TW201544328A - Layered film and process for producing layered film - Google Patents

Abstract

A layered film which comprises a supporting base and, formed on at least one surface thereof, a surface layer comprising a layer A and a layer B, characterized in that the layer B and the layer A are in contact with each other and disposed in this order from the supporting base side and that the layer A, layer B, and supporting base have 25 DEG C storage moduli (hereinafter, referred to as EA25, EB25, and EC25) and 120 DEG C storage moduli (hereinafter, referred to as EA120, EB120, and EC120), as measured with a microhardness meter, which satisfy the following requirements. Requirement 1 EA25 < EB25 ≤ EC25 Requirement 2 EB120 ≤ EA120 < EC120 Requirement 3 EA25 ≤ 100 MPa This layered film combines scratch resistance, in particular, resistance to repeated abrasion, with moldability.

Description

Method for manufacturing laminated film and laminated film

The present invention relates to a laminated film in which scratch resistance is particularly resistant to over-peeling and moldability.

In recent years, a plastic film including a surface layer containing a synthetic resin or the like is used for the purpose of optical materials such as color filters, flat surface displays, and surface protection of automobile bodies (such as damage prevention or antifouling property).

For these surface layers, from the viewpoint of surface protection, scratch resistance is required as an important characteristic. In general, the "hard-coating material" is used to impart scratch resistance by using a so-called "hard-coating material", and various pre-polymerizations including an organic decane-based or polyfunctional acrylic-based method are used as described in Non-Patent Document 1. a coating composition such as a material or an oligomer, a "highly crosslinked density material" formed by coating-drying-heating or UV curing, or an "organic-inorganic hybrid material" in which various surface-modifying fillers are further combined. The surface hardness of the coating film is improved.

On the other hand, in the surface layer, in addition to the scratch resistance as a necessary property, various properties such as chemical resistance, oil resistance, and moldability are required depending on the application. In particular, the moldability is due to, for example, only making the coating film hard, Since the shape is prone to "cracking" or "peeling", it is required to be difficult to damage, but the softness of scratch resistance and moldability coexist.

In the hard coat material, as a laminated film in which the scratch resistance and the moldability are combined, Patent Document 1 proposes a laminated film which is a laminated film provided with a hard coat layer on at least one surface of the base film. The maximum surface hardness of the hard coat layer measured by an ultra-fine hardness meter is 0.05 GPa or more and 4.0 GPa or less, and the crack elongation in a 100° C. environment is 15% or more and less than 250%.

On the other hand, Patent Documents 2 and 3 propose to use a so-called "self-healing material" film which repairs damage on the surface by deformation of the elastic recovery range of the material of the surface layer, and achieves scratch resistance, and then Patent Document 4 proposes an active energy ray-curable coating agent comprising an epoxy resin or an oxetane resin as a material which improves the moldability by improving the elongation property of the self-healing material. a resin composition of at least one resin (A) selected from a vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray-sensing catalyst (C), characterized in that: The alcohol (B) is at least 1 selected from the group consisting of a polyol (B1) having a main chain comprising a carbon-carbon bond, a polycarbonate polyol (B2), a polyester polyol (B3), and a polyether polyol (B4). Polyols."

In addition, in another method of improving the moldability of the self-healing material, Patent Document 5 proposes a laminate having a self-healing layer, which is attached to at least one side of the resin substrate, as an invention focusing on the laminated structure. a layered body with a self-healing layer in which the stress relieving layer and the self-healing layer are laminated in this order, characterized in that the self-healing layer is composed of at least a soft synthetic resin and is in contact with the self-repairing layer. The hardness H of the stress relaxation layer of the layer measured by nano indentation is equal to or lower than the hardness H of the self-healing layer measured by nanoindentation.

[Previous Technical Literature] [Non-patent literature]

[Non-Patent Document 1] Plastic Hard Coating Application Technology Co., Ltd. CMC Publishing 2004

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-184284

[Patent Document 2] International Publication No. 2011/136042

[Patent Document 3] Japanese Patent Laid-Open No. Hei 11-228905

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-284613

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-5766

However, the molded body of the above-mentioned "hard-coating material" is used for the surface layer, and although the surface hardness is extremely high, it is often damaged or damaged in daily life, and the inventors have investigated this and learned that Although the hard coating material has a high surface hardness, if it is repeatedly rubbed with a soft cloth or the like, fine scratches are formed on the surface, and the surface becomes cloudy.

On the other hand, the present inventors confirmed the materials proposed in Patent Document 2 and Patent Document 3, and learned that they are born in daily life. It is difficult to damage during the life, and even if it is repeatedly rubbed, the scar will be recovered by the self-repairing function, and the abrasion resistance of the hard coating material is equal to or higher than that of the hard coating material.

However, it is known that since the self-healing material is a soft material, it seems to have excellent moldability at first glance, but if it is actually molded, it will be on the surface layer at the surface layer immediately after molding or during storage after molding. There is a crack (fracture), or a situation in which the surface layer is peeled off as a starting point.

Further, in Patent Documents 4 and 5, it has been proposed to coexist self-repairability and moldability as one of the problems, but it has been confirmed by the inventors that the effects of either of them are in the case of cracking or repeated rubbing during molding. Not enough. Further, none of Patent Documents 1 to 5 has reached the configuration in which the present invention is conceived. Accordingly, an object of the present invention is to provide a laminated film which is excellent in scratch resistance, and which is resistant to over-peeling and moldability.

In order to solve the above problems, the inventors of the present invention have completed the following invention by repeating the results of intensive research. That is, the present invention is as follows.

(1) A laminated film having a laminated film comprising a surface layer of an A layer and a B layer on at least one side of a supporting substrate, characterized in that a B layer and an A layer are supported from the side of the supporting substrate. In this order, the storage elastic modulus of 25° C. (hereinafter _{referred to} as E _A25 , E _B25 , E _C25 ) measured by a micro hardness tester of the A layer, the B layer, and the support substrate, and the storage elastic modulus at 120° C. (The following are E _A120 , E _B120 , E _C120 ) The following conditions are met: Condition 1 E _A25 <E _B25 ≦E _C25 ; Condition 2 E _B120 ≦E _A120 <E _C120 ; Condition 3 E _A25 ≦100MPa.

(2) The laminated film according to (1), wherein the A layer, the B layer, and the support substrate satisfy the following conditions, and the 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 referred to as 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 of the layer B (hereinafter referred to as T _B ) satisfies the following conditions; and the condition 7 is 0.1 μm ≦ T _B ≦ 5 μm.

(5) The laminated film according to any one of (1) to (4) wherein, in the cross section perpendicular to the substrate of the surface layer, from the surface of the surface layer, 10% of the thickness of the surface layer According to the atomic force microscope, the elastic modulus E1, E2, and E3 of each position of 50% (hereinafter referred to as position 1), 50% (hereinafter referred to as position 2), and 99% (hereinafter referred to as position 3) satisfy the following conditions, conditions 8 E1≦E2<E3; Condition 9 E1≦100MPa; Condition 10 E3≧1GPa.

(6) A method for producing a laminated film according to any one of the above aspects, wherein the surface layer is composed of two or more types of coating materials. The material is applied to the support substrate one by one, dried and hardened to form.

(7) A method for producing a laminated film, which is as described in the above (1) to (5) The method for producing a laminated film according to any one of the preceding claims, wherein the surface layer is formed by simultaneously applying two or more types of coating compositions onto a support substrate, drying and curing.

According to the present invention, it is possible to provide a laminated film which is excellent in scratch resistance, and which is resistant to over-peeling and moldability.

1‧‧‧ layer in contact with layer B in the surface layer (layer A)

2‧‧‧Layer in contact with the support substrate (layer B)

3‧‧‧Support substrate (C layer)

4‧‧‧ Surface layer containing layers A and B

5‧‧‧10% of the thickness of the surface layer from the surface of the surface layer (position 1)

6‧‧‧From the surface of the surface layer, 50% of the thickness of the surface layer (position 2)

7‧‧‧From the surface of the surface layer, 99% of the thickness of the surface layer (position 3)

8‧‧‧Multilayer sliding die

9‧‧‧Multi-layer slot die

10‧‧‧Single layer slot die

Fig. 1 is a view showing an example of a cross-sectional view showing a configuration of a laminated film of the present invention.

Fig. 2 is a view showing an example of a cross-sectional view of the structure of the laminated film of the present invention.

Fig. 3 is a cross-sectional view showing an example of a method of forming a surface layer in the present invention.

Fig. 4 is a cross-sectional view showing an example of a method of forming a surface layer in the present invention.

Fig. 5 is a cross-sectional view showing an example of a method of forming a surface layer in the present invention.

[Formation of the Invention]

In order to achieve the above problems, the inventors of the present invention have (1) the reason that the self-healing material is excellent in the scratch resistance of the hard coating material in the actual use environment; (2) the soft self-healing material is stored immediately after molding or after molding. At the time of the occurrence of cracks (fractures) in the surface layer or the reason why the surface layer was peeled off as a starting point, the following examination was carried out in detail.

First, the above (1) will be described. The formation of scars on the plastic surface is affected by three factors: "pressure", "hardness of the wiper" and "number of wipes". The reason why the hard coating material is likely to occur in the actual use environment is the damage forming mechanism due to the actual use environment, that is, "in the actual use environment, the hardness of the surface is low, but on the other hand, the number of contacts is very high. "." In the hard coating material, even if the hardness of the wiper is low, or the pressure at the time of wiping is low, and the scratch is not caused by the surface, the internal strain which does not cause damage on the surface of the material remains. This will be accumulated as strain due to the increase in the number of wipes. As a result, it is considered that in a hard coating material having a high hardness and a small strain range capable of elastic deformation, it exceeds the allowable range of strain and finally forms a flaw. On the other hand, it is considered that the self-healing material is strong in the actual use environment, and the reason for the repeated rubbing is effective because the elastic recovery range of the material is large, and even if it is rubbed under the aforementioned conditions, the strain can be released without forming a flaw. .

Next, the above (2) will be described. In the surface layer, a material which exhibits self-healing property by elastic recovery is used in the surface layer, and a laminated film of a general thermoplastic resin is used for the substrate, since the surface layer becomes "entropy elastomer = rubber elastic body" Since the support substrate is an "energy elastomer", it can be said that it is formed of a material that is greatly different from the mechanical behavior of heat. When such a film is heated and molded, the support substrate is plastically deformed and fixed, but the self-healing layer is deformed in the elastic deformation range, so that the supported substrate is stretched in the elongation direction. Residual stress occurs in the surface layer. Moreover, it is considered that if it is in the latter step, for example, due to injection molding Further heating, or high temperature in the use environment, will result in an increase in the elastic modulus of the surface layer due to the entropy elastomer, and the fracture limit will be reached in the case where the elongation at the time of molding is large. And the rupture occurred.

