CN104903102B

CN104903102B - Stack membrane

Info

Publication number: CN104903102B
Application number: CN201380069404.XA
Authority: CN
Inventors: 石田康之; 岩谷忠彦; 高田育; 金度均; 道添纯二
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2013-01-09
Filing date: 2013-12-16
Publication date: 2017-12-19
Anticipated expiration: 2033-12-16
Also published as: CN104903102A; TWI609784B; WO2014109177A1; TW201429721A; JPWO2014109177A1; KR102281542B1; KR20150113950A; JP6375946B2

Abstract

The problem to be solved by the present invention is that, there is provided a kind of stack membrane, meet mouldability, self-repairability, design, reflecting feel, anti-finger printing.The stacked film of the present invention, it is characterised in that there is superficial layer at least one side of supporting base material, superficial layer meets following 1~conditions of condition 3：60 ° of mirror surface lusters are more than 60% specified in 1.JIS Z8741 (1997)；2. the receding contact angle θ of oleic acid_rFor more than 50 °；3. apply 0.5mN loadings in 10 seconds in micro-hardness tester measure, the maximum displacement of the thickness direction of above-mentioned layer is less than more than 1.0 μm 3.0 μm, the creeping displacement amount of the thickness direction of above-mentioned layer is less than more than 0.05 μm 0.5 μm, when loading is released untill 0mN, the permanent displacement amount of the thickness direction of above-mentioned layer is less than more than 0.2 μm 0.7 μm.

Description

Laminated film

Technical Field

The present invention relates to a laminated film having excellent design properties and fingerprint resistance, while satisfying both molding follow-up properties and scratch resistance required for molding materials.

Background

A molding material used for decorative molding or the like is provided with a surface-hardened layer in order to prevent damage during molding and damage during use of an article after molding. However, since the surface-hardened layer has insufficient elongation following molding, cracks occur during molding, a thin film is broken in an extreme case, or the surface-hardened layer is peeled off, and therefore the following means is generally used: a surface-hardened layer may be formed after molding, or the molded article may be completely cured by heating or irradiation with active rays after molding in a semi-cured state. However, since the molded article is three-dimensionally processed, it is very difficult to provide a surface-hardened layer in the post-processing, and in the case of molding in a semi-cured state, mold fouling may occur depending on molding conditions. In view of the above, a scratch-resistant material that follows molding is expected, and a "self-healing material" or a "self-healing material" that can self-heal slight damage or deformation in its elastic recovery range is attracting attention.

Among these self-repairing materials, a material capable of recognizing a repair process of a flaw is also drawing attention from the viewpoint that the "design property" of a molding material can be improved when used for an exterior component since the function thereof can be directly recognized. As the self-healing or self-healing materials described above, the materials of patent documents 1 and 2 have been proposed.

On the other hand, in applications requiring a strong glossy feeling, a higher reflectance, and transparency, in particular, there is a problem that a fingerprint (here, a fingerprint refers to a pattern formed by lines (ridges) protruding from openings of sweat glands in the skin of a fingertip, and a trace of the pattern adhering to the surface of an object) is easily recognized by a person's finger contacting the surface in daily life, and if it is not easily erased, an unpleasant impression that the pattern looks dirty is given. In particular, recently, electronic devices such as smart phones, touch panels, keyboards, remote controllers for televisions and air conditioners are increasing, and for example, there are problems that fingerprints are attached by grasping a housing of the devices, the fingerprints are conspicuous, and the feeling of cleanliness is impaired.

In response to such a problem, patent documents 3 and 4 propose a member having a characteristic that a fingerprint is not easily attached to the surface of an article, is not easily recognized, or can be easily erased (hereinafter, the physical properties are referred to as fingerprint resistance).

Documents of the prior art

Patent document

Patent document 1: international publication No. 2011/36042

Patent document 2: japanese laid-open patent publication No. 11-228905

Patent document 3: japanese laid-open patent publication No. 2009-122416

Patent document 4: japanese patent laid-open publication No. 2011-

Disclosure of Invention

Problems to be solved by the invention

The present inventors have confirmed that the techniques of patent documents 1 and 2 proposed as the self-healing materials described above have a problem of insufficient fingerprint resistance although excellent in moldability and self-healing properties.

In the techniques of patent documents 3 and 4, the present inventors have confirmed fingerprint resistance under various conditions and have only satisfied these characteristics, and thus the effect of making fingerprints inconspicuous or easily wiping off fingerprints is insufficient. These materials do not exhibit moldability and self-repairability, and are techniques that cannot be combined with the techniques of patent documents 1 and 2.

Accordingly, an object of the present invention is to provide a laminated film that satisfies moldability, self-repairability, design properties, gloss, and fingerprint resistance.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have completed the following invention. Namely, the present invention is as follows.

< 1 > a laminated film characterized by having a surface layer on at least one side of a supporting substrate, the surface layer satisfying the following conditions 1 to 3:

condition 1: a 60 DEG specular gloss specified in JIS Z8741 (1997) of 60% or more;

condition 2: receding contact Angle θ of oleic acid_rIs more than 50 degrees;

condition 3: the maximum displacement in the thickness direction of the surface layer when a load of 0.5mN is applied for 10 seconds in the micro hardness measurement is 1.0 μm or more and 3.0 μm or less,

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

when the load is removed to 0mN, the permanent displacement amount of the surface layer in the thickness direction is 0.2 μm or more and 0.7 μm or less.

< 2 > the laminated film according to < 1 >, the advancing contact angle theta of oleic acid of the above surface layer_aReceding contact Angle θ_rSatisfies the following formula (1):

(θ_a-θ_r) Formula (1) is less than or equal to 15 degrees.

< 3 > the laminated film according to < 1 > or < 2 >, wherein the oleic acid absorption coefficient A of the surface layer is_bThe content of the organic acid is more than 30,

wherein, the absorption coefficient of oleic acid is A_bThe volume (V) determined from the shape of the droplets at the time of discharge from a syringe was determined by dropping 2. mu.l of oleic acid onto the surface layer₁) And the area of the drop part during dropping (S)₁) Volume (V) after 10 hours at 25 ℃ in the absence of wind₂) And the thickness (T) of the surface layer, which is a value obtained by the following formula (2):

A_b＝(V₁-V₂)/(S₁× T) formula (2).

< 4 > the laminate film according to any one of < 1 > to < 3 >, wherein F derived from fluorine in the surface layer is measured by a time-of-flight 2-ion mass spectrometer (TOF-SIMS)^-Fragment ions (M/Z ═ 19) exist uniformly in the plane and are derived from Si (CH) of dimethyl siloxane₃)⁺The fragment ion (M/Z43) is present in any of the following ways:

island-like,

A network-like form,

Island-like and mesh-like.

< 5 > the laminate film according to any one of < 1 > to < 4 >, wherein Si (CH) derived from dimethylsiloxane is contained in the surface layer₃)⁺The occupancy rate of the region in which the fragment ions are present is 30% to 70%.

