TWI663061B - Laminated film and manufacturing method of laminated film - Google Patents

Abstract

The present invention is a laminated film, which is formed on at least one side of a supporting substrate with a laminated film including a surface layer of A layer and B layer, and is characterized in that: layer B and layer A are from the supporting substrate side Connected in this order, the storage elastic modulus of layer A, layer B, and the supporting substrate measured at 25 ° C by a micro hardness tester (the following are E _A25 , E _B25 , and E _C25 ), and the storage elastic modulus at 120 ° C The numbers (the following are E _A120 , E _B120 , and E _C120 ) satisfy 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 present invention provides a laminated film which has abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

Description

Laminated film and manufacturing method of laminated film

The present invention relates to a laminated film which has abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

In recent years, a plastic film provided with a surface layer containing a synthetic resin or the like has been used for the purpose of protecting an optical material such as a color filter, a flat display, and the surface of a car body (such as preventing damage or imparting antifouling properties).

From the viewpoint of surface protection, these surface layers require scratch resistance as an important characteristic. Generally, a so-called "hard coating material" is used to impart abrasion resistance, and this "hard coating material" uses various prepolymers described in Non-Patent Document 1 to include an organic silane-based or polyfunctional acrylic system. Coating compositions such as polymers, oligomers, "high cross-link density materials" formed by coating-drying-heating or UV curing, or "organic-inorganic hybrid materials" using various surface-modified fillers, etc., The surface hardness of the coating film is improved.

On the other hand, from the standpoint of surface protection, the surface layer requires a variety of properties such as chemical resistance, oil resistance, and moldability depending on the application in addition to scratch resistance as required characteristics. In particular, moldability is because if the coating film is only hardened, The shape is prone to "cracking" or "peeling", so it is required to coexist with soft scratch resistance and moldability which are difficult to damage.

In a hard-coating material, as a laminated film having both abrasion resistance and moldability, Patent Document 1 proposes "a laminated film, which is a laminated film in which a hard coat layer is provided on at least one side of a base film. The maximum value of the surface hardness of the hard coating layer measured by the ultra-micro hardness meter is 0.05 GPa or more and 4.0 GPa or less, and the elongation at break at 100 ° C 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 the damage on the surface by deforming the elastic recovery range of the material of the surface layer to achieve scratch resistance, and then In addition, as a material that improves moldability by improving the elongation of self-healing materials, Patent Document 4 proposes "an active energy ray-curable coating agent comprising an epoxy resin and an oxetane resin. A resin composition of at least one resin (A) selected from vinyl ether resin, a polyol (B) having a number average molecular weight of 400 or more, and an active energy ray induction catalyst (C), which are characterized by: The alcohol (B) is at least 1 selected from the group consisting of a polyol (B1), a polycarbonate polyol (B2), a polyester polyol (B3), and a polyether polyol (B4) having a main chain including a carbon-carbon bond. Kind of polyol. "

As another method for improving the moldability of a self-healing material, as an invention focusing on a laminated structure, Patent Document 5 proposes "a laminated body with a self-healing layer, which is on at least one side of a resin substrate On the surface, a layered body with a self-healing layer laminated with a stress relaxation layer and a self-healing layer in this order is characterized in that the self-healing layer is composed of at least a soft synthetic resin and contacts the self-healing The hardness H of the layer of the stress relaxation layer measured by nano indentation is the same as or lower than the hardness H of the self-healing layer measured by nano indentation. "

[Prior 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 No. 2009-184284

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

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

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

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

However, the molded article using the aforementioned "hard coating material" on the surface layer has extremely high surface hardness, but it is often damaged or damaged in daily life. The inventors have investigated this and learned that Although the "hard coating material" has a high surface hardness, if it is rubbed repeatedly with a soft cloth or the like, fine scratches occur on the surface and the surface becomes cloudy.

In contrast, the present inventors confirmed the materials proposed in Patent Document 2 and Patent Document 3, and learned that It is difficult to be damaged in life, and even if it is rubbed repeatedly, the scar will be restored by the self-repairing function, and the scratch resistance of the hard coating material is equal to or higher than that of the hard coating material.

However, I learned that since the self-healing material is a soft material, it seems that the moldability is excellent at first glance. However, if the molding is actually performed, it will be on the surface layer and on the surface layer immediately after molding or during storage after molding. There are cracks (cracks), or the surface layer is peeled off using this as a starting point.

In addition, Patent Documents 4 and 5 propose coexistence of self-healing property and moldability as one of the problems. However, the inventors have confirmed that the effects of either are cracking or rubbing during molding. Not enough. In addition, none of Patent Documents 1 to 5 has reached the conception of the structure of the present invention. Therefore, an object of the present invention is to provide a laminated film which has abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

In order to solve the above problems, the present inventors repeated the results of intensive studies, and completed the following inventions. That is, the present invention is as follows.

(1) A laminated film, which is a laminated film including a surface layer of A and B layers on at least one side of a supporting substrate, and is characterized in that the B layer and the A layer are formed from the supporting substrate side. This sequence is connected, the storage elastic modulus at 25 ° C (hereinafter E _A25 , E _B25 , E _C25 ) and the storage elastic modulus at 120 ° C measured by a micro hardness tester of layer A, layer B, and the supporting substrate. (The following are E _A120 , E _B120 , and E _C120 ) satisfy the following conditions, 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 above-mentioned layer A, layer B, and supporting substrate satisfy the following conditions, condition 40 <E _C25 -E _B25 <5GPa; condition 5 0 <E _A120 -E _B120 <50MPa.

(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 B layer (hereinafter referred to as T _B ) satisfies the following conditions; Condition 7 0.1 μm ≦ T _B ≦ 5 μm.

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

(6) A method for manufacturing a laminated film, which is the method for manufacturing a laminated film according to any one of (1) to (5), wherein the surface layer is composed of two or more kinds of coating materials. The material is sequentially applied to a support substrate, and is formed by drying and curing.

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

According to the present invention, it is possible to provide a laminated film having abrasion resistance, particularly repeated rub resistance, and coexistence with moldability.

1‧‧‧The layer in contact with layer B (layer A)

2‧‧‧layer in contact with the supporting substrate (layer B)

3‧‧‧ support substrate (C layer)

4‧‧‧ Surface layer including layer A and layer 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‧‧‧Multi-layer sliding die

9‧‧‧Multi-layer Slot Die

10‧‧‧Single-layer slit die

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

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

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

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

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

[Form of Implementing Invention]

In order to achieve the above-mentioned problems, the present inventors have pointed out (1) the reason why self-healing materials are more resistant to scratches than hard-coated materials in actual use environments; (2) the soft self-healing materials are stored immediately after molding, or after storage In this case, the reason for the occurrence of cracks (cracks) in the surface layer, or the peeling of the surface layer with the cracks as the starting point, was examined in detail to achieve the following examination.

First, (1) will be described. The formation of flaws on the plastic surface is affected by three factors: "pressure", "hardness of the wiper" and "number of wipes". The reason why hard coating materials are easy to appear in the actual use environment is due to the flaw formation mechanism in the actual use environment, that is, "the hardness of the person who rubs the surface is low in the actual use environment, but on the other hand, the number of contacts is very high ". For hard-coated materials, even if the hardness of the wiper is low, or the pressure during the brushing is low, and the surface does not cause damage to the surface with a single wipe, the internal strain that does not cause damage to the surface of the material will remain, This will accumulate strain as the number of "scratches" increases. 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, a flaw is finally formed beyond the allowable range of the strain. On the other hand, the reason that self-healing materials are strong in actual use environment and effective for repeated rubbing is because the elastic recovery range of the material is large, and even if rubbing under the aforementioned conditions, strain can be released without forming scars. .

Next, (2) will be described. The materials described in Patent Documents 2 to 3 use a material that exhibits self-healing by elastic recovery in the surface layer, and a laminated film of a general thermoplastic resin in the base material. Since the surface layer becomes "entropy elastomer = rubber elastomer" ", The supporting substrate becomes an" energy elastomer ", so it can be said that it is formed of materials that have very different mechanical behaviors with respect to heat. If such a film is heated and molded, although the supporting substrate is plastically deformed and fixed, the self-healing layer is deformed in the elastic deformation range, so the supported substrate is stretched in the elongation direction. , Residual stress occurs in the surface layer. Furthermore, it is considered that if it is subjected to a later step, such as by injection molding, Further heating, or a high temperature in the use environment, will cause the elasticity of the surface layer to increase due to the entropy elastomer, and reach the breaking limit when the elongation during molding is large. , And rupture occurred.

Therefore, the present inventors have found that a laminated film having a surface layer having the following structure is used as a surface layer of the laminated film, and one side has the excellent abrasion resistance as described above, especially the repeated rub resistance under an actual use environment, One side has sufficient molding adaptability.