Therefore, the present inventors have found that a laminated film having a surface layer of the following structure is used as a surface layer of a laminated film, and has excellent scratch resistance as described above, especially in the actual use environment, There is sufficient molding adaptability on one side.

First, as shown in Fig. 1, the laminated film of the present invention has a surface layer including an A layer and a B layer on at least one side of the support substrate 3, and a B layer, A from the side of the support substrate. The layers are connected in this order.

In the surface layer, the layer of the second layer (the layer 1 in FIG. 1 , that is, the layer A) from the side of the support substrate, and the layer that contacts the support substrate (the layer 2 in FIG. 1 , that is, the layer B). , storage substrate (3 in Fig. 1, hereinafter referred to as layer C), storage elastic modulus at 25 ° C measured by a micro hardness tester (hereinafter E _A25 , E _B25 , E _C25 ), 120 ° C The storage elastic modulus (hereinafter E _A120 , E _B120 , E _C120 ) satisfies the following conditions; Condition 1 E _A25 <E _B25 ≦E _C25

Condition 2 E _B120 ≦E _A120 <E _C120

Condition 3 E _A25 ≦100MPa.

Here, Condition 1 shows the elastic modulus at 25 ° C, that is, the A layer (the layer in the surface layer that contacts the B layer) and the B layer (the layer in the surface layer that contacts the supporting substrate) in the use temperature at which the laminated film is actually used. ), the relationship between the storage elastic modulus of the C layer (support substrate). It means that the C layer has the highest storage elastic modulus, while the B layer has a higher storage modulus than the A layer and the storage elastic modulus is the same as or lower than the C layer, while the A layer has the lowest storage modulus and is better. For E _A25 <E _B25 <E _C25 .

With such a configuration, the B layer has sufficient cohesive force, and the surface layer has sufficient adhesion to the C layer, and is preferably less likely to be peeled off even if it is repeatedly rubbed during actual use, which is preferable.

The surface layer may include other layers as long as it includes the A layer and the B layer. That is, the configuration of the surface layer may be three or more layers as in Fig. 3, and the elastic modulus system of the layer (as the Z layer) closer to the surface side than the A layer is not particularly limited, but The Z layer is close to the elastic modulus of the A layer. Here, the Z layer may have other functions such as antifouling property, fingerprint resistance, dye resistance, antireflection property, antiglare property, and antistatic property.

The storage elastic modulus measured by a microhardness tester described above is a value measured by a microhardness tester by forming an ultrathin section of a cross section of the surface layer of the laminated film. The details of the specific measurement method and calculation method will be described later.

If the order of the elastic modulus is reversed to be E _A25 > E _B25 > E _C25 , the strain release by the elastic recovery of the surface layer may not be performed, and there is a case where it is not resistant to repeated rubbing. In addition, when the order of the exchange is E _B25 >E _A25 >E _B25 or the like, the stress concentration portion is formed in the layer, and peeling may occur in the vicinity thereof.

Further, Condition 2 shows the relationship between the elastic modulus at 120 ° C, that is, the elastic modulus of the A layer, the B layer, and the C layer in the vicinity of the molding temperature of the laminated film, meaning that the B layer has the lowest elastic modulus or The A layer is the same, while the A layer has a lower elastic modulus than the C layer, and the C layer has the highest elastic modulus. More preferably E _B120 <E _A120 <E _C120 .

By having such a configuration, the elastic modulus of the B layer is lower than that of the A layer at the time of molding, so that residual stress does not remain in the A layer, and even in the subsequent steps, heating and use environment It is also preferable that cracking is less likely to occur in the lower temperature.

If the order of the elastic modulus is exchanged, that is, E _A120 ≦E _B120 <E _C120 , the residual stress will accumulate during molding due to the above mechanism, and there will be heating in the subsequent steps and use environment. Cracking occurs at high temperatures.

Here, Condition 3 shows a preferred range of the elastic modulus (E _A25 ) of the A layer at 25 ° C. The value of E _A25 is preferably 100 MPa or less, more preferably 50 MPa or less, and particularly preferably 20 MPa or less. If the value of E _A25 exceeds 100 MPa, the release of strain due to elastic recovery may be insufficient when repeatedly rubbed. In addition, although the value of E _A is small, there is no particular obstacle in achieving this problem. However, if it is 1 MPa or less, adhesion may occur on the surface, and it may be impractical from the viewpoint of surface protection.

Furthermore, it is preferable to satisfy the following conditions 4 and 5.

Condition 4 0<E _C25 -E _B25 <5GPa

Condition 5 0 < E _{A120 -} E _B120 < 50 MPa.

Here, the condition 4 is a range showing a difference between the preferred storage elastic modulus of the B layer and the C layer at a temperature in the actual use environment of the laminated film, more preferably 100 MPa < E _{C25 -} E _B25 < 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, so that the resistance to repeated rubbing may be lowered. If E _C25 -E _B25 becomes zero, as a result, since the difference in the elastic modulus between the A layer and the B layer becomes large, the stress concentration at the interface between the layers of the A layer and the B layer becomes large, and there is a rubbing of the hard material. And the scar is easy to remain.

Further, Condition 5 shows a range of a difference in a preferred storage elastic modulus between the A layer and the B layer at the molding temperature, more preferably 0 < E _{A120 -} E _B120 < 30 MPa, and particularly preferably 0 < E _{A120 -} E _B120 <10MPa.

When E _A120 -E _{B120 is} 50 MPa or more, the adhesion between the surface layer and the supporting substrate may be insufficient during the molding process, and wrinkles may occur. Further, when the E _B120 side is larger than the E _A120 , residual stress is generated at the interface between the A layer and the B layer during molding, and cracking or peeling may occur easily.

Further, it is preferable that the surface layer satisfies the following condition 6.

Condition 6 60 ° C ≦ Tg _B ≦ 130 ° C

Here, Condition 6 shows a preferred range of the glass transition temperature of the layer (B layer) in contact with the support substrate among the surface layers, and is preferably 60 ° C ≦ Tg _B ≦ 100 ° C.

The glass transition temperature is a value obtained by the maximum value of the temperature dispersion of the ratio of the storage elastic modulus to the loss elastic modulus (loss tangent) measured by the micro hardness meter. The 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 lowered, so that the peeling at room temperature or the rubbing by the hard material may cause the scar to easily remain. Happening. Further, in the case where the glass transition temperature of the layer B is higher than 130 ° C, it may be easily broken or peeled off during molding due to the conditions.

Further, it is preferred that the surface layer satisfies the following condition 7; Condition 7 0.1 μm ≦ T _B ≦ 5 μm.

Here, Condition 7 shows a preferable range of the thickness (T _B ) of the layer (B layer) in contact with the supporting substrate in the surface layer, more preferably 0.5 μm ≦ T _B ≦ 3 μm. If the thickness of the layer B is thinner than 0.1 μm, the ability to cause residual stress between the surface layer and the supporting substrate during the absorption molding may be slightly weakened, and if it is thicker than 5 μm, the surface layer may be present. The adhesion to the support substrate is slightly weakened.

As shown in Fig. 2, the laminated film of the present invention has a laminated film comprising a surface layer of the A layer and the B layer on at least one side of the support substrate, preferably perpendicular to the base layer of the surface layer. In the cross section of the material, from the surface of the surface layer, at the position of 10% of the thickness of the surface layer (hereinafter referred to as position 1; position 5 in Fig. 2), 50% (hereinafter referred to as position 2; In the position of 6), 99% (hereinafter referred to as position 3; position 7 in Fig. 2), the elastic modulus E1, E2, and E3 of the atomic force microscope satisfy the following conditions: 8. Conditions 9. Condition 10; Condition 8 E1≦E2<E3

Condition 9 E1≦100MPa

Condition 10 E3≧1GPa.

The condition 8 is intended to be such that the elastic modulus increases from the surface side toward the substrate side in the thickness direction of the surface layer, and preferably E1 ≦ E2 < E3, more preferably E1 < E2 < E3.

If the order is reversed, that is, E1>E2>E3, the strain release due to elastic recovery cannot be performed on the outermost surface, so that it is not resistant to repeated rubbing, and even if the hardness of the outermost surface is high, Since the strain modulus of the lower portion is low and the strain is increased, the scratch resistance may be lowered by rubbing with a material having a high pressure or a high hardness.

Condition 9 shows a preferable range of the elastic modulus (E1) of the surface side of the surface layer. The value of E1 is preferably 100 MPa or less, more preferably 50 MPa or less, and particularly preferably 20 MPa or less. If the value of E1 exceeds 100 MPa, the release of strain due to elastic recovery when the rubbing is repeated will be insufficient. In addition, although the value of E1 is small, there is no particular obstacle in achieving this problem. However, if it is 1 MPa or less, adhesion may occur on the surface, and it may be impractical from the viewpoint of surface protection.

Condition 10 shows a preferred range of the elastic modulus (E3) of the support substrate side of the surface layer. The value of E3 is preferably 1 GPa or more, more preferably 2 GPa or more, and particularly preferably 3 GPa or more. When the value of E3 is less than 1 GPa, the surface hardness may become insufficient, and the durability against rubbing due to a hard material may be insufficient. For the scratch resistance, the higher the value of E3, the better, but practically, from the viewpoint of folding endurance or workability, the material which can be used as the surface layer on the laminated film is about 100 GPa. .

Here, the measurement of the storage elastic modulus, the loss elastic modulus, and the glass transition temperature of the surface layer will be described. These measurements were carried out using an ultra-micro hardness tester (Tribo Indenter, manufactured by Hysitron Co., Ltd.) to obtain an analog-to-digital map image (storing elastic modulus (E') image and loss elastic modulus (E") image.

For example, the laminated film is embedded in an electric epoxy resin (Quetol 812 manufactured by Nisshin EM Co., Ltd.) and hardened, and an ultrathin slicer is used. (Ultracut S manufactured by LEICA Co., Ltd.) An ultrathin section of a cross section of a surface layer of a laminated film was produced as a measurement sample, and the measurement was performed under the following conditions, and the elastic modulus was calculated using a Hertz contact theory.

Measuring device: Tribo Indenter manufactured by Hysitron

Use indenter: Diamond Cubecorner indenter (curvature radius 50nm)

Measuring field of view: about 30mm square

Measuring frequency: 200Hz

Measuring environment: room temperature ‧ in the atmosphere

Contact load: 0.3μN

The principle of measurement by an ultra-micro hardness 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 expressed by the formula (1).