< 6 > the multilayer film according to any one of < 1 > -5 >, wherein a color difference △ E containing specular reflection light defined in JIS Z8730(2009) and JIS Z8722(2009) before and after the attachment of a simulated fingerprint on the surface layer is provided under the following conditions_ab(di: 8 ℃) Sb10W10 is 0.4 or less, and does not contain the color difference △ E of the regular reflection light_ab(de: 8 ℃) Sb10W10 is 4 or less,

simulating a fingerprint attachment condition: a dispersion of 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 μm was made to be 1.0g/m²Adhered to a silicone rubber having Ra of 3 μm as defined in JIS B0601 (2001) and rubber hardness of 50 as defined in JIS K6253 (1997), and adhered to a surface to be treated at 30 kPa.

< 7 > the laminate film according to any one of < 1 > to < 6 >, wherein the surface layer satisfies the following formulae (3) and (4):

K_0.5less than or equal to 3 type (3)

K_0.5-K₁₀More than or equal to 1 type (4)

Wherein,

K_0.5＝[(△E_SCI-0.5)²+(△E_SCE-0.5)²]^1/2formula (5)

K₁₀＝[(△E_SCI-10)²+(E_SCE-10)²]^1/2Formula (6)

△E_SCI-0.5、△E_SCE-0.5Respectively means that:

△ E defined in JIS Z8730(2009) and JIS Z8722(2009) measured 30 minutes after the attachment of the simulated fingerprint on the surface layer by the following method was used as a reference in the state before the attachment of the simulated fingerprint on the surface layer_ab(di: 8 ℃ C.) Sb10W10 and △ E_ab(de：8°)Sb10W10，

△E_SCI-10、△E_SCE-10Respectively means that:

△ E defined in JIS Z8730(2009) and JIS Z8722(2009) measured 10 hours after the attachment of the simulated fingerprint on the surface layer by the following method was used as a reference in the state before the attachment of the simulated fingerprint on the surface layer_ab(di: 8 ℃ C.) Sb10W10 and △ E_ab(de：8°)Sb10W10，

Simulating a fingerprint attachment condition: a dispersion of 70% by mass of oleic acid and 30% by mass of silica having a number average particle size of 2 μm was made to be 1.0g/m²Adhered to a silicone rubber having Ra of 3 μm as defined in JIS B0601 (2001) and rubber hardness of 50 as defined in JIS K6253 (1997), and adhered to a surface to be treated at 30 kPa.

< 8 > the laminated film according to any one of < 1 > to < 7 >, wherein,

median diameter (D) of oil droplets formed when an analog fingerprint is attached to the surface layer by the following method, calculated from area-based frequency distribution_P) Satisfies the following formulae (7) and (8):

D_P0.5less than or equal to 80 mu m type (7)

(D_P0.5-D_P10)/D_P0.5More than or equal to 0.5 type (8)

D_P0.5: a median diameter calculated from an area-based frequency distribution of oil droplets constituting the simulated fingerprint measured 30 minutes after the simulated fingerprint was attached,

D_P10: a median diameter calculated from an area-based frequency distribution of oil droplets constituting the simulated fingerprint measured 10 hours after the simulated fingerprint was attached,

simulating a fingerprint attachment condition: a dispersion of 70% by mass of oleic acid and 30% by mass of silica having a number average particle size of 2 μm was made to be 1.0g/m²Adhered to a silicone rubber having Ra of 3 μm as defined in JIS B0601 (2001) and rubber as defined in JIS K6253 (1997), and adhered to a surface to be treated at 30kPaThe hardness was 50.

< 9 > the laminated film according to any one of < 1 > to < 8 >, wherein,

the surface layer was subjected to a simulated fingerprint adhesion and simulated fingerprint erasure test under the following conditions, and the color difference △ E including the specular reflection light after the simulated fingerprint erasure test based on the state before the simulated fingerprint adhesion, which was obtained according to JIS Z8730(2009) and JIS Z8722(2009), was measured_ab(di: 8 ℃ C.) Sb10W10, △ E_SCI-2And a color difference △ E not including specular reflection light after the simulated fingerprint erasure test based on the state before the simulated fingerprint is attached_ab(de: 8 ℃ C.) Sb10W10 i.e. △ E_SCE-2Satisfying the following formula (9),

((△E_SCI-2)²+(△E_SCE-2)²)^1/2less than or equal to 2.0 type (9)

The conditions for the simulated fingerprint attachment and simulated fingerprint erasure tests were as follows,

simulated fingerprint attachment conditions: a dispersion of 70% by mass of oleic acid and 30% by mass of silica having a number average particle size of 2 μm was made to be 1.0g/m²Adhered to a silicone rubber having Ra of 3 μm as defined in JIS B0601 (2001) and rubber hardness of 50 as defined in JIS K6253 (1997), and adhered to a surface to be treated under a pressure of 30kPa,

simulated fingerprint erasure conditions: the simulated fingerprint attached under the above conditions was wiped 3 times with a nonwoven fabric at a pressure of 30kPa and a speed of 5 cm/sec.

< 10 > the laminated film according to any one of < 1 > to < 9 >, characterized in that,

the resin contained in the surface layer has the following (1) to (3):

(1) (poly) caprolactone segments,

(2) A urethane bond,

(3) A segment containing at least one member selected from the group consisting of a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkenyl group, a fluoroalkylene group, and a fluoroalkyleneoxy group (hereinafter referred to as a fluorochemical segment).

< 11 > the laminated film according to < 10 >, characterized in that,

the fluorine compound chain segment is a fluoropolyether chain segment.

< 12 > the laminated film according to < 10 > or < 11 >, characterized in that,

the resin contained in the surface layer has (4) a (poly) siloxane segment and/or a polydimethylsiloxane segment.

Effects of the invention

According to the present invention, a laminated film satisfying moldability, self-repairability, design properties, gloss, and fingerprint resistance can be obtained.

Drawings

FIG. 1 is a weight-indentation depth profile of an indentation load/relief load test using a regular triangular pyramid for a laminate film of the present invention;

FIG. 2 shows Si (CH) derived from dimethylsiloxane in the laminated film of the present invention₃)⁺An example of a case where the fragment ion (M/Z ═ 43) exists in an island shape;

FIG. 3 shows Si (CH) derived from dimethylsiloxane in the laminated film of the present invention₃)⁺An example of a case where the fragment ions (M/Z: 43) exist in a mesh shape;

FIG. 4 shows Si (CH) derived from dimethylsiloxane in the laminated film of the present invention₃)⁺Examples of the case where the fragment ions (M/Z: 43) exist in an island shape or a mesh shape.

Detailed Description

In order to satisfy the above-mentioned problems, i.e., moldability, self-repairability, design properties, gloss, and fingerprint resistance, the multilayer film of the present invention has a surface layer on at least one surface of a support substrate, and the maximum displacement amount in the thickness direction, creep displacement amount, and permanent displacement amount at the time of releasing a load of the surface layer preferably satisfy the following specific ranges.

From the viewpoints of moldability, self-repairability, and design, the laminated film of the present invention has a maximum displacement amount in the thickness direction of the surface layer of 1.0 μm or more and 3.0 μm or less, more preferably 1.0 μm or more and 1.7 μm or less, and a creep displacement amount in the thickness direction of the surface layer of 0.05 μm or more and 0.5 μm or less, more preferably 0.2 μm or more and 0.5 μm or less, when a load of 0.5mN is applied for 10 seconds in a microhardness measurement, and has a permanent displacement amount in the thickness direction of the surface layer of 0.2 μm or more and 0.7 μm or less, more preferably 0.4 μm or more and 0.65 μm or less, when the load is released to 0 mN.