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

Among the aforementioned surface layers, the second layer (1 in FIG. 1, that is, layer A) and the layer that contacts the supporting substrate (2 in FIG. 1, that is, layer B) from the supporting substrate side are preferred. 2. The storage elastic modulus of the supporting substrate (3 in the first figure, hereinafter referred to as layer C) measured at 25 ° C (hereinafter _{referred to} as E _A25 , E _B25 , E _C25 ) and 120 ° C by a micro hardness tester. Storage modulus of elasticity (E _A120 , E _B120 , E _C120 below) meets 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 layer A (the layer in contact with the layer B in the surface layer) and the layer B (the layer in contact with the supporting substrate in the surface layer) at the operating temperature at which the laminated film is actually used ), The relationship between storage elastic modulus of layer C (supporting substrate). Means that layer C has the highest storage elastic modulus, while layer B has a higher storage elastic modulus than layer A and has the same or lower storage elastic modulus than layer C, and layer A has the lowest storage elastic modulus, which is better. It is E _A25 <E _B25 <E _C25 .

By having such a structure, the B layer system has sufficient cohesion, and the surface layer has sufficient adhesion to the C layer, and it is not easy to peel off even after repeated rubbing in actual use, so it is preferable.

The surface layer may include other layers as long as it includes the A layer and the B layer. That is, the structure of the surface layer may be composed of three or more layers as shown in FIG. 3. In this case, the elastic modulus of the layer closer to the surface side than the A layer (referred to as the Z layer) is not particularly limited. Preferably, the Z layer is close to the elastic modulus of the A layer. Here, the Z layer may have other functions such as antifouling, fingerprint resistance, dyeing resistance, antireflection, antiglare, and antistatic properties.

The aforementioned storage elastic modulus measured by a micro-hardness tester is a value measured by a micro-hardness tester which indicates an ultra-thin slice of the cross-section of the surface layer of a laminated film. The details of specific measurement methods and calculation methods will be described later.

If the order of this modulus of elasticity is E _A25 > E _B25 > E _{C25 on the} contrary, the strain release by the elastic recovery of the surface layer will not be able to be performed, and there may be cases of resistance to repeated rubbing. In addition, if the order is changed, that is, E _B25 > E _A25 > E _B25, etc., a stress concentration portion may be formed in the layer, and peeling may occur in the vicinity.

In addition, Condition 2 shows the elastic modulus at 120 ° C, that is, the relationship between the elastic modulus of the A layer, the B layer, and the C layer near the forming temperature of the laminated film, which means that the B layer system has the lowest elastic modulus or is related to The A layer is the same, and the elastic modulus of the A layer is lower than that of the C layer. The C layer has the highest elastic modulus. More preferably, it is E _B120 <E _A120 <E _C120 .

With such a structure, the elastic modulus of the layer B becomes lower than that of the layer A during molding, so no residual stress will remain in the layer A, and even in the heating and use environment in the subsequent steps Cracking is not likely to occur at high temperatures, so it is preferred.

If the order of this elastic modulus is exchanged, it becomes E _A120 ≦ E _B120 <E _C120 . Due to the aforementioned mechanism, residual stress will accumulate during molding, and it will be heated and used in the subsequent steps. Cracking occurs at high temperatures.

Here, Condition 3 shows a preferable range of the elastic modulus (E _A25 ) of the layer A 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 during repeated rubbing. In addition, although the value of E _A is small, there is no particular obstacle in achieving cost, but if it is 1 MPa or less, adhesion may occur on the surface, which may be impractical from the viewpoint of surface protection.

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

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

Condition 50 0 <E _A120 -E _B120 <50MPa.

Here, Condition 4 shows the range of the difference in the preferred storage elastic modulus of the B layer and the C layer at the temperature under the actual use environment of the laminated film, more preferably 100 MPa <E _C25 -E _B25 <3GPa.

When E _C25 -E _{B25 is} 5 GPa or more, the adhesion of the surface layer to the supporting substrate will be insufficient, so that repeated rub resistance may be reduced. If E _C25 -E _B25 becomes zero, as a result, since the difference in elastic modulus between the A layer and the B layer becomes larger, the stress concentration at the interface between the A layer and the B layer becomes larger, and there will be rubbing by hard materials In addition, the scars are likely to remain.

In addition, Condition 5 shows the range of the difference in the preferred storage elastic modulus of the A layer and the B layer at the molding temperature, more preferably 0 <E _A120 -E _B120 <30MPa, and even more preferably 0 <E _A120 -E _B120 <10MPa.

If E _A120- E _{B120 is} 50 MPa or more, the adhesion between the surface layer and the supporting substrate becomes insufficient during the molding process, and wrinkles may occur. In addition, if the E _B120 side becomes larger than the E _A120 side, residual stress will occur at the interface between the A layer and the B layer during molding, and cracking or peeling may occur easily.

The surface layer preferably satisfies the following condition 6.

Condition 6 60 ℃ ≦ Tg _B ≦ 130 ℃

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

The glass transition temperature is a value obtained from the maximum value of the temperature dispersion of the ratio (loss tangent) of the storage elastic modulus to the loss elastic modulus measured by the micro hardness tester. The details of the measurement method are described later.

If the glass transition temperature of layer B is lower than 60 ° C, the adhesion between the surface layer and the supporting substrate will be reduced, so there will be scratches that are likely to remain due to peeling at room temperature or rubbing caused by hard materials. Happening. In addition, when the glass transition temperature of the layer B is higher than 130 ° C, it is likely that cracking or peeling may occur during molding due to conditions.

The surface layer preferably 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 (layer B) in contact with the supporting substrate in the surface layer, and more preferably 0.5 μm ≦ T _B ≦ 3 μm. If the thickness of the B layer is thinner than 0.1 μm, the ability to absorb the residual stress between the surface layer and the supporting substrate during molding may be slightly weakened. If it is thicker than 5 μm, there will be a surface layer The adhesion to the supporting substrate may be slightly weakened.

As shown in FIG. 2, the laminated film of the present invention is a laminated film having a surface layer including A layer and B layer on at least one side of a supporting substrate, preferably, the surface layer is perpendicular to the substrate 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; FIG. 2) The positions of 6 in the middle) and 99% (hereinafter referred to as position 3; position 7 in Fig. 2) of each position by the elastic modulus of the atomic force microscope E1, E2, E3 satisfy the following conditions 8. 9. Condition 10; Condition 8 E1 ≦ E2 <E3

Condition 9 E1 ≦ 100MPa

Condition 10 E3 ≧ 1GPa.

Condition 8 is intended to increase the elastic modulus from the surface side toward the substrate side in the thickness direction of the surface layer, and it is preferably E1 ≦ E2 <E3, and more preferably E1 <E2 <E3.

If this sequence is reversed, that is, E1> E2> E3, the strain release caused by elastic recovery cannot be performed on the outermost surface, so it will not be resistant to repeated rubbing, and even if the outermost surface hardness is high, Because the lower modulus of elasticity is lower and the strain becomes larger, when the material is rubbed by a high pressure or a high hardness material, the abrasion resistance may be reduced.

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 during repeated rubbing may become insufficient. In addition, although the value of E1 is small, there is no particular obstacle in achieving cost, but if it is 1 MPa or less, adhesion may occur on the surface, and it may not be practical from the viewpoint of surface protection.

Condition 10 shows a preferable 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. If the value of E3 is less than 1 GPa, the surface hardness may be insufficient, and the durability against rubbing by a hard material may be insufficient. In terms of scratch resistance, the higher the value of E3, the better, but practically, from the viewpoint of folding resistance and processability, about 100 GPa is the limit for the materials that can be used as the surface layer on the laminated film. .

Here, measurement of the storage elastic modulus, the loss elastic modulus, and the glass transition temperature of the surface layer will be described. These measurements can be performed using an ultra-micro hardness tester (Tribo Indenter manufactured by Hysitron Corporation) to obtain a modulus map image [storage elastic modulus (E ') image · loss elastic modulus (E ") image].

For example, the laminated film is embedded with an epoxy resin for display (Quetol 812 manufactured by Nisshin EM Co., Ltd.) and hardened, and then an ultra-thin microtome is used. (Ultracut S, manufactured by LEICA) was used to prepare an ultra-thin section of the cross section of the surface layer of the laminated film as a measurement sample, and the measurement was performed under the following conditions, and Hertz's contact theory was used to calculate the elastic modulus.

Measuring device: Tribo Indenter by Hysitron

Indenter: Diamond Cubecorner indenter (curvature radius 50nm)

Measurement field of view: about 30mm square

Measurement frequency: 200Hz

Measurement environment: room temperature, in the atmosphere

Contact load: 0.3μN

The measurement principle by the ultra-micro hardness tester will be described 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 E ^* is the composite elastic modulus of the indenter and the sample.

On the other hand, I believe that when the indenter contacts the outermost surface of the sample, the front end of the indenter is regarded as a spherical shape, and Hertz's contact theory regarding the contact between a sphere and a semi-infinite flat plate can be used. In Hertz's contact theory, the radius a of the indentation projection surface when the indenter is in contact with the sample is expressed by Equation (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 Equation (3), and E ^* can be calculated using Equations (1) to (3).

