups (hydroxyl groups). The hydroxyl group is preferably at the end of the resin containing a polycaprolactone segment.

  As a resin containing a polycaprolactone segment, polycaprolactone having a 2- to 3-functional hydroxyl group is particularly preferable. Specifically, polycaprolactone diol represented by the chemical formula 2,

Here, m + n is an integer of 4 to 35, m and n each is an integer of 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 polycaprolactone triol represented by the formula 3

Here, l + m + n is an integer of 3 to 30, l, m and n each is an integer of 1 to 28, R is CH ₂ CHCH ₂ , CH ₃ C (CH ₂ ) ₃ and CH ₃ CH ₂ C (CH ₂ ) ₃
And polycaprolactone-modified hydroxyethyl (meth) acrylates represented by the chemical formula 4

Here, n is an integer of 1 to 25 and R can be H or active energy ray polymerizable caprolactone such as 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 a polycaprolactone segment may contain (or be copolymerized with) other segments and monomers in addition to the polycaprolactone segment. For example, a polydimethylsiloxane segment, a polysiloxane segment described later, or a compound containing an isocyanate compound 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 repetitive abrasion is further improved, which is preferable.

  Next, a polyalkylene glycol segment refers to a segment represented by Chemical Formula 5. The polyalkylene glycols include those having 2 (dimers), 3 (trimers) of alkylene glycol repeating units, and oligomers having up to 11 alkylene glycol repeating units.

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

  It is preferable that the resin containing the polyalkylene glycol segment has at least one or more hydroxyl groups (hydroxyl groups). The hydroxyl group is preferably at the end of the resin containing a polyalkylene glycol segment.

  The resin containing a polyalkylene glycol segment is preferably a polyalkylene glycol (meth) acrylate having an acrylate group at the end 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 the self-healing property of the cured product.

  Examples of polyalkylene glycol (meth) acrylate contained in the coating composition used to form 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 6, chemical formula 7, and chemical formula 8, respectively.

  Polyethylene glycol (meth) acrylate:

  Polypropylene glycol (meth) acrylate:

  Polybutylene glycol (meth) acrylate:

Formula 6, Formula 7, are R in Formula 8 hydrogen (H) or methyl group _(-CH 3), m is an integer comprised between 2 to 11.

  In the present invention, preferably, a resin constituting a surface layer is produced by reacting a compound having an isocyanate group to be described later with a hydroxyl group of (poly) alkylene glycol (meth) acrylate to use as a urethane (meth) acrylate in the surface layer. (2) urethane bond and (3) (poly) alkylene glycol segment, which is preferable because it can improve the toughness of the surface layer and improve the self-repairing property.

  Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl as hydroxyalkyl (meth) acrylate simultaneously compounded in the urethanization reaction of a compound containing an isocyanate group and a polyalkylene glycol (meth) acrylate Examples are (meth) acrylates and the like.

  Next, the polycarbonate segment refers to a segment represented by chemical formula 9. Polycarbonates also include those in which the recurring units of the carbonate are such as 2 (dimers), 3 (trimers), and oligomers of up to 16 recurring units of the carbonate.

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

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

As a 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 to 16; R refers to an alkylene or cycloalkylene group having 1 to 8 carbon atoms.

  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 decreases, so the number of repeating is 10 or less. Is preferred. The polycarbonate diol may be a mixture of two or more polycarbonate diols having different numbers of repeating carbonate units.

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

  In addition, as polycarbonate diols used in the present invention, UH-CARB, UD-CARB, UC-CARB (Ube Industries, Ltd.), PLACCEL CD-PL, PLACCEL CD-H (Daicel Chemical Industries, Ltd.), Kuraray polyol C Products such as series (Kuraray Co., Ltd.) and Duranol series (Asahi Kasei Chemicals Co., Ltd.) can be suitably exemplified. These polycarbonate diols can also be used alone or in combination of two or more.

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

  In the present invention, preferably, the resin constituting the surface side of the surface layer is produced by reacting the compound containing an isocyanate group to be described later with the hydroxyl group of polycarbonate diol and using it as urethane (meth) acrylate on the surface side of the surface layer. May have the aforementioned (2) urethane bond and (1) polycarbonate diol segment, and as a result, the toughness of the surface layer can be improved and the self-repairing property can be improved, and the repetitive scratching property can be improved. Can.

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

  The resin which comprises the surface side of the said surface layer can improve the toughness of the whole surface layer because it has this coupling | bonding.

  By the coating composition A containing a commercially available urethane-modified resin, the resin constituting the surface side of the surface layer can have a urethane bond. Further, when forming the surface side of the surface layer, a coating composition A containing a compound containing an isocyanate group and a compound containing a hydroxyl group as a precursor is applied, dried and cured to form a urethane bond. Also, urethane bonds can be contained on the surface side of the surface layer.

  In the present invention, it is preferable to introduce a urethane bond into the resin constituting the surface side of the surface layer by reacting an isocyanate group and a hydroxyl group to form a urethane bond. By reacting the isocyanate group and the hydroxyl group to form a urethane bond, the toughness of the surface layer can be improved and the self-repairing property can be improved, whereby the repetitive abrasion can be improved.

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

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

  In the present invention, a compound containing an isocyanate group refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. The compound containing an isocyanate group is, for example, methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, tolylene diisocyanate. An isocyanurate body, an isocyanurate body of hexamethylene diisocyanate, a (poly) isocyanate such as a biuret body of hexamethylene isocyanate, and a block body of the above isocyanate can be mentioned.

  Among these isocyanate group-containing compounds, aliphatic isocyanates are preferable because they have high self-healing properties compared to alicyclic or aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Further, as the compound having an isocyanate group, an isocyanate having an isocyanurate ring is particularly preferable in terms of heat resistance, and an isocyanurate of hexamethylene diisocyanate is most preferable. An isocyanate having an isocyanurate ring forms a surface layer having both self-healing properties and heat resistance properties.

[Fluorinated compound segment, polysiloxane segment, polydimethylsiloxane segment]
In the laminated film of the present invention, the surface layer or the resin constituting the surface side of the surface layer has a segment including at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment Is preferred.