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

On the other hand, it is considered that when the indenter contacts the outermost surface of the sample, the front end of the indenter is regarded as a spherical shape, and the contact theory of Hertz concerning the contact of the spherical shape with the semi-infinite flat plate can be employed. In the contact theory of Hertz, the radius a of the indentation projection surface when the indenter is in contact with the sample is expressed by the formula (2).

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

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

The so-called modulus mapping is based on the Hertz contact theory described above, so that the indenter contacts the outermost surface of the sample, and the indenter is slightly vibrated during the test, and the amplitude and phase of the response to the vibration are obtained as a function of time. A method of obtaining K (measuring system stiffness) and D (sample damping) is obtained.

When the vibration is a simple harmonic oscillator, the sum of the forces of the indenter in the direction in which the sample enters (the detected load component) F(t) is expressed by the formula (4).

Here, the first term of the formula (4) indicates the force from the indenter shaft (m: the mass of the indenter shaft), and the second term of the formula (4) indicates the force from the viscous component of the sample, and the third formula (4) The term indicates the rigidity of the sample system and t indicates time. F(t) of the formula (4) is represented by the formula (5) due to time dependence.

F ( t )== F ₀ exp ( iωt ) (Expression 5)

Here, F ₀ is a constant and ω is an angular vibration number. If the equation (5) is substituted into the equation (4), and the equation (6) of the special solution of the ordinary differential equation is substituted, and the equation is solved, the relational expressions of the equations (7) to (10) can be obtained.

Here, Φ is a phase difference. Since the m-system is known for measurement, the vibration amplitude (h ₀ ), the phase difference (Φ), and the excitation vibration amplitude (F ₀ ) of the displacement can be measured by the equation (7)~ Equation (10) calculates K and D.

Consider E ^* as the storage elastic modulus (E'), and summarize the formulas (1) to (10). In the measurement system stiffness, Ks (=K-mω ² ) from the sample is used. 11) Calculate the storage elastic modulus.

The loss elastic modulus in the present invention can also be measured in the same manner as the measurement of the storage elastic modulus, and Ks from the sample is used in the measurement system stiffness in the above formula (8), and is combined with the formula (11). The summed equation (12) calculates the loss elastic modulus.

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 obtained from the ratio of the storage elastic modulus and the loss elastic modulus calculated above, and the resulting loss is obtained. The peak temperature of tangent (tan δ) is taken as the glass transition temperature (Tg).

In the present invention, the elastic modulus of the atomic force microscope is measured by a compression test of a probe of a very small portion, and the degree of deformation due to the pressing force is used, and the surface layer is measured using a cantilever having a known spring constant. The modulus of elasticity in the cross section at each position in the thickness direction. Specifically, the laminated film was cut, and the modulus of elasticity in the cross section at each position in the thickness direction of the surface layer was measured by an atomic force microscope. The details are described in the examples, but the cantilever obtained by measuring the force curve from the injection load of a maximum of 2 μN by using the atomic force microscope shown below, the probe at the tip end of the cantilever is brought into contact with the cross section of the surface layer. The amount of deflection Determination. The details are as follows.

Atomic Force Microscope: MFP-3DSA-J manufactured by ASYLUM Technologies

Cantilever: Cantilever arm made of NANOSENSORS "R150-NCL-10 (material Si, spring constant 48N/m, radius of curvature of the front end 150nm).

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 a planar state or a three-dimensional shape after molding as long as it has a surface layer exhibiting the above 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.

The layer of 2 or more is preferably a layer (A layer) in contact with the B layer and a layer (B layer) in contact with the support substrate in at least the surface layer, and the A layer, the B layer, and the support layer. The material system satisfies the aforementioned relationship.

The surface layer may have antifouling properties, anti-reflective properties, antistatic properties, electrical conductivity, heat ray reflectivity, and near infrared ray absorption in addition to the scratch resistance, particularly the over-peeling resistance and moldability, which are the subject of the present invention. Sex, electromagnetic shielding, easy to follow and other functions.

[support substrate]

The material of the support substrate used for the laminated film of the present invention may be either a thermoplastic resin or a thermosetting resin, or may be a homopolymeric tree. The fat may also be a copolymerization or a blend of two or more kinds. It is preferable that the resin which is a support base material is excellent in moldability, and it is preferable to use a thermoplastic resin.

As an example of the thermoplastic resin, a polyolefin resin such as polyethylene ‧ polypropylene ‧ polystyrene ‧ polymethyl pentene, an alicyclic polyolefin resin, a polyamide resin such as nylon 6 ‧ nylon 66, or the like can be used. Aromatic polyamide resin, polyester resin, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, chlorotrifluoroethylene resin, tetrafluoroethylene -6 fluoropropylene copolymer, fluororesin such as vinylidene fluoride resin, acrylic resin, methacrylic resin, polyacetal resin, polyglycolic acid resin, polylactic acid resin, and the like. The thermoplastic resin is preferably a resin having sufficient elongation and followability. From the viewpoint of strength, heat resistance, and transparency, the thermoplastic resin is preferably a polyester resin, a polycarbonate resin, or a methacrylic resin, and particularly preferably a polyester resin.

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

Moreover, various additives may be added to the support substrate. For example, an antioxidant, an antistatic agent, a crystal nucleating agent, inorganic particles, organic particles, a viscosity reducing agent, a thermal stabilizer, a slip agent, an infrared ray absorbing agent, an ultraviolet absorber, a dopant for refractive index adjustment, and the like. The support substrate may be of a single layer structure or a laminate structure.

On the surface of the support substrate, various surface treatments may be performed before the formation of the aforementioned surface layer. Examples of the surface treatment include pharmaceutical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and Ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

Further, on the surface of the support substrate, a functional layer such as an easy-adhesion layer, an antistatic layer, an undercoat layer, an ultraviolet absorbing layer or the like different from the surface layer of the present invention may be provided in advance, in particular, an easy-adhesion layer is provided. should.

[paint composition]

In the laminated film of the present invention, the coating composition is applied, dried, and cured by using a method for producing a laminated film to be described later on a supporting substrate, whereby a surface layer having a structure capable of achieving the physical properties can be formed. The term "coating composition" as used herein refers to a material comprising a solvent and a solute, which is applied to the above-mentioned support substrate, and which is capable of forming a surface layer by volatilizing a solvent, removing and hardening in a drying step. Here, the "type" of the coating composition means a liquid in which the type of the solute constituting the coating composition is partially different. This solute system contains The resin or the coating process can form a material of these materials (hereinafter referred to as a precursor), particles, and a polymerization initiator, a hardener, a catalyst, a homogenizer, an ultraviolet absorber, an antioxidant, and the like.

The laminated film of the present invention is preferably applied to the support substrate one by one or at the same time by using at least two kinds of paint compositions (hereinafter referred to as the paint composition A and the paint composition B) as described above. form.

Here, the coating composition A includes a liquid suitable for forming a second layer from the side of the support substrate from the surface layer, that is, the resin of the aforementioned A layer or a precursor, by using a support substrate in which the B layer is formed in advance. The layer A can be formed by coating, drying, hardening, or coating, drying, and hardening simultaneously with the formation of the B layer on the support substrate.

The coating composition B comprises a layer suitable for forming a surface layer in contact with the supporting substrate, that is, a liquid of the resin or precursor of the above-mentioned layer B, by coating, drying, hardening, or The B layer can be formed by coating, drying, and hardening simultaneously with the A layer on the surface side.

[Coating Composition A]

The coating composition A contains a liquid suitable for the material constituting the layer A in the surface layer or a precursor which can be formed, and preferably a resin or precursor containing the segments of the following (1) to (3) as a solute.

(1) a segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment, and a polyalkylene glycol segment

(2) urethane bond

(3) A segment comprising at least one selected from the group consisting of a fluorine compound segment, a polyoxyalkylene segment, and a polydimethylsiloxane chain segment.

Each segment included in the resin of the layer A in the surface of the surface layer can be confirmed by TOF-SIMS, FT-IR or the like.

Further, the mass parts of the above (1), (2), and (3) contained in the coating composition A are preferably (1) / (2) / (3) = 95/5 / 1 to 50 / 50. /15, more preferably (1) / (2) / (3) = 90/10/1 ~ 60 / 40/10. The details of (1), (2), and (3) will be described below.

The details of the (1) polycaprolactone segment, the polycarbonate segment, and the polyalkylene glycol segment are as follows, but the resin of the layer A in the surface constituting the surface layer has such a segment. , the self-healing property of the surface layer can be improved, and the repetitive rubbing property can be improved.

The details of the urethane bond are as follows. However, since the resin of the layer A in the surface constituting the surface layer has the bond, the toughness of the entire surface layer can be improved.

The details of the fluoropolyether segment will be described later, but the resin constituting the surface layer contains such a substance, so that molecules exhibiting low surface energy can be present in the highest surface at a high density, and the surface repetitive wiping property will be Upgrade.

[Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]

First, the polycaprolactone segment refers to the segment shown in Chemical Formula 1. The polycaprolactone also contains an oligomer such as a repeating unit of caprolactone of 1 (monomer), 2 (dimer), 3 (trimer), or a repeating unit of caprolactone to 35. .

n is an integer from 1 to 35.

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

In the case of a resin containing a polycaprolactone segment, polycaprolactone having a 2 to 3 functional hydroxyl group is particularly preferred. Specifically, polycaprolactone diol represented by Chemical Formula 2 can be used.

Here, m+n is an integer of 4 to 35, and m and n are each an integer of 1 to 34, and R is C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ , and C(CH ₃ ) ₃ (CH ₂ ). ₂ ; or polycaprolactone triol of Chemical Formula 3,

Here, l+m+n is an integer of 3 to 30, and l, m, and n are each an integer of 1 to 28, and R is CH ₂ CHCH ₂ , CH ₃ C(CH ₂ ) ₃ , and CH ₃ CH ₂ C ( CH ₂ ) ₃

a polycaprolactone polyol; or a polycaprolactone-modified hydroxyethyl (meth)acrylate represented by Chemical Formula 4,

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

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

Further, in the present invention, it is preferred that the polycaprolactone segment in the resin containing the polycaprolactone segment has a weight average molecular weight of 500 to 2,500, and more preferably a weight average molecular weight of 1,000 to 1,500. Since the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, the effect of self-healing is more exhibited, and the repetitive wiping property is more improved and better.

Next, the polyalkylene glycol segment means a segment represented by Chemical Formula 5. In the polyalkylene glycol, the repeating unit such as the alkanediol is also 2 (dimer), 3 (trimer), or the repeating unit of the alkanediol up to 11 Oligomer.

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

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

The resin containing a polyalkylene glycol segment is preferably a polyalkylene glycol (meth) acrylate having an acrylate group at the terminal end for imparting elasticity. The number of acrylate functional groups (or methacrylate functional groups) of the polyalkylene glycol (meth) acrylate is not limited, but is preferably monofunctional from the viewpoint of self-repairability of the cured product.