The so-called modular mapping is based on the above-mentioned Hertzian contact theory. The indenter is brought into contact with the outermost surface of the sample, the indenter is slightly vibrated during the test, and the amplitude and phase of the response to vibration are obtained as a function of time. The difference is the method of determining K (measurement system stiffness) and D (sample damping).

If this vibration is a simple harmonic oscillator, the total (force component detected) F (t) of the force of the indenter in the intrusion direction of the sample is expressed by Equation (4).

Here, the first term of formula (4) represents the force from the indenter shaft (m: mass of the indenter shaft), the second term of formula (4) represents the force from the viscous component of the sample, and the third term of formula (4) The term represents the rigidity of the sample system, and t represents time. F (t) in formula (4) is expressed as formula (5) due to time correlation.

F ( t ) == F ₀ exp ( iωt ) ... (Eq. 5)

Here, F ₀ is a constant, and ω is an angular vibration number. If the equation (5) is substituted into the equation (4), the special solution of the ordinary differential equation (6) 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. The m system is known at the time of measurement. Therefore, when measuring the test body, the vibration amplitude (h ₀ ), phase difference (Φ), and excitation vibration amplitude (F ₀ ) of the displacement can be measured by the equation (7) ~ Equation (10) calculates K and D.

E ^{* is} regarded as the storage elastic modulus (E '), and the formulas (1) to (10) are summarized. In the stiffness of the measurement system, Ks (= K-mω ² ) from the sample is used to express ( 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. Among the stiffness of the measurement system in the aforementioned formula (8), Ks from the sample is used, and it is combined with the formula (11). The aggregated formula (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. From the ratio of the storage elastic modulus and the loss elastic modulus calculated previously, a loss tangent (tan δ) is obtained, and the obtained loss is calculated. The peak temperature of the tangent (tan δ) is taken as the glass transition temperature (Tg).

The elastic modulus measurement by the atomic force microscope in the present invention is a compression test of a very small portion of the probe. The degree of deformation caused by the pushing force is measured using a cantilever with a known spring constant to determine the surface layer. The modulus of elasticity in the cross section at each position in the thickness direction. Specifically, the laminated film was cut, and the elastic modulus in the cross section of each position in the thickness direction of the surface layer was measured by an atomic force microscope. The details are described in the examples. However, an atomic force microscope shown below can be used to bring the probe at the tip of the cantilever into contact with the cross section of the surface layer. The cantilever can be obtained by measuring the force curve with a maximum indentation load of 2 μN. Deflection Determination. The details are described later.

Atomic force microscope: MFP-3DSA-J manufactured by ASYLUM Technology

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

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

[Laminated film and surface layer]

The laminated film of the present invention may be in a planar state or a three-dimensional shape after molding as long as it has a surface layer exhibiting the aforementioned physical properties. Here, the "surface layer" in the present invention is preferably formed of at least two layers.

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

As the above 2 or more layers, it is preferable that at least the aforementioned surface layer has a layer in contact with layer B (layer A), a layer in contact with support substrate (layer B), and layer A, layer B, and support substrate The material system satisfies the aforementioned relationship.

In addition to the abrasion resistance which is the subject of the present invention, the surface layer is a combination of rubbing resistance and moldability, it can also have antifouling properties, antireflective properties, antistatic properties, electrical conductivity, hot-line reflectivity, and near-infrared absorption. Properties, electromagnetic wave shielding, easy adhesion and other functions.

[Support substrate]

The material constituting the support substrate used in the laminated film of the present invention may be any of a thermoplastic resin and a thermosetting resin, or may be a homopolymer tree. The lipid may be a copolymer or a blend of two or more kinds. Since it is more preferable that the resin system constituting the supporting substrate has good moldability, a thermoplastic resin is preferred.

Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene; alicyclic polyolefin resins; polyamide resins such as nylon 6 and nylon 66; Aromatic polyamide resin, polyester resin, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene -6 Fluoropropylene copolymers, vinylidene fluoride resins and other fluorine resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, etc. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. From the viewpoint of strength, heat resistance, and transparency, the thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin, or a methacrylic resin, and particularly preferably a polyester resin.

The polyester resin in the present invention is a general term for a polymer having an ester bond as a main chain of a main chain, and is obtained by polycondensation of an acid component, an ester thereof, and a diol component. Specific examples include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalate, and polybutylene terephthalate. Moreover, it is also possible to co-polymerize other dicarboxylic acid and its ester or diol component as an acid component or a diol component. Among these, in terms of transparency, dimensional stability, heat resistance, etc., particularly preferred are polyethylene terephthalate and polyethylene 2,6-naphthalate.

Various additives can be added to the supporting substrate. For example, antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, dopants for refractive index adjustment, and the like. The supporting substrate may have any of a single-layer structure and a laminated structure.

Various types of surface treatments may be performed on the surface of the supporting substrate before forming the aforementioned surface layer. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and Ozone oxidation treatment. Among these, a glow discharge treatment, an ultraviolet irradiation treatment, a corona discharge treatment, and a flame treatment are preferable, and a glow discharge treatment and an ultraviolet treatment are more preferable.

In addition, on the surface of the supporting substrate, functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorbing layer that are different from the surface layer of the present invention may be provided in advance. should.

[Coating composition]

The laminated film of the present invention is a surface layer having a structure capable of achieving the aforementioned physical properties by applying, drying, and curing a coating composition by using a method for producing a laminated film described later on a supporting substrate. The "coating composition" as used herein refers to a material containing a solvent and a solute, which is coated on the aforementioned support substrate, and is capable of forming a surface layer by volatilizing the solvent, removing, and curing in a drying step. Here, the "kind" of a coating composition means a liquid in which the kind of the solute constituting the coating composition differs in part. This solute contains Resins or various additives (such as precursors), particles, and polymerization initiators, hardeners, catalysts, leveling agents, ultraviolet absorbers, antioxidants, etc. that can form them during the coating process.

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

Here, the coating composition A contains a liquid suitable for forming the second layer from the supporting substrate side of the surface layer, that is, the resin or precursor of the aforementioned layer A, and the supporting substrate on which the layer B is formed in advance is used. Coating, drying, and hardening can be performed on the substrate, or coating, drying, and hardening can be performed simultaneously with the formation of the layer B on the supporting substrate to form the layer A.

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

[Coating composition A]

The coating composition A is a liquid containing a material suitable for constituting the layer A in the surface layer or a precursor that can be formed, and preferably a resin or precursor containing the following segments (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 containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment, and a polydimethylsiloxane segment.

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

The mass fractions of (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. Details of (1), (2), and (3) will be described below.

The details of the aforementioned (1) polycaprolactone segment, polycarbonate segment, and polyalkylene glycol segment are as described later, but since the resin constituting the A layer in the surface of the surface layer described above has such segments , Which can improve the self-healing ability of the surface layer, and improve repeated scrubbing.

The details of the urethane bond are described later, but since the resin of the A layer in the surface constituting the surface layer has the bond, the toughness of the entire surface layer can be improved.

The details of the aforementioned fluoropolyether segment are described later, but by including these in the resin system constituting the surface layer, molecules exhibiting low surface energy can be present on the outermost surface at a high density, and the surface's repetitive rubbing effect will be caused. Promotion.

[Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]

First, the polycaprolactone segment refers to a segment represented by Chemical Formula 1. Polycaprolactone also includes oligomers in which the repeating units of caprolactone are 1 (monomer), 2 (dimer), 3 (trimer), or repeating units of caprolactone up to 35 .

n is an integer from 1 to 35.

The resin containing a polycaprolactone segment is preferably one having at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the terminal of a resin containing a polycaprolactone segment.

As for the resin containing a polycaprolactone segment, a polycaprolactone having a 2 to 3 functional hydroxyl group is particularly preferred. Specifically, a polycaprolactone diol represented by Chemical Formula 2 may be used,

Here, m + n is an integer from 4 to 35, m and n are each an integer from 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 represented by Chemical Formula 3,

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

And other polycaprolactone polyols; or polycaprolactone-modified (meth) acrylate hydroxyethyl esters shown in 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 other active energy ray polymerizable caprolactones include polycaprolactone-modified hydroxypropyl (meth) acrylate, polycaprolactone-modified hydroxybutyl (meth) acrylate, and the like.

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

In the present invention, the weight average molecular weight of the polycaprolactone segment in the resin containing the polycaprolactone segment is preferably 500 to 2,500, and more preferably the weight average molecular weight is 1,000 to 1,500. If the weight-average molecular weight of the polycaprolactone segment is 500 to 2,500, the self-healing effect will be more exhibited, and the repetitive rubbing property will be more improved and better.

Next, the polyalkylene glycol segment is a segment represented by Chemical Formula 5. Polyalkylene glycols also include those in which the repeating unit of the alkanediol is 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 is preferably one having at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the terminal of a resin containing a polyalkylene glycol segment.