  Furthermore, a paint composition A comprising a resin containing a segment containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment, and a polydimethylsiloxane segment, or a coating composition A containing a precursor, By using one, the resin which comprises the surface side of a surface layer can have these.

  Hereinafter, the fluorine compound segment, the polysiloxane segment, and the polydimethylsiloxane segment will be described.

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

  Here, fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoroalkanediyl group, fluorooxyalkanediyl group means hydrogen of alkyl group, oxyalkyl group, alkenyl group, alkanediyl group, oxyalkanediyl group. Part or all is a substituent substituted with fluorine, and each is a substituent mainly composed of a fluorine atom and a carbon atom, and there may be a branch in the structure, and a structure having these portions is A plurality of linked dimers, trimers, oligomers, and polymer structures may be formed.

  Further, as the fluorine compound segment, a fluoropolyether segment is preferable, and this is a site composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., more preferably represented by the chemical formula 5 and the chemical formula 6 It is as already stated that it is a fluoropolyether segment.

  The fluoropolyether segment is a segment composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group and the like, and is a structure represented by the chemical formula 12 and the chemical formula 13.

Here, n1 is an integer of 1 to 3, n2 to n5 is an integer of 1 or 2, k, m, p and s are integers of 0 or more, and p + s is 1 or more. Preferably, n1 is 2 or more, n2 to n5 are integers of 1 or 2, more preferably, n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.
The chain length of this fluoropolyether segment has a preferable range, and the number of carbon atoms is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. If the number of carbon atoms is 3 or less, the surface energy is not sufficiently reduced, so the oil repellency may decrease. If the number of carbon atoms is 13 or more, the solubility in the solvent may decrease, and the quality of the surface layer may decrease.

  When the resin contained in the surface layer contains a fluorine compound segment, the coating composition A preferably contains the following fluorine compound D. The fluorine compound D is a compound represented by the chemical formula 14.

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

  The reactive site refers to a site that reacts with other components by external energy such as heat or light. As such a reactive site, a silanol group in which an alkoxysilyl group and an alkoxysilyl group are hydrolyzed from the viewpoint of reactivity, a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, etc. It can be mentioned. Among them, vinyl, allyl, alkoxysilyl, silyl ether or silanol, an epoxy and acryloyl (methacryloyl) are preferable from the viewpoint of reactivity and handling.

  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-perfluorooctylethyltrichloride Chlorosilane, 2-perfluorooctylisocyanate 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-permer 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 methacrylate Hexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoro And pentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyl trifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol and the like.

The fluorine compound D may have a plurality of fluoropolyether moieties per molecule.
Examples of the commercially available fluorine compound D include RS-75 (DIC Corporation), Optool DAC-HP (Daikin Industries, Ltd.), C10GACRY, C8HGOL (oil and fat product corporation), and the like. You can use the products of

  Next, the polysiloxane segment will be described. In the present invention, the polysiloxane segment refers to a segment represented by chemical formula 15 described later.

  Here, the polysiloxane includes both low molecular weight ones (so-called oligomers) in which the repeating units of the siloxane are about 100 and high molecular weight ones (so-called polymers) in which the repeating units of the siloxanes exceed 100.

R ₁ and R ₂ are either a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, each having at least one or more of them, and n is an integer of 100 to 300.

  Although the details of the polysiloxane segment and the polydimethylsiloxane segment will be described later, when the resin constituting the surface layer has these segments, the heat resistance and the weather resistance are improved, and the scratch resistance due to the lubricity of the surface layer Can be improved. More preferably, it is preferable from the viewpoint of lubricity to include a polydimethylsiloxane segment represented by Chemical Formula 16 described later.

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

  Resins containing a polysiloxane segment include tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxypropyltritriol. Organo silica sol dispersed in a completely or partially hydrolyzate of a silane compound having a hydrolyzable silyl group such as alkoxysilane, γ-methacryloxypropyl alkyl dialkoxysilane, or an organic solvent, hydrolyzable silyl group on the surface of organosilica sol The thing etc. which added the hydrolysis silane compound of these can be illustrated.

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

  When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, the surface is obtained using a coating composition containing a resin (copolymer) containing a polysiloxane segment having a hydroxyl group and a compound containing an isocyanate group. By forming the layer, it is possible to efficiently form a surface layer having a polysiloxane segment and a urethane bond.

  Next, the polydimethylsiloxane segment is described. In the present invention, the polydimethylsiloxane segment refers to a segment represented by Chemical Formula 16. The polydimethylsiloxane includes both low molecular weight ones (so-called oligomers) in which the repeating unit of dimethylsiloxane is 10 to 100 (so-called oligomers) and high molecular weight ones (so-called polymers) in which the repeating units of dimethylsiloxane exceed 100.

  m is an integer of 10 to 300.

  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 of the surface layer can be improved and the frictional resistance can be reduced. As a result, repetitive abrasion can be improved.

  In the present invention, as the resin containing a polydimethylsiloxane segment, it is preferable to use a copolymer in which a vinyl monomer is copolymerized with the polydimethylsiloxane segment.

  In order to improve the toughness of the surface layer, it is preferable that the resin containing a polydimethylsiloxane segment is 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 paint composition containing a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group is used Once the surface layer is formed, the surface layer can be efficiently provided with the polydimethylsiloxane segment and the urethane bond.

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

  When the polymer initiator method is used, the polymer azo radical polymerization initiator represented by the chemical formula 17 can be used to copolymerize with other vinyl monomers. Also, a two-step polymerization is carried out by copolymerizing a peroxy monomer and a polydimethylsiloxane having an unsaturated group at low temperature to introduce a peroxide group into a side chain, and copolymerizing the prepolymer with a vinyl monomer. You can also do

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

In the case of using a polymer chain transfer method, for example, after adding HS-CH ₂ COOH, HS-CH ₂ CH ₂ COOH, etc. to a silicone oil represented by the chemical formula 18 to obtain a compound having an SH group, A block copolymer can be synthesized by copolymerizing the silicone compound and a 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 the chemical formula 19, that is, a methacrylic ester of polydimethylsiloxane with a vinyl monomer. it can.

  m is an integer of 10 to 300.