The polyalkylene glycol (meth) acrylate contained in the coating composition used for forming the surface layer may, for example, be polyethylene glycol (meth) acrylate or polypropylene glycol (meth) acrylate. , polybutylene glycol (meth) acrylate. Each is a structure represented by the following Chemical Formula 6, Chemical Formula 7, and Chemical Formula 8.

Polyethylene glycol (meth) acrylate:

Polypropylene glycol (meth) acrylate:

Polybutylene glycol (meth) acrylate:

In Chemical Formula 6, Chemical Formula 7, and Chemical Formula 8, R is hydrogen (H) or methyl (-CH ₃ ), and m is an integer of 2 to 11.

In the present invention, it is preferred to react an isocyanate group-containing compound described later with a hydroxyl group of a (poly)alkylene glycol (meth) acrylate to use a urethane (meth) acrylate as a surface layer. The resin constituting the surface layer thereby has (2) a urethane bond and a (3) (poly) alkanediol segment, and as a result, the surface layer is enhanced in toughness and at the same time the self-healing property is improved. Better.

When the isocyanate group-containing compound and the polyalkylene glycol (meth) acrylate are subjected to the urethanation reaction, the (meth)acrylic acid can be exemplified as the simultaneously mixed hydroxyalkyl (meth)acrylate. Hydroxyethyl ester, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and the like.

Next, the polycarbonate segment refers to the segment shown in Chemical Formula 9. In the polycarbonate, an oligomer such as a repeating unit of a carbonate of 2 (dimer), 3 (trimer), or a repeating unit of a carbonate to 16 is also included.

n is an integer from 2 to 16.

R ₄ means an alkylene group or a cycloalkyl group having 1 to 8 carbon atoms.

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

In the case of a resin containing a polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferred. Specifically, it is represented by Chemical Formula 10.

Polycarbonate diol: . . Chemical formula 10

n is an integer from 2 to 16. R is an alkylene group or a cycloalkyl group having a carbon number of 1 to 8.

The number of repetitions of the polycarbonate diol-based carbonate unit may be several, but if the number of repetitions of the carbonate unit is too large, the strength of the cured product of the urethane (meth) acrylate may decrease, so The number is preferably 10 or less. Further, the polycarbonate diol may be a mixture of two or more kinds of polycarbonate diols having different numbers of repeating carbonate units.

The polycarbonate diol is preferably one having a number average molecular weight of from 500 to 10,000, more preferably from 1,000 to 5,000. If the number average molecular weight is less than 500, it may become difficult to obtain suitable flexibility. Further, when the number average molecular weight exceeds 10,000, heat resistance or solvent resistance may be lowered, and the above-described degree is suitable.

Further, as for the polycarbonate diol used in the present invention, UH-CARB, UD-CARB, UC-CARB (Ube Industries, Ltd.), PLACCEL CD-PL, and PLACCEL CD-H (DAICEL) can be suitably exemplified. Chemical Industry Co., Ltd., KURARAY Polyol C Series (KURARAY Co., Ltd.), Duranol Series (Asahi Kasei Chemical Co., Ltd.) and other products. These polycarbonate diols can be used singly or in combination of two or more kinds.

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

In the present invention, it is preferred that the isocyanate group-containing compound described later is reacted with the hydroxyl group of the polycarbonate diol, and the urethane (meth) acrylate is used as the surface side of the surface layer. Further, the resin constituting the surface side of the surface layer can have the aforementioned (2) urethane bond and (1) polycarbonate diol segment, and as a result, the surface layer can be enhanced in toughness and at the same time self-repairing. Sexual ascension can improve the repetitiveness.

[Compound containing a urethane bond and an isocyanate group] In the present invention, the "urethane bond" means a bond represented by Chemical Formula 11.

Since the resin constituting the surface side of the surface layer has this bond, the toughness of the entire surface layer can be improved.

The coating composition A contains a commercially available urethane-modified resin, whereby the resin layer constituting the surface side of the surface layer may have a urethane bond. Further, when the surface side of the surface layer is formed, the coating composition A containing the isocyanate group-containing compound as a precursor and the hydroxyl group-containing compound may be applied, dried, and cured to thereby form an aminocarboxylic acid. The ester bond is formed while the surface side of the surface layer contains a urethane bond.

In the present invention, it is preferred to react an isocyanate group with a hydroxyl group to form a urethane bond, thereby introducing a urethane bond into the resin constituting the surface side of the surface layer. By reacting an isocyanate group with a hydroxyl group to form a urethane bond, the surface layer is enhanced in toughness and at the same time the self-healing property is improved, so that the repetitive rubbing property can be improved.

Further, in the case of the above-mentioned resin containing a polycaprolactone segment, a polycarbonate segment, a polyalkylene glycol segment, or a hydroxyl group, it is also possible to use such a resin as a precursor by heat or the like. The urethane bond is formed between the compounds containing the isocyanate group.

When a surface layer is formed by using a compound containing an isocyanate group, a resin containing a polyoxyalkylene segment having a hydroxyl group described later, or a resin having a polydimethylsiloxane chain having a hydroxyl group, The toughness and self-healing properties of the surface layer can also improve the smoothness of the surface. It is also better from the point of view of repetitive wiping.

In the present invention, the isocyanate group-containing compound means a resin containing an isocyanate group or a monomer or oligomer containing a cyanate group. Examples of the isocyanate group-containing compound include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of toluene diisocyanate, and trimethylolpropane adduct of hexamethylene diisocyanate. , trimethylolpropane adduct of isophorone diisocyanate, isomeric cyanurate of toluene diisocyanate, isomeric cyanurate of hexamethylene diisocyanate, hexamethylene isocyanate A (poly)isocyanate such as a biuret or a blocked body of the above isocyanate.

Among these isocyanate group-containing compounds, aliphatic isocyanates are preferred for self-healing properties compared to alicyclic or aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Further, the isocyanate group-containing compound is particularly preferably an isocyanate having an isomeric cyanate ring, particularly preferably a hexamethylene diisocyanate. An isocyanate having an isomeric cyanate ring forms a surface layer having both self-healing properties and heat resistance properties.

[Fluoride segment, polyoxyalkylene segment, polydimethylsiloxane chain segment]

In the laminated film of the present invention, preferably, the resin constituting the surface layer or the surface side of the surface layer has a segment, and the segment comprises a component selected from the group consisting of a fluorine-containing compound segment, a polyoxyalkylene segment, and a poly At least one of the group of dimethyloxane segments.

Furthermore, the resin containing the segment or the precursor can be used. The coating composition A is used for one of the coating compositions forming the surface layer, whereby the resin constituting the surface side of the surface layer has the same, wherein the segment contains a component selected from the group consisting of a fluorine-containing compound segment and a polyfluorene oxide. At least one of a group of an alkane segment and a polydimethyloxyalkylene segment.

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

First, the fluorine compound segment means a segment comprising at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluoroalkylalkanediyl group.

Here, the fluoroalkyl group, the fluoroalkyl group, the fluoroalkenyl group, the fluoroalkanediyl group, and the fluorooxyalkyldiyl group are an alkyl group, an oxyalkyl group, an alkenyl group, an alkanediyl group, or an oxyalkyldiyl group. Any one of hydrogen or a substituent substituted with fluorine, either of which is a substituent mainly composed of a fluorine atom and a carbon atom, may have a branch in the structure, or may form a portion having such a portion. A complex of dimers, trimers, oligomers, and polymer structures is constructed.

Further, the fluorine compound segment is preferably a fluoropolyether segment, and this includes a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group or the like, and more preferably a chemical formula 5 or a chemical formula. The fluoropolyether segment represented by 6 is as already described.

The fluoropolyether segment is a segment represented by Chemical Formula 12 or Chemical Formula 13 and includes a segment such as a fluoroalkyl group, an oxyfluoroalkyl group or an oxyfluoroalkanedion group.

Here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, and k, m, p, and s are integers of 0 or more, and p+s is 1 or more. Preferably, n1 is 2 or more, and 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 the fluoropolyether segment is preferably in a range of 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. When the carbon number is 3 or less, the oil repellency may be lowered due to insufficient reduction in surface energy, and when the solubility in the solvent is decreased at 13 or more, the grade of the surface layer may be lowered.

When the resin contained in the surface layer contains a fluorine compound segment, it is preferred that the coating composition A described above contains the following fluorine compound D. This fluorine compound D is a compound represented by Chemical Formula 14.

R ^f1 -R ₇ -D ¹ ...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, and three Structure, D ¹ represents a reactive site.

This reactive site refers to a site that reacts with other components due to external energy such as heat or light. As such a reactive site, alkoxyalkylene and alkoxydecane are mentioned from the viewpoint of reactivity. A hydrolyzed stanol group, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryl group, a methacryl group or the like. Among them, from the viewpoint of reactivity and handleability, a vinyl group, an allyl group, an alkoxyalkyl group, a decyl ether group or a stanol group, or an epoxy group or a propylene group (methacryl) is preferred.醯) base.

An example of the fluorine compound D is a compound shown below. There may be mentioned: 3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, 3,3,3-trifluoropropyltriisopropoxydecane, 3,3,3-trifluoropropyltrichloromethane, 3,3,3-trifluoropropyltriisocyanate decane, 2-perfluorooctyltrimethoxydecane, 2-perfluorooctylethyltriethoxy Baseline, 2-perfluorooctylethyltriisopropoxydecane, 2-perfluorooctylethyltrichlorodecane, 2-perfluorooctyl isocyanate decane, 2,2,2-trifluoroethyl acrylate Ester, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexyl Ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluoroindole Ethyl 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, tetrafluoropropene base Ethyl ester, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorodecyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2 , 2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutyl ethyl 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-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropane Methyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, eight Fluoryl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorodecyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate Ester, hexafluorobutyl methacrylate, tripropylene decyl-heptadecafluorodecenyl-pentaerythritol, and the like.

Further, the fluorine compound D may have a plurality of fluoropolyether sites per molecule.

Examples of the commercially available fluorine compound D include RS-75 (DIC Co., Ltd.), Optool DAC-HP (DAIKIN Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Co., Ltd.), and the like. These products can be utilized.

Next, the polyoxyalkylene segment is described. In the present invention, the polyoxyalkylene segment refers to a segment represented by Chemical Formula 15 which will be described later.

Here, the polyoxyalkylene contains a repeating unit of a decane having a low molecular weight of about 100 (so-called oligomer) and two repeating units of a decane having a high molecular weight of more than 100 (so-called polymer). By.

Any one of R ₁ and R ₂ -based hydroxyl groups or alkyl groups having 1 to 8 carbon atoms has at least one or more of the formulas, and n is an integer of 100 to 300.

