KR20150113950A - Laminated film - Google Patents

Abstract

A problem to be solved by the present invention is to provide a laminated film which satisfies formability, self-repellency, designability, glossiness, and transparency. The laminated film of the present invention is a laminated film having a surface layer on at least one surface of a supporting substrate, and the surface layer satisfies the following properties 1 to 3.
1. 60% specular gloss specified by JIS Z8741 (1997) is 60% or more
2. The receding contact angle (θ _r ) of oleic acid is 50 ° or more
3. The micro-hardness meter according to claim 1, wherein a maximum displacement in the thickness direction of the layer is 1.0 占 퐉 or more and 3.0 占 퐉 or less when a 0.5 mN load is applied for 10 seconds, and the amount of creep displacement in the thickness direction of the layer is 0.05 占 퐉 or more and 0.5 占 퐉 or less , When the load is released to 0 mN, the amount of permanent displacement of the layer in the thickness direction is 0.2 탆 or more and 0.7 탆 or less

Description

Laminated film {LAMINATED FILM}

The present invention relates to a laminated film excellent in designability and transparency as well as compatibility with moldability and scratch resistance required for a molding material.

In the molding material used for decorative molding or the like, a surface hardening layer is provided to prevent scratches during molding and scratches during use of the molded product. However, in the surface hardening layer, since the elongation following the forming is insufficient, cracking occurs at the time of molding, the film breaks at the extreme case, or the surface hardening layer is peeled off. Therefore, Or molding it in a semi-cured state, and then completely curing it by heating, active ray irradiation or the like is applied. However, since the molded article is processed in three dimensions, it is very difficult to form a surface hardened layer in subsequent processing. In the case of molding in a semi-hardened state, the case of causing mold contamination have. In view of the above, a "self-repairing material" or a "self-healing material" which is able to self-repair a deformation of its own elastic recovery range with scratches of hardness is attracted attention.

Further, among these self-restoration materials, materials capable of recognizing the repair process of scratches can directly recognize the functions thereof. Therefore, when used in an exterior member, the "designability" of the molding material can be increased, It is attracting attention. As the self-repairing or self-healing material as described above, the materials of Patent Documents 1 and 2 have been proposed.

On the other hand, in applications where a strong luster, higher reflectance, and transparency are required particularly in molding materials, fingerprints of a human being come into contact with the surface in everyday life (here, the fingerprint is a line in which the opening of the sweat glands (A ridge formed by a ridge) and a mark attached to the surface of the object) are easily visible, and if it can not be wiped easily, there is a problem that an unpleasant impression is given that the outer appearance is contaminated. In recent years, electronic appliances operated by fingers such as smart phones, touch panels, keyboards, remote controls for television and air conditioners, and the like are increasing. For example, fingerprints are attached by gripping housings of these devices, There is a problem that it is damaged.

With respect to such a problem, a member having the property that the fingerprint is hardly adhered to the surface of the article, is hard to be visually recognized, or that the attached fingerprint can be easily wiped off (hereinafter referred to as " 4.

International Publication No. 2011/136042 Japanese Patent Application Laid-Open No. 11-228905 Japanese Patent Application Laid-Open No. 2009-122416 Japanese Patent Application Laid-Open No. 11-99744

As a result of checking by the inventors of the inventions of Patent Documents 1 and 2 which have been proposed as the above-mentioned self-restoration materials, there is a problem that moldability and self-repairability are excellent, but insufficiency is insufficient.

As a result of the inventors of the present invention, the inventors of the present invention have found that, by satisfying these characteristics, it is possible to prevent the fingerprints from being conspicuous or to wipe off the fingerprints Was insufficient. These materials do not show moldability or self-repellency, and they were impossible to be combined with the techniques of the above-described Patent Documents 1 and 2. [

Therefore, a problem to be solved by the present invention is to provide a laminated film that satisfies formability, self-repellency, designability, glossiness, and transparency.

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have completed the following inventions. That is, the present invention is as follows.

≪ 1 > A laminated film having a surface layer on at least one surface of a support substrate, wherein the surface layer satisfies the following 1 to 3.

1. 60% specular gloss specified by JIS Z8741 (1997) is 60% or more

2. The receding contact angle (θ _r ) of oleic acid is 50 ° or more

3. The micro-hardness measurement method according to any one of claims 1 to 3, wherein a maximum displacement amount in the thickness direction of the surface layer when a 0.5 mN load is applied for 10 seconds is 1.0 占 퐉 or more and 3.0 占 퐉 or less,

The amount of creep displacement in the thickness direction of the surface layer is 0.05 탆 or more and 0.5 탆 or less,

When the load is released to 0 mN, the amount of permanent displacement of the surface layer in the thickness direction is 0.2 탆 or more and 0.7 탆 or less

&Lt; 2 > The laminated film according to < 1 &gt;, wherein the advancing contact angle [theta] _a and the receding contact angle [theta] r of oleic acid in the surface layer satisfy the following formula (1).

(? _{a -} ? _r )? 15? Equation (1)

<3> The laminated film according to <1> or <2>, wherein the oleic acid absorption coefficient (A _b ) of the surface layer is 30 or more.

The oleic acid absorption coefficient A _b means the volume (V ₁ ) determined from the droplet shape at the time of discharging oleic acid from the syringe, the area (S ₁ ) of the adhered portion at the time of deposition, ( ₂ ) from the volume (V ₂ ) after holding for 10 hours in a no-wind condition and the thickness (T) of the surface layer.

A _b = (V ₁ -V ₂ ) / (S ₁ × T) (2)

<4> In the surface layer, F-fragment ions (M / Z = 19) derived from fluorine, which are measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS), are uniformly present in the plane and dimethylsiloxane The laminated film according to any one of <1> to <3>, wherein the Si (CH ₃ ) ⁺ fragment ion (M / Z = 43)

· Exists in island shape

· Exists in a net shape

· Exists in island shape and mesh shape

<5> A semiconductor device according to any one of <1> to <4>, wherein the surface layer has a occupancy rate of 30% or more and 70% or less in a region where Si (CH ₃ ) ⁺ fragment ions derived from the dimethylsiloxane are present &Lt; / RTI &gt;

<6> The color difference ΔE ^* _ab (di: 8 °) Sb10W10 specified by JIS Z8730 (2009) and JIS Z8722 (2009) before and after the simulated fingerprint is attached under the following conditions 0.4 or less Further, the color difference DELTA E ^* _ab (de: 8 DEG) of the specular reflected light removal Sb10W10 is 4 or less.

Simulated fingerprint attachment conditions: A dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 was prepared in the same manner as described in JIS K6253 (1997) with a Ra of 3 占 퐉 as defined in JIS B0601 A rubber rubber having a rubber hardness of 50 specified is attached to 1.0 g / m ² on the silicone rubber and attached to the surface to be treated at 30 kPa.

<7> The laminated film according to any one of <1> to <6>, wherein the surface layer satisfies the following formulas (3) and (4).

K _{0 .5?} 3 Equation (3)

K _{0 .5} -K _10? 1 Equation (4)

here,

_{K 0 .5 = [(ΔE SCI} -0.5) 2 + (ΔE SCE -0.5) 2] 1/2 Equation (5)

K ₁₀ = [(ΔE _{SCI -10} ) ² + (ΔE _{SCE -10} ) ² ] ^1/2 (6)

ΔE _{SCI -0.5} , ΔE _{SCE -0.5} :

On the basis of a state before attaching the simulated fingerprint in the following manner on the surface layer, simulated from the fingerprint adhesion was measured after 30 minutes JIS Z8730 (2009), and ΔE ^* _ab (di specified in JIS Z8722 (2009): 8 ° ) Sb10W10, and? E ^* _ab (de: 8 °) Sb10W10, respectively.

? E _{SCI- 10} ,? E _{SCE -10} :

On the basis of a state before attaching the simulated prints by the above method to the surface layer, ΔE ^* _ab as specified in the JIS Z8730 (2009) and JIS Z8722 (2009) measured after the simulation 10 hours from the fingerprint adhesion (di: 8 °) Sb10W10 and? E ^* _ab (de: 8 °) Sb10W10, respectively.

Simulated fingerprint attachment conditions: A dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 was prepared in the same manner as described in JIS K6253 (1997) with a Ra of 3 占 퐉 as defined in JIS B0601 A rubber rubber having a rubber hardness of 50 specified is attached to 1.0 g / m ² on the silicone rubber and attached to the surface to be treated at 30 kPa.

(8) The median diameter (D _P ) calculated from the area reference frequency distribution of the remains formed when the simulated fingerprint is attached to the surface layer in the following manner satisfies the following expressions (7) and The laminated film according to any one of < 1 > to < 7 >

D _{P0 .5} &amp; le; 80 mu m Equation (7)

_{(D P0 .5 -D P10) /} D P0 .5 ≥0.5 (8)

D _{P0 .5:} a median diameter calculated from the area-based frequency distribution of remains that makes up a mock fingerprint measurement after 30 minutes from the attachment of the mock fingerprint

D _P10 : the median diameter calculated from the area reference frequency distribution of the remains constituting the simulated fingerprint measured 10 hours after the above-mentioned simulated fingerprint is attached

Simulated fingerprint attachment conditions: A dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 was prepared in the same manner as described in JIS K6253 (1997) with a Ra of 3 占 퐉 as defined in JIS B0601 A rubber rubber having a rubber hardness of 50 specified is attached to 1.0 g / m ² on the silicone rubber and attached to the surface to be treated at 30 kPa.

<9> The simulated fingerprint attachment and the simulated fingerprint wipe test are performed on the surface layer under the following conditions and the simulated fingerprint is wiped based on the state before the simulated fingerprint is obtained according to JIS Z8730 (2009) and JIS Z8722 (2009) The color difference ΔE ^* _ab (di: 8 °) Sb10W10 (hereinafter referred to as ΔE _{SCI- 2} ) including the regular reflection light after the stamina test and the color difference ΔE of the regular reflection light removal after the simulated fingerprint wiping test _{^{* ab (de: 8 °)}} Sb10W10 ( since, ΔE _{SCE -2} &quot;) which is characterized by satisfying the following formula (9), <1> to <8> in which the laminated film according to one of the preceding.

(? E _{SCI -2} ) ² + (? E _{SCE -2} ) ² ? ^{1/2? 2.0} Equation (9)

Condition of simulated fingerprint attachment and simulated fingerprint wipe test

- Simulated fingerprint attachment conditions: The dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 has a Ra of 3 占 퐉 as defined by JIS B0601 (2001), and JIS K6253 (1997) In which 1.0 g / m &lt; ² &gt; is adhered to a silicone rubber having a rubber hardness of 50 specified in Table 1, and the surface of the silicone rubber is adhered to the surface at a pressure of 30 kPa.

· Simulated fingerprint wipe condition: The simulated fingerprint attached with the above conditions was rubbed 3 times at a pressure of 30 kPa at a rate of 5 cm / sec with a nonwoven fabric

<10> The laminated film according to any one of <1> to <9>, wherein the resin contained in the surface layer has the following (1) to (3).

(1) a (poly) caprolactone segment,

(2) a urethane bond,

(3) a segment containing 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 (hereinafter referred to as a fluorine compound segment)

<11> The laminated film according to <10>, wherein the fluorine compound segment is a fluoro polyether segment.

<12> The laminated film according to <10> or <11>, wherein the resin contained in the surface layer has (4) a (poly) siloxane segment and / or a polydimethylsiloxane segment.

INDUSTRIAL APPLICABILITY According to the present invention, a laminated film satisfying formability, self-repellency, designability, glossiness, and transparency can be obtained.

Fig. 1 is a weighted-indentation depth chart when a press-in load / unload test is performed on a laminated film of the present invention using a regular triangular pyramid. Fig.
2 is an example of a case where Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane exist in an island shape in the laminated film of the present invention.
3 is an example of a case where Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane exist in a mesh shape in the laminated film of the present invention.
4 is an example of the case where Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane exist in an island shape and a net shape in the laminated film of the present invention.

The laminated film of the present invention is a laminated film having a surface layer on at least one surface of a supporting substrate in order to satisfy the above problems, that is, the formability, self-reproductivity, designability, glossiness, It is preferable that the maximum displacement amount, the creep displacement amount, and the permanent displacement amount when releasing the load satisfy the following specific range.

From the viewpoints of moldability, self-repairability, and designability, the laminated film of the present invention has a maximum displacement amount in the thickness direction of the surface layer of 1.0 m or more and 3.0 m or less when a 0.5 mN load is applied for 10 seconds in the microhardness measurement, The thickness of the surface layer in the thickness direction when the load is released to 0 mN and the amount of creep displacement in the thickness direction of the surface layer is 0.05 탆 or more and 0.5 탆 or less, more preferably 0.2 탆 or more and 0.5 탆 or less, The displacement amount is 0.2 탆 or more and 0.7 탆 or less, and more preferably 0.4 탆 or more and 0.65 탆 or less.

If the maximum displacement amount in the thickness direction of the surface layer is larger than 3.0 mu m, the self-repairing property of the surface layer may become incomplete. When the maximum displacement amount in the thickness direction of the surface layer is smaller than 1.0 mu m, the designability of the surface layer, May be worse.

Even when the amount of creep displacement in the thickness direction of the surface layer is larger than 0.5 占 퐉 or smaller than 0.05 占 퐉, the self-repairing property or the design property may become incomplete.

If the permanent displacement amount in the thickness direction of the surface layer is larger than 0.7 mu m, visible scratches may occur even after self-repair of the surface layer, resulting in deterioration of the appearance. From the viewpoint of self-restorability of the surface layer, the smaller the smaller the amount of permanent displacement, the better. However, since the self-restoring material is usually subjected to plastic deformation, the lower limit of the amount of permanent displacement is considered to be 0.2 탆 in this measuring method. A method of measuring the maximum displacement amount, the creep displacement amount, and the permanent displacement amount in the thickness direction of the measurement of the microhardness meter will be described later.

From the viewpoint of luster, the laminated film of the present invention preferably has a specular glossiness in a specific range, and is a value measured by 60 占 specular gloss specified by JIS Z8741 (1997), preferably 60% or more , More preferably 70% or more, and particularly preferably 80% or more. If the specular gloss is less than 60%, the glossy feeling may be felt to be insufficient. The upper limit of the mirror surface gloss varies depending on the refractive index of the material, but is about 180% when a general material is used.

From the viewpoint of transparency, the laminated film of the present invention preferably has a receding contact angle? _R of oleic acid to the surface layer of 50 ° or more, more preferably 55 ° or more, and particularly preferably 60 ° or more.

The method and the meaning of the receding contact angle will be described later. There is no problem in that the receding contact angle is high. On the other hand, when the receding contact angle is lower than 50 deg., The fingerprint component tends to adhere slowly,

It is also preferable that the relation between the advancing contact angle? _A and the receding contact angle? _R of the fingerprint component of the surface layer satisfies the above-mentioned formula (1), particularly regarding the emotion, particularly the fingerprint wipeability.

(? _{a -} ? _r )? 15? Equation (1)

This is because the fingerprint polishability is governed by two factors of "ease of transfer to the material to wipe the fingerprint composition" and "ease of movement of the fingerprint composition on the surface layer", and the former is referred to as a receding contact angle, (1), which means that the attached fingerprints can be easily wiped off.

It is preferable that the advancing contact angle? _A and the receding contact angle? _R of the oleic acid in the surface layer satisfy the above formula (1), that is, 15 ° or less, more preferably 12 ° or less, desirable. If the value of the formula (1) is 0 or a positive value, it is preferable that the value be smaller. On the other hand, if the value is larger than 15, the wipeability of the fingerprint is insufficient.

Here, the receding contact angle and the forward contact angle will be described. The contact angle of the liquid on the solid surface is originally a thermodynamic quantity and takes one value when the system is determined. However, in practice, when the liquid moves the solid surface, the contact angle of the advancing direction and the contact angle of the opposite side (retreat side) do not take the same value in many cases. At this time, the contact angle of the traveling method is referred to as a forward contact angle, and the contact angle on the opposite side is referred to as a backward contact angle.