  As a vinyl monomer used for a copolymer with polydimethylsiloxane, for example, 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-methylol acrylamide, N, N-dimethyl acrylamide, N, N-dimethylaminoethyl ester Methacrylates, N, N-diethylaminoethyl methacrylate, diacetotone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol and the like can be mentioned.

  In addition, polydimethylsiloxane-based 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 and the like It is preferable to manufacture by the solution-polymerizing method in alcohol solvent etc. of this in an individual or mixed solvent.

  If necessary, a polymerization initiator such as benzoyl peroxide or azobisisobutyl nitrile is used in combination. The polymerization reaction is preferably carried out 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 10% by mass of all components of the polydimethylsiloxane copolymer in terms of the lubricity and the stain resistance 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 a paint composition used to form a surface layer, other segments etc. are contained (copolymerized) in addition to the polydimethylsiloxane segment. May be For example, polycaprolactone segments and polysiloxane segments may be contained (copolymerized).

  Coating compositions used to form the surface layer include copolymers of polycaprolactone segments and polydimethylsiloxane segments, copolymers of polycaprolactone segments and polysiloxane segments, polycaprolactone segments and polydimethylsiloxane segments, and poly It is possible to use a copolymer with a siloxane segment or the like. 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-based 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-based At the time of copolymer synthesis, a polycaprolactone segment and a polysiloxane segment can be appropriately added and copolymerized.

[Coating composition B]
Coating composition B has a surface hardness higher than that of layer A by being applied, dried and cured on a supporting substrate, and is a liquid capable of forming a material, and a resin or precursor suitable for forming layer B including.

  The coating composition B may be either a thermosetting resin or an ultraviolet curing resin, or may be a blend of two or more.

  The thermosetting resin in the present invention comprises a hydroxyl group-containing resin and a polyisocyanate compound, and examples of the hydroxyl group-containing resin include acrylic polyol, polyether polyol, polyester polyol, polyolefin polyol, polycarbonate polyol and urethane polyol. And they may be one or more blends. If the hydroxyl value of the resin containing a hydroxyl group is in the range of 1 to 200 mg KOH / g, it is preferable from the viewpoint of durability, hydrolysis resistance and adhesion when it is used as a coating film. When the hydroxyl value is less than 1 mg KOH / g, curing of the coating hardly progresses, and the durability and strength may be reduced. On the other hand, when the hydroxyl value is larger than 200 mg KOH / g, the adhesion may be reduced because the cure shrinkage is too large.

  The acrylic polyol containing a hydroxyl group in the present invention is obtained, for example, by polymerizing an acrylic ester or a methacrylic ester as a component. Such an acrylic resin can be easily obtained, for example, by copolymerizing a carboxylic acid group-containing monomer such as (meth) acrylic acid, itaconic acid or maleic anhydride, if necessary, using (meth) acrylic acid ester as a component. It can be manufactured. Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylhexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate Etc. As such an acrylic polyol containing a hydroxyl group, for example, DIC Corporation; (trade name "Aklidic" (registered trademark) series etc.), Taisei Fine Chemical Co., Ltd. (trade name "Acrit" (registered trademark) series etc.) , Nippon Shokubai Co., Ltd .; (trade name "AkReset" (registered trademark) series etc.), Mitsui Chemical Co., Ltd .; (trade name "Takelac" (registered trademark) UA series) etc., and these products can be mentioned. Can be used.

  The polyether polyol containing a hydroxyl group in the present invention includes polyethylene glycol or triol, polypropylene glycol or triol, polybutylene glycol or triol, polytetramethylene glycol or triol, and addition weights of oxyalkylene compounds having different carbon numbers. Examples include united and block copolymers. As such polyether polyols containing a hydroxyl group, Asahi Glass Co., Ltd. (trade name "EXENOL" (registered trademark) series etc.), Mitsui Chemicals Co., Ltd. (trade name "ACTOCOL" (registered trademark) series etc) These products can be used.

  Examples of the polyester polyol having a hydroxyl group in the present invention include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol and cyclohexanedimethanol, for example, succinic acid, adipine Aliphatic polyester polyols reacted as essential raw material components with aliphatic dibasic acids such as acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decamethylene dicarboxylic acid, cyclohexane dicarboxylic acid, ethylene glycol , An aromatic polyester obtained by reacting an aliphatic glycol such as propylene glycol and butanediol with an aromatic dibasic acid such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as essential raw material components Tel polyols.

  As polyester polyols containing such a hydroxyl group, DIC Corporation (brand name "Polylite" (registered trademark) series etc.), Kuraray Co., Ltd. (brand name "Kuraray polyol" (registered trademark) series etc.), Takeda Yakuhin Kogyo Co., Ltd. (trade name “Takelac” (registered trademark) U series) can be mentioned, and these products can be used.

  The polyolefin-based polyol having a hydroxyl group in the present invention includes polymers and copolymers of diolefins having 4 to 12 carbon atoms such as butadiene and isoprene, and diolefins having 4 to 12 carbon atoms and 2 to 22 carbon atoms. Among the copolymers of α-olefins of the above, it is a compound containing a hydroxyl group. The method for containing a hydroxyl group is not particularly limited, and for example, there is a method of reacting a diene monomer with hydrogen peroxide. Furthermore, the remaining double bond may be saturated aliphatically by hydrogen bonding. As such polyolefin-based polyols containing a hydroxyl group, Nippon Soda Co., Ltd. (trade name "NISSO-PB" (registered trademark) G series etc.), Idemitsu Kosan Co., Ltd .; (trade name "Poly bd" (registered trademark) Series, "Epol" (registered trademark) series etc.) can be mentioned, and these products can be used.

  As a polycarbonate polyol containing a hydroxyl group in the present invention, for example, a polycarbonate polyol obtained using only dialkyl carbonate and 1,6-hexanediol can be used, but as a diol having a lower crystallinity, 1 It is preferable to use a polycarbonate polyol obtained by copolymerizing 2,6-hexanediol with 1,4-butanediol, 1,5-pentanediol or 1,4-cyclohexanedimethanol.

  As a polycarbonate polyol containing such a hydroxyl group, a copolymer polycarbonate polyol, Asahi Kasei Chemicals Corporation (trade names "T5650J", "T5652", "T4671", "T4672", etc.), Ube Industries, Ltd .; It is possible to cite the trade name "ETERNA CLL" (registered trademark) UM series etc., and these products can be used.