If the maximum displacement amount in the thickness direction of the surface layer is greater than 3.0 μm, the self-repairability of the surface layer may be incomplete, and if the maximum displacement amount in the thickness direction of the surface layer is less than 1.0 μm, the design of the surface layer, that is, the recognizability in the recovery process may be deteriorated.

If the creep displacement amount in the thickness direction of the surface layer is more than 0.5 μm or less than 0.05 μm, the self-repairability or the design property may be incomplete.

If the permanent displacement amount in the thickness direction of the surface layer is greater than 0.7 μm, recognizable damage may remain even after the self-repair of the surface layer, and the appearance may deteriorate. In addition, from the viewpoint of self-repairability of the surface layer, it is better that the amount of permanent displacement is smaller, but in general, since the self-repairing material is plastically deformed, the lower limit of the amount of permanent displacement in the present measurement method is considered to be 0.2 μm. The method of measuring the maximum displacement amount, creep displacement amount, and permanent displacement amount in the thickness direction measured by these microhardometers will be described later.

From the viewpoint of the glossy feeling, the laminated film of the present invention preferably has a specular gloss within a specific range, and preferably has a specular gloss of 60% or more, more preferably 70% or more, and particularly preferably 80% or more, as measured by a specular gloss of 60 ° defined in JISZ8741 (1997). When the specular gloss is less than 60%, the feeling of gloss may be felt to be insufficient. The upper limit of the specular gloss also depends on the refractive index of the material, but is about 180% in the case of using a general material.

In the laminated film of the present invention, the receding contact angle θ of oleic acid of the surface layer is set to be smaller than that of the laminated film of the present invention_rPreferably 50 ° or more, more preferably 55 ° or more, and particularly preferably 60 ° or more.

As described later, the measurement method and meaning of the receding contact angle are such that there is no problem when the receding contact angle is high, but on the other hand, when the receding contact angle is less than 50 °, the fingerprint component gradually becomes liable to adhere, and the fingerprint resistance may be lowered.

Further, with respect to fingerprint resistance, particularly fingerprint erasability, the advancing contact angle θ of the fingerprint component of the above surface layer_aReceding contact angle theta_rThe relationship (2) preferably satisfies the above expression (1).

(θ_a-θ_r) Less than or equal to 15 degree type (1)

This means that, in view of the fact that the fingerprint wiping property is governed by two factors of "ease of transfer of fingerprint components to the wiping material" and "ease of movement of fingerprint components on the surface layer", the former can be expressed by a receding contact angle and the latter can be expressed by an advancing contact angle, and if the formula (1) is satisfied in combination, the adhered fingerprint can be easily wiped off.

Preferably advancing contact angle theta of oleic acid of the above surface layer_aReceding contact Angle θ_rThe angle satisfying the above formula (1) is 15 ° or less, more preferably 12 ° or less, and particularly preferably 10 ° or less. The value of the formula (1) is preferably as small as 0 or a positive value, while if the value is larger than 15 °, the fingerprint erasure is not sufficient, and there may be cases where the fingerprint erasure is insufficientFingerprint resistance is reduced.

Here, the receding contact angle and advancing contact angle will be described. The contact angle of a liquid on a solid surface is essentially a thermodynamic quantity, and if the system is fixed, it should be 1 value. However, in practice, when a liquid moves on a solid surface, the contact angle in the advancing direction and the contact angle on the opposite side (receding side) are often not the same value. The contact angle in the advancing direction at this time is referred to as an advancing contact angle, and the contact angle on the opposite side is referred to as a receding contact angle.

The advancing contact angle and the receding contact angle have values obtained by several measurement methods, but preferably values obtained by the expansion-contraction method. As another method, there is a roll off method, but this method requires a mass of a liquid droplet when calculating an advancing contact angle and a receding contact angle, and is not suitable because a phenomenon different from actual fingerprint adhesion is observed because a large oil droplet (several mm or more) is required compared to an oil droplet size (diameter 1 to 20 μm) when a fingerprint adheres, for convenience of measurement.

Here, measurement by the expansion-contraction method will be described. The value of advancing contact angle obtained by the expansion-contraction method is represented by an average value of contact angles when the contact angle becomes constant, which is measured continuously a plurality of times when a liquid (oleic acid) is applied to a surface layer to expand a liquid droplet. Similarly, the receding contact angle value is represented by an average value of contact angles when the contact angle is constant, in which a liquid (oleic acid) is applied to the surface layer, the liquid droplet is gradually discharged to expand, the liquid droplet is then sucked, and the contact angle of the liquid droplet is continuously measured a plurality of times while the liquid droplet is contracting. Specifically, for example, in the case of discharging and sucking (expanding and contracting a droplet) a liquid between 1 and 50 μ L, the following can be determined: the advancing contact angle was measured at intervals of 1. mu.L from 1. mu.L to 50. mu.L when the droplet was discharged, and the receding contact angle was measured at intervals of 1. mu.L from 50. mu.L to 1. mu.L when the droplet was sucked, and the values were determined when the contact angle of the droplet became substantially constant during the expansion or contraction of the liquid. The contact angle in the extensional shrinkage method can be measured using, for example, Drop Master (manufactured by synhony interfacial science corporation).

In the laminated film of the present invention, the oleic acid absorption coefficient a of the surface layer is preferably a coefficient of the oleic acid absorption of the surface layer from the viewpoint of having both self-repairability and fingerprint resistance_bIs 30 or more.

This is in addition to the reduction by increasing the receding contact angle θ_rThe oleic acid absorption coefficient A is an index showing the ability of the fingerprint component to be deposited by absorbing the deposited fingerprint component into the coating film and to disappear from the surface, in addition to the amount of the deposited fingerprint component_b. Specifically, when oleic acid is adhered, the oleic acid absorption coefficient per unit volume a is calculated from the volume and the adhering area of the oleic acid deposit immediately after the adhesion, the volume of the oleic acid deposit after a certain period of time has elapsed, and the thickness of the surface layer of the molding material_bPreferably 30 or more, and more preferably 40 or more.

On the other hand, the oleic acid absorption coefficient A for the above surface layer_bThe higher the amount of the fingerprint component is, the better the fingerprint component is, but the lower the amount of the fingerprint component is, the more the amount of the fingerprint component is, the more the amount of the fingerprint component.

Absorption coefficient of oleic acid A_bThe specific measurement method comprises the following steps: about 2. mu.l of oleic acid was dropped on the surface layer having the thickness T, and the volume (V) was determined from the shape of the droplet when discharged from the syringe₁) And the area of the drop part during dropping (S)₁) Volume (V) after 10 hours at 25 ℃ in the absence of wind₂) The dimensionless quantity obtained by the following formula (2) is used.

A_b＝(V₁-V₂)/(S₁× T) formula (2)

Here, for V₁、V₂、S₁There are several measurement methods, and the measurement can be performed by, for example, a contact angle measuring device DM500 by synechia interface chemical corporation and Drop Master by the same company analytical software. The detailed procedure of the measurement will be described later. The method for measuring the thickness T of the surface layer is also described below.