The value of the advancing contact angle and the retreating contact angle are values by several measuring methods, but the value by the expansion-contraction method is preferable. As another method, there is a tilting angle method. However, this method requires a mass of liquid droplet in the calculation of the advancing contact angle and the receding contact angle, and also requires a large remnant (the diameter is 1 to 20 mu m) (Several millimeters or more), it is not suitable because a phenomenon different from an actual fingerprint attachment is observed.

Here, the measurement by the expansion-contraction method will be described. The value of the advancing contact angle by the expansion-contraction method is represented by an average value of a point at which the contact angle is fixed by continuously measuring the contact angle of the liquid droplet plural times when a liquid (oleic acid) is added to the surface layer to expand the liquid droplet. Likewise, the value of the receding contact angle is obtained by continuously applying a liquid (oleic acid) on the surface layer to gradually expand the liquid droplet to expand the liquid droplet, and then sucking the liquid droplet to shrink the liquid droplet, , And the contact angle is expressed as an average value at a predetermined point. Specifically, for example, when the liquid is ejected-sucked (droplet is shrunk) between 1 and 50 μL, the advancing contact angle is between 1 μL and 50 μL at the time of ejecting the droplet, and the receding contact angle is 50 μL To 1 μL at 1 μL intervals and determine the value at which the contact angle of the liquid droplet is almost constant during expansion or contraction of the liquid. The contact angle in the expansion shrinkage method can be measured using, for example, Drop Master (manufactured by Kyowa Chemical Co., Ltd.).

From the viewpoint of achieving both self-restoration performance and good weatherability, it is preferable that the oleic acid absorption coefficient (A _b ) of the surface layer of the laminated film of the present invention is 30 or more.

This not only reduces the adherence amount of the fingerprint component due to the above-mentioned height of the receding contact angle _r , but also removes the adhered fingerprint component from the surface by absorbing the adhered fingerprint component. The index indicating the ability is an oleic acid absorption coefficient A _b ). Specifically, it is calculated from the volume and adhesion area of the oleic acid adherent immediately after adhesion, the volume of the oleic acid adhering after a certain period of time, and the thickness of the surface layer of the molding material, and the oleic acid absorption coefficient per unit volume A _b ) is preferably 30 or more, more preferably 40 or more.

On the other hand, the oleic acid absorption coefficient (A _b ) of the surface layer is preferably high in view of the water absorbency of the fingerprint component, but is preferably 200 or less from the viewpoint of reducing the adhesion amount and enhancing the overall feeling.

A specific measuring method of the oleic acid absorption coefficient (A _b ) is a method of dropping about 2 μl of oleic acid into the surface layer of the thickness (T), measuring the volume (V ₁ ) obtained from the droplet shape at the time of discharging from the syringe, Refers to a dimensionless amount obtained by the following formula (2) from the area (S ₁ ), the volume (V ₂ ) after holding at 25 ° C for 10 hours in a no-wind condition.

A _b = (V ₁ -V ₂ ) / (S ₁ × T) (2)

Here, there are several measurement methods for V ₁ , V ₂ , and S _1. For example, the measurement can be performed by a contact angle measuring apparatus DM500 and a simulation analysis software DropMaster by Kyowa Kaimagawa Kagaku Kabushiki Kaisha. Details of the measurement will be described later. A method of measuring the thickness (T) of the surface layer will also be described later.

In addition, it is preferable that the surface layer expressing such characteristics exists in a specific form in both the oil-repellent material and the lipophilic material on the outermost surface. More specifically, F ^- fragment ions (M / Z = 19) derived from fluorine, which is measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) It is preferable that Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane exist in an island shape, exist in a net shape or exist in an island shape and a net shape, It is more preferable that the F ^- fragment ion is &quot; uniformly present &quot; in the plane and the Si (CH ₃ ) ⁺ fragment ion exists in the island shape and mesh shape.

This is because, in order for the surface layer of the present invention to exhibit the property of minimizing the adherence amount of the fingerprint component and absorbing the attached fingerprint component from the surface by absorbing the adhered fingerprint component into the coating film, The amount of adhesion of the fingerprint component is reduced and the compound containing the dimethylsiloxane as a hydrophilic residue is present in a fine island shape or a net shape, It is thought that the fingerprint is diffused into the surface and the surface layer through a lipophilic portion existing in an island shape or a net shape present in the fingerprint image. A method for measuring the outermost surface layer of the surface layer by the time-of-flight secondary ion mass spectrometer (TOF-SIMS) will be described in the section of the embodiment.

The term &quot; uniformly present &quot; as used herein refers to a variation coefficient of the secondary ion intensity at the entire measurement point measured by a flight time type secondary ion mass spectrometer in a range of 100 μm × 100 μm at a height of 128 points × width of 128 points Is within 0.4.

As shown in Fig. 2, when the secondary ion intensity of the measurement point Si (CH ₃ ) ⁺ is plotted, the "existence in island shape" means that the secondary ion intensity of the measurement point does not reach the boundary value corresponding to 20% (Except that it is caught on the outer periphery of the drawing). Details of the boundary values will be described later. In reality, the upper limit of the size of the islands is assumed to be accommodated within the measurement range by the flying time type secondary ion mass spectrometer. Under the measurement conditions described above, the islands having a diameter of 50 탆 or less are considered as islands. On the other hand, the lower limit of the size is not particularly limited as long as it can be distinguished by the above conditions, but it actually depends on the spatial resolution of the measuring apparatus, and is about 0.8 mu m in the above-described measurement conditions.

As shown in FIG. 3, when the secondary ion intensity of the Si (CH ₃ ) ⁺ fragment is shown, the region existing below the above-mentioned boundary value exists in an island shape.

"Present in an island shape and the mesh shape" means, when it shows a secondary ion intensity of Si (CH ₃₎ ⁺ fragment 4, present in an area and the mesh shape is present in the island-like in the measuring range Indicates that all of the areas are present. It is more preferable that the presence of the Si (CH ₃ ) ⁺ fragment ion exists in the form of islands and meshes. This is because, compared with the case of "exists in an island shape" Direction, and is superior in the capability of reducing the adhesion amount of the fingerprint contamination as compared with the case of "present in a net shape".

The occupancy of the region in which Si (CH ₃ ) ⁺ fragment ions derived from the dimethylsiloxane is present is preferably 30% or more and 70% or less, more preferably 30% or more and 50% or less, more preferably 30% or more and 40% Is particularly preferable. Here, the occupancy rate refers to a ratio of a point where Si (CH ₃ ) ⁺ fragment ions are present in a boundary value or more among all the measurement points. To describe in further embodiment for the method of calculating the share, when the Si (CH ₃₎ ⁺ region of the fragment ions are present (in other words derived from dimethyl siloxane, which is Si (CH ₃₎ ⁺ fragment ions derived from dimethylsiloxane present Is less than 30%, the ability to absorb the attached fingerprint component into the coating film is insufficient, and the disappearance of fingerprint contamination may be lowered. On the other hand, when the ratio exceeds 70%, the adhesion amount of fingerprint contamination is reduced May be deteriorated.

In addition, it is also possible to use a distribution map that is distributed on any straight line perpendicular or parallel to the direction of the sides of the diagram (for example, Figs. 2 and 3) showing the secondary ion intensity of the &quot; mapping diagram &quot; (Si (CH ₃ ) , And Si (CH ₃ ) ⁺ fragment ions are each preferably divided into 30 탆 or less, more preferably 20 탆 or less. If the value exceeds the above value, the ability to reduce the adhesion amount of fingerprint contamination may be lowered. On the other hand, the lengths of the line segments in which the Si (CH ₃ ) ⁺ fragment ions do not reach the boundary value on the same straight line are preferably divided into 50 탆 or less, more preferably 30 탆 or less. If it exceeds the above value, the ability to absorb the attached fingerprint component into the coating film is insufficient, and the disappearance of the fingerprint contamination may be lowered in some cases. Further, the lower limit of the length is not particularly limited if it can be classified by the above conditions, but it actually depends on the spatial resolution of the measuring instrument, and is estimated to be about 0.8 mu m in the above-described measurement conditions.

On the other hand, in order to solve the problems of the present invention, in addition to the mechanical and surface scientific properties of the surface layer described above, the optical characteristics when the simulated fingerprints close to the actual fingerprint composition are adhered to the surface layer under certain conditions under the following specific conditions , It is preferable that the color difference including regularly reflected light before and after attachment of the simulated fingerprint and the color difference of regularly reflected light removal are within a specific range.

Here, the "color difference including regularly reflected light" refers to a color difference measured in "a condition including a component that becomes specular reflection from a specimen in geometric condition (c)" described in JIS Z8722 (2009) Refers to a chrominance difference measured in a condition except for a component that becomes mirror-surface reflection from the sample under the geometric condition (c).

Concretely, the color difference (? E ^* _ab (di: 8 °) Sb10W10) including the regularly reflected light specified by JIS Z8730 (2009) and JIS Z8722 , More preferably 0.2 or less, and particularly preferably 0.1 or less. Since it is a color difference before and after a simulated fingerprint, it is preferable that the color difference is small, but when it is adhered under the same conditions, the lower limit is about 0.01 from the limit of the material and the limit of the measurement method. The chrominance difference (ΔE ^* _ab (de: 8 °) Sb10W10) of the regularly reflected light removal specified in JIS Z8730 (2009) and JIS Z8722 (2009) is preferably 4 or less, More preferably 3 or less, and particularly preferably 2 or less. Since it is a color difference before and after a simulated fingerprint, it is preferable that the color difference is small, but when it is adhered under the same conditions, the lower limit is about 0.05 from the limit of the material and the limit of the measurement method. If the color difference of the regular reflection light before and after the simulated fingerprint attachment and the color difference of the regular reflection light removal before and after the simulated fingerprint attachment are 0.4 and 4 respectively, the fingerprint attachment trace may be clearly recognized. The procedure of the specific simulated fingerprint transfer is as follows.

Simulated fingerprint attachment conditions: A dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 was prepared in the same manner as described in JIS K6253 (1997) with a Ra of 3 占 퐉 as defined in JIS B0601 1.0 g / m &lt; ² &gt; is attached to a specified silicone rubber having a rubber hardness of 50, and this is attached to the surface to be treated at 30 kPa.

In the molding material of the present invention, it is preferable that the color difference including the regularly reflected light and the regularly reflected light removed before and after the attachment of the simulated fingerprint is set to a specific value or less, and the amount of decrease in the chromatic aberration over time is set to a specific value or more . This corresponds to the effect that the surface layer absorbs the fingerprint component as described above. Specifically, it is as follows.

First, with respect to the color difference of the simulated fingerprint adhesion before and regularly reflected light including the color difference and the regularly reflected light of the removal of the adhesion immediately after, the parameter K _{0 .5} represented by the following formula (5) is more preferable than the preferred, more than 23 . If the value is more than 3, a trace of fingerprint attachment tends to be visible, and it may be difficult to obtain sufficient penetration effect of the above-mentioned fingerprint.

_{K 0 .5 = [(ΔE SCI} -0.5) 2 + (ΔE SCE -0.5) 2] 1/2 Equation (5)

Here, the ΔE _{SCI -0.5} indicates the color difference before and after attachment of the simulated fingerprint, and indicates the color difference (ΔE ^* _ab (di: 8 °) Sb10W10) including regularly reflected light specified by JIS Z8730 (2009) and JIS Z8722 , And ΔE _{SCE -0.5} are the color differences before and after attachment of the simulated fingerprint, and indicate the color difference (ΔE ^* _ab (de: 8 °) Sb10W10) of regularly reflected light removal.

? E ^* _ab (di: 8?) Sb10W10 and? E ^* _ab (de: 8 °) Sb10W10 are physical quantities having equivalent dimensions and correspond to distances from the origin in a two- to reduce the parameter K _{0 .5} corresponds to reducing the visibility of fingerprints before and after simulated fingerprint adhesion. Also it may be said that the smaller is the parameter K _{0 .5} excellent in anti-fingerprint adhesion, in the material of this invention having a high gloss and clarity to a problem, in order to recognize the change with time exceeds the effect of which will be described later prints 1 It is realistic to do.

Immediately after the above-mentioned simulated fingerprint attachment means 30 minutes after the simulated fingerprint is attached to the surface of the molding material by the following method of attaching the simulated fingerprint.

In addition, the amount of decrease in the chronological decline of the color difference before and after the above-mentioned simulated fingerprint attachment, that is, the value of the left side of the following formula (4) is preferably 1 or more, and more preferably 1.2 or more. If the value of the left side of the following formula (4) is less than 1, it may be difficult to obtain a loss of fingerprint contamination.

K _{0 .5} -K _10? 1 Equation (4)

K _{0 .5,} where in the formula (4) is as described above, K ₁₀ is expressed by equation (6) below.

K ₁₀ = [(ΔE _{SCI -10} ) ² + (ΔE _{SCE -10} ) ² ] ^1/2 (6)

The ΔE _{SCI- 10} in the equation (6) is the color difference after standing for 10 hours under the condition of 25 ° C. and no wind for 10 minutes before the simulated fingerprint is attached and after the simulated fingerprint is attached, and is the regular reflection light specified by JIS Z8730 (2009) and JISZ8722 point ^{to: (8 °) Sb10W10 ΔE *} ab (di), ΔE SCE -2 , the color difference of the regular reflection of the removal of the same color difference samples including: refers to a _{^{(ΔE * ab (de 8 °}} ) Sb10W10).

The surface layer exhibiting such characteristics shows the characteristic shape and the behavior at a time when the fingerprint component is attached. One is preferable that the size of the remains constituting the simulated fingerprint on the molding material of the present invention is small. This is because the visibility of the fingerprint is increased as the area occupied by the portion of the surface of the molding material on the surface of the molding material increases. Therefore, by using the projection of the surface of the molding material in the direction of the surface of the molding material, The shape of the ruins can be evaluated with the distribution of the area reference frequency that has been applied. In the area reference frequency distribution, the diameter at which the cumulative frequency becomes N% of the whole is denoted by D _N. Among them, the diameter of N = 50 is particularly called the median diameter (hereinafter referred to as D _P ). In the present invention, it preferred that the median diameter (D _{P0 .5)} calculated from the area-based frequency distribution remains immediately after the simulated fingerprint adhesion 80㎛ or less, and more preferably not more than 70㎛, particularly preferably not more than 50㎛ . If this value is exceeded, the fingerprint may be easily visible from scattering of light due to the ruins. _.5 D _P0 is because no visible fingerprints The smaller the value, the lower limit value does not exist, but is particularly difficult in the point of view of view of a fingerprint, while when the number is less than 100nm, the surface remains or agglomeration by the free energy, or Volatilizing, the liquid droplet of 100 nm or less is practically absent.

Further, after the simulated fingerprint attachment, 25 ℃, no wind, when as a 10-hour median size of the remains to be calculated from the area-based frequency distribution of a copper material surfaces value under the condition D _P10, median diameter immediately after the fingerprint for the change-in-time simulation attachment the median size normalized value to _{(D P0 .5), (D} P0 .5 -D P10) / D P0 .5 , there is a preferred value. Specifically, this value is preferably 0.5 or more, and particularly preferably 0.6 or more. If this value is less than 0.5, the fingerprint may remain in a state in which the fingerprint remains visible even after a lapse of time. In addition, the simulated fingerprints were attached and then wiped off in a similar manner as described above, and the reflection color before and after attachment was measured by two methods of regular reflection light removal and regular reflection light removal, It is preferable that the color difference after wiping satisfies the above-mentioned formula (9) in terms of fingerprint wipe. This is based on the fact that the human eye recognizes the contamination caused by the fingerprint or the fingerprint by the change of the glossiness and the change of the color and the change of the glossiness is corrected by the color difference including the regular reflection light, , And it is found that it becomes difficult to recognize the fingerprint in a range that satisfies Expression (9) in which these values are integrated.