The details of the polyoxyalkylene segment and the polydimethyloxyalkylene segment are as follows, but the resin constituting the surface layer has heat resistance, weather resistance, or improvement due to such a segment. Scratch resistance due to the lubricity of the surface layer. More preferably, it is preferable to include a polydimethylsiloxane chain segment represented by Chemical Formula 16 to be described later from the viewpoint of lubricity.

In the present invention, a partial hydrolyzate of a hydrocarbyl alkylene group-containing decane compound, an organic cerium sol or a coating composition in which a hydrolyzable decane compound having a radical polymer is added to the organic cerium sol may be used as a polyfluorene. The resin of the oxyalkylene segment is used.

The resin containing a polyoxyalkylene segment may, for example, be a tetraalkoxydecane, a methyltrialkoxydecane, a dimethyldistenoxydecane or a γ-glycidoxypropyltrialkoxydecane. , γ-glycidoxypropyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy A wholly or partial hydrolyzate of a hydrolyzable alkylene group-containing decane compound, or an organic cerium sol dispersed in an organic solvent, or a hydrolyzed decane compound having a hydrolyzable decyl group added to the surface of the organic cerium sol.

Further, in the present invention, the resin containing a polyoxyalkylene segment may contain (copolymerize) another segment or the like in addition to the polyoxyalkylene segment. For example, a monomer component having a polycaprolactone segment or a polydimethylsiloxane chain segment may be contained (copolymerized).

When the resin containing a polyoxyalkylene segment has a hydroxyl group In the case of a copolymer, if a surface layer is formed by using a coating composition comprising a polyoxyalkylene group-containing resin (copolymer) having a hydroxyl group and an isocyanate group-containing compound, the polymer layer can be efficiently formed. a surface layer of an oxyalkylene segment and a urethane bond.

Next, the polydimethylsiloxane chain segment is described. In the present invention, the so-called polydimethylsiloxane chain segment means a segment represented by Chemical Formula 16. In polydimethyloxane, a repeating unit comprising dimethyloxane is a low molecular weight of 10 to 100 (so-called oligomer) and a repeating unit of dimethyloxane having a molecular weight of more than 100 Both of them (so-called polymers).

m is an integer from 10 to 300.

The resin constituting the surface side of the surface layer, if it has a polydimethyl siloxane chain segment, the polydimethyl siloxane chain segment is disposed on the surface of the surface layer. By virtue of the polydimethylsiloxane chain segment being disposed on the surface of the surface layer, the surface layer is lubricated to reduce frictional resistance. As a result, the repetitive wipeability can be improved.

In the present invention, as the resin containing a polydimethylsiloxane chain segment, a copolymer in which a vinyl monomer is copolymerized in a polydimethylsiloxane chain segment is preferably used.

In order to enhance the strength and toughness of the surface layer, The resin of the dimethyloxyalkylene segment is preferably a monomer which is copolymerized with a hydroxyl group which reacts with an isocyanate group.

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

When the resin containing a polydimethylsiloxane chain segment is a copolymer of a vinyl monomer, it may be any of a block copolymer, a graft copolymer, and a random copolymer. When a copolymer containing a polydimethylsiloxane chain segment and a vinyl monomer is referred to as a polydimethylsiloxane derivative. The polydimethylsiloxane coupled copolymer can be produced by a living polymerization method, a polymer initiator method, a polymer chain transfer method, or the like. However, in consideration of productivity, it is preferred to use a polymer initiator. Method, polymer chain transfer method.

When a polymer initiator method is used, a polymer azo-based radical polymerization initiator represented by Chemical Formula 17 can be used to copolymerize with another vinyl monomer. Further, a two-stage polymerization may be carried out by copolymerizing a peroxymonomer with a polydimethylsiloxane having an unsaturated group at a low temperature to synthesize a prepolymer having a peroxide group introduced into a side chain. And prepolymerizing the prepolymer with a vinyl monomer.

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

When the polymer chain transfer method is used, for example, HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH may be added to the polyoxosulfonate represented by Chemical Formula 18 to form a compound having an SH group, and then SH may be used. The chain is transferred to copolymerize the oxime compound with a vinyl monomer, thereby synthesizing the block copolymer.

m is an integer from 10 to 300.

In order to synthesize a polydimethyl siloxane-based graft copolymer, for example, a compound represented by Chemical Formula 19, that is, a methacrylate of polydimethyl siloxane or the like, may be copolymerized with a vinyl monomer, whereby The graft copolymer is easily obtained.

m is an integer from 10 to 300.

The vinyl monomer used for the copolymer of polydimethyl methoxy oxane may, for example, be methyl acrylate or ethyl acrylate. , n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Ester, 2-ethylhexyl methacrylate, octadecyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-A Styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, allyl ring Oxypropyl propyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylol acrylamide, N, N-di Methyl acrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, diethyl propylene decylamine, 2-hydroxy acrylate Ethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol .

Further, the polydimethylsiloxane oxide copolymer is preferably an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or ethyl acetate. An ester solvent such as butyl acetate or an alcohol solvent such as ethanol or isopropyl alcohol, which is produced by a solution polymerization method, alone or in a mixed solvent.

A polymerization initiator such as benzamidine peroxide or azobisisobutyronitrile may be used in combination as needed. The polymerization reaction is preferably carried out at 50 to 150 ° C for 3 to 12 hours.

The amount of the polydimethyl siloxane chain in the polydimethyl siloxane derivative copolymer of the present invention is lubricity or pollution resistance to the surface layer The property is preferably from 1 to 30% by mass based on 100% by mass of all the components of the polydimethylsiloxane-based copolymer. Further, the polydimethylsiloxane chain segment preferably has a weight average molecular weight of 1,000 to 30,000.

In the present invention, as the coating composition used for forming the surface layer, when a resin containing a polydimethylsiloxane chain segment is used, in addition to the polydimethylsiloxane chain segment, it may contain (copolymerization) ) Other segments, etc. For example, it is also possible to contain (copolymerization) a polycaprolactone segment or a polyoxyalkylene segment.

In the coating composition used for forming the surface layer, a copolymer of a polycaprolactone segment and a polydimethylsiloxane chain segment, a copolymerization of a polycaprolactone segment and a polyoxyalkylene segment may be used. a copolymer of a polycaprolactone segment and a polydimethylsiloxane chain segment and a polyoxyalkylene segment. The surface layer obtained by using such a coating composition may have a polycaprolactone segment and a polydimethylsiloxane chain segment and/or a polyoxyalkylene segment.

In a coating composition for forming a surface layer having a polycaprolactone segment, a polyoxyalkylene segment, and a polydimethylsiloxane chain segment, a polydimethylsiloxane derivative, a poly The reaction of caprolactone and polyoxyalkylene can be carried out by appropriately adding a polycaprolactone segment and a polyoxyalkylene segment during the synthesis of the polydimethylsiloxane copolymer.

[Coating Composition B]

The coating composition B is a liquid which can form a material having a surface hardness higher than that of the A layer by coating, drying, and hardening on a supporting substrate, and contains a resin or a precursor suitable for forming the layer B.

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

The thermosetting resin in the present invention contains a hydroxyl group-containing resin and a polyisocyanate compound, and examples of the hydroxyl group-containing resin include acrylic polyol, polyether polyol, polyester polyol, and polyolefin polyol. An alcohol, a polycarbonate polyol, a urethane polyol, or the like may be one type or a mixture of two or more types. When the hydroxyl group-containing resin has a hydroxyl value of from 1 to 200 mgKOH/g, it is preferable from the viewpoint of durability, hydrolysis resistance, and adhesion when the film is formed. When the hydroxyl value is less than 1 mgKOH/g, the curing of the coating film hardly proceeds, and the durability or strength may be lowered. On the other hand, when the hydroxyl value is more than 200 mgKOH/g, since the hardening shrinkage is too large, the adhesion may be lowered.

The hydroxyl group-containing acrylic polyol in the present invention is obtained, for example, by polymerizing an acrylate or a methacrylate as a component. In such an acrylic resin, for example, a (meth) acrylate may be used as a component, and if necessary, a carboxylic acid group-containing monomer such as (meth)acrylic acid, itaconic acid or maleic anhydride may be copolymerized, whereby it is easy to Manufacturing. Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). ) butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, cyclohexyl (meth)acrylate, methylhexyl (meth)acrylate, cyclododecan (meth)acrylate, (meth)acrylic acid Ester and the like. For example, DIC Co., Ltd. (trade name "Acrydic" (registered trademark) series), Dacheng Fine Chemical Co., Ltd.; (product name "Acrit") (registered trademark) series, etc., Japan Catalyst Co., Ltd.; (trade name "Acryset" (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd.; (trade name "Takelac" (registered trademark) UA series), etc. These products can be utilized.

The polyoxyl polyol containing a hydroxyl group in the present invention may, for example, be polyethylene glycol or triol, polypropylene glycol or triol, polytetramethylene glycol or triol, polytetramethylene. A diol or a triol, and an addition polymer or a block copolymer of the oxyalkylene compounds having different carbon numbers. As such a polyether polyol containing a hydroxyl group, Asahi Glass Co., Ltd.; (trade name "Excenol" (registered trademark) series), Mitsui Chemicals Co., Ltd.; (trade name "Actcol" ( Registered trademarks, etc.), can use such products.

The hydroxyl group-containing polyester polyol in the present invention may, for example, be ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol or cyclohexane. An aliphatic diol such as an alkyl dimethanol or the like, and, for example, succinic acid, adipic acid, sebacic acid, fumaric acid, suberic acid, sebacic acid, 1,10-decamethylene dicarboxylic acid, cyclohexane An aliphatic polyester polyol in which an aliphatic dibasic acid such as a dicarboxylic acid is reacted as an essential raw material component; or an aliphatic diol such as ethylene glycol, propylene glycol or butylene glycol, and, for example, terephthalic acid, An aromatic polyester polyol obtained by reacting an aromatic dibasic acid such as phthalic acid or naphthalene dicarboxylic acid as an essential raw material component.

Examples of such a polyester polyol containing a hydroxyl group include DIC Co., Ltd.; (trade name "Polylite" (registered trademark) series), and KURARAY Co., Ltd.; (trade name "KURARAY polyol") (registered trademark) series, etc.), Takeda Pharmaceutical Industry Co., Ltd.; (trade name "Takelac" (registered trademark) U series), which can be used.