In addition, as for the surface layer exhibiting such characteristics, it is preferable that both the oleophobic material and the oleophilic material exist in a specific form on the outermost surface. More specifically, F derived from fluorine measured by time-of-flight type 2-time ion mass spectrometer (TOF-SIMS) of the surface layer is preferable^-Fragment ions (M/Z ═ 19) "exist uniformly" in plane, while Si (CH) derived from dimethylsiloxane₃)⁺The fragment ion (M/Z ═ 43) "exists in an island shape", "in a mesh shape", or "exists in an island shape and a mesh shape", and more preferably F^-Fragment ions exist "uniformly" in plane, and Si (CH)₃)⁺Fragment ions "exist in islands and meshes".

This is considered to be because, in order to show the characteristic that the surface layer of the present invention absorbs the attached fingerprint component into the coating film and disappears from the surface by reducing the amount of attachment of the fingerprint component as much as possible, the outermost surface of the surface layer is uniformly coated with the fluorine-containing compound in the plane to exhibit high oil repellency, thereby reducing the amount of attachment of the fingerprint component, and the fingerprint component slightly attached to the surface is diffused into the outermost surface and the surface layer through the island-like or mesh-like lipophilic portion existing on the surface by the presence of the lipophilic dimethylsiloxane-containing compound in fine island-like or mesh-like form, and as a result, the fingerprint stain disappears. In addition, with respect to the measuring method of the outermost surface of the surface layer using the time-of-flight type 2-order ion mass spectrometer (TOF-SIMS), the description is made in the items of the examples.

The term "uniformly present" means that the coefficient of variation of the 2-fold ion intensity is within 0.4 at all measurement points measured at 128 points in the vertical direction × 128 points in the range of 100 μm × 100 μm in a time-of-flight 2-fold ion mass spectrometer.

"island-like" means Si (CH) at the measurement point measured as shown in FIG. 2₃)⁺The periphery of the sample was surrounded by a portion not satisfying the critical value corresponding to 20% of the maximum intensity (excluding the outer portion of the graph) at the ion intensity of (2).The details of the threshold value are described later. The upper limit of the size of the island is set to be substantially within the measurement range of the time-of-flight type 2-order ion mass spectrometer, and the island having a circumscribed circle diameter of 50 μm or less is set as the measurement condition. On the other hand, the lower limit of the size is not particularly limited as long as it can be discriminated by the above-mentioned conditions, but actually depends on the spatial resolution of the measuring instrument, and is suggested to be about 0.8 μm in the above-mentioned measurement conditions.

"present in a mesh form" means that Si (CH) is shown in the figure as shown in FIG. 3₃)⁺At 2 nd ion intensity of the fragment, the region below the critical value is present in an island shape.

"island-like and mesh-like" means that Si (CH) is shown in the figure as shown in FIG. 4₃)⁺When the fragment had an ionic strength of 2X, the island-like regions and the mesh-like regions were present together in the measurement range. As Si (CH)₃)⁺The reason why the mode of existence of fragment ions is more preferably "in an island shape or a mesh shape" is considered to be that the diffusion of fingerprint stains in the surface direction of the outermost surface of the surface layer is superior as compared with the case of "existence in an island shape", and the ability of reducing the amount of fingerprint stains adhering is superior as compared with the case of "existence in a mesh shape".

Further, the above-mentioned Si (CH) derived from dimethylsiloxane₃)⁺The occupancy rate of the region where the fragment ions are present is preferably 30% to 70%, more preferably 30% to 50%, and particularly preferably 30% to 40%. Here, the occupancy means that Si (CH) is present at all measurement points₃)⁺The fraction of spots where fragment ions are present above the critical value. The calculation method of occupancy is described in the items of examples, but Si (CH) derived from dimethylsiloxane₃)⁺Region where fragment ions exist (in other words, Si (CH) derived from dimethylsiloxane₃)⁺A portion where fragment ions exist) less than 30%, the attached fingerprint may be sometimes classified intoThe ability to absorb the stain into the coating film is insufficient, and the fingerprint stain disappearance is reduced, and if it exceeds 70%, the ability to reduce the amount of fingerprint stain adhering may be reduced.

In addition, in the vertical or parallel direction to the "map" (indicating Si (CH))₃)⁺Si (CH) distributed on an arbitrary 1-line in the edge direction of a graph of the ion intensity of 2-fold of the fragment (for example, FIGS. 2 and 3))₃)⁺The length of each line segment in which fragment ions exist is preferably 30 μm or less, and more preferably 20 μm or less. If the amount exceeds the above value, the ability to reduce the amount of fingerprint stain adhering may be reduced. On the other hand, Si (CH) on the same straight line₃)⁺The lengths of the line segments in which the fragment ions do not satisfy the critical value are preferably divided into 50 μm or less, and more preferably 30 μm or less. If the amount exceeds the above value, the ability to absorb the fingerprint component adhering to the coating film may be insufficient, and the fingerprint stain disappearing property may be lowered. The lower limit of the length is not particularly limited as long as it can be distinguished by the above conditions, but actually depends on the spatial resolution of the measuring instrument, and is suggested to be about 0.8 μm under the above measurement conditions.

On the other hand, in order to solve the problem of the present invention, in addition to the above-mentioned mechanical and surface scientific properties of the surface layer, it is preferable that the color difference including the regular reflection light and the color difference not including the regular reflection light before and after the adhesion of the simulated fingerprint, which is a composition similar to an actual fingerprint, is in a specific range as the optical characteristic when the simulated fingerprint is adhered to the surface layer under a specific condition as shown below.

Here, "chromatic aberration including specular reflection light" refers to chromatic aberration measured under "the condition that a component that is reflected from a sample is included in the geometrical condition c" described in JIS Z8722(2009), "and" chromatic aberration not including specular reflection light "refers to chromatic aberration measured under" the condition that a component that is reflected from a sample is removed in the geometrical condition c ".

Specifically, the color difference before and after the attachment of the fingerprint is simulated, andit means the color difference (△ E) including regular reflection light defined in JIS Z8730(2009) and JIS Z8722(2009)_ab(di: 8 ℃) Sb10W10) is preferably 0.4 or less, more preferably 0.2 or less, particularly preferably 0.1 or less, the smaller the difference in color before and after the attachment of a fingerprint is simulated, the better the smaller the difference is, but when the attachment is performed under the same conditions, the lower limit is about 0.01 due to the limit of the material and the limit of the measurement method, and the difference in color before and after the attachment of a fingerprint is simulated, and the difference in color is defined as the difference in color without specular reflection (△ E) defined in JIS Z8730(2009) and JIS Z8722(2009)_ab(de: 8 ℃) Sb10W10) is preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. The lower limit is about 0.05 because of the material limit and the measurement method limit when the fingerprint is adhered under the same condition. If the color difference between the reflected light before and after the attachment of the pseudo fingerprint and the color difference between the reflected light after and before the attachment of the pseudo fingerprint and the reflected light without the reflected light exceeds 0.4 and 4, respectively, the trace of the attachment of the fingerprint may be clearly recognized. The procedure for the specific simulated fingerprint transfer is as follows.