  The urethane polyol containing a hydroxyl group in the present invention is obtained, for example, by reacting a polyisocyanate compound and a compound containing at least two hydroxyl groups in one molecule in such a ratio that the hydroxyl group is excessive to the isocyanate group. It is obtained. As a polyisocyanate compound used in that case, hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate etc. are mentioned. Further, as a compound containing at least two hydroxyl groups in one molecule, polyhydric alcohols, polyester diols, polyethylene glycols, polypropylene glycols, polycarbonate diols and the like can be mentioned.

  The polyisocyanate compound used for the thermosetting resin in the present invention refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. The compound containing an isocyanate group is, for example, methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, tolylene diisocyanate. An isocyanurate body, an isocyanurate body of hexamethylene diisocyanate, a (poly) isocyanate such as a biuret body of hexamethylene isocyanate, and a block body of the above isocyanate can be mentioned. As a polyisocyanate compound used for such a thermosetting resin, Mitsui Chemical Co., Ltd .; (trade name "Takenate" (registered trademark) series etc.), Nippon Polyurethane Industry Co., Ltd .; (trade name "Colonate" (registered trademark) (Such as “Duranate” (registered trademark) series), DIC Corporation (such as “branded“ Burnock ”(registered trademark) series); Can be used.

  As the UV curable resin in the present invention, polyfunctional acrylate monomers, oligomers, alkoxysilanes, alkoxysilane hydrolysates, alkoxysilane oligomers, urethane acrylate oligomers and the like are preferable, and polyfunctional acrylate monomers, oligomers, urethane acrylate oligomers are more preferable. .

  Examples of polyfunctional acrylate monomers include polyfunctional acrylates having two or more (meth) acryloyloxy groups in one molecule and modified polymers thereof, and specific examples thereof include pentaerythritol tri (meth) acrylate and pentaerythritol Tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate And pentaerythritol triacrylate hexane methylene diisocyanate urethane polymer can be used. These monomers can be used alone or in combination of two or more.

  Moreover, as a polyfunctional acrylic composition marketed, Mitsubishi Rayon Co., Ltd .; (trade name "Dia Beam" (registered trademark) series etc.), Nippon Synthetic Chemical Industry Co., Ltd .; (trade name "SHIKOH" (registered trademark) ), Nagase & Co., Ltd .; (trade name "Denacole" (registered trademark) series, etc.), Shin-Nakamura Chemical Co., Ltd .; (trade name "NK Ester" series, etc.), DIC, Inc .; (“Aronix” (registered trademark) series, etc.), NOF Corporation (“Blenmar” (registered trademark) series, etc.), Nippon Kayaku Co., Ltd. Name "KAYARAD" (registered trademark) series etc., Kyoeisha Chemical Co., Ltd .; (trade name "light ester" series etc.) It is possible to use these products.

  Acrylic polymers may also be used to impart the aforementioned properties. The acrylic polymer contains no unsaturated group, and more preferably has a weight average molecular weight of 5,000 to 200,000, and a glass transition temperature of 20 to 200 ° C. If the glass transition temperature of the acrylic polymer is less than 20 ° C., the hardness may decrease, and if it exceeds 200 ° C., the elongation may not be sufficient. The more preferable range of the glass transition temperature is 50 to 150 ° C.

  Moreover, the said acrylic polymer can provide hardness by having a hydrophilic functional group. Specifically, hydrophilic functional groups such as (meth) acrylic acid having a carboxyl group, itaconic acid, fumaric acid, maleic acid, etc., or 2-hydroxyethyl (meth) acrylate having a hydroxyl group, hydroxypropyl (meth) acrylate, etc. A hydrophilic functional group can be introduced into the acrylic polymer by copolymerizing the unsaturated monomer having the above with the unsaturated monomer.

  The weight average molecular weight of the acrylic polymer is preferably 5,000 to 200,000. When the weight-average molecular weight is less than 5,000, the hardness may be insufficient, and when the weight-average molecular weight exceeds 200,000, the moldability including the coatability and the toughness become insufficient. There is. The weight average molecular weight can be adjusted by the blending amount of the polymerization catalyst, the chain transfer agent and the type of the solvent used.

  The content of the acrylic polymer is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass in the total solid content of the coating composition B. By setting the content to 1% by mass or more, the elongation is remarkably improved, and by setting the content to 50% by mass or less, the hardness can be maintained, which is preferable.

[solvent]
The paint composition A and the paint composition B preferably contain a solvent. The number of types of solvent is preferably one or more and 20 or less, more preferably one or more and ten or less, and still more preferably one or more and six or less. Here, the term "solvent" refers to a substance that is liquid at normal temperature and normal pressure and can be removed from the coating film by evaporating substantially the entire amount in the drying step after application.

  Here, the type of solvent is determined by the molecular structure constituting the solvent. That is, those having the same elemental composition and different bonding relations even if the number and type of functional groups are the same (structural isomers), which are not the above-mentioned structural isomers but in any three-dimensional space Those that do not overlap properly (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are treated as different solvents.

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

  Various polymerization initiators, curing agents and catalysts can be used. Further, the polymerization initiator, the curing agent and the catalyst may be used alone, respectively, or a plurality of polymerization initiators, curing agents and catalysts may be used simultaneously. Furthermore, an acidic catalyst, a thermal polymerization initiator or a photopolymerization initiator may be used in combination. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of thermal polymerization initiators include peroxides and azo compounds. Moreover, as an example of a photoinitiator, an alkyl phenone type compound, a sulfur-containing type compound, an acyl phosphine oxide type compound, an amine type compound etc. are mentioned.

  From the viewpoint of curability, the photopolymerization initiator is preferably an alkylphenone compound. Specific examples of the alkylphenone compound 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-cyclohyxyl-phenyl ketone, 2-methyl-1-phenylpropan-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.