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

Examples of the polyalkylene glycol (meth) acrylate contained in the coating composition used to form the surface layer include polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate. Polybutylene glycol (meth) acrylate. Each has the 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 from 2 to 11.

In the present invention, it is preferred that an isocyanate group-containing compound to be described later be reacted with the hydroxyl group of (poly) alkanediol (meth) acrylate to be used as a urethane (meth) acrylate in the surface layer. In this way, the resin constituting the surface layer can have (2) urethane bonds and (3) (poly) alkanediol segments, and as a result, the toughness of the surface layer can be improved and at the same time, self-healing ability can be improved. And better.

When the isocyanate group-containing compound is urethanated with a polyalkylene glycol (meth) acrylate, the (meth) acrylic acid hydroxyalkyl (meth) acrylic acid may be exemplified as (meth) acrylic acid Hydroxyethyl ester, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.

Next, the polycarbonate segment refers to a segment represented by Chemical Formula 9. Polycarbonates also include oligomers in which the repeating units of carbonate are 2 (dimer), 3 (trimer), or repeating units of carbonate up to 16.

n is an integer from 2 to 16.

R _{4 is} an alkylene or cycloalkylene group having 1 to 8 carbon atoms.

The polycarbonate segment-containing resin is preferably one having at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the terminal of a resin containing a polycarbonate segment.

As for the resin containing a polycarbonate segment, the polycarbonate diol which has a bifunctional hydroxyl group is especially preferable. Specifically, it is represented by Chemical Formula 10.

Polycarbonate diol :. ． ． Chemical formula 10

n is an integer from 2 to 16. R means an alkylene group or a cycloalkylene group having 1 to 8 carbon atoms.

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 will be reduced, so the repetition is repeated. The number is preferably 10 or less. The polycarbonate diol may be a mixture of two or more polycarbonate diols having different carbonate unit repeat numbers.

The polycarbonate diol is preferably one having a number average molecular weight of 500 to 10,000, and more preferably 1,000 to 5,000. If the number average molecular weight is less than 500, it may become difficult to obtain suitable flexibility In addition, if the number average molecular weight exceeds 10,000, heat resistance or solvent resistance may be reduced, so the aforementioned degree is suitable.

As the polycarbonate diol used in the present invention, UH-CARB, UD-CARB, UC-CARB (Ube Industrial Co., Ltd.), PLACCEL CD-PL, 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 alone or in combination of two or more kinds.

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

In the present invention, it is preferred that an isocyanate group-containing compound described later reacts with the hydroxyl group of polycarbonate diol, and is used as a urethane (meth) acrylate on the surface side of the surface layer, whereby 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 strength and toughness of the surface layer can be improved, and at the same time, self-healing can be improved. Sexual improvement, can make repeated sexual improvement.

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

Since the aforementioned 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 system constituting the surface side of the surface layer can have a urethane bond. In addition, when forming the surface side of the surface layer, the coating composition A containing an isocyanate group-containing compound and a hydroxyl group-containing compound as precursors may be coated, dried, and hardened to thereby form amino formic acid. An ester bond is formed, and the surface side of a surface layer contains a urethane bond.

In the present invention, it is preferable that an urethane bond is formed by reacting an isocyanate group with a hydroxyl group to introduce a urethane bond into a resin constituting the surface side of the surface layer. By reacting an isocyanate group with a hydroxyl group to form a urethane bond, the toughness of the surface layer is improved, and at the same time, the self-healing property is improved, so that the repeated rubbing property can be improved.

In addition, in the case of a resin having a polycaprolactone segment, a polycarbonate segment, a polyalkylene glycol segment, or a hydroxyl group, the resin may be used as a precursor by heat or the like. The urethane bond is formed between the isocyanate group-containing compounds.

If the surface layer is formed using a compound containing an isocyanate group, a resin containing a polysiloxane group having a hydroxyl group, or a resin containing a polydimethylsiloxane group having a hydroxyl group, described below, The toughness and self-healing properties of the surface layer can also improve the surface slip From the standpoint of repeated scrubbing, it is also better.

In the present invention, the compound containing an isocyanate group means a resin containing an isocyanate group, or a monomer or oligomer containing a cyanate group. Examples of the isocyanate group-containing compound system include methylenebis-4-cyclohexyl isocyanate, trimethylolpropane adduct of toluene diisocyanate, and trimethylolpropane adduct of hexamethylene diisocyanate. , Trimethylolpropane adduct of isophorone diisocyanate, isotricyanate of toluene diisocyanate, isotricyanate of hexamethylene diisocyanate, hexamethylene isocyanate (Poly) isocyanates such as biuret bodies, and blocked bodies of the aforementioned isocyanates.

Among these isocyanate group-containing compounds, aliphatic isocyanates are better in self-healing properties than alicyclic or aromatic isocyanates. The isocyanate group-containing compound is more preferably a hexamethylene diisocyanate. In addition, the isocyanate group-containing compound is an isocyanate having an isotricyanate ring, which is particularly preferable in terms of heat resistance, and is most preferably an isotricyanate body of hexamethylene diisocyanate. An isocyanate having an isotricyanate ring forms a surface layer having both self-healing properties and heat resistance properties.

[Fluorine compound segment, polysiloxane segment, polydimethylsiloxane segment]

In the laminated film of the present invention, it is preferred that the resin constituting the surface layer or the surface side of the surface layer has a segment, and the segment system includes a segment selected from the group consisting of a fluorine compound segment, a polysiloxane segment, and a polymer At least one of the group of dimethylsiloxane segments.

Furthermore, resins or precursors containing segments can be used. The coating composition A is one of the coating compositions used to form the surface layer, and the resin constituting the surface side of the surface layer has the following. The segment contains a component selected from the group consisting of a fluorine compound segment and polysiloxane. At least one of a group of an alkane segment and a polydimethylsiloxane segment.

Hereinafter, these fluorine compound segments, polysiloxane segments, and polydimethylsiloxane segments will be described.

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

Here, fluoroalkyl, fluorooxyalkyl, fluoroalkenyl, fluoroalkanediyl, and fluorooxyalkanediyl are alkyl, oxyalkyl, alkenyl, alkanediyl, and oxyalkanediyl. Part of or all of the hydrogen substituents are substituted with fluorine, each of which is a substituent mainly composed of a fluorine atom and a carbon atom, and may have branches in the structure, and may also have a Dimers, trimers, oligomers, and polymer structures connected by plural structures.

The fluorine compound segment is preferably a fluoropolyether segment, which is a site containing a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, and the like, and more preferably Chemical Formula 5, Chemical Formula The fluoropolyether segment represented by 6 is as already described.

The aforementioned fluoropolyether segment is a segment including a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, and the like, and has a structure represented by Chemical Formula 12 and Chemical Formula 13.

Here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, k, m, p, and s are integers of 0 or more, and p + s is 1 or more. Preferably, n1 is 2 or more, n2 to n5 are integers of 1 or 2, more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.

The chain length of the fluoropolyether segment has a preferable range, and the number of carbons is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. When the carbon number is 3 or less, the surface energy may be insufficiently reduced, which may reduce the oil repellency. When the carbon number is 13 or more, the solubility of the solvent may be reduced, and the quality of the surface layer may be reduced.

When the resin system contained in this surface layer contains a fluorine compound segment, it is preferable that the aforementioned coating composition A 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, and R ₇ represents an alkanediyl group, an alkanetriyl group, and an ester structure, a urethane structure, an ether structure, Structure, D ¹ represents a reactive site.

The reactive site refers to a site that reacts with other components due to external energy such as heat or light. Examples of such reactive sites include alkoxysilyl and alkoxysilane from the viewpoint of reactivity. A hydrolyzed silanol group, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an allyl group, a methacryl group, and the like. Among these, from the viewpoints of reactivity and handleability, vinyl, allyl, alkoxysilyl, silyl ether, or silanol groups, or epoxy groups, acrylic fluorene (methacrylic acid) are preferred.醯) based.

An example of the fluorine compound D is a compound shown below. Examples include: 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxy Silane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltrichlorosilane, 2-perfluorooctylisocyanate silane, 2,2,2-trifluoroethylacrylic acid Ester, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutyl ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexyl Ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctyl ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecyl Ethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5- Methylhexyl ethyl acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropane base Enoate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexafluorononyl 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- Perfluorooctyl ethyl 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-hydroxypropyl Methyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octa Fluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate Esters, hexafluorobutyl methacrylate, tripropenyl-heptafluorononenyl-pentaerythritol, and the like.

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 Corporation), Optool DAC-HP (DAIKIN Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Corporation), etc., These products are available.

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

Here, the polysiloxane contains a low-molecular-weight (so-called oligomer) having a repeating unit of about 100 and a high-molecular-weight (a so-called polymer) having a repeating unit of silica exceeding 100. By.