Specifically, the simulated fingerprint attachment and the simulated fingerprint wiping test are performed on the surface layer under the following conditions, and the simulated fingerprint based on the state before the simulated fingerprint is obtained in accordance with JIS Z8730 (2009) and JIS Z8722 (2009) wipe the color difference of the regularly reflected light after the test include: color difference _{^{(ΔE * ab (di 8 °}} ) Sb10W10) = ΔE SCI -2 and simulated wiping simulating fingerprint with fingerprints attached relative to the state prior to the regularly reflected light removal after the test (ΔE ^* _ab (de: 8 °) to satisfy the Sb10W10) = ΔE _SCE-2 has the following formula (9), that is, the formula (9), the left side is larger than 2.0 is preferable, and 1.7 to less are more preferred 1.5 or less in the Particularly preferred. If the value of the left side of the equation (9) is 0 or a positive value, there is no problem to be small. On the other hand, if this value is larger than 2.0, the wipeability of the fingerprint is insufficient.

(? E _{SCI -2} ) ² + (? E _{SCE -2} ) ² ? ^{1/2? 2.0} Equation (9)

Here, the simulated fingerprint attachment condition is as described above, and the conditions of the simulated fingerprint wipe test are as follows.

- Simulated fingerprint wiping condition: The simulated fingerprint attached with the above conditions is rubbed with nonwoven fabric three times at a pressure of 30 kPa and a speed of 5 cm / sec.

In addition to the above mechanical, surface scientific and optical characteristics, it is preferable that the resin contained in the surface layer of the laminated film of the present invention has the following (1) to (3).

(1) a (poly) caprolactone segment,

(2) a urethane bond,

(3) a segment containing 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 (hereinafter referred to as a fluorine compound segment). Here, the term &quot; resin &quot; refers to a substance comprising a polymer compound, and the range includes a range from a polymer to an oligomer.

The (1) (poly) caprolactone segment indicates the segment represented by the formula (1), and the (2) urethane bond indicates the bond represented by the formula (2). And n is an integer of 1 to 35 in the general formula (1).

Details of the above (1) (poly) caprolactone segment, (2) urethane bond and (3) fluorine compound segment will be described later. (1) has a function of enhancing self- (3) reduces the surface energy, thereby raising the contact angle of the liquid constituting the fingerprint to reduce the adhesion amount.

More preferably, the fluorine compound segment is a fluoropolyether segment. The fluoropolyether segment is a segment including a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group and the like, and is a structure represented by the following formulas (3) and (4).

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

The details of the fluoropolyether segment will be described later, and the surface layer contains the fluoropolyether segment so that molecules exhibiting low surface energy on the outermost surface can be present at a high density.

The chain length of the fluoropolyether segment has a preferable range, and the number of carbon atoms is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. When the number of carbon atoms is 3 or less, the surface energy is not sufficiently lowered, and the oil repellency is sometimes lowered. When the number of carbon atoms is 13 or more, the solubility in a solvent is lowered.

The resin contained in the surface layer of the laminated film of the present invention preferably has (4) a (poly) siloxane segment and / or a polydimethylsiloxane segment. The (poly) siloxane segment refers to a segment represented by the general formula (5). The (poly) dimethylsiloxane segment refers to a segment represented by the formula (6).

R ₁ is either OH or an alkyl group having 1 to 8 carbon atoms. R ₂ is either OH or an alkyl group having 1 to 8 carbon atoms. and n is an integer of 100 to 300. [

m is an integer of 10 to 300;

The details of the (poly) siloxane segment and / or the polydimethylsiloxane segment will be described later. The surface layer has these segments, thereby improving the heat resistance and weather resistance and improving the scratch resistance due to the lubricity of the surface layer. Hereinafter, embodiments of the present invention will be described in detail.

[Laminated film and surface layer]

The laminated film of the present invention may be any of a plane shape (film, sheet, plate) and a three-dimensional shape (molded article) provided that it has a surface layer showing the characteristics of the present invention. Here, the surface layer in the present invention refers to a region adjacent to the thickness direction or the inward direction from the surface of the laminated film in the thickness direction (in the case of a planar shape) or inward direction (in the case of a three- It can be distinguished by having a boundary surface in which the shape and physical characteristics of water (particles, etc.) are discontinuous, and indicates a region having a finite thickness. More specifically, when the above-mentioned laminated film is observed from the surface in the thickness direction by various composition / element analysis devices (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscope (transmission type, scanning type) And is distinguished by the discontinuous interface.

The surface layer can be used for various purposes such as antireflection, antistatic, antifouling, conductivity, heat ray reflection, near-infrared ray absorption, electromagnetic wave shielding, and easy adhesion in addition to the moldability, designability, self- Function.

The thickness of the surface layer is not particularly limited, but is preferably from 5 탆 to 200 탆, more preferably from 10 탆 to 100 탆, and the thickness can be selected in accordance with the above-described other functions.

[Paint composition]

The laminated film of the present invention can be obtained by forming the above-described surface layer through a general coating process including coating, drying and curing the coating composition on a support substrate described later.

This coating composition contains at least the above-mentioned (poly) caprolactone segment, a urethane bond, a resin containing a fluorine compound segment, or a material capable of forming them in an application process (hereinafter referred to as a precursor) , The resin contained in the surface layer may have this segment.

In order to obtain the laminated film of the present invention, there are two types of coating compositions preferable for forming the surface layer on the supporting substrate.

The first type is a coating composition (hereinafter, referred to as a coating composition A) which preferably contains at least the following materials. In the curing step of the coating process, curing by heat or curing by heat and curing by an active energy ray Is a preferred coating composition.

· Fluorine compound D

Polycaprolactone polyol A or polycaprolactone polyol copolymer A

Compounds containing an isocyanate group

That is, the coating composition A is prepared by mixing a poly (caprolactone polyol A) or a polycaprolactone polyol copolymer A as a (poly) caprolactone segment, a compound containing the polyol and an isocyanate group as a precursor for forming a urethane bond as a fluorine compound segment And a fluorine compound D. Details of each of these materials will be described later.

The coating composition A preferably contains 11 mass% or more and 22 mass% or less of the isocyanate group-containing compound in a total solid concentration of 100 mass%. The coating composition A may also contain other crosslinking agents such as a melamine crosslinking agent such as alkoxymethylol melamine, an acid anhydride crosslinking agent such as 3-methyl-hexahydrophthalic anhydride, and an amine crosslinking agent such as diethylaminopropylamine Do. A crosslinking catalyst such as dibutyltin dilaurate or dibutyltin diethylhexate may be used in order to accelerate the reaction for forming a urethane bond, if necessary. Further, it is preferable to contain a polysiloxane and a polydimethylsiloxane which will be described later, and may also contain various additives such as a solvent, a photopolymerization initiator, and a leveling agent.

The second type is a coating composition (hereinafter referred to as a coating composition B) which preferably contains at least the following materials, and is preferably a coating composition which is preferably cured by an active energy ray in the curing step of the coating process , It has not only solved the problems of the present invention described above but also has an excellent resistance to contamination by cosmetics containing a preservative component such as a hand cream and the like (hereinafter referred to as cosmetic resistance) compared to the coating composition A .

· Fluorine compound D

Urethane (meth) acrylate B

Urethane (meth) acrylate C

That is, the coating composition B is a coating composition comprising at least one of urethane (meth) acrylate B and urethane (meth) acrylate C, a polycaprolactone segment described later, both of which contain a urethane bond, and the fluorine compound D is a fluorine compound segment .

The urethane (meth) acrylate B is excellent in self-repellency and the urethane (meth) acrylate C is a material having excellent cosmetic resistance. Specifically, the urethane (meth) acrylate B ) Are materials exhibiting specific properties, and by having these properties, self-restoration and cosmetic resistance are both achieved. The constituent materials of the above-mentioned coating composition will be described later.

The content ratio of urethane (meth) acrylate B and urethane (meth) acrylate C in coating composition B: (mass of urethane (meth) acrylate B / mass of urethane (meth) acrylate C) A range of 30/70 is preferred. The content ratio of urethane (meth) acrylate B and urethane (meth) acrylate C: mass of urethane (meth) acrylate B / mass of urethane (meth) acrylate C is 70/30 to 30/70 Outside the range, it may be difficult to achieve both self-restoration and cosmetic properties.

The coating composition B preferably contains polysiloxane, polydimethylsiloxane, polyalkylene glycol, and may further contain various additives such as a solvent, a photopolymerization initiator, a curing agent, and a catalyst.

[Supporting substrate]

The resin constituting the supporting substrate used in the laminated film of the present invention may be either a thermoplastic resin or a thermosetting resin, or may be homopolymerized or copolymerized or two or more blends. More preferably, the resin constituting the support base material is preferably a thermoplastic resin because of its good moldability.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polystyrene and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins, A fluororesin such as a polyvinylidene fluoride resin, a polyvinylidene fluoride resin, a polyvinylidene fluoride resin, a polyvinylidene fluoride resin, a polyvinylidene fluoride resin, a polyvinylidene fluoride resin, a polyvinylidene fluoride resin, Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is more preferably a polyester resin in view of strength, heat resistance and transparency.

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

In addition, the supporting substrate is preferably provided with various additives such as an antioxidant, an antistatic agent, a nucleating agent, an inorganic particle, an organic particle, a scoring agent, a heat stabilizer, a lubricant, an infrared absorber, an ultraviolet absorber, . The supporting substrate may be a single layer structure or a laminated structure.

The surface of the support substrate may be subjected to various surface treatments before forming the 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, glow discharge treatment, ultraviolet ray irradiation treatment, corona discharge treatment and flame treatment are preferable, and glow discharge treatment and ultraviolet ray treatment are more preferable.

[Fluorine compound segment, fluorine compound D]

In the present invention, it is preferable that the resin contained in the surface layer has a fluorine compound segment. The fluorine compound segment refers to a segment including at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group.

Here, a part of hydrogen contained in the alkyl group, oxyalkyl group, alkenyl group, alkanediyl group, oxyalkanediyl group, fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoroalkanediyl group, fluorooxyalkanediyl group, , Or both of them are fluorine-substituted substituents, all of which are mainly substituents composed of fluorine atoms and carbon atoms, may be branched in the structure, and may form a dimer, trimer, oligomer or polymer structure in which a plurality of these substituents are connected .

As the fluorine compound segment, a fluoropolyether segment is preferable, and it is a substituent group including a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group and the like, more preferably a fluoroalkyl group represented by the general formula The fluoropolyether segment is as described above.

In order for the resin contained in the surface layer to contain the fluorine compound segment, it is preferable that the above-mentioned coating composition A or the coating composition B contains the fluorine compound D. The fluorine compound D is a compound represented by the general formula (7).

Here, R ^f1 represents a fluorine compound segment, R ² represents an alkanediyl group, an alkanetriyl group, and an ester structure derived therefrom, a urethane structure, an ether structure and a triazine structure, and D ¹ represents a reactive site.

This reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such reactive sites include a silanol group in which an alkoxysilyl group and an alkoxysilyl group are hydrolyzed, a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group from the viewpoint of reactivity. Among them, a vinyl group, an allyl group, an alkoxysilyl group, a silyl ether group or a silanol group, an epoxy group and an acryloyl (methacryloyl) group are preferable from the viewpoints of reactivity and handling property.

An example of the fluorine compound D is a compound represented by the following formula. 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3- Perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluoroethoxy silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltrichlorosilane, 2-perfluorooctyl isocyanate silane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-tetrafluoroethoxy silane, Perfluorobutyl acrylate, 2-perfluorobutyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl- 2-hydroxypropyl acrylate, 2-perfluorooctyl ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate Perfluoro-3-methylbutyl ethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro Perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetra Hexafluorobutyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl acrylate, hexafluorobutyl acrylate, hexafluorobutyl acrylate, Perfluorobutyl methacrylate, 2-perfluorobutyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluoro Octyl ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate Perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2- Perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2- Hexafluoropentyl methacrylate, perfluoro-6-methyl octyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl Methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononyl-pentaerythritol, and the like.

The fluorine compound D may have a plurality of fluoropolyether segments per molecule.

Examples of the fluorine compound D commercially available include RS-75 (DIC Corporation), Optol DAC-HP (Daikin Kogyo Kabushiki Kaisha), C10GACRY and C8HGOL (Yasegawa Kasei Co., Ltd.) Products are available

[(Poly) caprolactone segment]

In the laminated film of the present invention, it is preferable that the resin contained in the surface layer has a (poly) caprolactone segment. Here, the (poly) caprolactone segment refers to the segment represented by the above-described formula (1). Further, the surface layer may have a (poly) caprolactone segment by forming a surface layer using a coating composition A or a coating composition B containing a resin containing a (poly) caprolactone segment.

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

As the resin containing the (poly) caprolactone segment, (poly) caprolactone having a hydroxyl group of 2 to 3 functional groups is particularly preferable. Specifically, (poly) caprolactone diol represented by the general formula (8)

(Wherein m + n is an integer from 4 to 35, and R is C ₂ H ₄ or C ₂ H ₄ OC ₂ H ₄ )

(Poly) caprolactone triol represented by the formula (9)

(CH ₂ ) ₃ , CH ₃ CH ₂ C (CH ₂ ) ₃ , and the like, wherein L + m + n is an integer from 3 to 30, and R is CH ₂ CHCH ₂ , CH ₃ C

(Poly) caprolactone-modified hydroxyethyl (meth) acrylate represented by Chemical Formula 10

(Wherein, n is an integer from 1 to 25, R is H or CH ₃₎

Can be used as the active energy ray-polymerizable caprolactone.

Herein, the term "active energy ray polymerization" refers to a property of crosslinking by an active energy ray such as UV or EB, and corresponds to a compound having a functional group such as a (meth) acrylate group. Examples of other active energy ray-polymerizable caprolactone include (poly) caprolactone-modified hydroxypropyl (meth) acrylate and (poly) caprolactone-modified hydroxybutyl (meth) acrylate.

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

In the present invention, the weight average molecular weight of the (poly) caprolactone segment in the resin containing the (poly) caprolactone segment is preferably 500 to 2,500, and more preferably 1,000 to 1,500. When the weight average molecular weight of the (poly) caprolactone segment is 500 to 2,500, it is preferable because the self-restoring effect is further manifested and the scratch resistance is further improved.

When the (poly) caprolactone segment is copolymerized or added separately, the content of the (poly) caprolactone segment in the total solid content concentration of 100 mass% of the coating composition used for forming the surface layer is 5 to 50 mass % Is preferable in terms of self-repairing property and stain resistance.

[Compound containing urethane bond, isocyanate group]

In the present invention, the urethane bond refers to a bond represented by the above-mentioned formula (2). The coating composition used for forming the surface layer contains a commercially available urethane-modified resin, so that the resin contained in the surface layer can have a urethane bond. Further, when forming a surface layer, a urethane bond may be formed in the coating step by applying a coating composition containing a compound containing an isocyanate group and a compound containing a hydroxyl group as a precursor, so that a urethane bond can be contained in the surface layer.

In the present invention, by reacting an isocyanate group with a hydroxyl group to form a urethane bond, the resin contained in the surface layer has a urethane bond. By reacting an isocyanate group with a hydroxyl group to form a urethane bond, the toughness of the surface layer can be improved and the self-repairing property can be improved.

When a resin containing the (poly) caprolactone segment described above, a resin containing a polysiloxane segment described later or a resin containing a polydimethylsiloxane segment or the like has a hydroxyl group, the resin and the precursor It is also possible to form a urethane bond with a compound containing an isocyanate group. When a surface layer is formed by using a resin containing an isocyanate group and a resin containing a (poly) siloxane segment having a hydroxyl group or a polydimethylsiloxane segment having a hydroxyl group, the surface layer may have toughness and elastic recovery properties ) And the slidability of the surface can be increased.

In the present invention, the compound containing an isocyanate group refers to a resin containing an isocyanate group or a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylol propane adduct of tolylene diisocyanate, trimethylol propane adduct of hexamethylene diisocyanate, trimethylol propane of isophorone diisocyanate An isocyanurate of isocyanurate of hexamethylene diisocyanate, a polyisocyanate of burette of hexamethylene isocyanate and the like, and a block of isocyanate, and the like.