  Moreover, if it is a range which does not inhibit the effect of the present invention, you may add a leveling agent, a ultraviolet absorber, a lubricant, an antistatic agent etc. to paint composition A and paint composition B which are used in order to form a surface layer. . Thus, the surface layer can contain a leveling agent, an ultraviolet light absorber, a lubricant, an antistatic agent, and the like. As an example of a leveling agent, an acrylic copolymer or silicone type and a fluorine type leveling agent are mentioned. Specific examples of the ultraviolet absorber include ultraviolet absorbers of benzophenone type, benzotriazole type, anilide oxalate type, triazine type and hindered amine type. Examples of antistatic agents include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts and the like.

[Method of producing laminated film]
The method for producing the laminated film of the present invention is to use a production method in which at least the coating composition A and the coating composition B described above are formed by applying, drying and curing on the supporting substrate mentioned above sequentially or simultaneously. More preferable.

  Here, "apply sequentially" is intended to form a surface layer by applying, drying and curing one kind of coating composition, and then applying, drying and curing different kinds of coating composition. doing. By appropriately selecting the type and the number of coating compositions used in the present manufacturing method, the magnitude and gradient of the elastic modulus of the surface side to the substrate side of the surface layer and the magnitude of the elastic modulus of the substrate and the surface layer are controlled. The form of the elastic modulus distribution in the surface layer can be controlled stepwise or continuously by appropriately selecting the type, composition, drying conditions and curing conditions of the coating composition.

  Another manufacturing method is a method of forming two or more coating compositions by applying, drying and curing "simultaneously" on a support substrate. The number of types of coating compositions is not particularly limited as long as it is two or more. Here, "simultaneous application" is intended to dry and cure after applying two or more types of liquid films on the support substrate in the application step.

In the present manufacturing method, when the coating composition described above is applied sequentially, a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Pat. No. 2,681,294) It is preferable to form a surface layer by applying to a supporting substrate etc. by the above) etc. Moreover, in the case of simultaneously applying the two or more kinds of coating compositions described above, after laminating the liquid films in order before application. "Multilayer slide die coat" to be applied (Fig. 3), "Multilayer slot die coat" to laminate simultaneously with application on a substrate (Fig. 4), undried state after forming one layer of liquid film on supporting substrate And any one of "wet-on-wet coat" (FIG. 5) or the like in which another layer is laminated.

  Then, 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, it is preferable that the drying step be accompanied by heating of the liquid film.

  As a drying method, heat transfer drying (adhesion to high heat object), convective heat transfer (hot air), radiant heat transfer (infrared ray), others (microwave, induction heating), etc. may be mentioned. 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 precisely make the drying speed uniform even in the width direction.

  Furthermore, a further curing operation (curing step) may be performed by irradiating heat or energy rays. In the curing step, when the coating composition A and the coating composition B are cured by heat, the temperature is preferably from room temperature to 200 ° C. or less, and from the viewpoint of activation energy of the curing reaction, 80 ° C. to 200 ° C. The following is more preferable, and 100 ° C. or more and 200 ° C. or less are more preferable.

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

Moreover, as a kind of ultraviolet ray lamp used when irradiating an ultraviolet-ray, a discharge lamp system, a flash system, a laser system, an electrodeless lamp system etc. are mentioned, for example. 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 preferable to perform ultraviolet irradiation under the conditions. Here, the illuminance of the ultraviolet light is the irradiation intensity received per unit area, and changes depending on the lamp output, the luminous spectrum efficiency, the diameter of the luminous bulb, the design of the reflecting mirror and the light source distance to the object to be irradiated. However, the illuminance does not change depending on the transport speed. Further, the ultraviolet integrated light quantity is the 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 proportional to the number of times of irradiation and the number of lamp lights.

[Application example]
Since the laminated film of the present invention is excellent in abrasion resistance, it can be widely used, for example, as an interior member of an electric appliance or a car, a building member, and the like.

  For example, glasses / sunglasses, cosmetic boxes, plastic molded articles such as food containers, housings for smartphones, touch panels, keyboards, home appliances such as remote controls for TVs and air conditioners, buildings, dashboards, car navigation / touch panels, rooms The present invention can be suitably used for vehicle interior parts such as mirrors, and surfaces of various printed materials.

  Next, the present invention will be described based on examples, but the present invention is not necessarily limited thereto.

<Fluorine compound D>
[Fluorine compound D1 methyl ethyl ketone / methyl isobutyl ketone solution]
As the fluorine compound D1, an acrylate compound containing a fluoropolyether moiety ("Megafuck" (registered trademark) RS-75 manufactured by DIC Corporation, a methyl ethyl ketone / methyl isobutyl ketone solution having a solid content concentration of 40% by mass) was used.

<Synthesis of Polysiloxane Compound>
[Polysiloxane (a)]
106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1 mass% hydrochloric acid are introduced into a 500 ml flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet pipe, After holding at ° C for 2 hours, ethanol was recovered while raising the temperature, and held at 180 ° C for 3 hours. Thereafter, it was cooled to obtain a viscous (poly) siloxane (a).

<Synthesis of Polydimethylsiloxane Compound>
[Polydimethyl siloxane block copolymer (a) toluene solution]
50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, (poly) dimethylsiloxane-based high molecular weight polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd. VPS-0501) 20 using the same apparatus as in the synthesis of the polysiloxane (a) Parts by mass, 18 parts by mass of methyl methacrylate, 38 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, 1 part by mass of methacrylic acid and 0.5 parts by mass of 1-thioglycerin are charged and reacted at 180 ° C. for 8 hours As a result, a toluene solution having a solid content concentration of 50% by mass of the polydimethylsiloxane block copolymer (a) was obtained.

[Polydimethyl siloxane compound (b)]
As the polydimethylsiloxane compound (b), EBECRYL 350 (bifunctional silicone acrylate) manufactured by Daicel-Cytec Co., Ltd. was used.

<Synthesis of Urethane Acrylate>
[Toluene solution of urethane acrylate 1]
50 parts by mass of toluene, isocyanurate modified type of hexamethylene diisocyanate (manufactured by Mitsui Chemicals, Inc., 50 parts by mass of "Takenate" (registered trademark) D-170N), polycaprolactone modified hydroxyethyl acrylate (manufactured by Daicel Chemical Industries, Ltd. Plaxel FA5) 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 maintained at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate 1 having a solid content concentration of 50% by mass.