Simulating a fingerprint attachment condition: a dispersion of 70% by mass of oleic acid and 30% by mass of silica having a number average particle diameter of 2 μm was prepared at a ratio of 1.0g/m²Adhered to a silicone rubber having Ra of 3 μm as defined in JIS B0601 (2001) and rubber hardness of 50 as defined in JIS K6253 (1997), and adhered to a surface to be treated at 30 kPa.

In the molding material of the present invention, it is preferable that the color difference between the specular reflection light-containing material and the specular reflection light-free material before and immediately after the attachment of the simulated fingerprint is a specific value or less, and the amount of temporal decrease in the color difference is a specific value or more. This corresponds to the effect of making the above fingerprint components disappear by being absorbed by the surface layer. Specifically, the following is given.

First, regarding the color difference including the regular reflection light and the color difference without the regular reflection light between before and immediately after the attachment of the simulated fingerprint, a parameter K shown in the following formula (5)_0.5Preferably 3 or less, more preferably 2 or less. If the number exceeds 3, the fingerprint mark may be easily recognized and may become too largeIt is difficult to obtain a sufficient penetrating effect of the attached fingerprint.

K0_.5＝[(△E_SCI。0.5)²+(△E_SCE-0.5)²]^1/2Formula (5).

Here, △ E described above_SCI。0.5The color difference before and after the attachment of the fingerprint is simulated, and is the color difference (△ E) containing the regular reflection light defined in JIS Z8730(2009) and JIS Z8722(2009)_ab(di：8°)Sb10W10)，△E_SCE-0.5The color difference before and after the attachment of the fingerprint was simulated, and the color difference was determined to be a color difference without the normally reflected light (△ E)_ab(de：8°)Sb10W10)。

△E*_ab(di: 8 ℃ C.) Sb10W10 and △ E_ab(de: 8 °) Sb10W10 are physical quantities having equivalent dimensions, and the parameter K corresponding to the distance from the origin is reduced in a plane coordinate system having the respective values as axes_0.5This is equivalent to reducing the visibility of the fingerprint before and after the attachment of the analog fingerprint. Furthermore, although it can be said that the parameter K_0.5The smaller the size, the more excellent the fingerprint adhesion preventing property is, but in the material having a high gloss and transparency which is the subject of the present invention, the parameter K is used for the purpose of recognizing the effect of the change of fingerprint with time which will be described later_0.5In reality, it exceeds 1.

The term "immediately after the attachment of the pseudo fingerprint" means 30 minutes after the pseudo fingerprint is attached to the surface of the molding material by the method of attaching the pseudo fingerprint described later.

The amount of temporal decrease in the color difference before and after the attachment of the pseudo fingerprint, that is, the left side value of the following expression (4), is preferably 1 or more, and more preferably 1.2 or more. If the left value of the following formula (4) is less than 1, the feeling of disappearance of the fingerprint stain may be difficult to obtain.

K_0.5-K₁₀More than or equal to 1 type (4)

Here, K in the formula (4)_0.5As mentioned above, K₁₀Represented by the following formula (6).

K₁₀＝[(△E_SCI-10)²+(△E_SCE-10)²]^1/2Formula (6)

△ E in formula (6)_SCI-10Is a color difference between before the attachment of the simulated fingerprint and after the attachment of the simulated fingerprint is left standing at 25 ℃ for 10 hours in a calm state, and is a color difference (△ E) containing specular reflection light defined in JIS Z8730(2009) and JIS Z8722(2009)_ab(di：8°)Sb10W10)，△E_SCE-2Means the color difference of the same sample without the normally reflected light (△ E%_ab(de：8°)Sb10W10)。

For a surface layer exhibiting these characteristics, oil droplets formed when the fingerprint component is attached exhibit a unique shape and behavior with time. One of them is that the size of the oil droplets constituting the above-mentioned pseudo fingerprint on the molding material of the present invention is preferably made small. This is because the shape of the oil droplets can be evaluated by using an area-based frequency distribution in which the frequency distribution of the oil droplet diameter is weighted by the area, using a projection image of the oil droplets with respect to the surface direction of the molding material. In the area reference frequency distribution, the diameter of N% of the cumulative frequency of the area reference frequency distribution is represented by D_N. The diameter at which N is 50 is particularly referred to as the median diameter (hereinafter referred to as D)_P). In the present invention, the median diameter D calculated from the area-based frequency distribution of oil droplets immediately after the attachment of the simulated fingerprint_P0.5Preferably 80 μm or less, more preferably 70 μm or less, and particularly preferably 50 μm or less. If the value deviates from this value, the fingerprint may be easily recognized due to scattering of light by the oil droplets. Due to D_P0.5The smaller the value, the less visible the fingerprint becomes, so there is no particular lower limit from the viewpoint of making it less visible, but on the other hand, if it is several 100nm or less, the oil droplets are aggregated or volatilized by the surface free energy, so there are practically no droplets of 100nm or less.

Further, the same material table was left standing at 25 ℃ for 10 hours in the absence of wind after the attachment of the simulated fingerprintThe median diameter of oil droplets calculated from the area-based frequency distribution of the surface was defined as D_P10The time variation of the median diameter was measured to simulate the median diameter D immediately after the fingerprint was attached_P0.5Normalized value, i.e. (D)_P0.5-D_P10)/D_P0.5There are preferred values. Specifically, the value is preferably 0.5 or more, and particularly preferably 0.6 or more. If this value is smaller than 0.5, the fingerprint may remain in a recognized state even after the passage of time. It is preferable in terms of fingerprint erasability that the pseudo fingerprint is adhered under a certain condition as described above, then erased, the reflected colors before adhering and after erasing are measured by 2 methods including regular reflection light and no regular reflection light, and the color difference after erasing with the state before adhering as a reference satisfies the above expression (9). Focusing on the fact that human eyes recognize fingerprints from changes in gloss and colors or cause stains in fingerprints, the change in gloss is evaluated by color differences including regular reflection light, and the change in color is evaluated by color differences not including regular reflection light, and it has been found that it is difficult to recognize fingerprints within a range satisfying expression (9) which combines these values.

Specifically, it is preferable that the surface layer is subjected to a simulated fingerprint adhesion and simulated fingerprint erasure test under the following conditions, and that the color difference (△ E) including the specular reflection light after the simulated fingerprint erasure test based on the state before the simulated fingerprint adhesion is determined in accordance with JIS Z8730(2009) and JIS Z8722(2009)_ab(di：8°)Sb10W10)＝△E_SCI-2And a color difference (△ E) after a simulated fingerprint erasure test based on a state before the simulated fingerprint is attached, the color difference being free from specularly reflected light_ab(de：8°)Sb10W10)＝△E_SCE-2The formula (9) satisfies the following formula (9), i.e., the left side of the formula (9) is 2.0 or less, more preferably 1.7 or less, and particularly preferably 1.5 or less. The left side value of expression (9) is not problematic even if it is small as long as it is 0 or a positive value, but if it is greater than 2.0, the fingerprint erasure may be insufficient, and as a result, fingerprint resistance may be reduced.

((△E_SCI-2)²+(△E_SCE-2)²)^1/2Less than or equal to 2.0 type (9)

Here, the simulated fingerprint attachment condition is as described above, and the simulated fingerprint erasure test condition is as follows.