The polyolefin-based polyol containing a hydroxyl group in the present invention is a polymer and copolymer of a diene having 4 to 12 carbon atoms such as butadiene or isoprene, and a carbon number of 4 to Among the copolymers of 12 diolefins and carbon atoms 2 to 22 α-olefins, a hydroxyl group-containing compound is contained. The method of containing a hydroxyl group is not particularly limited, and for example, there is a method of reacting a diene monomer with hydrogen peroxide. Furthermore, it is also possible to saturate and fatate by hydrogen bonding the remaining double bonds. Examples of such a polyolefin-based polyol containing a hydroxyl group include Japan Soda Co., Ltd.; (trade name "NISSO-PB" (registered trademark) G series), and Idemitsu Kosan Co., Ltd.; Products such as the "Poly bd" (registered trademark) series and the "Epol" (registered trademark) series can be used.

For the polycarbonate polyol containing a hydroxyl group in the present invention, for example, a polycarbonate polyol obtained by using only dialkyl carbonate and 1,6-hexanediol can be used, but the crystallinity is further improved. The lower point is preferably obtained by copolymerizing 1,6-hexanediol, 1,4-butanediol, 1,5-pentanediol or 1,4-cyclohexanedimethanol as a diol. Polycarbonate polyol.

As a polycarbonate polyol containing such a hydroxyl group, Asahi Kasei Chemical Co., Ltd., which is a copolymerized polycarbonate polyol; (trade name "T5650J", "T5652", "T4671", "T4672" ", etc.), Ube Industries Co., Ltd.; (trade name "ETERNACLL" (registered trademark) UM series, etc.), such products can be used.

Hydroxyl group-containing urethane diversity in the present invention The alcohol is obtained, for example, by reacting a polyisocyanate compound with a compound containing at least two hydroxyl groups in one molecule, in a ratio of a hydroxyl group to an isocyanate group. Examples of the polyisocyanate compound used at that time include hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, and isophorone diisocyanate. Further, examples of the compound containing at least two hydroxyl groups in one molecule include a polyhydric alcohol, a polyester diol, polyethylene glycol, polypropylene glycol, and polycarbonate diol.

The polyisocyanate compound used for the thermosetting resin in the present invention means a resin containing an isocyanate group or a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, a trimethylolpropane adduct of toluene diisocyanate, and a trimethylolpropane adduct of hexamethylene diisocyanate. Trimethylolpropane adduct of isophorone diisocyanate, isomeric cyanurate of toluene diisocyanate, isomeric cyanurate of hexamethylene diisocyanate, hexamethylene isocyanate (poly)isocyanate such as diurea or the like, and a terminal block of the above isocyanate. The polyisocyanate compound used for such a thermosetting resin includes Mitsui Chemicals Co., Ltd.; (trade name "Takenate" (registered trademark) series), and Japan Polyurethane Industry Co., Ltd.; (trade name "Coronate" (registered trademark) series, etc.), Asahi Kasei Chemicals Co., Ltd.; (product name "Duranate" (registered trademark) series, etc.), DIC Corporation; (product name "Burnock" (registered trademark) series Etc.), you can use these products.

In the ultraviolet curable resin of the present invention, Preferred as polyfunctional acrylate monomer, oligomer, alkoxydecane, alkoxydecane hydrolysate, alkoxydecane oligomer, urethane acrylate oligomer, etc., more preferably polyfunctional Acrylate monomer, oligomer, urethane acrylate oligomer.

As an example of the polyfunctional acrylate monomer, a polyfunctional acrylate having two or more (meth) acryloxy groups in one molecule and a modified polymer thereof can be used, and specific examples thereof are pentaerythritol three (for example) Methyl) acrylate, pentaerythritol tetra(meth) acrylate, dipentaerythritol tri(meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate hexane methylene diisocyanate urethane polymer, and the like. These single systems may be used alone or in combination of two or more.

In addition, Mitsubishi Rayon Co., Ltd.; (product name "Diabeam" (registered trademark) series), Japan Synthetic Chemical Industry Co., Ltd.; (product name) "SHIKOH" (registered trademark) series, etc., Nagase Industry Co., Ltd.; (product name "Denacol" (registered trademark) series), Shin-Nakamura Chemical Co., Ltd.; (product name "NK Ester" series, etc.), DIC Co., Ltd.; (trade name "UNIDIC" (registered trademark), etc.), East Asia Synthetic Co., Ltd.; ("Aronix" (registered trademark) series, etc.), Nippon Oil Co., Ltd.; ("Blemmer" (registered trademark) Series, etc., Nippon Kayaku Co., Ltd.; (trade name "KAYARAD" (registered trademark) series), Kyoeisha Chemical Co., Ltd.; (product name "Light Ester" series, etc.), etc. product.

Further, in order to impart the aforementioned characteristics, an acrylic polymer can also be used. The acrylic polymer preferably contains no unsaturated groups, has a weight average molecular weight of 5,000 to 200,000, and a glass transition temperature of 20 to 200 °C. When the glass transition temperature of the acrylic polymer is less than 20 ° C, the hardness may be lowered, and the elongation at 200 ° C may be insufficient. More preferred glass transition temperatures range from 50 to 150 °C.

Further, the acrylic polymer can impart hardness by having a hydrophilic functional group. Specifically, it can be obtained by using a (meth)acrylic acid, itaconic acid, fumaric acid, maleic acid or the like having a carboxyl group or a 2-hydroxyethyl 2-(meth)acrylate having a hydroxyl group. The unsaturated monomer having a hydrophilic functional group such as hydroxypropyl acrylate is copolymerized with the above-mentioned unsaturated monomer, and a hydrophilic functional group is introduced into the acrylic polymer.

The weight average molecular weight of the aforementioned acrylic polymer is preferably from 5,000 to 200,000. When the weight average molecular weight is less than 5,000, the hardness may be insufficient. When the weight average molecular weight exceeds 200,000, moldability or toughness including coating properties may be insufficient. Further, the weight average molecular weight can be adjusted by the amount of the polymerization catalyst or the chain transfer agent and the type of the solvent to be used.

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

[solvent]

The coating composition A and the coating composition B preferably contain a solvent. The number of types of the solvent is preferably one type or more and 20 types or less, and more It is preferably one type or more and 10 types or less, and more preferably one type or more and six or less types. The term "solvent" as used herein refers to a substance which can be almost completely evaporated in the drying step after coating, and which is liquid at normal temperature and normal pressure, which is removed from the coating film.

Here, the kind of the solvent is determined by the molecular structure constituting the solvent. That is, even if the same element composition and the type and number of functional groups are the same, those having different binding relationships (structural isomers), non-foreseen structural isomers, but adopting any configuration in the 3 dimensional space cannot completely overlap. (stereoisomers) are considered to be solvents of different types. For example, 2-propanol and n-propanol are regarded as different solvents.

[Other additives]

The coating composition A and the coating composition B preferably contain a polymerization initiator or a hardener or a catalyst. The polymerization initiator and the catalyst are used to promote the hardening of the surface layer. In the case of the polymerization initiator, it is preferred that the components contained in the coating composition start or promote the polymerization, condensation or crosslinking reaction caused by an anion, a cation, a radical polymerization reaction or the like.

Various materials can be used for the polymerization initiator, the hardener, and the catalyst. Further, the polymerization initiator, the curing agent, and the catalyst may be used singly or in combination with a plurality of polymerization initiators, hardeners, and catalysts. Further, an acid catalyst or a thermal polymerization initiator may be used in combination. Examples of the acidic catalyst include an aqueous hydrochloric acid solution, formic acid, acetic acid, and the like. Examples of the thermal polymerization initiator include a peroxide and an azo compound. Further, examples of the photopolymerization initiator include an alkylphenone compound, a sulfur-containing compound, a mercaptophosphine oxide compound, and an amine compound. Things and so on.

The photopolymerization initiator is preferably an alkylphenone compound from the viewpoint of hardenability. Specific examples of the alkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone and 2,2-dimethoxy-1,2-diphenylethan-1-one. 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-phenyl)- 1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-phenyl)-1-butane, 2-benzyl-2 -Dimethylamino-1-(4-morpholinophenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 -[4-(4-morpholinyl)phenyl]-1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1-[4-( 2-ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxydiethylene, and the like The material is quantified by a polymer.

Further, as long as the effect of the present invention is not impaired, a coating agent, a UV absorber, a lubricant, and an antistatic agent may be added to the coating composition A and the coating composition B used to form the surface layer. Wait. Thereby, the surface layer may contain a leveling agent, an ultraviolet absorber, a slip agent, an antistatic agent, and the like. Examples of the leveling agent include an acrylic copolymer, a fluorene-based, and a fluorine-based leveling agent. Specific examples of the ultraviolet absorber include diphenylketone, benzotriazole, oxalic acid, and And a hindered amine-based UV absorber. Examples of the antistatic agent include metal salts such as a lithium salt, a sodium salt, a potassium salt, a phosphonium salt, a phosphonium salt, a magnesium salt, and a calcium salt.

[Manufacturing method of laminated film]

The method for producing a laminated film of the present invention is more preferably used by using at least the aforementioned coating composition A and coating composition B, either sequentially or simultaneously. A manufacturing method in which the above-mentioned support substrate is coated-dried-hardened.

Here, "sequential coating" is intended to form a surface layer by applying-drying-hardening one type of coating composition, and then applying-drying-hardening a different type of coating composition. By appropriately selecting the type and number of the coating composition used in the present manufacturing method, the size or gradient of the surface side-substrate side elastic modulus of the surface layer, and the elastic modulus of the substrate and the surface layer can be controlled. The size and the shape of the elastic modulus distribution in the surface layer can be controlled stepwise or continuously by appropriately selecting the type, composition, drying conditions, and hardening conditions of the coating composition.

The other manufacturing method is a method in which two or more types of coating compositions are simultaneously applied, dried, and cured on a support substrate. The number of types of the coating composition is not particularly limited as long as it is two or more types. Here, the "simultaneous coating" means that two or more types of liquid films are applied to the support substrate in the coating step, and then dried and cured.

In the production method, when the coating composition is applied successively, it is preferably by dip coating, roll coating, wire bar coating, gravure coating or die coating (U.S. Patent No. No. 2681294, etc., coated on a support substrate or the like to form a surface layer

In addition, when the coating composition of the above two types or more is applied at the same time, the "multilayer sliding die coating" (Fig. 3) which is applied by laminating the liquid film in the state before the application may be applied, or simultaneously on the substrate. "Multilayer slit die coating" (Fig. 4) for coating and lamination, formed on a support substrate After one layer of the liquid film, one of the "wet-on-wet coating" (Fig. 5) of the other layer is laminated in an undried state.

Next, the liquid film which has been applied to the support substrate or the like is dried. It is preferred to carry out the heating of the liquid film in the drying step in addition to completely removing the solvent from the obtained laminated film.