[Toluene solution of urethane acrylate 2]
Mix 100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanatohexanoate, and 119 parts by mass of polycarbonate diol (Plaxel CD-210HL, manufactured by Daicel Chemical Industries, Ltd.), and raise the temperature to 40 ° C. I kept it for a while. Then, 28 parts by mass of 2-hydroxyethyl acrylate, 5 parts by mass of dipentaerythritol hexaacrylate and 0.02 parts by mass of hydroquinone monomethyl ether are added and maintained at 70 ° C. for 30 minutes, and then 0.02 parts by mass of dibutyltin laurate In addition, it was kept at 80 ° C. for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate 2 having a solid concentration of 50% by mass.

[Toluene solution of urethane acrylate 3]
50 parts by mass of isocyanurate modified product of hexamethylene diisocyanate (Mitsui Chemical Co., Ltd. “Takenate” (registered trademark) D-170N, isocyanate group content: 20.9 mass%), polyethylene glycol monoacrylate (manufactured by NOF Corporation) 53 parts by mass of "Blenmer" (registered trademark) AE-150 (hydroxyl value: 264 (mg KOH / g)), 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were charged. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction solution to obtain a toluene solution of urethane acrylate 3 having a solid concentration of 50% by mass.

[Acrylic Polyol 1]
As the acrylic polyol 1, an acrylic polyol containing a hydroxyl group (“Takelac” (registered trademark) UA-702 manufactured by Mitsui Chemicals, Inc., solid content concentration 50 mass%, hydroxyl value: 50 mg KOH / g) was used.

[Acrylic Polyol 2]
As the acrylic polyol 2, an acrylic polyol containing a hydroxyl group (“Acrydic” (registered trademark) A-823 manufactured by DIC Corporation, solid content concentration 50 mass%, hydroxyl value 30 mg KOH / g) was used.

[Isocyanate Compound 1]
As the isocyanate compound, tolylene diisocyanate ("Coronato" (registered trademark) (C) Coronate L, Japan Polyurethane Industry Co., Ltd., solid content concentration 75% by mass, NCO content 13.5% by mass) was used.

[Multifunctional acrylate 1]
As the polyfunctional acrylate monomer 1, dipentaerythritol hexaacrylate ("KAYARAD" DPHA Nippon Kayaku Co., Ltd. make, solid content concentration 100 mass%) was used.

[Polyfunctional acrylate 2]
As the polyfunctional acrylate 2, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-3310B, manufactured by Japan Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) was used.

[Polyfunctional acrylate 3]
As the polyfunctional acrylate 3, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-1700B, manufactured by Japan Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) was used.

[Multifunctional acrylate 4]
As the polyfunctional acrylate 4, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-2750B, manufactured by Japan Synthetic Chemical Industry Co., Ltd., solid content concentration 100 mass%) was used.

[Synthesis of Acrylic Polymer 1]
24 parts by mass of dilauroyl peroxide (Perroyl L made by Nippon Oil Co., Ltd.) is added to 495 parts by mass of methyl ethyl ketone and dissolved by heating at 70 ° C. for 30 minutes to dissolve 50 parts by mass of methacrylic acid, 90 parts by mass of butyl acrylate, methyl methacrylate A solution obtained by mixing 100 parts by mass and 2.4 parts by mass of 4-methyl-2,4-diphenylpentene-1 (manufactured by NOFMER MSD manufactured by NOF Co., Ltd.) was added dropwise over 4 hours, and was stirred and polymerized. Then, the mixture was further stirred at 80 ° C. for 2 hours to obtain a methyl ethyl ketone solution (weight average molecular weight 6,000) of an acrylic polymer 1 having a solid content concentration of 35 mass% containing a hydrophilic functional group.

<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 content concentration of 40% by mass.
Solid content 40% by mass of fluorine compound D1-3.8 parts by mass of methyl ethyl ketone / methyl isobutyl ketone solution-Solid content 50% by mass of urethane acrylate 1-50 parts by mass of toluene solution 50 parts by mass of urethane acrylate 3 % -Toluene solution 50 parts by mass ethylene glycol monobutyl ether 10 parts by mass photoradical polymerization initiator 1.5 parts by mass ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

[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 40% by mass.

Solid content 40% by mass of fluorine compound D1-3.8 parts by mass of methyl ethyl ketone / methyl isobutyl ketone solution Solid content 50% by mass of urethane acrylate 1-25 parts by mass of toluene solution 50 parts by mass of urethane acrylate 3 % -Toluene solution 75 parts by mass Ethylene glycol monobutyl ether 10 parts by mass Photoradical polymerization initiator 1.5 parts by mass ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

[Coating composition A3]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid content concentration of 40% by mass.
Solid content 40% by mass of fluorine compound D1-3.8 parts by mass of methyl ethyl ketone / methyl isobutyl ketone solution Solid content 50% by mass of urethane acrylate 2-toluene 75 parts by mass solid content concentration of urethane acrylate 3 % -Toluene solution 25 parts by mass ethylene glycol monobutyl ether 10 parts by mass photoradical polymerization initiator 1.5 parts by mass ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

[Coating composition A4]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid content concentration of 40% by mass.
-Multifunctional acrylate 1 100 parts by mass-0.75 parts by mass of a radical photopolymerization initiator ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B1 having a solid content concentration of 20% by mass.
-Acrylic polyol 1 100 parts by mass-Isocyanate compound 18.8 parts by mass-Multifunctional acrylate 2 22.9 parts by mass-Acrylic polymer 1 13 parts by mass-Photoradical polymerization initiator 0.69 parts by mass ("IRGACURE" (registered trademark) ) 184 BASF Japan Ltd.).

[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 20% by mass.
-Acrylic polyol 1 100 parts by mass-Isocyanate compound 18.8 parts by mass-Acrylic polymer 1 9.6 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 20% by mass.
-Acrylic polyol 2 100 parts by mass-Isocyanate compound 11.8 parts by mass-Acrylic polymer 1 8.8 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 20% by mass.
-Acrylic polyol 1 100 parts by mass-Isocyanate compound 18.8 parts by mass-Multifunctional acrylate 3 12 parts by mass-Acrylic polymer 1 11.4 parts by mass-Photoradical polymerization initiator 0.36 parts by mass ("IRGACURE" (registered trademark) ) 184 BASF Japan Ltd.).