Among these isocyanate group-containing compounds, aliphatic isocyanates are preferred because they have higher self-repairing properties than alicyclic or aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Further, the isocyanate group-containing isocyanate compound is particularly preferable from the viewpoint of heat resistance, and the isocyanurate compound of hexamethylene diisocyanate is most preferable. The isocyanate having an isocyanurate ring forms a surface layer having both self-restoring property and heat-resistant property.

[Urethane (meth) acrylate B, urethane (meth) acrylate C]

(Meth) acrylate B, which is excellent in self-repellency, and urethane (meth) acrylate C, which is excellent in resistance to cosmetics, in order to impart the property of cosmetic resistance in addition to self- It is preferable to use the coating composition B.

Urethane (meth) acrylate B is, a compound having a urethane bond in the molecule, urethane (meth) acrylate, a mixture of B and the photoinitiator, the UV illumination by the high-pressure mercury lamp of 400mW / cm ^2, a cured in a thickness 30㎛ Means a urethane (meth) acrylate whose physical properties of a layer (hereinafter referred to as X layer) fall within the following range.

1. When oleic acid is applied to the surface of the X layer and the growth rate of the X layer is maintained at 60 占 폚 for 1 hour is not more than 45 mass%

2. The maximum displacement in the thickness direction of the X layer when a 0.5 mN load was applied for 10 seconds in the microhardness measurement was 1.0 탆 or more and 3.0 탆 or less

3. The microhardness tester according to 2 above, wherein the amount of creep displacement in the thickness direction of the X layer is not less than 0.4 μm and not more than 0.7 μm.

In addition, urethane (meth) acrylate is C, a compound having a urethane bond in the molecule, a mixture of urethane (meth) acrylate C and a photoinitiator, to ultraviolet rays by a high pressure mercury lamp light intensity of 400mW / cm ^2, a thickness 30㎛ Means a urethane (meth) acrylate whose physical properties of a cured layer (hereinafter referred to as Y layer) fall within the following range.

1. When the oleic acid is applied to the surface of the Y layer and held at 60 DEG C for 1 hour, the mass increase rate of the Y layer is 5.0 mass% or less

2. The maximum displacement amount in the thickness direction of the Y layer when a 0.5 mN load is applied for 10 seconds in microchannel measurement is 0.2 mu m or more and 3.0 mu m or less

3. The microhardness tester according to 2 above, wherein the amount of creep displacement in the thickness direction of the Y layer is 0.02 탆 or more and 0.35 탆 or less.

(Meth) acrylate B, and the urethane (meth) acrylate B has a (poly) caprolactone segment, and the urethane (meth) acrylate B has a When urethane (meth) acrylate C has a (poly) alkylene glycol (meth) segment, a surface layer having better self-restoration and cosmetic resistance can be obtained. This is because the (poly) alkylene glycol segment having excellent cosmetic property is localized on the surface at the time of curing due to the difference between the surface tension and the intermolecular force, and the (poly) caprolactone segment having excellent self- Is more remarkable.

Particularly, the mass (m) of the (1) (poly) alkylene glycol segment in the resin contained in the surface layer and the mass (n) of the (3) (poly) caprolactone segment in the resin contained in the surface layer satisfy 0.3n ? N, more preferably satisfies 0.3n? M? 5n, and more preferably satisfies 0.65n? M? 1.20n. The mass (m) of the (1) (poly) alkylene glycol segment in the resin contained in the surface layer and the mass (n) of the (3) (poly) caprolactone segment in the resin contained in the surface layer satisfy 0.3n &lt; , The segregation of each segment at the time of curing becomes more conspicuous and a surface layer having better self-restoration and cosmetic resistance can be obtained. The mass (m) of the (1) (poly) alkylene glycol segment in the resin contained in the surface layer and the mass (n) of the (3) (poly) caprolactone segment in the resin contained in the layer A satisfy 0.3n & 10 n is not satisfied, the dispersibility of each segment at the time of curing described above becomes high, so that the elliptical material may be weakened.

[(Poly) siloxane segment]

In the present invention, it is preferable that the surface layer has (4) a (poly) siloxane segment and / or a polydimethylsiloxane segment. In the present invention, the (poly) siloxane segment refers to the segment represented by the above-mentioned formula (5).

(4) In order for the surface layer to have (poly) siloxane segments, the above-mentioned coating composition used for forming the surface layer can be made to contain a resin containing a (poly) siloxane segment.

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

The resin containing the (poly) siloxane segment may be selected from the group consisting of tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacrylate Organosilica sol dispersed in a completely or partially hydrolyzed silane compound having a hydrolyzable silyl group such as oxypropyl trialkoxysilane and? -Methacryloxypropyl alkyl dialkoxysilane or an organic solvent, an organosilica sol dispersed in an organic solvent, And a hydrolyzed silane compound of a decomposable silyl group is added.

In the present invention, the resin containing the (poly) siloxane segment may contain (copolymerize) other segments other than the (poly) siloxane segment. For example, a monomer component having a (poly) caprolactone segment and a polydimethylsiloxane segment may be contained (copolymerized).

In the present invention, it is preferable that a resin containing a (poly) siloxane segment is copolymerized with a monomer having a hydroxyl group reactive with an isocyanate group. When a monomer containing a hydroxyl group reactive with an isocyanate group is copolymerized with a resin containing a (poly) siloxane segment, the toughness of the surface layer is improved.

(Poly) siloxane segment is a copolymer having a hydroxyl group, a surface layer is formed using a coating composition comprising a resin (copolymer) containing a (poly) siloxane segment having a hydroxyl group and a compound containing an isocyanate group , A surface layer having a (poly) siloxane segment and a urethane bond can be efficiently formed.

Even when the (poly) siloxane segment is copolymerized or added separately, if the (poly) siloxane segment is contained in an amount of 1 to 20 mass% in 100 mass% of the total components of the coating composition used for forming the surface layer, Is preferable from the viewpoint of durability, stain resistance, weather resistance, and heat resistance. The 100 mass% of the total components of the coating composition does not contain a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

[Polydimethylsiloxane segment]

In the present invention, the polydimethylsiloxane segment refers to the segment represented by the above-described formula (6).

When the resin contained in the surface layer has (4) a polydimethylsiloxane segment, the polydimethylsiloxane segment is coordinated to the surface of the surface layer. When the polydimethylsiloxane segment is coordinated to the surface of the surface layer, the lubricity of the surface layer surface is improved and the frictional resistance can be reduced. As a result, the occurrence of scratches can be suppressed.

In order for the surface layer to have a (poly) siloxane segment and / or a polydimethylsiloxane segment, a coating composition used for forming a surface layer can be obtained by including a resin containing a polydimethylsiloxane segment. In the present invention, as the resin containing a polydimethylsiloxane segment, it is preferable to use a copolymer in which a vinyl monomer is copolymerized with a polydimethylsiloxane segment.

For the purpose of improving the toughness of the surface layer, it is preferable that the resin containing the polydimethylsiloxane segment is copolymerized with a monomer having a hydroxyl group reactive with an isocyanate group. When a resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group and a surface layer is formed using a coating composition comprising a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group, It is possible to efficiently form a surface layer having a polydimethylsiloxane segment and a urethane bond.

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

In the case of using the polymer initiator method, the polymeric azo radical polymerization initiator

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

Can be copolymerized with other vinyl monomers. It is also possible to carry out a two-step polymerization in which a prepolymer obtained by copolymerizing a peroxide monomer and a polydimethylsiloxane having an unsaturated group at a low temperature and introducing a peroxide group into the side chain is synthesized and the prepolymer is copolymerized with the vinyl monomer.

In the case of using the polymer chain transfer method, for example, the silicone oil represented by the general formula (12)

(m is an integer of 10 to 300)

, HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH is added to give a compound having an SH group, followed by copolymerization of the corresponding silicone compound and the vinyl monomer using the SH group chain transfer to synthesize a block copolymer .

In order to synthesize a polydimethylsiloxane-based graft copolymer, for example, a compound represented by the formula (13)

(m is an integer of 10 to 300)

That is, a graft copolymer can be easily obtained by copolymerizing methacrylate or the like of polydimethylsiloxane with a vinyl monomer.

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

Examples of the polydimethylsiloxane copolymer include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; alcohols such as ethanol, isopropyl alcohol And the like are preferably used alone or in a mixed solvent by a solution polymerization method.

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

The amount of the polydimethylsiloxane segment in the polydimethylsiloxane copolymer in the present invention is preferably 1 to 30% by mass based on 100% by mass of the total components of the polydimethylsiloxane copolymer in terms of lubricity and stain resistance of the surface layer . The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

Even when the polydimethylsiloxane segment is copolymerized or added separately, if the amount of the dimethylsiloxane segment is 1 to 20 mass% in 100 mass% of the total components of the coating composition used for forming the surface layer, It is preferable from the viewpoints of stain resistance, weather resistance, and heat resistance. The 100 mass% of the total components of the coating composition does not contain a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

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

The coating composition used for forming the surface layer includes a copolymer of a (poly) caprolactone segment and a polydimethylsiloxane segment, a copolymer of a (poly) caprolactone segment and a (poly) siloxane segment, a (poly) caprolactone segment, It is possible to use a copolymer of a dimethylsiloxane segment and a (poly) siloxane segment. The surface layer obtained by using such a coating composition can have a (poly) caprolactone segment and a polydimethylsiloxane segment and / or a (poly) siloxane segment.

The reaction of the polydimethylsiloxane copolymer, (poly) caprolactone and (poly) siloxane in the coating composition used for forming the surface layer having the (poly) caprolactone segment, the (poly) siloxane segment and the polydimethylsiloxane segment , A (poly) caprolactone segment and a polysiloxane segment may be appropriately added and copolymerized in the synthesis of a polydimethylsiloxane copolymer.

[(Poly) alkylene glycol segment]

In the present invention, it is preferable that the surface layer has a (poly) alkylene glycol segment. In the present invention, the (poly) alkylene glycol segment refers to a segment represented by the general formula (14).

Provided that n is an integer of 2 to 4 and m is an integer of 2 to 11. [

The alkylene glycol is a glycol having 2 to 4 carbon atoms (n). The number (m) of repeating units of the alkylene glycol is 2 to 11, preferably 3 to 6. When the number of carbon atoms (n) of the alkylene glycol is more than 4, or when the number (m) of repeating units of the alkylene glycol is more than 11, the molecular chain of the alkylene glycol becomes long and the crosslinking density of the cured product becomes low, The hardness thereof is lowered, and the coating film strength, scratch resistance and the like may be lowered. On the other hand, when the number of recurring units (m) of the alkylene glycol is less than 2, the molecular chain of the alkylene glycol is shortened and the cross-linking density of the cured product becomes high and the cured product loses its flexibility. The workability may be lowered.

By forming a surface layer using a coating composition comprising a resin containing a (poly) alkylene glycol segment, the surface layer can have a (poly) alkylene glycol segment.

The resin containing the (poly) alkylene glycol segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the terminal of the resin containing the (poly) alkylene glycol segment.

As the resin containing the (poly) alkylene glycol segment, a (poly) alkylene glycol (meth) acrylate having an acrylate group at the terminal is preferred in order to impart elasticity. The number of the acrylate functional group (or methacrylate functional group) of the (poly) alkylene glycol (meth) acrylate is not limited, but is most preferably monofilament in terms of self-restoring property of the cured product.

Examples of the (poly) alkylene glycol (meth) acrylate contained in the coating composition used for forming the surface layer include (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol Butylene glycol (meth) acrylate. Are the structures represented by the following formulas (15), (16) and (17), respectively.

(Poly) ethylene glycol (meth) acrylate:

(Poly) propylene glycol (meth) acrylate:

(Poly) butylene glycol (meth) acrylate:

In the formulas (15), (16) and (17), R is hydrogen (H) or a methyl group (-CH ₃ ), and m is an integer of 2 to 11.

Of these polyalkylene glycol (meth) acrylates, (poly) ethylene glycol (meth) acrylates in which the number of carbon atoms of the alkylene glycol (m) is 2 are particularly preferable. (Poly) ethylene glycol (meth) acrylate has the smallest number of carbon atoms (n) in the formula (14), it can contribute to compatibility between the cosmetic property and scratch resistance of the resulting cured product.

In the present invention, preferably, the above-mentioned isocyanate group-containing compound is reacted with a hydroxyl group of (poly) alkylene glycol (meth) acrylate to form a surface layer as urethane (meth) acrylate, And (3) (poly) alkylene glycol segments. As a result, it is possible to improve the toughness of the surface layer and improve the self-repellency.

In the urethanization reaction of the above-mentioned isocyanate group-containing compound with (poly) alkylene glycol (meth) acrylate, hydroxyalkyl (meth) acrylate, long chain alcohol and the like can be compounded. By blending the hydroxyalkyl (meth) acrylate, the hardness of the surface layer as the cured product can be increased. By blending a long-chain alcohol, the surface activity of the surface layer as a cured product can be enhanced, and as a result, scratch resistance can be improved. This long-chain alcohol is a compound included in the concept of the long-chain alkyl group-containing compound.

Examples of the hydroxyalkyl (meth) acrylate which is simultaneously blended during the urethanation reaction between a compound containing an isocyanate group and (poly) alkylene glycol (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (Meth) acrylate, hydroxybutyl (meth) acrylate, and the like.

Examples of long-chain alcohols that are simultaneously blended during the urethanation reaction between a compound containing an isocyanate group and (poly) alkylene glycol (meth) acrylate include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, Polyoxyethylene monostearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, glycerol monostearate, and the like. Particularly preferred long-chain alcohols include polyether-modified long-chain alcohols such as polyether-modified cetyl alcohol. This is because use of a polyether-modified long-chain alcohol can impart an antistatic effect to the surface layer which is a cured product.

The urethane formation reaction of the compound containing an isocyanate group with the (poly) alkylene glycol (meth) acrylate is carried out in the presence of a catalyst, a polymerization inhibitor and the like in an organic solvent. The reaction temperature in the urethanization reaction is preferably from room temperature to 100 ° C, and the reaction time is preferably from 1 to 10 hours. When the reaction temperature is lower than room temperature or the reaction time is shorter than 1 hour, the progress of the reaction may be delayed and the yield of the desired urethane (meth) acrylate may be lowered. On the other hand, when the reaction temperature exceeds 100 ° C or when the reaction time is longer than 10 hours, side reactions may easily occur.

Examples of the organic solvent used in the urethane formation reaction between the compound containing an isocyanate group and (poly) alkylene glycol (meth) acrylate include aromatic hydrocarbon solvents such as toluene and xylene; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; And ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. Examples of the catalyst include dibutyltin laurate, dibutyltin diethylhexoate and dibutyltin sulfite. Examples of the polymerization inhibitor include hydroquinone monomethyl ether and the like.

[Solvent, solvent E]

The coating composition A and the coating composition B may contain a solvent. The number of kinds of the solvent is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less.

Here, the term &quot; solvent &quot; refers to a substance which is liquid at room temperature and normal pressure, capable of evaporating substantially the entire amount in the drying step after application.

Here, the type of the solvent is determined according to the molecular structure constituting the solvent. (Stereoisomer) which does not completely overlap even if it is taken in any three-dimensional space in the three-dimensional space (stereoisomer), that is, the same elemental composition and the same kind of substance and the same number of functional groups Are handled as solvents different in kind. For example, 2-propanol and n-propanol are treated as different solvents.

When a solvent is contained, it is preferable that the solvent exhibits the following characteristics (Condition 1).

Condition 1 When the relative evaporation rate of solvent E is 0.3 or less when the solvent having the lowest relative evaporation rate (ASTM D3539-87 (2004)) based on n-butyl acetate is referred to as solvent E

Here, the relative evaporation rate based on the n-butyl acetate of the solvent is the evaporation rate measured in accordance with ASTM D3539-87 (2004). Specifically, it is a value defined as a relative value of the evaporation rate based on the time required for 90% by mass evaporation of n-butyl acetate under dry air.