Each of R ₁ and R ₂ is a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, each of which has at least one or more in the formula, and n is an integer of 100 to 300.

The details of the aforementioned polysiloxane segment and the polydimethylsiloxane segment are described later, but the resin constituting the surface layer can improve heat resistance, weather resistance, or improve due to the presence of these segments. Scratch resistance due to the lubricity of the surface layer. It is more preferable that it includes a polydimethylsiloxane segment represented by Chemical Formula 16 described later from the viewpoint of lubricity.

In the present invention, a partially hydrolyzed product of a hydrolyzable silane-containing silane compound, an organic silica sol, or a coating composition in which a hydrolyzable silane compound having a radical polymer is added to the organic silica sol can be used as the polysilicon-containing Resin resin is used.

Examples of the resin containing a polysiloxane segment are tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane Γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxy Complete or partial hydrolysates of hydrolyzable silane-based silane compounds, such as silanes, or organic silica sols dispersed in organic solvents, and hydrolyzed silane compounds having hydrolyzable silane groups added to the surface of the organosilica sols.

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

When the resin containing a polysiloxane segment has a hydroxyl group In the case of a copolymer, if a surface layer is formed by using a coating composition containing a resin (copolymer) containing a polysiloxane group having a hydroxyl group and an isocyanate group-containing compound, a polysilicon having a high efficiency can be formed. Surface layer of oxane segment and urethane bond.

Next, the polydimethylsiloxane segment will be described. In the present invention, the so-called polydimethylsiloxane segment refers to a segment represented by Chemical Formula 16. In polydimethylsiloxane, low molecular weight individuals (so-called oligomers) containing repeating units of dimethylsiloxane of 10 to 100 and high molecular weights having repeating units of dimethylsiloxane in excess of 100 Both (so-called polymers).

m is an integer from 10 to 300.

If the resin constituting the surface side of the surface layer has a polydimethylsiloxane segment, the polydimethylsiloxane segment will be arranged on the surface of the surface layer. The polydimethylsiloxane segment is arranged on the surface of the surface layer, and the lubricity of the surface layer is improved, which can reduce the friction resistance. As a result, it is possible to improve the repetitive rubbing property.

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

In order to improve the toughness of the surface layer, The resin of the dimethylsiloxane segment is preferably a monomer copolymerized with a hydroxyl group having a reaction with an isocyanate group, and the like.

When the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, if a resin containing a polydimethylsiloxane segment containing a hydroxyl group (copolymer) and an isocyanate-containing resin are used To form a surface layer by using a coating composition of a base-based compound, a surface layer having a polydimethylsiloxane segment and a urethane bond can be efficiently formed.

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

When the polymer initiator method is used, a polymer azo radical polymerization initiator represented by Chemical Formula 17 can be used to copolymerize with other vinyl monomers. It is also possible to carry out two-stage polymerization, which is a prepolymer in which a peroxide group is introduced into a side chain by copolymerizing a peroxy monomer and a polydimethylsiloxane having an unsaturated group at a low temperature. And copolymerize 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 chain transfer method using a polymer, for example based on polyethylene oxide of silicon oil represented by Chemical Formula 18, the additional HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH or the like made after the compound having SH group of the SH A block copolymer is synthesized by copolymerizing the siloxane compound with a vinyl monomer by chain transfer of a radical.

m is an integer from 10 to 300.

In order to synthesize a polydimethylsiloxane-based graft copolymer, for example, a compound represented by Chemical Formula 19, that is, a methacrylate of polydimethylsiloxane and the like can be copolymerized with a vinyl monomer, thereby Instead, a graft copolymer is easily obtained.

m is an integer from 10 to 300.

Examples of the vinyl monomer used in the copolymer with polydimethylsiloxane include methyl acrylate and 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, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-formyl Styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, allyl ring Oxypropyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-hydroxymethacrylamide, N, N-di Methacrylamide, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, diethylammonium acrylamide, 2-hydroxyacrylic acid Ethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol .

The polydimethylsiloxane 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. Ester solvents such as butyl acetate, alcohol solvents such as ethanol, isopropanol, and the like, alone or in a mixed solvent, are produced by a solution polymerization method

If necessary, a polymerization initiator such as benzamidine peroxide, azobisisobutyronitrile and the like is used in combination. The polymerization reaction is preferably performed at 50 to 150 ° C for 3 to 12 hours.

The amount of polydimethylsiloxane segments in the polydimethylsiloxane-based copolymer in the present invention, the lubricity or pollution resistance on the surface layer In terms of performance, it is preferably 1 to 30% by mass based on 100% by mass of all components of the polydimethylsiloxane copolymer. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

In the present invention, when a resin containing a polydimethylsiloxane segment is used as a coating composition for forming a surface layer, in addition to the polydimethylsiloxane segment, it may contain (copolymerization) ) Other links and so on. For example, it may contain (copolymerize) a polycaprolactone segment or a polysiloxane segment.

In the coating composition used to form the surface layer, a copolymer of a polycaprolactone segment and a polydimethylsiloxane segment, and a copolymerization of a polycaprolactone segment and a polysiloxane segment can be used. Polymer, polycaprolactone segment and copolymer of polydimethylsiloxane segment and polysiloxane segment. The surface layer obtained by using such a coating composition is capable of having a polycaprolactone segment and a polydimethylsiloxane segment and / or a polysiloxane segment.

In a coating composition used to form a surface layer having a polycaprolactone segment, a polysiloxane segment, and a polydimethylsiloxane segment, a polydimethylsiloxane copolymer, a polysiloxane The reaction between caprolactone and polysiloxane can be carried out by appropriately adding a polycaprolactone segment and a polysiloxane 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 layer A by coating, drying, and hardening on a supporting substrate, and includes a resin or precursor suitable for forming the layer B.

The coating composition B may be any one of a thermosetting resin and an ultraviolet curing resin, and 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. Examples of the hydroxyl group-containing resin include acrylic polyols, polyether polyols, polyester polyols, and polyolefin-based polyols. Alcohols, polycarbonate polyols, urethane polyols, etc. may be one type or a mixture of two or more types. When the hydroxyl group-containing resin has a hydroxyl value in the range of 1 to 200 mgKOH / g, it is preferable from the viewpoints of durability, hydrolysis resistance, and adhesiveness when it becomes a coating film. When the hydroxyl value is less than 1 mgKOH / g, hardening of the coating film hardly proceeds, and durability or strength may be reduced. On the other hand, when the hydroxyl value is more than 200 mgKOH / g, the curing shrinkage is too large, and the adhesion may be reduced.

The hydroxyl-containing acrylic polyol in the present invention is obtained by, for example, polymerizing acrylate or methacrylate as a component. Such an acrylic resin can be easily prepared by, for example, using a (meth) acrylate as a component and copolymerizing a carboxylic acid group-containing monomer such as (meth) acrylic acid, itaconic acid, and maleic anhydride as needed. Manufacturing. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) ) Butyl acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl ester, cyclohexyl (meth) acrylate, methylhexyl (meth) acrylate, cyclododecyl (meth) acrylate, isopropyl (meth) acrylate Esters, etc. Examples of such a hydroxyl group-containing acrylic polyol include DIC Corporation; (trade name "Acrydic" (registered trademark) series, etc.), Dacheng Fine Chemical Co., Ltd .; (trade 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 are available.

Examples of the polyether polyol containing a hydroxyl group in the present invention include polyethylene glycol or triol, polypropylene glycol or triol, polybutylene glycol or triol, and polytetramethylene. Diols or triols, and addition polymers or block copolymers of such alkylene oxide compounds having different carbon numbers. Examples of such a hydroxyl-containing polyether polyol include Asahi Glass Co., Ltd .; (trade name "Excenol" (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd .; (trade name "Actcol" ( (Registered trademark) series, etc.), these products can be used.

Examples of the hydroxyl-containing polyester polyol in the present invention include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, and cyclohexane. Aliphatic diols such as alkanedimethanol, and, for example, succinic acid, adipic acid, sebacic acid, fumaric acid, suberic acid, azelaic 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, butylene glycol, and, for example, terephthalic acid, methane An aromatic polyester polyol in which an aromatic dibasic acid such as phthalic acid and naphthalenedicarboxylic acid reacts as an essential raw material component.

Examples of such hydroxyl-containing polyester polyols include DIC Corporation; (trade name "Polylite" (registered trademark) series, etc.), KURARAY Corporation; (trade name "KURARAY Polyol") (Registered trademark) series, etc.), Takeda Pharmaceutical Industry Co., Ltd .; (brand name "Takelac" (registered trademark) U series), can use these products.