In addition to the above-described mechanical, surface-scientific, and optical properties, the resin contained in the surface layer of the laminated film of the present invention preferably has the following (1) to (3).

(1) (poly) caprolactone segments,

(2) A urethane bond,

(3) A segment containing at least one member selected from the group consisting of a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkenyl group, a fluoroalkylene group, and a fluoroalkoxyalkylene group (hereinafter referred to as a fluorochemical segment). Here, the resin means a substance containing a high molecular compound, and the range thereof includes a range from a polymer to an oligomer.

The (1) caprolactone segment means a segment represented by chemical formula 1, and the (2) urethane bond means a bond represented by chemical formula 2. In addition, in chemical formula 1, n is an integer of 1 to 35.

The details of the (1) caprolactone segment, (2) the urethane bond (3) and the fluorine compound segment are as described later, but the self-repairability is improved by (1), the strong toughness of the surface layer is improved and the self-repairability is improved, and the contact angle of the liquid constituting the fingerprint is increased and the amount of adhesion is reduced by (3) lowering the surface energy.

More preferably, the fluorine compound segment is a fluoropolyether segment. The fluoropolyether segment is a segment containing a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkoxyalkylene group, or the like, and has a structure represented by chemical formulas (3) and (4).

CF_n1H_(3-n1)-(CF_n2H_(2-n2))_kO-(CF_n3H_(2-n3))_mO- … chemical formula 3

-(CF_n4H_(2-n4))_pO-(CF_n5H_(2-n5))_sO- … chemical formula 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 2 or more, n2 to n5 are integers of 1 or 2, more preferably, n1 is 3, n2 and n4 are integers of 2, and n3 and n5 are integers of 1 or 2.

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

The chain length of the fluoropolyether segment is preferably within a range, and the number of carbon atoms is preferably 4 to 12, more preferably 4 to 10, and particularly preferably 6 to 8. When the number of carbon atoms is 3 or less, the surface energy is not sufficiently reduced, and thus the oil repellency may be reduced, and when the number of carbon atoms is 13 or more, the solubility in a solvent may be reduced, and thus the grade of the surface layer may be reduced.

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

R₁Is any one of OH or alkyl with 1-8 carbon atoms. R₂Is OH or alkyl with 1-8 carbon atomsAny one of the above. n is an integer of 100-300.

m is an integer of 10 to 300.

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

[ laminated film and surface layer ]

The laminate film of the present invention may have any of a planar shape (film, sheet, plate) and a three-dimensional shape (molded body) as long as it has a surface layer exhibiting the characteristics of the present invention. Here, the surface layer in the present invention means a region extending from the surface of the laminated film in the thickness direction (in the case of a planar shape) or in the inner direction (in the case of a three-dimensional shape), and can be distinguished from an adjacent region in the thickness direction or in the inner direction by having a boundary surface in which the elemental composition, the shape of a content (particles, etc.), and the physical properties are discontinuous, and means a region having a limited thickness. More specifically, when the laminated film is observed in a cross section in the thickness direction from the surface by various composition/element analyzers (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscopes (transmission type, scanning type), or optical microscopes, the above-mentioned discontinuous boundary surface can be distinguished.

The surface layer may have other functions such as antireflection, antistatic, antifouling, electrical conductivity, heat ray reflection, near infrared ray absorption, electromagnetic wave shielding, and adhesion facilitation, in addition to moldability, design properties, self-repairability, gloss, and fingerprint resistance, which are the objects of the present invention.

The thickness of the surface layer is not particularly limited, but is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm, and can be selected according to the other functions described above.

[ coating composition ]

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

The coating composition contains at least a resin containing the (poly) caprolactone segment, the urethane bond, or the fluorine compound segment, or a material capable of forming them in a coating process (hereinafter referred to as a precursor), and by using the coating composition in a production method described later, the resin contained in the surface layer can be made to have these segments.

In order to obtain the laminated film of the present invention, preferred coating compositions for forming a surface layer on a supporting substrate are the following 2 types.

The type 1 is a coating composition (hereinafter referred to as coating composition a) preferably containing at least the following materials, and is preferably a coating composition which is cured by heat in the curing step of the above-mentioned coating process, or which is cured by heat and cured by active energy rays.

Fluorine compounds D

Polycaprolactone polyol A, or polycaprolactone polyol copolymer A

Compounds containing isocyanate groups

Namely, the coating composition a contains: polycaprolactone polyol a or polycaprolactone polyol copolymer a as a (poly) caprolactone segment; the above polyol as a precursor for forming a urethane bond and an isocyanate group-containing compound; a fluorine compound D as a fluorine compound segment. Details of these materials are described later.

The coating composition a preferably contains the isocyanate group-containing compound in an amount of 11 to 22 mass% based on 100 mass% of the total solid content concentration. The coating composition a may further contain: melamine crosslinking agents such as alkoxymethylolmelamine, acid anhydride crosslinking agents such as 3-methyl-hexahydrophthalic anhydride, and amine crosslinking agents such as diethylaminopropylamine. In order to promote the urethane bond formation reaction, a crosslinking catalyst such as dibutyltin dilaurate or dibutyltin diethylhexanoate may be used as necessary. Further, it preferably contains polysiloxane and polydimethylsiloxane described later, and may further contain various additives such as a solvent, a photopolymerization initiator, and a leveling agent.

Next, type 2 is preferably a coating composition containing at least the following materials (hereinafter referred to as coating composition B), preferably a coating composition which is cured by active energy rays in the curing step of the coating process, and has a characteristic of having excellent resistance to contamination by a cosmetic containing an oil and fat component such as a hand cream (hereinafter referred to as cosmetic resistance) as compared with coating composition a in order to solve the above-described problem of the present invention.

Fluorine compounds D

Urethane (meth) acrylate B

Urethane (meth) acrylate C

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

The urethane (meth) acrylate B is excellent in self-repairability, and the urethane (meth) acrylate C is a material excellent in cosmetic resistance, specifically, a material in which each of the layers (X layer and Y layer) formed by curing alone exhibits specific characteristics, and has both self-repairability and cosmetic resistance due to these characteristics. The constituent materials of the coating composition are described below.

The content ratio of the urethane (meth) acrylate B and the urethane (meth) acrylate C in the coating composition B: the mass of the urethane (meth) acrylate B/the mass of the urethane (meth) acrylate C is preferably 70/30 to 30/70. When the content ratio of the urethane (meth) acrylate B and the urethane (meth) acrylate C: if the mass of the urethane (meth) acrylate B/the mass of the urethane (meth) acrylate C) deviates from the range of 70/30 to 30/70, it may be difficult to achieve both the self-repairing property and the cosmetic resistance.

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

[ supporting base Material ]

The resin constituting the support substrate used in the laminated film of the present invention may be a thermoplastic resin or a thermosetting resin, a homopolymeric resin, a copolymer, or a blend of 2 or more types. More preferably, the resin constituting the support base material is a thermoplastic resin because of its good moldability.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene/polypropylene/polystyrene/polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6/nylon 66, aromatic polyamide resins, polyester resins, polycarbonate resins, polyarylate resins, polyacetal resins, polyphenylene sulfide resins, fluorine resins such as tetrafluoroethylene resins/trifluoroethylene resins/chlorotrifluoroethylene resins/tetrafluoroethylene-hexafluoropropylene copolymers/vinylidene fluoride resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic resins, polylactic resins, and the like. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is particularly preferably a polyester resin from the viewpoint of strength, heat resistance, and transparency.