Examples of the drying method include heat transfer drying (adhesion to a hot object), convection heat transfer (hot air), radiation heat transfer (infrared light), and other (microwave, induction heating). Among them, in the production method of the present invention, it is preferable to use a method of convective heat transfer or radiation heat transfer in order to make the drying speed uniform even in the width direction.

Further, a further hardening operation (hardening step) by irradiating heat or energy rays may be performed. In the hardening step, the coating composition A and the coating composition B are used, and in the case of heat curing, preferably from room temperature to 200 ° C or less, from the viewpoint of the activation energy of the hardening reaction, it is more preferable It is 80 ° C or more and 200 ° C or less, and more preferably 100 ° C or more and 200 ° C or less.

Further, when it is cured by the active energy ray, it is preferably an electron beam (EB line) and/or an ultraviolet ray (UV line) from the viewpoint of versatility. Further, when curing by ultraviolet rays, it is preferable that the oxygen concentration is as low as possible from the viewpoint of preventing oxygen barrier, and it is more preferable to cure in a nitrogen atmosphere (nitrogen flushing). When the oxygen concentration is high, the hardening of the outermost surface is hindered, the hardening of the surface is insufficient, and the fingerprint resistance is insufficient.

Moreover, the type of the ultraviolet lamp used when irradiating ultraviolet rays may, for example, be a discharge lamp method, a flash mode, a laser method, an electrodeless lamp method, or the like. When the ultraviolet ray is hardened by a high-pressure mercury lamp of a discharge lamp type, the illuminance of the ultraviolet ray is ultraviolet ray at a condition of 100 to 3,000 mW/cm ² , more preferably 200 to 2,000 mW/cm ² , and particularly preferably 300 to 1,500 mW/cm ² . preferably is irradiated, the accumulated light quantity of ultraviolet at 100 ~ 3,000mJ / cm ^2, more preferably 200 ~ 2,000mJ / cm ^2, particularly preferably at 300 ~ 1,500mJ / cm ² of conditions appropriate to ultraviolet irradiation. Here, the illuminance of the ultraviolet ray is the irradiation intensity per unit area, which varies depending on the lamp output, the luminescence spectral efficiency, the diameter of the illuminating bulb, the design of the mirror, and the distance from the light source of the object to be irradiated. However, the illuminance does not vary with the transport rate. Further, the amount of accumulated ultraviolet light is the amount of irradiation energy per unit area, which is the total amount of photons reaching the surface. The cumulative amount of light is inversely proportional to the illumination rate through the light source and is proportional to the number of illuminations and the number of lamps.

[Example of use]

The laminated film of the present invention is excellent in scratch resistance and can be widely used in, for example, an electrically-formed product, an interior member of an automobile, a building member, and the like.

For example, it can be applied to household appliances such as glasses, sunglasses, packaging boxes, food containers, plastic molded parts, smart phone cases, touch panels, keyboards, televisions, and air conditioners. Vehicle interiors such as instrument panels, driving navigators, touch panels, interior mirrors, and the like, and the respective surfaces of various printed materials.

[Examples]

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

<fluorine compound D>

[Fluorochemical D1 methyl ethyl ketone / methyl isobutyl ketone solution]

As the fluorine compound D1, an acrylate compound ("Megafac" (registered trademark) RS-75 DIC Co., Ltd. solid content concentration of 40% by mass of methyl ethyl ketone / methyl isobutyl ketone was used. Solution).

<Synthesis of polyoxyalkylene compounds>

[polyoxane (a)]

In a 500 ml-capacity flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen introduction tube, 106 parts by mass of ethanol, 320 parts by mass of tetraethoxydecane, 21 parts by mass of deionized water, and 1 part by mass of 1 mass were charged. After maintaining hydrochloric acid at 85 ° C for 2 hours, ethanol was recovered and the temperature was maintained at 180 ° C for 3 hours. Then, it is cooled to obtain a viscous (poly) alkane (a).

<Synthesis of polydimethyl siloxane compound>

[Polydimethyloxane-based block copolymer (a) toluene solution]

Using the same apparatus as the synthesis of polyoxyalkylene (a), 50 parts by mass of toluene and 50 parts by mass of methyl isobutyl ketone and 20 parts by mass of polydimethyl siloxane-based polymer polymerization start are added. Agent (VPS-0501 manufactured by Wako Pure Chemical Co., Ltd.), 18 parts by mass of methyl methacrylate, 38 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, and 1 part by weight The methacrylic acid and 0.5 part by mass of 1-thioglycerol were reacted at 180 ° C for 8 hours to obtain a toluene solution having a solid concentration of 50% by mass of the polydimethylsiloxane-based block copolymer (a).

[Polydimethyloxane compound (b)]

As the polydimethyl siloxane compound (b), EBECRYL350 (bifunctional, polyoxy 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, 50 parts by mass of hexamethylene diisocyanate modified type of isocyanurate ("Takenate" (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc.), 76 parts by mass Polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by DAICEL Chemical Co., Ltd.), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were kept at 70 ° C for 5 hours. Then, 79 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate 1 having a solid concentration of 50% by mass.

[A solution of urethane acrylate 2 in toluene]

100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate, and 119 parts by mass of polycarbonate diol (Placcel CD-210HL manufactured by DAICEL Chemical Industry Co., Ltd.) were mixed, and the temperature was raised to 40. Hold for 8 hours until °C. 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 were added, and after maintaining at 70 ° C for 30 minutes, 0.02 parts by mass of lauric acid was added. Dibutyltin, kept at 80 ° C for 6 hours. Further, 97 parts by mass of toluene was finally added to obtain a toluene solution of urethane acrylate 2 having a solid concentration of 50% by mass.

[Lylic acid acrylate 3 toluene solution]

50 parts by mass of a modified isocyanurate modified from hexamethylene diisocyanate (Takenate (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc., isocyanate group content: 20.09% by mass), 53 mass Polyethylene glycol monoacrylate ("Blemmer" made by Nippon Oil Co., Ltd. ( Registered trademark) AE-150 (hydroxyl value: 264 (mgKOH/g)), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether. Then, the reaction was carried out by maintaining at 70 ° C for 5 hours. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction liquid 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 acid polyol ("Takelac" (registered trademark) UA-702, manufactured by Mitsui Chemicals, Inc., solid content concentration: 50% by mass, hydroxyl value: 50 mgKOH/g) was used.

[Acrylic Polyol 2]

As the acrylic polyol 2, a hydroxyl group-containing acrylic polyol ("Acrydic" (registered trademark) A-823 DIC Co., Ltd. solid content concentration: 50% by mass, hydroxyl value: 30 mgKOH/g) was used.

[Isocyanate Compound 1]

As the isocyanate compound, toluene diisocyanate ("Coronate" (registered trademark) Coronate L Japan Polyurethane Industrial Co., Ltd. solid content concentration: 75 mass% NCO content 13.5 mass%) was used.

[Polyfunctional acrylate 1]

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

[Polyfunctional acrylate 2]

As the multifunctional acrylate 2, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-3310B Japanese synthetic chemistry is used. Industrial Co., Ltd., solid content concentration of 100% by mass).

[Polyfunctional acrylate 3]

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

[Polyfunctional acrylate 4]

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

[Synthesis of Acrylic Polymer 1]

24 parts by mass of dilauroyl peroxide (manufactured by Peroyl L Oil Co., Ltd.) was added to 495 parts by mass of methyl ethyl ketone, and heated at 70 ° C for 30 minutes to dissolve, and it was dropped for 4 hours. 50 parts by mass of methacrylic acid, 90 parts by mass of butyl acrylate, 100 parts by mass of methyl methacrylate, and 2.4 parts by mass of 4-methyl-2,4-diphenylpentene-1 (Nofmer) A solution of MSD Nippon Oil Co., Ltd.) 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 the acrylic polymer 1 having a hydrophilic component concentration of 35% by mass.

<The blending of the coating composition A>

[Coating composition A1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 having a solid concentration of 40% by mass.

‧The solid content concentration of the fluorine compound D1 is 40% by mass - 3.8 parts by mass of the methyl ethyl ketone / methyl isobutyl ketone solution

("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating composition A2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid concentration of 40% by mass.

("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating composition A3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid concentration of 40% by mass.

("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating composition A4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid concentration of 40% by mass.

("Irgacure" (registered trademark) 184 BASF Japan Co., 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.

("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating composition B2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B2 having a solid concentration of 20% 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.

[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.

("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating composition B5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B5 having a solid concentration of 20% by mass.

("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating composition B6]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B6 having a solid concentration of 20% by mass.

("Irgacure" (registered trademark) 184 BASF Japan Co., Ltd.).

<Manufacturing method of laminated film>

[Method 1 for forming a laminated film]

As a support substrate (a layer to be a layer C), "Lumirror" (registered trademark) U48 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm coated with an adhesive coating material on a PET resin film was used. Applying the coating composition B to the support substrate by using a continuous coating device by a slit die coater to adjust the discharge flow rate from the slit so that the thickness of the dried surface layer becomes a predetermined film thickness Secondly, the drying step is carried out under the following conditions. The step of hardening and hardening, while forming a layer B on the support substrate.

"drying step"

Supply air temperature and humidity: temperature: 80 ° C

Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec

Wind direction: coated side: parallel to the surface of the substrate, reverse coated side: vertical to the surface of the substrate

Residence time: 2 minutes

"hardening step"

Cumulative light amount: 120mJ/cm ²

Oxygen concentration: atmospheric environment.

Furthermore, using the same device, on the B layer obtained above The coating flow rate from the slit was adjusted so that the thickness of the surface layer after drying became a predetermined film thickness, and the coating composition A was applied, and then the drying step and the curing step were carried out under the following conditions to obtain a laminated film.

"drying step"

Supply air temperature and humidity: temperature: 80 ° C

Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec

Wind direction: coated side: parallel to the surface of the substrate, reverse coated side: vertical to the surface of the substrate

Residence time: 2 minutes

"hardening step"

Cumulative light amount: 120mJ/cm ²

Oxygen concentration: 200 ppm (volume ratio) or less.

[Method for producing laminated film 2]

As a support substrate (a layer that becomes a C layer), used as a PET resin film "Lumirror" (registered trademark) U48 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm is applied to the adhesive. The coating material B is applied to the support substrate by using a continuous coating apparatus of a slit die coater to adjust the discharge flow rate of the slit so that the thickness of the surface layer after drying becomes a predetermined film thickness. The conditions described are subjected to a drying step and a hardening step to form a B layer on the support substrate.

"drying step"

Supply air temperature and humidity: temperature: 80 ° C

Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec

Wind direction: coated side: parallel to the surface of the substrate, reverse coated side: vertical to the surface of the substrate

Residence time: 2 minutes

Further, using the same apparatus, the coating material A was applied to the layer B obtained above, and the discharge flow rate by the slit was adjusted so that the thickness of the surface layer after drying became a predetermined film thickness, followed by the following conditions. A drying step and a hardening step were carried out to obtain a laminated film.