When the relative evaporation rate of the solvent E is larger than 0.3, the time required for the orientation to the surface of the fluorine compound D is shortened, resulting in deterioration of glossiness. The lower limit of the relative evaporation rate of the solvent E is not particularly limited as long as it is a solvent that can be removed from the coating film by evaporation in the drying process.

(Relative evaporation rate: 0.25), isophorone (relative evaporation rate: 0.026), diethylene glycol monobutyl ether (relative evaporation rate: 0.004), diacetone alcohol (relative evaporation rate: 0.15) , Ethylene glycol monoethyl ether acetate (relative evaporation rate: 0.2), nonylphenoxyethanol (relative evaporation rate: 0.25), propylene glycol monoethyl ether (relative evaporation rate: 0.1) .

[Other additives]

The coating compositions A and B preferably contain a polymerization initiator, a curing agent and a catalyst. The polymerization initiator and the catalyst are used to promote curing of the surface layer. As the polymerization initiator, it is preferable that the component contained in the coating composition can initiate or accelerate polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization reaction or the like.

Various polymerization initiators, curing agents and catalysts may be used. The polymerization initiator, the curing agent and the catalyst may be used alone, or a plurality of polymerization initiators, a curing agent and a catalyst may be used at the same time. Further, an acidic catalyst, a thermal polymerization initiator or a photopolymerization initiator may be used in combination. Examples of the acidic catalyst include hydrochloric acid aqueous solution, formic acid, and acetic acid. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include an alkylphenon-based compound, a sulfur-containing compound, an acylphosphine oxide-based compound, and an amine-based compound.

As the photopolymerization initiator, an alkylphenone-based compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone-type compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2.2-dimethoxy-1,2-diphenylethane- 2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1 - (4-methylphenyl) -1-butane, 2- (dimethylamino) -2 - [(4-methylphenyl) Phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1- [4- (2 2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and those obtained by high- .

To the extent that the effect of the present invention is not impaired, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent and the like may be added to the coating compositions A and B used for forming the surface layer. Thus, the surface layer may contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like. Examples of the leveling agent include an acrylic copolymer or a silicon-based or fluorine-based leveling agent. Specific examples of ultraviolet absorbers include benzophenone, benzotriazole, oxalyl oxalate, triazine, and hindered amine ultraviolet absorbers. Examples of the antistatic agent include a metal salt such as a lithium salt, a sodium salt, a potassium salt, a rubidium salt, a cesium salt, a magnesium salt, and a calcium salt.

[Production method of laminated film]

The surface layer formed on the surface of the laminated film of the present invention is preferably formed by applying the above-mentioned coating composition onto the above-mentioned supporting substrate, followed by drying-curing.

The method for producing the laminated film by coating is not particularly limited, but the coating composition may be applied to a support substrate or the like by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Patent No. 2681294) It is preferable to form the surface layer by coating. Among these coating methods, a gravure coating method or a die coating method is more preferable as a coating method.

Subsequently, the liquid film applied on the supporting substrate or the like is dried. From the viewpoint of moving the fluorine compound D in the liquid film formed by coating to the surface and segregating the fluorine compound segment on the outermost surface of the surface layer in addition to completely removing the solvent from the laminated film to be obtained, .

Examples of the drying method include dry heating (close contact with a hot object), convection heating (hot wind), radiant heat (infrared), and other (microwave, induction heating). Among them, in the production method of the present invention, it is preferable to use convection heat transfer or radiation heat transfer since the drying speed must be uniform even in the width direction precisely.

The drying process is generally divided into (A) an expiratory drying period and (B) a decreasing rate drying period, and since the diffusion of solvent molecules into the atmosphere on the surface of the liquid film is the rate of drying, The drying rate is governed by the partial pressure of the evaporating solvent in the atmosphere, the wind speed and the temperature, and the film surface temperature is constantly determined by the hot air temperature and the partial pressure of the solvent evaporated in the atmosphere. In the latter case, since the diffusion of the solvent in the liquid film is controlled, the drying rate does not exhibit a constant value in this section, but is continuously lowered, controlled by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature is raised. Here, the drying rate refers to the amount of solvent evaporation per unit time and per unit area, which is in the dimension of g · m ^-2 · s ^-1 .

The drying rate is preferably in the range of 10 g · m ^-2 · s ^-1 or less, more preferably 5 g · m ^-2 · s ^-1 or less. The lower limit value is preferably 0.1 g · m ^-2 · s ^-1 or more. By setting the drying speed in the constant rate drying zone to this range, it is possible to prevent unevenness caused by nonuniform drying speed.

It is not particularly limited to a specific wind speed and temperature if a drying speed in the range of 0.1 gm ^-2 s ^-1 or more and 10 gm ^-2 s ^-1 or less is obtained.

In the method for producing a laminated film of the present invention, the fluorine compound D is aligned with the evaporation of the remaining solvent in the rate drying step. Since a time for orientation is required in this process, there is a preferable range for the rate of temperature rise of the film surface in the rate-reduction drying period, preferably 5 deg. C / second or less, and more preferably 1 deg. C / second or less.

Further, a curing operation (curing process) of a further layer may be performed by irradiating heat or an energy ray. When the coating composition A is used in the curing step, it is preferably from room temperature to 200 캜, more preferably from 100 캜 or higher to 200 캜 or lower from the viewpoint of the activation energy of the curing reaction, More preferably 200 ° C or lower.

In the case of curing by an active energy ray, it is preferable to be electron beam (EB line) and / or ultraviolet ray (UV ray) in view of versatility. In the case of curing by ultraviolet rays, oxygen inhibition can be prevented, so that the oxygen concentration is preferably as low as possible, and it is more preferable to cure under a nitrogen atmosphere (nitrogen purge). When the oxygen concentration is high, the curing of the outermost surface is inhibited, the surface hardening becomes insufficient, and the transparency sometimes becomes insufficient. Examples of the ultraviolet lamp used for irradiating ultraviolet rays include a discharge lamp system, a flash system, a laser system, and an electrodeless lamp system. The case where an ultraviolet curing method using the discharge lamp is a high pressure mercury lamp, the illuminance of ultraviolet rays of 100 to 3,000mW / cm ^2, preferably 200 to 2,000mW / cm ^2, more preferably 300 to where the 1,500mW / cm ² preferable to perform the UV irradiation in the conditions, the accumulated light quantity of ultraviolet light from 100 to 3,000mJ / cm ^2, preferably 200 to 2,000mJ / cm ^2, more preferably ultraviolet ray irradiation under the condition that 300 to 1,500mJ / cm ² Is more preferable. Here, the illuminance of ultraviolet rays is an irradiation intensity per unit area and varies depending on the lamp output, the efficiency of the light emission spectrum, the diameter of the light emission valve, the design of the reflector, and the light source distance from the irradiated object. However, the illuminance does not change depending on the conveying speed. The ultraviolet accumulated light amount is the total amount of photons reaching the surface, which is the irradiation energy received per unit area. The accumulated light amount is inversely proportional to the irradiation speed passing through the light source, and is proportional to the number of times of irradiation and the number of lamps.

Example

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

<Fluorine compound D>

[Fluorine compound D1]

As the fluorine compound D1, an acrylate compound ("Megaface" RS-75 DIC, solid content concentration of 40 mass% solvent (toluene and methyl ethyl ketone) 60 mass%) containing a fluoropolyether segment was used.

[Fluorine compound D2]

As a fluorine compound D2, a siloxane compound containing a fluoropolyether segment (KY-108, solid content concentration of 20 mass% solvent (methanol and isopropyl alcohol: 80 mass%) manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

[Fluorine compound D3]

A bifunctional acrylate compound (FPTMG-A retention product, solid content concentration 100% by mass) containing a fluoropolyether segment (fluorotetraethylene glycol segment) was used as the fluorine compound D3.

[Fluorine compound D4]

As the fluorine compound D4, an acrylate compound containing a fluoroalkyl segment (triacryloyl-heptadecafluorononyl-pentaerythritol hexaacrylate solid content concentration: 100% by mass) was used.

[Fluorine compound D5]

As the fluorine compound D5, an acrylate compound containing a fluoroalkyl segment (pentaacryloyl-heptadecafluorononyl-dipentaerythritol hexaacrylate solid content concentration: 100% by mass) was used.

<Synthesis of polysiloxane>

[Polysiloxane (a)]

106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water and 1 part by mass of 1% by mass hydrochloric acid were put into a 500 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube, After being maintained for 2 hours, ethanol was recovered while raising the temperature and maintained at 180 캜 for 3 hours. Thereafter, the mixture was cooled to obtain a viscous polysiloxane (a).

[Polysiloxane (b)]

In a 500 ml capacity flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube, 106 parts by mass of ethanol, 270 parts by mass of methyltrimethoxysilane, 23 parts by mass of? -Methacryloxypropylmethyldimethoxysilane, 100 parts by mass of deionized water , 1 mass part of 1 mass% hydrochloric acid and 0.1 mass part of hydroquinone monomethyl ether were charged and reacted at 80 deg. C for 3 hours to synthesize a polysiloxane (b). This was adjusted to 50 mass% with methyl isobutyl ketone.

&Lt; Synthesis of polydimethylsiloxane compound >

[Polydimethylsiloxane-based block copolymer (a)]

50 parts by mass of toluene and 50 parts by mass of methyl isobutyl ketone, 20 parts by mass of a polydimethylsiloxane-based polymer polymerization initiator (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, 1 part by mass of methacrylic acid and 0.5 part by mass of 1-thioglycerol were charged, To obtain a polydimethylsiloxane-based block copolymer (a). The obtained block copolymer had a solid content concentration of 50% by mass (solvent (toluene and methyl isobutyl ketone) was 50% by mass).

[Polydimethylsiloxane-based graft copolymer (b)]

50 parts by mass of toluene and 50 parts by mass of isobutyl acetate were charged using the apparatus used for the synthesis of the polysiloxane (a), and the temperature was elevated to 110 占 폚. Separately, 32 parts by mass of methyl methacrylate, 32 parts by mass of caprolactone methacrylate (PLACCEL FM-5, manufactured by Daicel Chemical Industries, Ltd.), 17 parts by mass of 2-hydroxyethyl methacrylate, , 20 parts by mass of an end-capped methacryl group-containing polydimethylsiloxane (AK-32 manufactured by Toagosei Co., Ltd.), 1 part by mass of methacrylic acid and 2 parts by mass of 1,1-azobiscyclohexane-1-carbonitrile . This mixed monomer was added dropwise to the above mixed solution of toluene and butyl acetate over 2 hours. Thereafter, the reaction was carried out at 110 DEG C for 8 hours to obtain a polydimethylsiloxane graft copolymer (b) having a hydroxyl group at a solid concentration of 50 mass%. The obtained block copolymer (b) had a solid concentration of 50 mass% (solvent (toluene and isobutyl acetate) was 50 mass%).

[Polydimethylsiloxane-based block copolymer (c)]

50 parts by mass of toluene and 50 parts by mass of methyl isobutyl ketone, 20 parts by mass of a polydimethylsiloxane-based polymer polymerization initiator (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, 1 part by mass of methacrylic acid and 0.5 part by mass of 1-thioglycerol were charged, To obtain a polydimethylsiloxane-based block copolymer (c). The obtained block copolymer (c) had a solid content concentration of 50 mass% (solvent (toluene and methyl isobutyl ketone) was 50 mass%).

[Polydimethylsiloxane-based graft copolymer (d)]

20 parts by mass of methyl methacrylate, 26 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of polysiloxane (a), 1 part by mass of methacrylic acid, Except that 20 parts by mass of a polydimethylsiloxane-based graft copolymer (b) was used in place of 20 parts by mass of a polydimethylsiloxane-based graft copolymer (X-22-174DX, manufactured by Shinetsu Chemical Industry Co., d) was synthesized. The obtained graft copolymer (d) had a solid content concentration of 50% by mass (solvent: 50% by mass of toluene and isobutyl acetate).

[Polydimethylsiloxane compound (e)]

As the polydimethylsiloxane compound (e), EBECRYL 350 (bifunctional, silicone acrylate), manufactured by Daicel-Cytech Co., Ltd. was used.

[Polydimethylsiloxane compound (f)]

As the polydimethylsiloxane compound (f), EBECRYL1360 (hexafunctional, silicone acrylate), manufactured by Daicel-Cytech Co., Ltd. was used.

<Synthesis of urethane (meth) acrylate B>

[Urethane (meth) acrylate B1]

50 parts by mass of toluene, 50 parts by mass of an isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 50 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate , 76 parts by mass of fulxel FA5 manufactured by Kosaka Kikai Co., Ltd., 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and maintained at 70 DEG C for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate B1 having a solid concentration of 50% by mass.

[Urethane (meth) acrylate B2]

50 parts by mass of toluene, 25 parts by mass of an isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 25 parts by mass of (poly) caprolactone modified hydroxyethyl acrylate 162.8 parts by mass of fulxel FA10 manufactured by Kosaka Kikai Co., Ltd., 0.02 part by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and maintained at 70 占 폚 for 5 hours. Thereafter, 137.8 parts of toluene was added to obtain a toluene solution of urethane (meth) acrylate B2 having a solid content concentration of 50 mass%. The repeating number of caprolactone units per acrylate monomer residue in this urethane (meth) acrylate is 10.

[Urethane (meth) acrylate B3]

50 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI, manufactured by Kyowa Hakko Kagin Co., Ltd.) and 100 parts by mass of polycarbonate diol (manufactured by Daicel Chemical Industries, 210HL) were mixed, and the temperature was raised to 40 占 폚 and held for 8 hours. Then, 28 parts by mass of 2-hydroxyethyl acrylate (Light Ester HOA, manufactured by Kyushu Chemical Industry Co., Ltd.), 5 parts by mass of dipentaerythol hexaacrylate (M-400 manufactured by Toagosei Co., Ltd.) 0.02 parts by mass of methyl ether was added and the mixture was maintained at 70 占 폚 for 30 minutes. Then, 0.02 parts by mass of dibutyltin laurate was added and the mixture was maintained at 80 占 폚 for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate B3 having a solid content concentration of 50 mass%.

[Urethane (meth) acrylate B4]

50 parts by mass of toluene, 50 parts by mass of an isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 50 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate , 8 parts of polydimethylsiloxane (X-22-160AS manufactured by Shinetsu Chemical Industry Co., Ltd.), 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether And the mixture was kept at 70 캜 for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate B4 having a solid content concentration of 50% by mass.

[Urethane (meth) acrylate B5]

, 50 parts by mass of toluene, 34 parts by mass of an isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), (poly) caprolactone modified hydroxyethyl acrylate 57 parts by mass of Fulcell FA10 manufactured by Takara Shuzo Co., Ltd.), 57 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Fulcell FA3 manufactured by Daicel Chemical Industries, Ltd.), 0.02 part by mass of dibutyltin laurate, And 0.02 parts by mass of monomethyl ether were mixed and maintained at 70 占 폚 for 5 hours. Thereafter, 137.8 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate B5 having a solid content concentration of 50% by mass.

<Synthesis of urethane (meth) acrylate C>

[Urethane (meth) acrylate C1]

50 parts by mass of toluene, 50 parts by mass of a biuret-modified type of hexamethylene diisocyanate (Duranate 24A-90CX manufactured by Asahi Kasei Chemicals Co., Ltd., nonvolatile material: 90% by mass, isocyanate content: 21.2% by mass) 92 parts by mass of lactone-modified hydroxyethyl acrylate (Flaccel FA2D manufactured by Daicel Chemical Industries, Ltd.), 0.02 part by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and maintained at 70 占 폚 for 5 hours Respectively. Then, 82 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate C1 having a solid content concentration of 50% by mass. The repeating number of the caprolactone unit per acrylate monomer residue in this urethane (meth) acrylate is 2.

[Urethane (meth) acrylate C2]

50 parts by mass of toluene, 50 parts by mass of an isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 50 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate 114 parts by mass of fulxel FA3 manufactured by Takara Shuzo Co., Ltd., 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were added, and the mixture was maintained at 70 占 폚 for 3 hours. Thereafter, 118.2 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate C2 having a solid concentration of 50% by mass. The repeating number of caprolactone units per acrylate monomer residue in this urethane (meth) acrylate is 3.