[Coating composition B5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B5 having a solid content concentration of 20% by mass.
-Multifunctional acrylate 4 100 parts by mass-Acrylic polymer 1 15 parts by mass-Photoradical polymerization initiator 3 parts by mass ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B6]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B6 having a solid content concentration of 20% by mass.
-Acrylic polyol 1 100 parts by mass-Isocyanate compound 18.8 parts by mass-Multifunctional acrylate 3 3.6 parts by mass-Acrylic polymer 1 10.1 parts by mass-Photo radical polymerization initiator 0.11 parts by mass ("IRGACURE" Registered trademark) 184 BASF Japan Ltd.).

<Method of manufacturing laminated film>
[Method 1 for producing laminated film]
A 100 μm thick “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc.) was used as a supporting substrate (a layer to be a C layer) in which an easily adhesive coating was applied on a PET resin film. Paint composition B is applied onto a supporting substrate using a continuous coating apparatus with a slot die coater, adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes a specified film thickness, and then The drying step and the curing step were carried out under the conditions of to form a B layer on the supporting substrate.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: Atmosphere.

Furthermore, using the same apparatus, the coating composition A is applied onto the B layer obtained above by adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes the specified thickness, Subsequently, 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: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: 200 ppm (volume ratio) or less.

[Method 2 for producing laminated film]
A 100 μm thick “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc.) was used as a supporting substrate (a layer to be a C layer) in which an easily adhesive coating was applied on a PET resin film. Paint composition B is applied onto a supporting substrate using a continuous coating apparatus with a slot die coater, adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes a specified film thickness, and then The drying step and the curing step were carried out under the conditions of to form a B layer on the supporting substrate.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Further, using the same apparatus, the coating composition A was applied onto the B layer obtained above by adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes the specified thickness. Then, the drying step and the curing step were performed under the following conditions to obtain a laminated film.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: 200 ppm (volume ratio) or less.

[Method 3 for producing laminated film]
A 100 μm thick “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc.) was used as a supporting substrate (a layer to be a C layer) in which an easily adhesive coating was applied on a PET resin film. Paint composition A is applied onto a supporting substrate using a continuous coating apparatus with a slot die coater, adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes a specified thickness, and then The drying step and the curing step were performed under the conditions of to form an A layer on the supporting substrate.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: 200 ppm (volume ratio) or less.

  The laminated film of Examples 1-13 and Comparative Examples 1-2 was created by the above method. The method for producing the above-mentioned laminated film corresponding to each example and comparative example, the paint composition to be used, and the film thickness of each layer are described in Table 1.

<Evaluation of laminated film>
The performance evaluation shown below is implemented about the produced lamination film, and the obtained result is shown in Table 2. Unless otherwise specified, measurement was carried out three times at different locations for one sample in each example and comparative example, and the average value was used.

[Measurement of storage modulus, glass transition temperature]
A. Confirmation of cross section of laminated film The laminated film is cut out with a cutter, embedded with an epoxy resin for electron microscope (Quetol 812 manufactured by Nisshin EM Co., Ltd.), and after curing the epoxy resin in an oven at 60 ° C. for 48 hours, Ultra Ultra-thin sections of about 100 nm in thickness were produced with a microtome (Ultracut S, manufactured by Leica).

  The prepared ultra-thin section is mounted on a 100 mesh Cu grid made by Soken Shoji Co., and TEM observation is performed at an accelerating voltage of 100 kV using a Hitachi transmission electron microscope (TEM) H-7100 FA to observe the cross section of the laminated film The location of the surface layer and the supporting substrate was confirmed.

B. Measurement using an ultra-microhardness tester Above, using the ultra-thin section as a sample, using an ultra-microhardness tester (Tribo Indenter manufactured by Hysitron), obtain a modulus mapping image of the surface layer and the support base material, and storage elastic modulus, The loss elastic modulus was calculated, the loss tangent (tan δ) was determined from the ratio of the storage elastic modulus to the loss elastic modulus, and the temperature at the peak value of the obtained loss tangent (tan δ) was taken as the glass transition temperature (Tg).
The measurement conditions are shown below.
Measuring device: Hybotron Tribo Indenter
Usage indenter: Diamond Cubecorner indenter (curvature radius of 50 nm)
Measuring field of view: Approximately 30 mm square Measuring frequency: 10 Hz
Measurement atmosphere: −20 ° C. to 120 ° C. Contact load in air: 0.3 μN.

[Measurement of elastic modulus by atomic force microscope]
Cross sections of the laminated films of Examples 1 to 13 and Comparative Examples 1 to 2 are cut out by a freezing microtome method, and the cross sections are fixed as a measurement surface to a dedicated sample fixing base, and atomic force microscope (AFM) manufactured by Asylum Technology "AFM" Using MFP-3DSA-J and NANOSENSORS cantilever “R150-NCL-10 (material Si, spring constant 48 N / m, tip radius of curvature 150 nm)”, force curve in Contact mode perpendicular to the thickness direction of the surface layer (Cantilever movement speed 2 μm / s, maximum indentation load 2 μN) was measured.

  Based on the above measurement method, the elastic modulus (E1) at a position 10% (Position 1) from the surface of the surface layer in the thickness direction of the surface layer, the elastic modulus (E2) 99% at a position (position 2) 50% The elastic modulus (E3) of the% position (position 3) was determined. Specifically, the laminated film was cut, and the elastic modulus at each position in the thickness direction in the surface layer cross section was measured.

[Crack elongation]
The laminated film was cut into short pieces of length 150 mm × width 10 mm in the longitudinal direction and width direction, and used as a sample. Using a tensile tester (Tensilon UCT-100 manufactured by ORIENTEC Co., Ltd.), a tensile test was performed with an initial tensile chuck distance of 50 mm and a tensile speed of 10 mm / min. The measurement atmosphere at this time is 23 ° C. and 65 RH%. When stretching, observe the sample during stretching and stop when a crack (crack) occurs visually in any part of the sample (Adjust the elongation when stopping to be an integer of 5) ). As for the sample to be measured from the next time, the sample whose elongation elongation was lowered by 5% from the elongation at the time of stopping is sequentially taken, and finally the crack does not enter visually in any part of the sample I went to elongation.