The polyester resin in the present invention is a generic term for polymers having an ester bond as a main bond chain of a main chain, and can be obtained by polycondensing an acid component and an ester thereof with 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, esters thereof, or glycol components as an acid component or a glycol component. Among them, polyethylene terephthalate and polyethylene-2, 6-naphthalate are particularly preferable from the viewpoint of transparency, dimensional stability, heat resistance and the like.

Various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, inorganic particles, organic particles, a viscosity reducing agent, a heat stabilizer, a lubricant, an infrared absorber, an ultraviolet absorber, a refractive index adjusting dopant, and the like may be added to the support base. The support substrate may be of a single layer construction or a laminated construction.

Various surface treatments may also be applied to the surface of the support base before the formation of the above-described 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, reactive plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among them, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment are preferable, and glow discharge treatment and ultraviolet treatment are more preferable.

[ fluorochemical segment, fluorochemical 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 means a segment containing at least 1 selected from the group consisting of a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkenyl group, a fluoroalkylene group, and a fluoroalkoxyalkylene group.

Here, the fluoroalkyl group, fluoroalkoxy group, fluoroalkenyl group, fluoroalkylene group, and fluoroalkoxyalkylene group refer to substituents in which a part or all of hydrogen atoms in the alkyl group, oxyalkyl group, alkenyl group, alkylene group, and oxyalkylene group is substituted with fluorine, and any of these substituents is a substituent mainly composed of a fluorine atom and a carbon atom, and may have a branched chain in the structure, or may form a dimer, trimer, oligomer, or polymer structure in which a plurality of these substituents are bonded.

In addition, as the above-mentioned fluorine compound segment, a fluoropolyether segment which is a substituent formed of a fluoroalkyl group, a fluoroalkoxy group, a fluoroalkoxyalkylene group, or the like is preferable, and a fluoropolyether segment represented by chemical formulas (3) and (4) is more preferable.

The resin contained in the surface layer preferably contains a fluorine compound segment, and the coating composition a or the coating composition B preferably contains a fluorine compound D. The fluorine compound D is a compound represented by chemical formula 7.

R^f1-R²-D¹… chemical formula 7

Herein, R is¹Represents a fluorine compound segment, R²Represents an alkylene group, an alkylidene group, an ester structure, a carbamate structure, an ether structure, a triazine structure derived from them, D¹Indicating a reactive site.

The reactive site is a site that reacts with other components by external energy such as heat or light. From the viewpoint of reactivity, such reactive sites include alkoxysilyl groups and silanol groups obtained by hydrolysis of alkoxysilyl groups, and carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups. Among them, vinyl groups, allyl groups, alkoxysilyl groups, silyl ether groups, silanol groups, epoxy groups, and acryloyl (methacryloyl) groups are preferable from the viewpoint of reactivity and handling properties.

One example of the fluorine compound D is a compound represented by the following chemical formula. Examples thereof include: 3, 3-trifluoropropyltrimethoxysilane, 3,3, 3-trifluoropropyltriethoxysilane, 3,3, 3-trifluoropropyltriisopropoxysilane, 3,3, 3-trifluoropropyltrichlorosilane, 3,3, 3-trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltrichlorosilane, 2-perfluorooctylisocyanatosilane, 2,2, 2-trifluoroethylacrylate, 2,2,3,3, 3-perfluoropropylacrylate, 2-perfluorobutylethylacrylate, 3-perfluorobutylacrylate, 2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, perfluoropropylmethacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctyl ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecyl ethyl acrylate, 2-perfluoro-3-methylbutyl ethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexyl ethyl acrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexadecafluorooctanyl methacrylate, hexadecafluorononyl acrylate, hexadec, Hexafluorobutyl acrylate, 2,2, 2-trifluoroethyl methacrylate, 2,2,3,3, 3-perfluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorobutyl-2-hydroxypropyl methacrylate, and mixtures thereof, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctylmethacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol, and the like.

Further, the fluorine compound D may contain a plurality of fluoropolyether segments per 1 molecule.

Commercially available examples of the fluorine compound D include RS-75 (DIC), オプツール DAC-HP (ダイキン, Inc.), C10GACRY and C8HGOL (oil and fat products Co., Ltd.), and these products can be used.

[ (Poly) caprolactone segments ]

In the laminated film of the present invention, the resin contained in the surface layer preferably has a (poly) caprolactone segment, and the (poly) caprolactone segment is preferably a segment represented by the above chemical formula 1. In addition, the surface layer is formed using the coating composition a or the coating composition B containing the resin containing the (poly) caprolactone segment, whereby the surface layer may have the (poly) caprolactone segment.

The (poly) caprolactone segment-containing resin preferably contains at least 1 or more hydroxyl groups (hydroxyl groups). The hydroxyl group is preferably located at the end of the resin containing the (poly) caprolactone segment.

The (poly) caprolactone segment-containing resin is particularly preferably (poly) caprolactone having 2 to 3 functional hydroxyl groups. Specifically, the (poly) caprolactone diol represented by chemical formula 8, a diol of the formula,

(where m + n is an integer of 4 to 35, and R is C₂H₄Or C₂H₄OC₂H₄) Or (poly) caprolactone triol shown in chemical formula 9,

(where l + m + n is an integer of 3 to 30, and R is CH₂CHCH₂、CH₃C(CH₂)₃、CH₃CH₂C(CH₂)₃)

And (poly) caprolactone-modified hydroxyethyl (meth) acrylate represented by chemical formula 10

(where n is an integer of 1 to 25, and R is H or CH)₃)

And active energy ray-polymerizable caprolactone.

Here, the active energy ray polymerizability refers to a property of crosslinking by active energy rays such as UV and EB, and corresponds to a compound having a functional group such as a (meth) acrylate group. Examples of the 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 a (poly) caprolactone segment may contain (or copolymerize) other segments or monomers in addition to the (poly) caprolactone segment. For example, the compound may contain (or copolymerize) a polydimethylsiloxane segment, a (poly) siloxane segment, or an isocyanate compound, which will be described later.

In the present invention, the weight average molecular weight of the (poly) caprolactone segment in the (poly) caprolactone segment-containing resin is preferably 500 to 2500, and the preferred weight average molecular weight is 1000 to 1500. The (poly) caprolactone segment preferably has a weight average molecular weight of 500 to 2500, since the self-repairable effect is further exhibited and the scratch resistance is further improved.

When the (poly) caprolactone segment is copolymerized, if it is added separately, it is preferable in terms of self-repairability and contamination resistance if the content of the (poly) caprolactone segment is 5 to 50 mass% in 100 mass% of the total solid content concentration of the coating composition for forming the surface layer.