[Urethane (meth) acrylate C3]

50 parts by mass of an isocyanurate-modified product of hexamethylene diisocyanate (Takenate D-170N, manufactured by Mitsui Chemicals, Inc., content of isocyanate group: 20.9% by mass), 50 parts by mass of polyethylene glycol monoacrylate (manufactured by Nippon Kayaku Co., , 42 parts by mass of dimmer AE-90 and a hydroxyl value of 332 (mgKOH / g), 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether. Then, the reaction was carried out at 70 DEG C for 5 hours. After completion of the reaction, 92 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction solution to obtain a toluene solution of urethane (meth) acrylate C3 having a solid concentration of 50% by mass.

[Urethane (meth) acrylate C4]

Except that 53 mass parts of polyethylene glycol monoacrylate was replaced with blender AE-150 (hydroxyl value: 264 (mgKOH / g)) and MEK of reaction solution was changed to 102 mass parts in urethane (meth) acrylate C3. A toluene solution of urethane (meth) acrylate C4 was obtained in the same manner as the urethane (meth) acrylate C3.

[Urethane (meth) acrylate C5]

Except that 68 mass parts of polyethylene glycol monoacrylate was replaced with 68 mass parts of blemish AE-200 (hydroxyl value: 205 (mgKOH / g)) and 118 mass parts of the reaction solution in urethane (meth) acrylate C3. A toluene solution of urethane (meth) acrylate C5 was obtained in the same manner as the urethane (meth) acrylate C3.

[Urethane (meth) acrylate C6]

(Urethane (meth) acrylate) was obtained in the same manner as in Example 1 except that 142 parts of the polyethylene glycol monoacrylate was replaced with 142 parts by mass of the blender AE-400 (hydroxyl value: 98 (mgKOH / g) ) Acrylate C3 to obtain a toluene solution of urethane (meth) acrylate C6.

[Urethane (meth) acrylate C7]

50 parts by mass of 1,3-bisisocyanate methylcyclohexane, 100 parts by mass of hydroxyalkyl acrylate, 0.05 parts by mass of dibutyltin laurate and 2 parts by mass of hydroquinone were added, and the mixture was maintained at 70 占 폚 for 3 hours. Thereafter, aging was carried out at 85 캜 for 2 hours to obtain a toluene solution of urethane (meth) acrylate C7.

<Combination of Coating Composition A>

[Coating composition A1-1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-1 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-2 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 2 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-3 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 10 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-4 having a solid content concentration of 40 mass%.

Fluorine compound D2 solution (solid concentration 20 mass%) 12 mass parts

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-5 having a solid content concentration of 40% by mass.

Fluorine compound D3 2.4 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-6]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-6 having a solid content concentration of 40% by mass.

Fluorine compound D4 2.4 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-7]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-7 having a solid content concentration of 40% by mass.

Fluorine compound D5 2.4 parts by mass

Polycaprolactone polyol (polycaprolactone triol diacetate Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo K.K.) 15 parts by mass

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-8]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-8 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Propylene glycol monoethyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A1-9]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1-9 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[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.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

17 parts by mass of a compound having an isocyanate group (manufactured by Takenate D-170N manufactured by Mitsui Chemicals, Inc., isocyanurate of hexamethylene diisocyanate)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[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 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

8 parts by mass of a compound having an isocyanate group (manufactured by Takenate D-170N manufactured by Mitsui Chemicals, Inc., isocyanurate of hexamethylene diisocyanate)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[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.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

Polydimethylsiloxane-based graft copolymer (b) 100 parts by mass

12 parts by mass of a compound having an isocyanate group (tocinate D-170N available from Chisso Chemical Industry Co., Ltd., isocyanurate of hexane methylene diisocyanate)

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 312 manufactured by Kagaku Kogyo K.K., weight average molecular weight 1250) 15 parts by mass

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A6]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (c) solution (solid content concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A7]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (Desmodur N3200 manufactured by Buretche Bayer AG, hexamethylene diisocyanate)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A8]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 having a solid content concentration of 40% by mass.

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

15 parts by mass of a compound having an isocyanate group (hexanediol diisocyanate isocyanurate available from Chisso Chemical Co., Ltd., Takenate D-170N)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass.

[Coating composition A9]

<Combination of raw material A8>

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

36 parts by mass of a compound having an isocyanate group (Takenate D-170N manufactured by Mitsui Chemicals, Inc., isocyanurate of hexamethylene diisocyanate)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A10]

<Combination of raw material A9>

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A10 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

15 parts by mass of Polycaprolactone polyol (Polycaprolactone triol Diacel Flaxel 308, weight average molecular weight 850, manufactured by Kagaku Kogyo Kabushiki Kaisha)

25 parts by mass of a compound having an isocyanate group (manufactured by Takenate D-170N manufactured by Mitsui Chemicals, Inc., isocyanurate of hexamethylene diisocyanate)

Polydimethylsiloxane-based block copolymer (a) Solution (solids concentration: 50% by mass) 75 parts by mass

Polysiloxane (a) 10 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A11]

<Combination of raw material B1>

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A11 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

12 parts by mass of a compound having an isocyanate group (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by DIC Corporation, Bunko DN-950, solids concentration: 75% by mass)

Polydimethylsiloxane-based graft copolymer (d) Solution (solid content concentration: 50% by mass) 100 parts by mass

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition A12]

<Combination of raw material A11>

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A12 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 6 parts by mass

Polydimethylsiloxane-based graft copolymer (b) 100 parts by mass

25 parts by mass of a compound having an isocyanate group (tocinate D-170N available from Chisso Chemical Industry Co., Ltd., isocyanurate of hexane methylene diisocyanate)

1 part by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

<Combination of Coating Composition B>

[Coating composition B1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B1 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.8 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C1 solution (solid concentration 50% by mass) 50 parts by mass

10 parts by mass of phthalic acid monohydroxyethyl acrylate (M-5400, solid content concentration 100% by mass, manufactured by Toagosei Co., Ltd.)

10 parts by mass of toluene

Ethylene glycol monobutyl ether 10 parts by mass

3 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals K.K.).

[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 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.8 parts by mass

Urethane (meth) acrylate B2 solution (solid content concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C2 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[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 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.8 parts by mass

Urethane (meth) acrylate B2 solution (solid content concentration 50% by mass) 70 parts by mass

Urethane (meth) acrylate C2 solution (solid concentration 50% by mass) 30 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[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 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.8 parts by mass

Urethane (meth) acrylate B3 solution (solid concentration 50% by mass) 30 parts by mass

Urethane (meth) acrylate C2 solution (solid content concentration 50% by mass) 70 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[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 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.8 parts by mass

Urethane (meth) acrylate B3 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C1 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[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 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.8 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C3 solution (solid concentration 50 mass%) 50 mass parts

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-1 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-2 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 1.3 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-3 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40 mass%) 6.3 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-4 having a solid content concentration of 40 mass%.

Fluorine compound D2 solution (solid concentration 20% by mass) 7.5 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-5 having a solid content concentration of 40 mass%.

Fluorine compound D3 1.5 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-6]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-6 having a solid content concentration of 40 mass%.

Fluorine compound D4 1.5 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-7]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-7 having a solid content concentration of 40% by mass.

Fluorine compound D5 1.5 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-8]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-8 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Propylene glycol monoethyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-9]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-9 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-10]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-10 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Polydimethylsiloxane compound (e) 3 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Paint composition B7-11]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-11 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Polydimethylsiloxane compound (f) 3 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-12]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-12 having a solid content concentration of 40% by mass.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Polydimethylsiloxane compound (e) 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B7-13]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B7-13 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Polydimethylsiloxane compound (e) 25 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B8]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B8 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C5 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B9]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B9 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C6 solution (solid concentration 50 mass%) 50 mass parts

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B10]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B10 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B4 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

Ethylene glycol monobutyl ether 10 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B11]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B11 having a solid content concentration of 40 mass%.

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate C4 solution (solid concentration 50% by mass) 50 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B12]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B11 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 100 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B13]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B13 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B2 solution (solid content concentration 50% by mass) 100 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B14]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B14 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B2 solution (solid content concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate B1 solution (solid concentration 50% by mass) 50 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B15]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B15 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B3 solution (solid content concentration 50% by mass) 80 parts by mass

Urethane (meth) acrylate C2 solution (solid concentration 50% by mass) 20 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B16]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B16 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B3 solution (solid content concentration 50% by mass) 80 parts by mass

Urethane (meth) acrylate B2 solution (solid concentration 50 mass%) 20 mass parts

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B17]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B17 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate B3 solution (solid concentration 50% by mass) 50 parts by mass

Urethane (meth) acrylate B2 solution (solid content concentration 50% by mass) 50 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating composition B18]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B18 having a solid content concentration of 40 mass%.

Fluorine compound D1 solution (solid content concentration: 40% by mass) 3.6 parts by mass

Urethane (meth) acrylate C7 solution (solid concentration 50% by mass) 100 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

[Coating Composition X, Coating Composition Y]

The respective components of the urethane (meth) acrylate B (B1 to B5) and the urethane (meth) acrylate C (C1 to C7) were mixed in the following proportions and diluted with methyl ethyl ketone to obtain a solid content concentration of 40% (X1 to X5) and Y (Y1 to Y7) were obtained.

Urethane (meth) acrylate B or C solution (solid concentration 50% by mass) 100 parts by mass

1.5 parts by mass of a photo radical polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.).

&Lt; Method of producing laminated film &

[Preparation of laminated film A]

(Registered trademark) U46 (manufactured by TORAY KABUSHIKI CO., LTD.) Having a thickness of 100 mu m on which an easy-to-adhere coating agent is applied is applied on a polyethylene terephthalate resin (hereinafter also referred to as " PET " Respectively. The above coating composition A (A1-1 to A12) was applied by using a continuous coating apparatus having a slot die coater so that the thickness after drying was adjusted to 30 占 퐉 by adjusting the discharge flow rate from the dieslot. The conditions of the drying process and the curing process applied to the liquid film during application, drying and curing are as follows.

The first drying step

Blowing temperature and humidity : Temperature: 80 ° C

Wind velocity : Coating side: 5 m / sec, Anti-coating side: 5 m / sec

Wind direction : Coating side: parallel to the substrate side, semi-coated side: perpendicular to the substrate side

Residence time : 1 minute

The second drying step

Blowing temperature and humidity : Temperature: 160 ° C

Wind velocity : Application side: 10 m / sec, Anti-application side: 10 m / sec

Wind direction : Coating side: perpendicular to the substrate side, semi-coated side: perpendicular to the substrate side

Residence time : 2 minutes

Curing process

Irradiation power: 400 W / cm ² , cumulative light quantity: 120 mJ / cm ²

Oxygen concentration: 0.1% by volume.

The wind speed and the temperature and humidity were measured by a hot wire anemometer (MODEL 6034, anemomaster air speed and air volume meter manufactured by Nihon Canon Max. Co., Ltd.). Subsequently, storage (aging) was performed at 20 占 폚 for 14 days to obtain laminated films of Examples A1-1 to A7 and Comparative Examples A1 to A5.

[Production B of laminated film]

(Registered trademark) U46 (manufactured by Toray Industries, Inc.) having a thickness of 100 mu m and an easy-to-adhere coating agent applied on a PET resin film was used as a supporting substrate. The coating compositions B (B1 to B18), the coating composition X (X1 to X5) and the coating composition Y (Y1 to Y7) were coated with a continuous coating device having a slot die coater, And the discharge flow rate from the lot was adjusted and applied. The conditions of the drying wind applied to the liquid film during application, drying and curing are as follows.

Drying process

Blowing temperature and humidity : Temperature: 80 ℃, Relative humidity: 1% or less

Wind velocity : Coating side: 5 m / sec, Anti-coating side: 5 m / sec

Wind direction : Coating side: parallel to the substrate side, semi-coated side: perpendicular to the substrate side

Residence time : 2 minutes

Curing process

Irradiation power: 400 W / cm ² , cumulative light quantity: 120 mJ / cm ²

Oxygen concentration: 0.1% by volume.

In addition, as the wind speed and the temperature and humidity, a measured value by a hot wire anemometer (Anemomaster wind speed and air volume meter MODEL6034 manufactured by Nihon Canon Max. Co., Ltd.) was used. The laminated films X (X1 to X5), urethane (meth) acrylate C (B1) to B5 for evaluating the properties of Examples B1 to B10, Comparative Examples B1 to B8 and urethane (Y1 to Y7) for evaluating the properties of the films (C1 to C17).

<Evaluation of urethane (meth) acrylate B and urethane (meth) acrylate C>

[Mass increase rate upon application of oleic acid]

The laminated films X and Y coated with a coating composition containing urethane (meth) acrylate B and urethane (meth) acrylate C were cut out to a length of 200 mm x 200 mm on the support substrate obtained by the above-mentioned method, and the mass A. And fixed on a bakelite plate. Oleic acid was applied on the X layer or Y layer side in a length of 100 mm width x 100 mm. When applied, a plastic fence was made to prevent oleic acid from flowing out (that is, it was coated with oleic acid in an amount larger than that absorbed by the laminated film). This was stored in an oven heated to 60 DEG C for 1 hour. After storage, the laminated film was wiped off using a high-jigger until the laminated film became transparent, and the laminated film was preserved for 24 hours under an atmosphere of 23 캜 (that is, the coating composition not absorbed in the laminated film was wiped away). Then, the mass of the film was measured as B. The mass increase rate due to oleic acid at this time was obtained from the following equation. The measurement was carried out three times each, and the average value was adopted.

(B-A) / (100 x t x d) x 100

t: thickness of X layer or Y layer (cm) before application of oleic acid,

d is a specific gravity (g / cm ² ) of the X layer or Y layer before the oleic acid application.

Here, the specific gravity of the X layer and the Y layer was measured in accordance with a density gradient tube method (JIS K7112 (1999)) using a single-blade knife to cut the sections of the X layer and the Y layer from the laminated film and using an aqueous solution of sodium bromide as a medium . At this time, the measurement was carried out on five specimens, and the average value was adopted.

The obtained results are shown in Tables 1 and 2.

&Lt; Evaluation of laminated film &

The laminated films thus produced were subjected to the following performance evaluations, and the obtained results are shown in Tables 3-1, 3-2, 4-1, 4-2, 5-1 and 5-2. Unless otherwise noted, the measurement was carried out three times while shifting the position of one sample in each of the examples and the comparative examples, and the average value was used.

[Surface gloss of 60 ° mirror surface]

The degree of gloss of the surface layer of the laminated film was measured using VG7000 manufactured by Nippon Denshoku Kogyo Kabushiki Kaisha, and the gloss of the surface of the laminated film was measured at 60 占 according to JIS Z8741 (1997) I was accepted.

[Oleic acid forward contact angle of the surface layer, retreat contact angle]

The advance contact angle and the retraction contact angle were measured by the expansion-contraction method, and they were subjected to the expansion-contraction method measurement manual of the device using a contact master meter, Drop Master DM-501 manufactured by Kyowa Chemical Industry Co., Ltd. Specifically, oleic acid (manufactured by Nacalai Spec. No. 1, Nacalai Tesque Co., Ltd.) was continuously discharged from the syringe at a liquid discharge rate of 8.5 占 / / sec to a final liquid quantity of 50 占,, and the shape of the droplet was discharged The photographs were taken 30 times every 0.5 seconds to the end, and the respective contact angles were obtained from the image using the integrated analysis software "FAMAS" attached to the apparatus. Since the contact angle in the expansion process of the droplet initially changes according to the expansion and shows a substantially constant behavior, when the contact angle data are arranged in the order of measurement and five consecutive points are selected in that order, The average value when the standard deviation of 5 points became 1 DEG or less for the first time was taken as the forward contact angle of the measurement, and this measurement was performed five times for one sample, and the average value was defined as the forward contact angle of the sample. The photographing is performed for a predetermined period of time before the start of the discharge and after the end of the discharge. However, in the analysis software, the photographing data before the start of the discharge and after the end of the discharge are excluded from the five points of data for calculating the contact angle.