The hydroxyl-containing polyolefin polyol in the present invention is a diene-based polymer and copolymer having 4 to 12 carbons such as butadiene or isoprene, and 4 to 12 carbons. Among the copolymers of diene of 12 and α-olefins having 2 to 22 carbons, compounds containing a hydroxyl group. There is no particular limitation on the method for causing the hydroxyl group to be contained, but for example, there is a method for reacting a diene monomer with hydrogen peroxide. In addition, the remaining double bonds can be hydrogenated to saturate the aliphatic. Examples of such hydroxyl-containing polyolefin-based polyols include Japan's Soda Co., Ltd .; (trade name "NISSO-PB" (registered trademark) G series, etc.), Idemitsu Kosan Co., Ltd .; "Poly bd" (registered trademark) series, "Epol" (registered trademark) series, etc.) can be used.

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

Examples of such hydroxyl-containing polycarbonate polyols include Asahi Kasei Chemical Co., Ltd. which copolymerizes polycarbonate polyols; (trade names "T5650J", "T5652", "T4671", "T4672 ", Etc.), Ube Industrial Co., Ltd .; (trade name" ETERNACLL "(registered trademark) UM series, etc.), these products can be used.

Hydroxyl-containing urethane polyhydric 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 such a manner that the hydroxyl group becomes excessive with respect to the isocyanate group. Examples of the polyisocyanate compound used at that time include hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, and the like. Examples of the compound containing at least two hydroxyl groups in one molecule include polyols, polyester diols, polyethylene glycols, polypropylene glycols, and polycarbonate diols.

The polyisocyanate compound used for the thermosetting resin in the present invention refers to a resin containing an isocyanate group, or a monomer or oligomer containing an isocyanate group. Examples of the isocyanate group-containing compound include methylenebis-4-cyclohexyl isocyanate, trimethylolpropane adduct of toluene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, Trimethylolpropane adduct of isophorone diisocyanate, isotricyanate of toluene diisocyanate, isotricyanate of hexamethylene diisocyanate, condensation of hexamethylene isocyanate (Poly) isocyanates such as diurea bodies, and blocked bodies of the above-mentioned isocyanates. Examples of the polyisocyanate compound used in such thermosetting resins include Mitsui Chemicals Co., Ltd. (trade name "Takenate" (registered trademark) series, etc.), Japan Polyurethane Industry Co., Ltd .; (Brand name "Coronate" (registered trademark) series, etc.), Asahi Kasei Chemical Co., Ltd .; (brand name "Duranate" (registered trademark) series, etc.), DIC Corporation; (brand name "Burnock" (registered trademark) series Etc.), these products can be used.

As far as the ultraviolet curable resin in the present invention is concerned, Multifunctional acrylate monomer, oligomer, alkoxysilane, alkoxysilane hydrolysate, alkoxysilane oligomer, urethane acrylate oligomer, etc. 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. As a specific example, pentaerythritol tris ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol pentaerythritol hexa (methyl) Group) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexanemethylene diisocyanate urethane polymer, and the like. These single systems can be used singly or in combination of two or more.

Examples of commercially available polyfunctional acrylic compositions include Mitsubishi Electric Corporation; (trade name "Diabeam" (registered trademark) series, etc.), Japan Synthetic Chemical Industry Co., Ltd .; (trade name) "SHIKOH" (registered trademark) series, etc.), Nagase Industry Co., Ltd .; (brand name "Denacol" (registered trademark) series, etc.), Shin Nakamura Chemical Co., Ltd .; (brand name "NK Ester" series, etc.), DIC Corporation; (brand name "UNIDIC" (registered trademark), etc.), East Asia Synthetic Corporation; ("Aronix" (registered trademark) series, etc.), Japan Oil Corporation; ("Blemmer" (registered trademark) Series, etc.), Nippon Kayaku Co., Ltd .; (brand name "KAYARAD" (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd .; (brand name "Light Ester" series, etc.), etc., can use these product.

In order to impart the aforementioned characteristics, an acrylic polymer may be used. The acrylic polymer is more preferably unsaturated group-free, 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 decrease, and the elongation beyond 200 ° C may be insufficient. A more preferred glass transition temperature is in the range of 50 to 150 ° C.

Moreover, the said acrylic polymer system can provide hardness because it has a hydrophilic functional group. Specifically, (meth) acrylic acid having a carboxyl group, itaconic acid, fumaric acid, maleic acid, or the like, or hydroxyethyl 2- (meth) acrylate having a hydroxyl group, An unsaturated monomer having a hydrophilic functional group such as hydroxypropyl acrylate is copolymerized with the unsaturated monomer, and a hydrophilic functional group is introduced into the acrylic polymer.

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

The content ratio of the acrylic polymer is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass of the total solid content of the coating composition B. Since the elongation is remarkably improved by setting it to 1% by mass or more, it is preferable to maintain the hardness by setting it to 50% by mass or less.

[Solvent]

It is preferable that the said coating composition A and coating composition B contain a solvent. The number of types of the solvent is preferably from 1 to 20 and more It is preferably from 1 to 10 types, particularly preferably from 1 to 6 types. The "solvent" as used herein refers to a substance that can be evaporated from the coating film in the drying step after coating and is a liquid at normal temperature and pressure.

Here, the type of the solvent is determined by the molecular structure constituting the solvent. That is, even if the same elemental composition and the same type and number of functional groups exist, those with different binding relationships (structural isomers) and those that are not the aforementioned structural isomers but cannot adopt any configuration in the three-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]

It is preferable that the said coating composition A and coating composition B contain a polymerization initiator, a hardening agent, or a catalyst. A polymerization initiator and a catalyst are used in order to accelerate hardening of a surface layer. The polymerization initiator is preferably one capable of starting or promoting the polymerization, condensation, or crosslinking reaction caused by anions, cations, radical polymerization reactions, or the like, of the components contained in the coating composition.

Various polymerization initiators, hardeners, and catalysts can be used. The polymerization initiator, curing agent, and catalyst may be used individually, or a plurality of polymerization initiators, curing agents, and catalysts may be used together. Furthermore, an acidic catalyst or a thermal polymerization initiator may be used in combination. Examples of the acidic catalyst include aqueous hydrochloric acid solution, formic acid, and acetic acid. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkyl phenone-based compounds, sulfur-containing compounds, fluorenylphosphine oxide-based compounds, and amine-based compounds. Things.

The photopolymerization initiator is preferably an alkyl phenone-based compound from the viewpoint of hardenability. Specific examples of the alkyl phenone-based compound include 1-hydroxy-cyclohexyl-phenyl-one, 2,2-dimethoxy-1,2-diphenylethyl-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) oxybisethylene, and the like Materials that have been quantified by polymers.

Moreover, as long as it is in the range which does not inhibit the effect of the present invention, a leveling agent, an ultraviolet absorber, a slip agent, and an antistatic agent may be added to the coating composition A and the coating composition B used for forming 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 acrylic copolymers, silicone-based, and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include diphenyl ketone, benzotriazole, anilide oxalate, and triphenyl UV absorbing agent of series and hindered amine series. Examples of the antistatic agent include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.

[Manufacturing method of laminated film]

The manufacturing method of the laminated film of the present invention is more preferably one in which at least the aforementioned coating composition A and coating composition B are sequentially or simultaneously applied. The manufacturing method of coating-drying-hardening on the aforementioned support substrate.

The "sequential coating" herein is intended to form a surface layer by coating-drying-hardening one type of coating composition and then coating-drying-hardening different types of coating composition. By appropriately selecting the type and number of the coating composition used in this manufacturing method, the size or gradient of the elastic modulus of the surface side of the surface layer to the substrate side, and the elastic modulus of the substrate and the surface layer can be controlled. The size can also control the shape of the elastic modulus distribution in the surface layer 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 kinds of coating compositions are coated, dried, and cured "simultaneously" on a supporting substrate. The number of types of coating composition is not particularly limited as long as it is two or more. Here, the "simultaneous coating" means that two or more types of liquid films are coated on the supporting substrate in the coating step, and then dried and hardened.

In this manufacturing method, when the coating method is to apply the aforementioned coating composition one by one, it is preferable to use a dip coating method, a roll coating method, a bar coating method, a gravure coating method, or a die coating method (U.S. Patent No. No. 2681294), etc., and coated on a supporting substrate and the like to form a surface layer

In addition, when the two or more types of coating compositions described above are applied simultaneously, it may be a "multi-layer sliding die coating" (Figure 3), which is applied after the liquid film is sequentially laminated in the state before coating, or simultaneously on the substrate. "Multi-layer slit die coating" (Fig. 4) of coating and lamination is performed on the substrate and formed on a supporting substrate After one layer of the liquid film, any one of "wet-on-wet coating" (Fig. 5) and the like of the other layer is laminated in an undried state.

Next, the liquid film which has been applied to a supporting substrate or the like is dried. In addition to completely removing the solvent from the obtained laminated film, it is preferable to accompany the heating of the liquid film in the drying step.