  The thin film cross section of the crack portion of the sample collected is cut out, the cross section is observed with a transmission electron microscope at a magnification of 3,000 times, and a crack is present if 50% or more of the average thickness of the surface layer is generated ( Among the samples in which it was determined that the surface layer was broken, the elongation value of the sample having the lowest elongation was taken as the crack elongation.

  And it measured with three samples cut out from a different place of the same level, and adopted the average value of those crack growth.

Thermoforming
The obtained laminated film is heated for 1 minute so that the film surface temperature reaches a predetermined temperature using a vacuum forming machine “FORMECH 300X” (manufactured by Shiromitsu Sangyo Co., Ltd.) using a far-infrared heater, and cylindrical Vacuum molding was performed using a mold (bottom diameter 50 mm) to form a laminated film. In addition, heating was subsequently performed at a temperature of 180 to 200 ° C. for 1 minute to complete curing completely. The state of being able to be molded along the mold was evaluated based on the following criteria using the degree of molding (a drawing ratio: molding height / bottom diameter).
A grade: It could be molded at a drawing ratio of 1.0 or more.
B-class: It could be molded at a drawing ratio of 0.6 or more and less than 1.0, but could not be molded at 1.0 or more.
C grade: It could be molded at a drawing ratio of 0.3 or more, less than 0.6, but could not be molded at 0.6 or more.
Class D: Only curved surface molding with a drawing ratio of less than 0.3 was possible, and molding was not possible with 0.3 or more.
Class E: Even if slightly bent, the film was broken or cracked.

Repeated abrasion resistance due to low hardness material of surface layer
After leaving the laminated film to stand at a temperature of 20 ° C for 12 hours, attach the whitenel cloth (made by No. 600 Kowa Co., Ltd.) to the tip (tip area of 1 cm ² ) of the eraser abrasion tester manufactured by Komitsu Seisakusho in the same environment. Then, the laminated film was subjected to a load of 500 g and reciprocated on the laminated film by 5 cm and reciprocation of 5,000 times and a load of 1,000 g, respectively, and reciprocated by 5 cm and 200 times to perform the following classification. In addition, it measured with three samples cut out from the location which the same level differs, and performed the following classification. The average value of the values of three samples subjected to classification was adopted.
10 points: no scratch 7 points: 1 to 10 flaws 4 points: 11 to 20 flaws 1 point: The surface layer of the test part is completely peeled off.

Self-healing property of surface layer
After leaving it to stand for 12 hours at a temperature of 20 ° C, apply the following load to a brass brush (made by TRUSCO) under the same load in the same environment, scratch it horizontally 5 times, and then recover the scratch after leaving for 5 minutes The judgment was made visually according to the following criteria. In addition, it measured with three samples cut out from the different location of the same level, and those average values were employ | adopted.
10 points: no damage remains at 1 kg load 7 points scratch remains at 1 kg load but 4 points do not leave a scratch at 700 g: scratch remains at 700 g load but 1 point does not leave a scratch at 500 g: load 500 g The wound will be left.

1 Layer in contact with layer B on surface layer (layer A)
2 Layer in contact with the support substrate (B layer)
3 Support base (C layer)
4 surface layer 5 including A layer and B layer From the surface of the surface layer, 10% of the surface layer thickness (position 1)
6 50% of the surface layer thickness from the surface of the surface layer (Position 2)
7 99% of the surface layer thickness from the surface of the surface layer (Position 3)
8 Multilayer Slide Die 9 Multilayer Slot Die 10 Single Layer Slot Die

  The laminated film according to the present invention is to impart scratch resistance, in particular, a function having both repeated abrasion resistance and moldability on the surface of each of plastic molded articles, home appliances, buildings, vehicle interiors and various printed matter. It can be used for

Claims (7)

A laminated film having a surface layer including an A layer and a B layer on at least one surface of a supporting substrate, wherein the B layer and the A layer are in contact in this order from the supporting substrate side, A layer, B Storage elastic modulus of the support substrate measured by a microhardness tester at 25 ° C (hereinafter, E _A25 , E _B25 , E _C25 ), 120 ° C. storage elastic modulus (hereinafter, E _A120 , E _B120 , E _C120 ) However, the laminated film characterized by satisfying the following conditions.
Condition 1 E A ₂₅ <E _{B 25} ≦ E _{C 25}
Condition 2 E _B120 ≦ E A ₁₂₀ <E _{C 120}
Condition 3 E A ₂₅ ≦ 100 MPa The laminated film according to claim 1, wherein the layer A, the layer B, and the supporting substrate satisfy the following conditions.
Condition 4 0 <E _C25 −E _B25 <5 GPa
Condition 5 0 <E _A120 -E _B120 <50 MPa The laminated film according to claim 1 or 2, wherein the glass transition temperature (hereinafter, Tg _B ) of the layer _B satisfies the following condition.
Condition 6 60 ° C. ≦ Tg _B ≦ 130 ° C. The laminated film according to any one of claims 1 to 3, wherein the thickness of the layer B (hereinafter referred to as T _B ) satisfies the following conditions.
Condition 7 0.1 μm ≦ T _B ≦ 5 μm In a cross section perpendicular to the substrate of the surface layer, 10% of the surface layer thickness (hereinafter referred to as position 1), 50% (hereinafter referred to as position 2), 99% (hereinafter referred to as position 2) from the surface of the surface layer The elastic modulus E1, E2, E3 by an atomic force microscope at each position of positions 3 and 4 satisfies the following condition, and the laminated film according to any one of claims 1 to 4 .
Condition 8 E1 ≦ E2 <E3
Condition 9 E1 ≦ 100 MPa
Condition 10 E3 1 1 GPa The method for producing a laminated film according to any one of claims 1 to 5, wherein the surface layer is formed by sequentially applying, drying, and curing two or more types of coating compositions on a supporting substrate. A method of producing a laminated film characterized in that it is formed. The method for producing a laminated film according to any one of claims 1 to 5, wherein the surface layer is formed by simultaneously applying two or more types of coating compositions on a supporting substrate, and drying and curing the same. A method of producing a laminated film characterized in that it is formed.