The receding contact angle was measured by continuously drawing the droplet at an initial droplet volume of 50 μL and a liquid droplet dispensing rate of 8.5 μL / sec until the shape of the droplet size reduction process was taken from the start of suction to the end of suction, Respectively. In addition, in the analysis software, the photographing data before the suction start and after the suction end are excluded from the data of five points for calculating the contact angle, before the suction start and after the suction end. Since the contact angle of the droplet contraction process initially changes according to the contraction and continues to become substantially constant, when the contact angle is arranged in the direction in which the droplet shrinks and five consecutive points are selected in that order, The average value when the standard deviation of the continuous five points became 1 DEG or less for the first time was taken as the receding contact angle of the measurement, and this measurement was performed five times for one sample, and the average value was defined as the receding contact angle of the sample. Further, depending on the sample, the contact angle of the liquid droplet contraction process is not fixed and continuously decreased continuously. For this, the receding contact angle is set to 0 deg.

[Absorption coefficient of oleic acid]

Among the values required for calculation of the oleic acid absorption coefficient, the volume of the oleic acid deposited on the surface layer and the area of the attachment region were measured using a Drop Master DM-501 contact angle gauge, manufactured by Kyowa Chemical Industry Co., Ltd., I followed the contact angle measurement manual. Specifically, a droplet of oleic acid (Naka-Rai standard first grade nacalai tesque) of 2 μL was made at the tip of the syringe, and the droplet was deposited on the surface of the molding material. Then, an image of the attached state was photographed, and integrated analysis software "FAMAS" Were used to calculate volume and contact area. With respect to the volume, the shape of the attachment remains was calculated as a cut-out sphere, and the contact area was calculated as the area of the dynamic circle when the contact line length was assumed to be the diameter of the source circle. The adherence was allowed to stand at 25 占 폚 for 10 hours under a no-wind condition, and then the volume was measured by the same measurement.

The thickness (T) of the surface layer was calculated based on the coating thickness at the time of forming the molding material. On the other hand, when the coating thickness is unknown, the thickness can be estimated on the basis of the presence of the discontinuous interface when the cross section is observed with an electron microscope (transmission type, scanning type) or an optical microscope, as described above.

[Time-of-flight secondary ion mass spectrometry: Measurement of F ^- fragment ion (M / Z = 19) by TOF-SIMS and Si (CH ₃ ) ⁺ fragment ion derived from dimethylsiloxane ^in-

F ^- fragment ions (M / Z) were measured by secondary ion mass spectrometry on the outermost surface of the laminated film using a time-of-flight secondary ion mass spectrometer TOF-SIMSV manufactured by ION TOF, and SURFACE LAB 6 = 19) and Si (CH ₃ ) ⁺ fragment ions derived from dimethylsiloxane were measured to determine the distribution of each fragment ion in the plane. The measurement conditions are as follows.

·Measuring conditions

Primary ion species: Bi ⁺

Primary ion current: 1.000 pA

Acceleration voltage: 25 kV

Detection Ion polarity: negative (F ^- ), positive (Si (CH ₃ ) ⁺ )

Measuring range: 100 탆 x 100 탆

Resolution: 128 × 128

Scan count: 36 times.

In the analysis of the measurement data, first, software using the built-in secondary ion mass spectrometer is used to calculate the two-dimensional positional information on the outermost surface of the laminated film and the secondary ion of each fragment ion at the corresponding position The intensity information was extracted. For the positional information, the measurement range set as the measurement condition is output as a lattice point of rectangular coordinates obtained by evenly dividing the measurement range by the numerical value of the resolution. The coefficient of variation of the secondary ionic strength can be calculated based on the value of the extracted secondary ionic strength. That is, the standard deviation and the average value of the secondary ion intensity are calculated using the values of all extracted secondary ion intensities, and the value of (standard deviation) / (mean value) is used as the coefficient of variation.

Next, using the software built in the secondary ion mass spectrometer, three-dimensional information obtained by adding the secondary ion intensity to the above-mentioned two-dimensional position information for each fragment ion is shown in Figs. 2 to 4 Plane mapping (mapping). At this time, the scale of the secondary ion intensity is automatically set by the software from the maximum value and the minimum value in the measurement area. On the other hand, in the portion with low detection intensity, the effect of oil repellency and lipophilic property expected in the chemical species originating from the fragment ion can not be sufficiently obtained. Specifically, 20% of the maximum value in the secondary ion intensity is bounded And the area not meeting this value was regarded as a region which does not substantially affect the chemical species of interest and was set as an area below the above-mentioned boundary value.

The plane distribution and the scale bar of the F ^- fragment ion (M / Z = 19) and the Si (CH ₃ ) ⁺ fragment ion derived from dimethylsiloxane obtained from this result were imaged with the image processing software EasyAccess Ver 6.7.1.23 And the white balance was adjusted so as to be accommodated in the tone curve of the 8-bit peak and the darkest parts, and the contrast was adjusted with reference to the scale bar so that the above-mentioned boundary value in the secondary ion distribution could be clearly discriminated . Subsequently, pixels were binarized using the image analyzing software ImageJ 1.45s with the above-described boundaries as a boundary, and only the plane distribution was cut out, and the area formed by the distribution regions of the respective fragment ions was calculated. Further, the area of the region was divided by the area across the measurement range, and the ratio and the occupancy rate of the region in which the fragment ions existed were obtained.

And, a time-of-flight secondary ion mass spectrometer, if the coefficient of variation of less than 0.4 secondary ion strength in the range of 100㎛ × 100㎛ a total measuring points measured by the vertical 128 dots × 128 dots horizontally, F ^- fragment Ions were &quot; uniformly present &quot;.

Further, as a result of observation of an image, as shown in Fig. 2, when the secondary ion intensity of Si (CH ₃ ) ^{+ at} the measurement point at which the measurement was made is shown, (Except that it is caught on the outer periphery of the drawing), the Si (CH ₃ ) ⁺ fragment ion was judged to exist in an island shape.

On the other hand, as a result of observing the image, when the secondary ion intensity of the Si (CH ₃ ) ⁺ fragment is shown as shown in Fig. 3, when the region below the above-mentioned boundary value exists in an island shape, (CH ₃ ) &lt; ^{+ &} gt ^; fragment ion existed in a net shape.

Or, as a result of observing the image, when the secondary ion intensity of the Si (CH ₃ ) ⁺ fragment is shown as shown in FIG. 4, the region existing in the island shape and the region existing in the mesh shape within the measurement range Si (CH ₃ ) &lt; ^{+ &} gt ^; fragment ions exist in an island shape and a mesh-like shape.

The following line profile analysis was carried out by extracting arbitrary columns and row information parallel or perpendicular to the above-described rectangular coordinates of the position information from the plane distribution. First, the extracted row or column was divided into two types, that is, a line segment in which each fragment ion exists and a line segment below the boundary value, based on the boundary value of the secondary ion intensity described above. Subsequently, the length of each line segment was calculated, and the average value thereof was determined.

[Breaking elongation of surface layer]

The laminated film was cut into a length of 10 mm width x 200 mm and held by a chuck so as to be elongated in the long side direction and stretched at a tensile speed of 100 mm / min by an Instron type tensile tester (MODEL 5848 manufactured by Instron Corporation). The measurement atmosphere at this time is 23 占 폚 占 65RH%. When the sample is stretched, a sample in the elongation is observed. When a crack (crack) occurs in the naked eye, the sample is stopped (the elongation at the stop is adjusted to be an integer multiple of 5 (%)). Samples to be measured from the next were taken at a rate lower than the elongation at rest by 5% in units of elongation, and the samples were sequentially picked up until the elongation at which no cracks finally occurred with the naked eye.

The cross section of the cracked portion of the collected sample is cut out and the surface layer is observed at a magnification of 30 mm or more on the observation screen of the transmission electron microscope so that a crack of 50% or more of the average thickness of the surface layer is generated (Cracking oil of the surface layer), and the elongation value of the sample having the lowest elongation among the cracked samples was regarded as the elongation at break. Then, the same measurement was performed three times in total, and the average value of the fracture elongation was determined as the fracture elongation of the surface layer.

[Maximum amount of displacement of the surface layer in the thickness direction, amount of creep displacement and amount of permanent displacement]

1 g of &quot; Hiberné Grease &quot; manufactured by Toray Dow Corning Co., Ltd. was applied to a smooth metal plate (Dyse steel: SKD-11), and the support substrate side of the laminated film was attached to the high- A filter paper was provided on the side of the surface layer of the film, and pressed with a hand press to prevent air from entering. A pressurized load / unload test was performed on a stationary sample obtained by this method using a triangular pyramid to obtain a weighted-indentation depth diagram (see Fig. 1).

From this graph, the amount of displacement (the amount of creep displacement) in the thickness direction when the load is applied and then removed is shown in the thickness direction when the load reaches 0.5 mN and is held continuously for 10 seconds, And the amount of displacement in the thickness direction (permanent displacement amount) when the load was released to 0 mN was obtained.

Apparatus: Dynamic ultra-micro-hardness meter "DUH-201" (manufactured by Shimadzu Corporation)

Used indenter: diamond-shaped triangular-pyramid indenter (115 ° angle between corners)

Measurement mode: 2

Maximum load: 0.5mN

Holding time when reaching 0.5mN load: 10 seconds

Load speed, Unloading speed: 0.1, 422mN / sec.

[Self-recovery property of surface layer]

The surface of the surface layer was subjected to the following load by applying the following load to a brass brush (manufactured by TRUSCO) in a circumferential environment at 20 캜 for 5 hours after being horizontally cleaned for 5 minutes, , And 4 or more points were judged as pass.

10 points: There is no scratch on 9.8N (1kg) load.

7 point: The load is 9.8N (in 1kg), but the 6.9N (700g in) is not scratched.

4 points: Scratches are left in 6.9N (700g in weight), but no scratches are left in 4.9N (in 500g).

1 point: Scratches are left in load 4.9N (in 500g).

[Designability of surface layer]

The surface of the surface layer was allowed to stand for 12 hours at a temperature of 20 占 폚 and then the surface of the surface layer was subjected to a horizontal load of 500 g with a brass brush (manufactured by TRUSCO Co., Ltd.) Judgment was made by visual observation, and at least 4 points were accepted.

10 points: All scratches are restored to less than 3 seconds.

7 points: All scratches are restored from 3 seconds to less than 10 seconds.

4 points: All scratches are recovered from 10 seconds to less than 30 seconds.

1 point: Miscellaneous (all scratches take more than 30 seconds to recover, scratches are not recovered, or scratches do not occur).

[How to attach a simulated fingerprint]

The adhesion of the simulated fingerprint to the target surface of the laminated film of the present invention is as follows: 1. production of a simulated fingerprint sheet; 2. transfer of the simulated fingerprint to silicone rubber; and 3. adhesion of the simulated fingerprint to the laminated film surface. Step.

1. Making a simulated fingerprint sheet

The following materials were weighed in the following proportions, and stirred with a magnetic stir bar for 30 minutes to obtain a coating material for producing a simulated fingerprint sheet.

Oleic acid 14 parts by mass

Silica particles (number average particle diameter 2 占 퐉) 6 parts by mass

Isopropyl alcohol 80 parts by mass

The number average particle diameter of the silica particles was observed and measured with a scanning electron microscope (SEM). The observation samples were prepared by mixing the silica particles with a dispersion medium (isopropyl alcohol) at a solid concentration of 5% by mass, dispersing them by ultrasonic waves, dropping them on a conductive tape, and drying them. The number average particle diameter is obtained by observing at a magnification that the number of primary particles per field of view is 10 or more and 50 or less, obtaining the diameter of the circumscribed circle of the primary particle from the obtained image, And the number average particle diameter was determined from the values measured for 100 primary particles.

This "simulated fingerprint sheet-forming coating material" was applied on a PET resin film as a supporting substrate by using a wire bar (# 7) on "Lum Mirror" U46 (TORAY KABUSHIKI CO., LTD.) Coated with an easy-to- And dried at 50 DEG C for 2 minutes to remove isopropyl alcohol to obtain a simulated fingerprint sheet in which a simulated fingerprint liquid (dispersion containing 70 mass% of oleic acid and 30 mass% of silica) uniformly spread on the film.

2. Transfer of mock fingerprint to silicone rubber

The surface of the silicone rubber having a rubber hardness of 50 specified in JIS K6253 (1997) was polished with a # 250 water-resistant paper to obtain Ra of 3 m defined in JIS B0601 (2001). Subsequently, the silicone rubber polished with the water-resistant paper was pressed to the simulated fingerprint sheet at 30 kPa. The adhesion amount (g / m ² ) of the simulated fingerprint liquid to the silicone rubber indicates the value obtained from the area difference of the silicone rubber and the difference in mass before and after adhesion, and as a result, it was 1.0 g / m ² .

3. Attachment of simulated fingerprint to laminated film surface

The simulated fingerprint was transferred to the surface of the laminated film at a pressure of 30 kPa to form a simulated fingerprint on the surface of the laminated film.

[How to wipe the mock fingerprints]

In the above method, a laminated film having a simulated fingerprint attached to a surface thereof was fixed on a flat plate, and points A and B were determined on the laminated film so that the interval was 10 cm. Then, a cellulosic long fiber nonwoven fabric gauze ("Haiza" gauze NT-4 manufactured by Matsushita Chemical Industries, Ltd.) having a size of 12.5 x 12.5 cm and a folded size was placed on the laminated film, and a pressure of 30 kPa was applied thereto. Woven fabric having a weight placed thereon was wiped off by making three reciprocations between points A and B at a speed of 5 cm / sec.

[Including regular reflection light before and after attaching fingerprint, color difference of clear reflection light removal]

A black vinyl tape was attached to the opposite surface of the molding material, and the reflection color before and after attachment of the above-mentioned simulated fingerprints was measured using a spectroscopic colorimeter CM-3600A manufactured by Konica Minolta Co., Ltd. according to JIS Z8722 (2009 (Di: 8 °) Sb10W10 condition using the specular reflection light trapping (de: 8 °) Sb10W10 condition using the specular reflection light trap, Was measured by CIE 1976 (L ^* a ^* b ^* ) described in JIS Z8730 (2009). The measurement after attachment of the simulated fingerprints was carried out on three kinds of samples immediately after the application, 30 minutes after the application, and 10 hours after the application.

(ΔE ^* _ab (di: 8 °) Sb10W10) and ΔE (abbreviated as ΔE) are calculated from the reflection color before attachment of the simulated fingerprint and the reflection color immediately after attachment of the simulated fingerprint according to the calculation method described in JIS Z8730 ^* _ab (de: 8 DEG) Sb10W10).

(ΔE ^* _ab (di: 8 °) Sb10W10) before and after applying the simulated fingerprint is 0.4 or less, and the color difference (ΔE ^* _ab (de: 8 °) 4 or less.

(ΔE * _ab (di: 8 °) Sb10W10, ΔE _{SCI -0.5} ) and (ΔE *) by the calculation method described in JIS Z8730 (2009) from the reflection color of the values before attachment and after 30 minutes from the attachment, _ab (de: 8 DEG) Sb10W10, DELTA E _{SCE -0.5} ). To continue on the basis of measured values, calculated parameter K _{0 .5,} defined by the equation (5), and a more than 2 to pass.

(ΔE ^* _ab (di: 8 °) Sb10W10, ΔE _{SCI- 10} ) and (ΔE ^* _ab (de: 8 °)) by the calculation method described in JIS Z8730 °) Sb10W10, ΔE _SCE-10 ). Subsequently, it based on the measurement, by calculating a parameter K _10, which is defined by the equation (6), and the less the difference between the parameter K _{0 .5} 1 to pass as shown in the equation (4).