Examples of the drying method include heat transfer drying (adherence to a hot object), convective heat transfer (hot air), radiant heat transfer (infrared), and other (microwave and induction heating). Among them, in the manufacturing method of the present invention, it is preferable to use a method of convective heat transfer or radiant heat transfer because the drying speed must be made uniform evenly 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. In the case of thermal curing, the temperature is preferably from room temperature to 200 ° C or lower. From the viewpoint of the activation energy of the curing reaction, it is more preferable. The temperature is 80 ° C to 200 ° C, and more preferably 100 ° C to 200 ° C.

In addition, in the case of hardening by active energy rays, in terms of versatility, electron rays (EB rays) and / or ultraviolet rays (UV rays) are preferred. In addition, when curing is performed by ultraviolet rays, it is preferred that the oxygen concentration be as low as possible from the viewpoint of preventing oxygen blocking, and it is more preferable that the curing is performed under a nitrogen atmosphere (nitrogen flushing). When the oxygen concentration is high, the hardening of the outermost surface is hindered, the hardening of the surface becomes insufficient, and the fingerprint resistance may become insufficient.

The types of ultraviolet lamps used when irradiating ultraviolet rays include, for example, a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When the ultraviolet light is hardened by a high-pressure mercury lamp using a discharge lamp method, the ultraviolet light is irradiated under conditions 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 ultraviolet rays is the irradiation intensity per unit area, which varies with the lamp output, the spectral efficiency of light emission, the diameter of the light bulb, the design of the reflector, and the distance from the light source of the object to be irradiated. However, the illuminance does not change with the transfer rate. The cumulative amount of ultraviolet light is the irradiation energy received per unit area, which is the total amount of photons reaching the surface. The accumulated light amount is inversely proportional to the irradiation speed under the passing light source, and is proportional to the number of irradiations and the number of lamps.

[Application example]

Since the laminated film of the present invention is excellent in abrasion resistance, it can be widely used in, for example, electrochemical components, automobile interior components, and building components.

For example, it can be applied to plastic products such as glasses, sunglasses, packaging boxes, food containers, housings for smart phones, touch panels, keyboards, remote controls for televisions, air conditioners, and buildings. , Dashboard, driving navigator, touch panel, interior mirrors and other vehicle interior products, as well as various surfaces of various printed materials.

[Example]

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

<Fluorine compound D>

[Fluorine compound D1 methyl ethyl ketone / methyl isobutyl ketone solution]

As the fluorine compound D1, an acrylate compound containing a fluoropolyether moiety ("Megafac" (registered trademark) RS-75, manufactured by DIC Corporation, methyl ethyl ketone / methyl isobutyl ketone with a solid content concentration of 40% by mass, was used. Solution).

<Synthesis of Polysiloxane Compound>

[Polysiloxane (a)]

In a 500 ml capacity flask equipped with a stirrer, thermometer, condenser, and nitrogen introduction tube, 106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1 part were added. % Hydrochloric acid, which was kept at 85 ° C for 2 hours, ethanol was recovered while the temperature was raised, and kept at 180 ° C for 3 hours. Then, it cooled, and the viscosity-adjusted (poly) siloxane (a) was obtained.

<Synthesis of Polydimethylsiloxane Compound>

[Polydimethylsiloxane block copolymer (a) toluene solution]

Using the same apparatus as the synthesis of polysiloxane (a), 50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, and 20 parts by mass of polydimethylsiloxane-based polymer were added. Agent (VPS-0501 manufactured by Wako Pure Chemical Industries, 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 parts by mass of 1-thioglycerin were reacted at 180 ° C. for 8 hours to obtain a toluene solution having a solid content concentration of 50% by mass of the polydimethylsiloxane block copolymer (a).

[Polydimethylsiloxane compound (b)]

As the polydimethylsiloxane compound (b), EBECRYL350 (bifunctional, polysiloxane) 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 isotricyanate modified type ("Takenate" (registered trademark) D-170N manufactured by Mitsui Chemicals Co., Ltd.), and 76 parts by mass of Polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by DAICEL Chemical Industry 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 the urethane acrylate 1 having a solid content concentration of 50% by mass.

[Toluene solution of urethane acrylate 2]

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. The temperature was maintained at 8 ° C for 8 hours. 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 was held at 80 ° C for 6 hours. Then, 97 parts by mass of toluene was finally added to obtain a toluene solution of the urethane acrylate 2 having a solid content concentration of 50% by mass.

[Toluene solution of urethane acrylate 3]

50 parts by mass of hexamethylene diisocyanate-modified isocyanurate ("Takenate" (registered trademark) D-170N, manufactured by Mitsui Chemicals Corporation, isocyanate group content: 20.9% by mass), 53% by mass Parts of polyethylene glycol monoacrylate ("Blemmer" manufactured 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. Thereafter, the reaction was carried out by keeping the temperature at 70 ° C for 5 hours. After the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction solution to obtain a toluene solution of the urethane acrylate 3 having a solid content concentration of 50% by mass.

[Acrylic polyol 1]

As the acrylic polyol 1, a hydroxyl group-containing acrylic polyol ("Takelac" (registered trademark) UA-702 manufactured by Mitsui Chemicals Co., Ltd., solid content concentration 50% by mass hydroxyl value: 50mgKOH / g) was used.

[Acrylic polyol 2]

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

[Isocyanate compound 1]

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

[Multifunctional acrylate 1]

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

[Multifunctional acrylate 2]

As the polyfunctional acrylate 2, a urethane acrylate oligomer ("SHIKOH" (registered trademark) UV-3310B) was used. Industrial Co., Ltd., solid content concentration 100% by mass).

[Multifunctional acrylate 3]

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

[Multifunctional acrylate 4]

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

[Synthesis of acrylic polymer 1]

24 parts by mass of dilauroyl peroxide (manufactured by Peroyl L Nippon Oil Co., Ltd.) was added to 495 parts by mass of methyl ethyl ketone, and the solution was dissolved by heating at 70 ° C for 30 minutes, and the solution was dripped over 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 MSD (Nippon Oil Co., Ltd.) solution, and stirred and polymerized. Then, it stirred at 80 degreeC for 2 hours, and obtained the methyl ethyl ketone solution (weight average molecular weight 6,000) of the acrylic polymer 1 containing the solid content concentration of the hydrophilic functional group of 35 mass%.

<Blend of Coating Composition A>

[Coating composition A1]

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

‧Solid component concentration of fluorine compound D1 is 40% by mass-3.8 parts by mass of 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 content 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 content 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 content 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 content 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 content 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 content concentration of 20% by mass.

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

<Manufacturing method of laminated film>

[Laminating film production method 1]

As a supporting substrate (the layer that becomes the C layer), "Lumirror" (registered trademark) U48 (manufactured by Toray Co., Ltd.) having a thickness of 100 µm and having an easily-adhesive coating applied to a PET resin film was used. Using a continuous coating device using a slit die coater on a supporting substrate, the coating composition B is applied so that the discharge flow rate from the slit is adjusted so that the thickness of the dried surface layer becomes a specified film thickness. Next, the drying step is performed under the following conditions And a hardening step to form a layer B on the supporting substrate.

"Drying step"

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

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

Detention time: 2 minutes

"Hardening step"

Cumulative light quantity: 120mJ / cm ²

Oxygen concentration: atmospheric environment.

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

"Drying step"

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

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

Detention time: 2 minutes

"Hardening step"

Cumulative light quantity: 120mJ / cm ²

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

[Laminated film production method 2]

Used as a support substrate (to be the layer of layer C), used in PET resin film "Lumirror" (registered trademark) U48 (manufactured by Toray Industries, Ltd.) with a thickness of 100 µm coated with an easily-adhesive coating. On a supporting substrate, a continuous coating device using a slit die coater is used to apply the coating composition B by adjusting the discharge flow rate from the slit so that the thickness of the surface layer after drying becomes a specified film thickness, and the second or lower A drying step and a hardening step are performed under the conditions described above to form a layer B on the supporting substrate.

"Drying step"

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: coating surface side: 5m / s, reverse coating surface side: 5m / s

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

Detention time: 2 minutes

Furthermore, using the same device, on the layer B obtained above, the coating composition A was applied so that the discharge flow rate from the slit was adjusted so that the thickness of the surface layer after drying became the specified film thickness, followed by the following conditions A drying step and a hardening step are performed to obtain a laminated film.

"Drying step"

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

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

Detention time: 2 minutes

"Hardening step"

Cumulative light quantity: 120mJ / cm ²

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

[Laminating film production method 3]

As a supporting substrate (the layer that becomes the C layer), "Lumirror" (registered trademark) U48 (manufactured by Toray Co., Ltd.) having a thickness of 100 µm and having an easily-adhesive coating applied to a PET resin film was used. On the supporting substrate, a continuous coating device using a slit die coater is used to adjust the discharge flow rate from the slit so that the thickness of the dried surface layer becomes a predetermined film thickness, and then coating composition A is applied, followed by the following A drying step and a hardening step are performed under the conditions described above to form an A layer on the supporting substrate.