"drying step"

Supply air temperature and humidity: temperature: 80 ° C

Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec

Wind direction: coated side: parallel to the surface of the substrate, reverse coated side: vertical to the surface of the substrate

Residence time: 2 minutes

"hardening step"

Cumulative light amount: 120mJ/cm ²

Oxygen concentration: 200 ppm (volume ratio) or less.

[Method for producing laminated film 3]

As a support substrate (a layer to be a layer C), "Lumirror" (registered trademark) U48 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm coated with an adhesive coating material on a PET resin film was used. The coating material A is applied to the support substrate by using a continuous coating apparatus of a slit die coater to adjust the discharge flow rate from the slit so that the thickness of the surface layer after drying becomes a predetermined film thickness. The conditions described are subjected to a drying step and a hardening step to form an A layer on the support substrate.

"drying step"

Supply air temperature and humidity: temperature: 80 ° C

Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec

Wind direction: coated side: parallel to the surface of the substrate, reverse coated side: vertical to the surface of the substrate

Residence time: 2 minutes

"hardening step"

Cumulative light amount: 120mJ/cm ²

Oxygen concentration: 200 ppm (volume ratio) or less.

The laminated film of Examples 1 to 13 and Comparative Examples 1 and 2 was produced by the above method. The method for forming the laminated film corresponding to each of the examples and the comparative examples, the coating composition to be used, and the film thickness of each layer are shown in Table 1.

<Evaluation of laminated film>

The performance evaluation shown below was carried out on the produced laminated film, and the results obtained are shown in Table 2. In addition to the case specified in advance, the measurement system is changed for each sample in each of the examples and comparative examples. The measurement was performed 3 times, and the average value thereof was used.

[Measurement of storage elastic modulus and glass transition temperature]

A. Confirmation of laminated film section

The laminated film was cut out with a cutter, and embedded in an electric epoxy resin (Quetol 812 manufactured by Nisshin EM Co., Ltd.), and the epoxy resin was hardened in an oven at 60 ° C for 48 hours, and then an ultrathin slicer (LEICA) was used. The company's Ultracut S) produces ultra-thin sections with a thickness of about 100 nm.

The ultrathin section produced was mounted on a Cu grid manufactured by Kasei Corporation, Inc., and a TEM observation was carried out using a Hitachi transmission electron microscope (TEM) H-7100FA at an acceleration voltage of 100 kV to observe the cross section of the laminated film. Confirm the surface layer and the place where the substrate is supported.

B. Determination of ultra-micro hardness tester

The ultrathin section was used as a sample, and an ultra-micro hardness tester (Tribo Indenter manufactured by Hysitron Co., Ltd.) was used to obtain a modulus-mapped image of the surface layer and the support substrate, and the storage elastic modulus, the loss elastic modulus, and the self-storage elasticity were calculated. The loss tangent (tan δ) is obtained by the ratio of the modulus to the loss elastic modulus, and the peak temperature of the resulting loss tangent (tan δ) is taken as the glass transition temperature (Tg).

The measurement conditions are shown below.

Measuring device: Tribo Indenter manufactured by Hysitron

Use indenter: Diamond Cubecorner indenter (curvature radius 50nm)

Measuring field of view: about 30mm square

Measuring frequency: 10Hz

Measuring environment: -20 ° C ~ 120 ° C ‧ in the atmosphere

Contact load: 0.3 μN.

[Determination of the elastic modulus of an atomic force microscope]

The laminated film of Examples 1 to 13 and Comparative Examples 1 and 2 was cut into a cross section by a cryosection method, and the cross section was fixed as a measurement surface to a dedicated sample fixing table, and an atomic force microscope (AFM) manufactured by ASYLUM Technology was used. "MFP-3DSA-J" and the cantilever "R150-NCL-10 (material Si, spring constant: 48 N/m, radius of curvature of the tip end 150 nm) manufactured by NANOSENSORS", and the force is measured perpendicularly in the thickness direction of the surface layer in the Contact mode. Curve (the movement speed of the cantilever is 2 μm/s, and the maximum indentation load is 2 μN).

According to the above-described measuring method, the elastic modulus (E1) at a position (position 1) of 10% from the surface of the surface layer, and the elastic modulus (position 2) at a position (position 2) of 10% from the surface of the surface layer (E2) ), the elastic modulus (E3) of 99% of the position (position 3). Specifically, the laminated film was cut, and the modulus of elasticity at each position in the thickness direction in the cross section of the surface layer was measured.

[rupture elongation]

The laminated film was cut into a rectangle having a length of 150 mm × a width of 10 mm in the longitudinal direction and the width direction as a sample. A tensile test was carried out using a tensile tester (Tensilon UCT-100 manufactured by ORIENTEC), a distance between the initial stretching chucks of 50 mm, and a tensile speed of 10 mm/min. The measurement environment at this time was 23 ° C ‧65 RH%. At the time of stretching, the sample in the stretch is observed, and if it is visually observed at any position of the sample, the crack (crack) is stopped (the elongation at the time of the stop is adjusted to be an integer of 5). The sample to be measured next was taken from the elongation at the time of stopping, and the sample having the elongation at a reduced rate of 5% by unit was sequentially collected, and finally proceeded to the extent that the position of the sample became visible without cracking by visual observation.

The cross section of the film of the ruptured portion of the collected sample was cut out, and the cross section was observed at a magnification of 3,000 times by a transmission electron microscope, and the occurrence of cracking of 50% or more of the average thickness of the surface layer was regarded as having cracks (destruction of the surface layer) Among the samples considered to be broken, the elongation value of the sample having the lowest elongation was taken as the crack elongation.

Then, three samples cut from different positions at the same level were used for measurement, and the average of their rupture elongations was used.

[thermoforming]

Using a vacuum molding machine "FORMECH300X" (manufactured by Shinko Kogyo Co., Ltd.), the obtained laminate film was heated for 1 minute using a far-infrared heater so that the surface temperature of the film became a predetermined temperature, and a cylindrical mold (bottom surface was used). The film was vacuum formed by a diameter of 50 mm to form a laminated film. Further, in order to completely complete the hardening, the temperature was maintained at 180 to 200 ° C, and heating was continued for 1 minute. The state of molding was completed along the mold, and the degree of molding (draw ratio: molding height/bottom diameter) was used, and evaluation was performed on the basis of the following.

Class A: It can be formed by deep drawing ratio of 1.0 or more.

Grade B: It can be molded at a deep draw ratio of 0.6 or more and less than 1.0, but it cannot be molded at 1.0 or more.

Grade C: It can be molded with a deep draw ratio of 0.3 or more and less than 0.6, but it cannot be molded with a thickness of 0.6 or more.

Class D: It is possible to form a curved surface with a deep drawing ratio of less than 0.3, and it is impossible to form it with a thickness of 0.3 or more.

Class E: The film breaks and ruptures even if it is only slightly bent.

[Repeat resistance of surface layer by low hardness material]

After placing the laminated film at a temperature of 20 ° C for 12 hours, the front end of the rubber abrasion tester (1 cm ² of the front end portion) was prepared in the same environment, and a white velvet fabric was attached [600 No. Hinghe Co., Ltd.). ], a load of 500 g was applied, and 5 cm, 5,000 times back and forth on the laminated film, and a load of 1,000 g was applied, and rubbed back and forth on the laminated film 5 cm, 200 times, and classified as follows. Further, three samples cut out from different positions at the same level were measured, and the following classifications were performed. The average of the values of the three samples that have been graded.

10 points: no scars

7: 1~10 scars

4 points: 11~20 scars

1 point: The surface layer of the test part is completely peeled off.

[self-healing of surface layer]

After being allowed to stand at a temperature of 20 ° C for 12 hours, the surface of the surface layer was applied to the surface of the surface layer by a brass brush (manufactured by TRUSCO) and the surface was scratched five times horizontally, and then visually judged according to the following criteria. The recovery state of the scar after 5 minutes of placement. Further, three samples cut out from different positions at the same level were measured, and the average values thereof were used.

10 o'clock: the load is 1kg and the scar does not remain.

7 o'clock: the wound will be left with a load of 1kg, but the scar will not remain at 700g.

4 o'clock: the wound will be left with a load of 700g, but the scar will not remain at 500g.

1 point: The load is 500g and the scar remains.

[Industrial availability]

The laminated film of the present invention can be used for imparting abrasion resistance, particularly repetitive wiping property and moldability, to the respective surfaces of plastic molded articles, home electric appliances, buildings, vehicle interiors, and various printed materials.

Claims (7)

A laminated film having a laminated film comprising a surface layer of an A layer and a B layer on at least one side of a supporting substrate, wherein the B layer and the A layer are in this order from the side of the supporting substrate The storage elastic modulus of 25 ° C measured by a micro hardness tester of the A layer, the B layer, and the support substrate (hereinafter, E _A25 , E _B25 , E _C25 ), and the storage elastic modulus at 120 ° C (below E _A120 , E _B120 , E _C120 ) meet the following conditions, condition 1 E _A25 <E _B25 ≦E _C25 ; condition 2 E _B120 ≦E _A120 <E _C120 ; condition 3 E _A25 ≦100MPa. The laminate film of claim 1, wherein the layer A, the layer B, and the support substrate satisfy the following conditions, condition 40 < E _{C25 -} E _B25 < 5 GPa; condition 5 0 < E _{A120 -} E _B120 < 50 MPa. The laminated film of claim 1 or 2, wherein the glass transition temperature (hereinafter referred to as Tg _B ) of the layer _B satisfies the following conditions, 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 B layer (hereinafter referred to as T _B ) satisfies the following condition, condition 7 0.1 μm ≦ T _B ≦ 5 μm. The laminated film according to any one of claims 1 to 4, wherein in the cross section perpendicular to the substrate of the surface layer, from the surface of the surface layer, at a position of 10% of the thickness of the surface layer (hereinafter referred to as position 1) ), the basis of each position of 50% (later regarded as position 2) and 99% (later regarded as position 3) The elastic modulus E1, E2, and E3 of the force microscope satisfy the following conditions, condition 8 E1 ≦ E2 < E3; condition 9 E1 ≦ 100 MPa; condition 10 E3 ≧ 1 GPa. A method for producing a laminated film according to any one of claims 1 to 5, wherein the surface layer is applied to the support base by applying two or more kinds of coating compositions one by one. The material is formed by drying and hardening. A method for producing a laminated film according to any one of claims 1 to 5, characterized in that the surface layer is simultaneously coated on a support base by coating two or more kinds of paint compositions The material is formed by drying and hardening.