[Color difference of clear reflection light removal before and after simulated fingerprint removal, clear reflection light removal after simulated fingerprint removal]

A black vinyl tape was attached to the opposite surface of the laminated film, and the reflection color before and after wiping of the above-mentioned simulated fingerprints was measured using a spectroscopic colorimeter CM-3600A manufactured by Konica Minolta Co., Ltd. according to JIS Z 8722 (De: 8 °) Sb10W10 using reflective mirror traps (di: 8 °), the reflection color including specularly reflected light is used as the reflection color of regular reflection light elimination (2009) (L ^* a ^* b ^* ) described in JIS Z8730 (2009) under the Sb10W10 condition.

(ΔE ^* _ab (di: a)) from the reflection color after the simulated fingerprint is removed from the reflection color after the simulated fingerprint is wiped by the calculation method described in JIS Z 8730 (2009) 8 °) Sb10W10) and (ΔE ^* _ab (de: 8 °) Sb10W10) were determined to obtain ΔE _SCI-2 as the former and ΔE _SCE-2 as the latter.

[Measurement of diameter of ruins]

The simulated fingerprints attached to the surface of the molding material in the same manner as in the above-mentioned simulated fingerprint attachment were stored for 24 hours at 25 DEG C and the surface projection images of the memories were photographed using differential interference microscopy and, using the image processing software of the obtained image was determined remains diameter (d _p) a, and the frequency on the basis of the result based on area distribution and changes of the cumulative frequency is obtained.

The detailed measurement procedure of the diameter d _{p of the} ruins will be described below.

First, the surface of the anti-fingerprint molding material having the simulated fingerprint attached thereto was imaged with a differential interference microscope at a magnification of 100 times. Next, the image is converted to grayscale by the image processing soft EasyAccess Ver6.7.1.23, the white balance is adjusted so that the shortest and darkest parts are accommodated in the 8-bit tone curve, and the contrast is adjusted so that the boundaries of the remains can be clearly discriminated Respectively. Subsequently, the pixels are binarized using the image analyzing software ImageJ 1.45s with the boundaries set as described above, and the area formed by the individual remains is calculated. Then, the diameter of the area Respectively.

[Frequency distribution of reference area of remains]

In the calculation of the area frequency reference distribution of the remains, the histogram was created based on the diameter d _{p of the} remains obtained by the above-described process. At this time, the diameter of the ruins was divided every 5 탆, and based on this, the histogram function of Microsoft Excel 2003 was used to perform layering. In order to assign a weight based on the area of the surface projection image to the histogram thus obtained, it is assumed that the representative area of each layer of the histogram is a circle in which the center value of each radix is a representative diameter. And then divided by the total area to obtain the area reference frequency distribution. Further, with respect to the area reference frequency distribution, the median diameter (D _P ) was obtained from the value of the diameter at the cumulative frequency of 50% by plotting the cumulative frequency with the ordinate axis frequency and the abscissa axis as the diameter of the ruins. Concretely, two layers with a cumulative frequency of 50% are specified from the histogram, and the two coordinates specified by the center value and the cumulative frequency of the diameter of the ruins of the layer are connected by a straight line, The median diameter (D _P ) was calculated as the diameter of the remains at the point where the cumulative frequency was 50%.

[Change over time of frequency distribution of area standard]

After the simulated fingerprints were attached to the surface of the molding material in the same manner as in the above-mentioned simulated fingerprint attachment, the molding materials were left for 30 minutes and 10 hours respectively at 25 DEG C and no-wind condition. The diameter of the ruins after 30 minutes and the diameter of ruins after 10 hours were measured by measuring the diameter of the ruins described above. In addition, the median diameter was calculated (D _{P0 .5)} and the median diameter (D _P10) after 10 hours after 30 minutes by the analysis set forth in the area of the reference frequency distribution there.

[Fingerprint (fingerprint adhesion)]

(Index fingerprint) is placed on a black screen with the side to be evaluated of the laminated film facing up, the finger (forefinger) pressing the fingerprint and the thumb are rubbed three times, and the finger (index finger) The visibility of the attached fingerprints was evaluated by the following evaluation criteria, and at least five points were determined as acceptable.

10 points: The fingerprint is not recognized or the difference between the fingerprint is not known.

7 point: Fingerprint can hardly be recognized, or fingerprint is not recognized.

5 points: Fingerprints are slightly visible, but do not bother.

3 points: The fingerprint is recognized.

One point: The fingerprint is clearly acknowledged, and it is very careful.

The above evaluation was performed on 10 subjects, and the average value was obtained. Rounded decimal places were treated as rounded.

[Munsung (Fingerprint Lossiness)]

As in the evaluation of the above-mentioned property, the visibility of fingerprints left to stand at 25 캜 for 10 hours under a no-wind condition after the transfer of the fingerprints was evaluated with respect to the above-mentioned evaluation " To 90 [deg.] (Looking directly above), and evaluated with a score of 10 out of 10. The visibility of the fingerprint after leaving was evaluated by the following evaluation criteria, and at least 7 points were passed.

10 points: The fingerprint is not recognized or the difference between the fingerprint is not known.

7 point: Fingerprint can hardly be recognized, or fingerprint is not recognized.

5 points: Fingerprints are slightly visible, but do not bother.

3 points: The fingerprint is recognized.

One point: The fingerprint is clearly acknowledged, and it is very careful.

The evaluation was performed on 10 subjects, and the average value was obtained. Rounded decimal places were treated as rounded.

[Myeongseong (fingerprint polishability)]

After the fingerprint was attached in the above-described manner, wiping was performed by using a cellulose long-fiber nonwoven fabric gauze having a folded size of 12.5 x 12.5 cm ("Haiza" gauze NT-4 manufactured by Moto Sanayaku Kagaku Co., Ltd.) Respectively. The fingerprint polishability was evaluated by visibility after wiping with a wiping method by the following evaluation criteria, and at least 5 points were passed.

10 points: If you wipe it once, you can hardly see it.

7 points: If you wipe it once, it will be almost unimportant.

5 points: Only one or two wipes will be contaminated, but if you wipe three times, you will hardly be able to see.

3 points: If you wipe 5 times, it will be almost unimportant.

1 point: Pollution remains even if wiped more than 5 times.

The evaluation was carried out for ten subjects, and the average value was obtained. Rounded decimal places were treated as rounded.

[My cosmetic property]

0.5 g of Atrix &quot; Hand Cream A &quot; (NO413) manufactured by Kao Corporation was applied to a sample cut in a square of 5 cm and left for 6 hours in an atmosphere at a temperature of 60 DEG C and a relative humidity of 95% Leave under the atmosphere for 30 minutes to wipe the surface clean with gauze. After standing for 24 hours in an atmosphere at a temperature of 25 占 폚 and a relative humidity of 65%, the state of the surface was observed, and determination was made according to the following criteria.

10 points: No occurrence of algae.

7 points: Almost no occurrence of algae.

4 points: It occurs when it is white, but it is clean when wiped.

1 point: Whitehead occurs. Even after wiping, it occurs again after standing for 24 hours in an atmosphere at a temperature of 25 ° C and a relative humidity of 65%.

The physical properties of the laminated films X and Y having the X layer and Y layer formed for evaluating the physical properties of the urethane acrylates B and C are shown in Tables 1 and 2 in Tables 3-1, 3-2, 4-1 and 4- 2, 5-1, and 5-2 were summarized. Evaluation items (60 ° mirror gloss, breaking strength, self-repellency, designability, cosmetic resistance, color difference before and after a simulated fingerprint, K _0.5 , K _0.5 -K ₁₀ , Fingerprint disappearance), and fading (fingerprint wiping)), it was judged that the problem was not met.

[Table 1]

[Table 2]

[Table 3-1-A]

[Table 3-1-B]

[Table 3-2-A]

[Table 3-2-B]

[Table 4-1-A]

[Table 4-1-B]

[Table 4-2-A]

[Table 4-2-B]

[Table 4-2-C]

[Table 4-2-D]

[Table 5-1-A]

[Table 5-1-B]

[Table 5-1-C]

[Table 5-2-A]

[Table 5-2-B]

[Table 5-2-C]

[Table 5-2-D]

[Table 5-2-E]

[Table 5-2-F]

1: maximum displacement 2: creep displacement
3: Permanent displacement amount 4: Displacement amount in the thickness direction (h (탆))
5: Load (P (mN)) 6: Weighted process
7: Holding process 8: Removal process
9, 11 and 13: regions in which Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane exist
10, 12, 14: Si (CH ₃ ) ⁺ fragment ions derived from dimethylsiloxane (M / Z = 43)
[Industrial applicability]
The laminated film according to the present invention can also be used for imparting similar functions to respective surfaces of plastic molded articles, household appliances, buildings, automobile interior parts, and various printed materials.

Claims (12)

A laminated film having a surface layer on at least one surface of a support substrate, wherein the surface layer satisfies the following 1 to 3:
1. 60% specular gloss specified by JIS Z8741 (1997) is 60% or more
2. The receding contact angle (θ _r ) of oleic acid is 50 ° or more
3. The micro-hardness measurement method according to any one of claims 1 to 3, wherein a maximum displacement amount in the thickness direction of the surface layer when a 0.5 mN load is applied for 10 seconds is 1.0 占 퐉 or more and 3.0 占 퐉 or less,
The amount of creep displacement in the thickness direction of the surface layer is 0.05 탆 or more and 0.5 탆 or less,
When the load is released to 0 mN, the amount of permanent displacement of the surface layer in the thickness direction is 0.2 탆 or more and 0.7 탆 or less The laminated film according to claim 1, wherein the advancing contact angle (? _A ) and the receding contact angle (? _R ) of oleic acid in the surface layer satisfy the following formula (1).
(? _{a -} ? _r )? 15? Equation (1) The laminated film according to claim 1 or 2, wherein the oleic acid absorption coefficient (A _b ) of the surface layer is 30 or more.
Here, the oleic acid absorption coefficient (A _b ) refers to the volume (V ₁ ) determined from the droplet shape at the time of discharging oleic acid from the syringe, the area (S ₁ ) of the adhered portion at the time of deposition, ( ₂ ) from the volume (V ₂ ) after holding for 10 hours in a no-wind condition and the thickness (T) of the surface layer.
A _b = (V ₁ -V ₂ ) / (S ₁ × T) (2) 4. The method according to any one of claims 1 to 3, wherein F ^- fragment ions (M / Z = 19) derived from fluorine, measured by a time-of-flight secondary ion mass spectrometer (TOF- SIMS) , And Si (CH ₃ ) ⁺ fragment ions (M / Z = 43) derived from dimethylsiloxane exist uniformly in this plane and exist in any one of the following.
· Exists in island shape
· Exists in a net shape
· Exists in island shape and mesh shape 5. The semiconductor device according to any one of claims 1 to 4, wherein occupancy of a region where Si (CH ₃ ) ⁺ fragment ions derived from dimethylsiloxane is present in the surface layer is 30% or more and 70% or less film. The image display device according to any one of claims 1 to 5, characterized in that the surface layer is provided with a color difference including regular reflection light specified in JIS Z8730 (2009) and JIS Z8722 (2009) before and after a simulated fingerprint is attached under the following conditions ? E ^* _ab (di: 8) Sb10W10 is 0.4 or less, and the color difference? E ^* _ab (de: 8 deg.) Of regularly reflected light is Sb10W10 is 4 or less.
Simulated fingerprint attachment conditions: A dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 was prepared in the same manner as described in JIS K6253 (1997) with a Ra of 3 占 퐉 as defined in JIS B0601 A rubber rubber having a rubber hardness of 50 specified is attached to 1.0 g / m ² on the silicone rubber and attached to the surface to be treated at 30 kPa. The laminated film according to any one of claims 1 to 6, wherein the surface layer satisfies the following formulas (3) and (4).
K _{0 .5?} 3 Equation (3)
K _{0 .5} -K _10? 1 Equation (4)
here,
_{K 0 .5 = [(ΔE SCI} -0.5) 2 + (ΔE SCE -0.5) 2] 1/2 Equation (5)
K ₁₀ = [(ΔE _{SCI -10} ) ² + (ΔE _{SCE -10} ) ² ] ^1/2 (6)
ΔE _{SCI -0.5} , ΔE _{SCE -0.5} :
On the basis of a state before attaching the simulated fingerprint in the following manner on the surface layer, simulated from the fingerprint adhesion was measured after 30 minutes JIS Z8730 (2009), and ΔE ^* _ab (di specified in JIS Z8722 (2009): 8 ° ) Sb10W10, and? E ^* _ab (de: 8 °) Sb10W10, respectively.
? E _{SCI- 10} ,? E _{SCE -10} :
On the basis of a state before attaching the simulated fingerprint in the following manner on the surface layer, simulated from the fingerprint adhesion was measured after 10 hours JIS Z8730 (2009), and ΔE ^* _ab (di specified in JIS Z8722 (2009): 8 ° ) Sb10W10, and? E ^* _ab (de: 8 °) Sb10W10, respectively.
Simulated fingerprint attachment conditions: A dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 was prepared in the same manner as described in JIS K6253 (1997) with a Ra of 3 占 퐉 as defined in JIS B0601 A rubber rubber having a rubber hardness of 50 specified is attached to 1.0 g / m ² on the silicone rubber and attached to the surface to be treated at 30 kPa. 8. The method according to any one of claims 1 to 7, wherein the median diameter (D _P ) calculated from the area reference frequency distribution of the remains formed when the simulated fingerprint is attached to the surface layer in the following manner is expressed by the following expression (7) and (8).
D _{P0 .5} &amp; le; 80 mu m Equation (7)
_{(D P0 .5 -D P10) /} D P0 .5 ≥0.5 (8)
D _{P0 .5:} a median diameter calculated from the area-based frequency distribution of remains that makes up a mock fingerprint measurement after 30 minutes from the attachment of the mock fingerprint
D _P10 : the median diameter calculated from the area reference frequency distribution of the remains constituting the simulated fingerprint measured 10 hours after the above-mentioned simulated fingerprint is attached
Simulated fingerprint attachment conditions: A dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 was prepared in the same manner as described in JIS K6253 (1997) with a Ra of 3 占 퐉 as defined in JIS B0601 A rubber rubber having a rubber hardness of 50 specified is attached to 1.0 g / m ² on the silicone rubber and attached to the surface to be treated at 30 kPa. 9. The method according to any one of claims 1 to 8, wherein the surface layer is subjected to a simulated fingerprint adhesion test and a simulated fingerprint polish test under the following conditions, and the simulation obtained in accordance with JIS Z8730 (2009) and JIS Z8722 (2009) The color difference ΔE ^* _ab (di: 8 °) Sb10W10 (hereinafter referred to as ΔE _{SCI -2} ) including the specular reflection light after the simulated fingerprint wiping test based on the state before the fingerprint is attached and the simulation Wherein the color difference DELTA E ^* _ab (de: 8 DEG) Sb10W10 (hereinafter referred to as DELTA E _SCE-2 ) of the regularly reflected light removed after the fingerprint polish test satisfies the following formula (9).
(? E _{SCI -2} ) ² + (? E _{SCE -2} ) ² ? ^{1/2? 2.0} Equation (9)
Condition of simulated fingerprint attachment and simulated fingerprint wipe test
- Simulated fingerprint attachment conditions: The dispersion containing 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 占 퐉 has a Ra of 3 占 퐉 as defined by JIS B0601 (2001), and JIS K6253 (1997) In which 1.0 g / m &lt; ² &gt; is adhered to a silicone rubber having a rubber hardness of 50 specified in Table 1, and the surface of the silicone rubber is adhered to the surface at a pressure of 30 kPa.
· Simulated fingerprint wipe condition: The simulated fingerprint attached with the above conditions is rubbed 3 times with a nonwoven fabric at a pressure of 30 kPa and a speed of 5 cm / sec. 10. The laminated film according to any one of claims 1 to 9, wherein the resin contained in the surface layer has the following (1) to (3).
(1) a (poly) caprolactone segment,
(2) a urethane bond,
(3) a segment containing 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 (hereinafter referred to as a fluorine compound segment) The laminated film according to claim 10, wherein the fluorine compound segment is a fluoro polyether segment. The laminated film according to claim 10 or 11, wherein the resin contained in the surface layer (4) has a (poly) siloxane segment and / or a polydimethylsiloxane segment.

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