"Drying step"

Supply air temperature and humidity: Temperature: 80 ℃

Wind speed: 5m / s on the coating side, 5m / s on the reverse coating side

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

Detention time: 2 minutes

"Hardening step"

Cumulative light quantity: 120mJ / cm ²

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

By the above methods, laminated films of Examples 1 to 13 and Comparative Examples 1 to 2 were prepared. Table 1 shows the methods for preparing the laminated films corresponding to the respective examples and comparative examples, the coating composition used, and the film thickness of each layer.

<Evaluation of laminated film>

The produced laminated film was subjected to performance evaluation shown below, and the results obtained are shown in Table 2. Except for the cases specified in advance, the measurement is performed in each of the examples and comparative examples by changing the position of one sample. Three measurements were performed, and the average value was used.

[Measurement of storage elastic modulus and glass transition temperature]

A. Confirmation of cross section of laminated film

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

The prepared ultra-thin section was mounted on a Cu mesh of 100 mesh manufactured by Oken Corporation, and a transmission electron microscope (TEM) H-7100FA manufactured by Hitachi was used for TEM observation at an acceleration voltage of 100 kV to observe the cross-section of the laminated film. Check the surface layer and the place where the substrate is supported.

B. Determination of ultra-micro hardness tester

Using the ultra-thin slice as a sample, an ultra-micro hardness tester (Tribo Indenter manufactured by Hysitron) was used to obtain the modulus mapping image of the surface layer and the supporting substrate, and the storage elastic modulus and the lost elastic modulus were calculated. The ratio of the modulus to the loss elastic modulus is used to obtain the loss tangent (tan δ), and the peak temperature of the obtained loss tangent (tan δ) is taken as the glass transition temperature (Tg).

The measurement conditions are shown below.

Measuring device: Tribo Indenter by Hysitron

Indenter: Diamond Cubecorner indenter (curvature radius 50nm)

Measurement field of view: about 30mm square

Measurement frequency: 10Hz

Measurement environment: -20 ℃ ~ 120 ℃ ‧in air

Contact load: 0.3 μN.

[Measurement of Elastic Modulus of Atomic Force Microscope]

Sections of the laminated films of Examples 1 to 13 and Comparative Examples 1 to 2 were cut out by a freezing section method, and the sections were used as measurement surfaces and fixed to a dedicated sample holder. An AFM (AFM) ) "MFP-3DSA-J" and cantilever "R150-NCL-10 (material Si, spring constant 48N / m, radius of curvature 150nm at the front end)" made by NANOSENSORS, measured the force perpendicularly in the thickness direction of the surface layer in the Contact mode Curve (movement speed of cantilever 2 μm / s, maximum indentation load 2 μN).

According to the above measurement method, for the thickness direction of the surface layer, the elastic modulus (E1) at a position (position 1) of 10% from the surface of the surface layer and the elastic modulus (E2) at a position (position 2) of 50% are obtained. ), The elastic modulus (E3) at the 99% position (position 3). Specifically, the laminated film is cut, and the elastic modulus of each position in the thickness direction in the cross section of the surface layer is measured.

[Rupture elongation]

A rectangular shape with a length of 150 mm and a width of 10 mm was cut out of the laminated film in the length direction and the width direction, and used as a sample. The tensile test was performed using a tensile tester (Tensilon UCT-100 manufactured by ORIENTEC), with an initial tension chuck distance of 50 mm and a tensile speed of 10 mm / min. The measurement environment at this time was 23 ° C · 65RH%. At the time of stretching, observe the sample during stretching, and stop visually if a crack (crack) occurs anywhere on the sample (adjust so that the elongation at the time of stopping becomes an integer of 5). The samples to be measured next were collected in order from the elongation at the time of the stoppage, and samples in which the elongation was reduced by 5% units were collected in order, and finally, the elongation at which no breakage occurred at any position of the sample was visually observed.

The film cross section of the fractured portion of the collected sample was cut out, and the cross section was observed with a transmission electron microscope at a magnification of 3,000 times, and the occurrence of cracking of more than 50% of the average thickness of the surface layer was regarded as cracking (there was damage to the surface layer ), And among the samples considered to be cracked, the elongation value of the sample with the lowest elongation is taken as the crack elongation.

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

[Thermoformability]

Using a vacuum forming machine "FORMECH300X" (manufactured by Singko Industries Co., Ltd.) and a far-infrared heater, the obtained laminated film was heated for 1 minute so that the film surface temperature became a predetermined temperature, and a cylindrical mold (bottom surface) was used. 50mm diameter) was vacuum formed to form a laminated film. Furthermore, in order to complete hardening completely, heating was continued for 1 minute so that temperature might become 180-200 degreeC. The degree of molding (deep drawing ratio: molding height / bottom surface diameter) was used in the state where the molding was completed along the mold, and the following criteria were used for evaluation.

Grade A: Formable with a deep draw ratio of 1.0 or more.

Class B: Moldable at a deep draw ratio of 0.6 or more and less than 1.0, but cannot be molded at 1.0 or more.

Class C: Moldable with a deep draw ratio of 0.3 or more and less than 0.6, but cannot be molded with 0.6 or more.

Class D: Only curved surfaces with a deep draw ratio of less than 0.3 are possible, and molding cannot be performed with 0.3 or more.

Grade E: Even if it is only slightly bent, film cracking and rupture occur.

[Surface layer's repeated rub resistance by low hardness material]

The laminated film was placed after 12 hours at temperature 20 ℃ is, in the same environment rubbing abrasion tester in the present light Seisakusho rubber tip end (the front end portion of the area of 1cm ^2), mounted Cashmere fabric [600 Kowa (Unit) manufactured ], A load of 500 g was applied to the laminated film at 5 cm and 5,000 strokes, and a load of 1,000 g was applied to the laminated film at 5 cm and 200 strokes, and the following classification was performed. In addition, measurement was performed on three samples cut from different positions of the same level, and the following classification was performed. The average of the values of the three samples that have been graded is used.

10 points: No scars

7 o'clock: 1 ~ 10 scars

4 points: 11 ~ 20 scars

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

[Self-healing properties of surface layer]

After standing at 20 ° C for 12 hours, the surface of the surface layer was scratched horizontally 5 times with a brass brush (manufactured by TRUSCO) under the same environment. The following load was applied, and then visually judged according to the following criteria Recovery of wounds after 5 minutes of standing. In addition, three samples cut from different positions of the same level were used for measurement, and their average values were used.

10 o'clock: 1kg load without scars

7 o'clock: 1kg of scar will remain, but 700g will not remain.

4 points: The wounds will remain at 700g, but not at 500g

1 point: A flaw remains at a load of 500 g.

[Industrial availability]

The laminated film of the present invention can be used to provide the functions of co-existence of scratch resistance and moldability to the respective surfaces of plastic molded products, home appliances, building or vehicle interior products, and various printed materials.

Claims (7)

A laminated film is a laminated film comprising a surface layer of layers A and B on at least one side of a supporting substrate, and is characterized in that the layers B and A are phased in this order from the side of the supporting substrate. Then, the storage elastic modulus at 25 ° C (hereinafter A _E25 , E _B25 , E _C25 ) and the storage elastic modulus at 120 ° C (the following is E _A120 , E _B120 , and E _C120 ) satisfy the following conditions, condition 1 E _A25 <E _B25 ≦ E _C25 ; condition 2 E _B120 ≦ E _A120 <E _C120 ; condition 3 E _A25 ≦ 100MPa. For example, the laminated film of claim 1, wherein the A layer, the B layer, and the supporting substrate satisfy the following conditions, condition 40 <E _C25 -E _B25 <5GPa; condition 50 <E _A120 -E _B120 <50MPa. For example, the laminated film of claim 1 or 2, wherein the glass transition temperature (hereinafter Tg _B ) of the layer _B satisfies the following conditions, and the condition 6 is 60 ° C ≦ Tg _B ≦ 130 ° C. For example, the laminated film of claim 1 or 2, wherein the thickness of the B layer (hereinafter referred to as T _B ) satisfies the following conditions, condition 7 0.1 μm ≦ T _B ≦ 5 μm. For example, the laminated film of claim 1 or 2, wherein in the cross section of the surface layer perpendicular to the substrate, 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), 50% (Hereinafter referred to as position 2) and 99% (hereinafter referred to as position 3). The elastic modulus of the atomic force microscope E1, E2, and E3 satisfy the following conditions, condition 8 E1 ≦ E2 <E3; condition 9 E1 ≦ 100MPa; condition 10 E3 ≧ 1GPa. A method for manufacturing a laminated film, which is the method for manufacturing a laminated film according to any one of claims 1 to 5, characterized in that the surface layer is sequentially coated on a supporting substrate by applying two or more kinds of coating compositions. The material is formed by drying and hardening. A method for manufacturing a laminated film, which is the method for manufacturing a laminated film according to any one of claims 1 to 5, characterized in that the surface layer is coated with two or more kinds of coating compositions on a supporting substrate simultaneously. The material is formed by drying and hardening.