[ urethane bond, isocyanate group-containing Compound ]

In the present invention, the urethane bond means a bond represented by the above chemical formula 2. The coating composition for forming the surface layer contains a commercially available urethane modified resin, so that the resin contained in the surface layer may have a urethane bond. In addition, when the surface layer is formed, a coating composition containing an isocyanate group-containing compound and a hydroxyl group-containing compound as precursors may be applied to form a urethane bond in the coating step and to form a urethane bond in the surface layer.

In the present invention, it is preferable that the resin contained in the surface layer has a urethane bond by reacting an isocyanate group with a hydroxyl group to generate 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-repairability can be improved.

When a hydroxyl group is contained in the resin containing the (poly) caprolactone segment, the resin containing the polysiloxane segment, the resin containing the polydimethylsiloxane segment, or the like, a urethane bond may be formed between the resin and the isocyanate group-containing compound as a precursor by heat or the like. When the surface layer is formed using a compound containing an isocyanate group and a resin containing a (poly) siloxane segment having a hydroxyl group or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the surface layer is preferably improved in toughness, elastic recovery (self-healing property) and surface sliding property.

In the present invention, the isocyanate group-containing compound means an isocyanate group-containing resin, a monomer having an isocyanate group, or an oligomer. Examples of the isocyanate group-containing compound include: polyisocyanates such as methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, and biuret of hexamethylene isocyanate, and closed products of the above isocyanates.

Among these isocyanate group-containing compounds, aliphatic isocyanates are preferable because they have high self-repairability as compared with alicyclic and aromatic isocyanates. The isocyanate group-containing compound is more preferably hexamethylene diisocyanate. The isocyanate group-containing compound is preferably an isocyanate having an isocyanurate ring, and most preferably an isocyanurate of hexamethylene diisocyanate, from the viewpoint of heat resistance. Isocyanates having isocyanurate rings form a surface layer having both self-repairability and heat resistance.

[ urethane (meth) acrylate B and urethane (meth) acrylate C ]

As described above, in order to impart the property of cosmetic resistance in addition to the self-repairability, it is preferable to use the coating composition B containing the urethane (meth) acrylate B having excellent self-repairability and the urethane (meth) acrylate C having excellent cosmetic resistance in the formation of the surface layer.

The urethane (meth) acrylate B is a compound having a urethane bond in the molecule, and means illumination intensity of 400mW/cm²The mixture of the urethane (meth) acrylate B and the photoinitiator was cured by ultraviolet light of the high-pressure mercury lamp to obtain a urethane (meth) acrylate having a layer thickness of 30 μm (hereinafter referred to as X layer) having the following physical properties.

1. When oleic acid was applied to the surface of the X layer and held at 60 ℃ for 1 hour, the rate of increase in mass of the X layer was 45 mass% or less.

2. In the measurement of micro hardness, when a load of 0.5mN is applied for 10 seconds, the maximum displacement amount in the thickness direction of the X layer is 1.0 μm to 3.0 μm.

3. In the micro hardness measurement of 2, the creep displacement amount in the thickness direction of the X layer was 0.4 μm to 0.7 μm.

The urethane (meth) acrylate C is a compound having a urethane bond in the molecule, and means a compound having an illuminance of 400mW/cm²The mixture of the urethane (meth) acrylate C and the photoinitiator is cured by ultraviolet light of the high-pressure mercury lamp to form a urethane (meth) acrylate having a layer thickness of 30 μm (hereinafter referred to as Y layer) having the following properties.

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

2. In the measurement of the microhardness, when a load of 0.5mN is applied for 10 seconds, the maximum displacement amount of the Y layer in the thickness direction is 0.2 μm to 3.0 μm.

3. In the microhardness measurement of 2 above, the creep displacement amount in the thickness direction of the Y layer was 0.02 μm to 0.35 μm.

Further, since the coating composition for forming the surface layer contains the urethane (meth) acrylate B having a (poly) caprolactone segment and the urethane (meth) acrylate C having a (poly) alkylene glycol (meth) segment, the surface layer having more excellent self-repairability and cosmetic resistance can be obtained. It is considered that the (poly) alkylene glycol segment having excellent cosmetic resistance is biased to the surface during curing due to the difference between the surface tension and the intermolecular force, and the (poly) caprolactone segment having excellent self-repairability is biased to the inner layer, thereby further improving the effect.

In particular, 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 preferably satisfy 0.3 n. ltoreq. m.ltoreq.10 n, more preferably satisfy 0.3 n. ltoreq. m.ltoreq.5 n, and still more preferably satisfy 0.65 n. ltoreq. m.ltoreq.1.20 n. When 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 0.3 n. ltoreq. m.ltoreq.10 n, the deviation of each segment at the time of the curing described above occurs more remarkably, and a surface layer more excellent in self-repairing property and cosmetic resistance can be obtained. When 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 do not satisfy 0.3n m 10n, the dispersibility of each segment during the curing may be increased and the segments may be weakened.

[ (Poly) siloxane segments ]

In the present invention, the surface layer preferably has (4) a (poly) siloxane segment and/or a polydimethylsiloxane segment. In the present invention, the (poly) siloxane segment means the segment represented by the above chemical formula 5.

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

In the present invention, a coating composition containing a partial hydrolysate of a silane compound having a hydrolyzable silyl group, an organosilicon sol, or a hydrolyzable silane compound having a radical polymerization component added to the organosilicon sol can be used as a resin having a polysiloxane segment.

Examples of the (poly) siloxane segment-containing resin include: a completely or partially hydrolyzed product of a silane compound having a hydrolyzable silyl group such as tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ -glycidoxypropylmethyltrialkoxysilane, γ -glycidoxypropylalkyldialkoxysilane, γ -methacryloxypropylmethyltrialkoxysilane or γ -methacryloxypropylalkyldialkoxysilane, an organic silica sol dispersed in an organic solvent, a hydrolyzed silane compound obtained by adding a hydrolyzable silyl group to the surface of an organic silica sol, or the like.

In the present invention, the resin containing a (poly) siloxane segment may contain (co) another segment in addition to the (poly) siloxane segment. For example, a monomer component having a (poly) caprolactone segment and a polydimethylsiloxane segment may be (copolymerized).

In the present invention, as the resin containing a (poly) siloxane segment, a monomer having a hydroxyl group reactive with an isocyanate group, or the like is preferably copolymerized. If a monomer having a hydroxyl group reactive with an isocyanate group or the like is copolymerized in the (poly) siloxane segment-containing resin, the toughness of the surface layer can be improved.

In the case where the resin containing a (poly) siloxane segment is a copolymer having a hydroxyl group, if the surface layer is formed using a coating composition containing a resin (copolymer) containing a (poly) siloxane segment having a hydroxyl group and a compound containing an isocyanate group, the surface layer having a (poly) siloxane segment and a urethane bond can be efficiently formed.

When the (poly) siloxane segment is copolymerized, if it is added separately, it is preferable in terms of self-repairability, stain resistance, weather resistance and heat resistance if the (poly) siloxane segment is 1 to 20 mass% of the total 100 mass% of the coating composition for forming the surface layer. The coating composition does not contain any solvent that does not participate in the reaction, based on 100% by mass of the total components. Comprising a monomer component participating in the reaction.

[ polydimethylsiloxane segment ]

In the present invention, the polydimethylsiloxane segment means the segment represented by the above chemical 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. The polydimethylsiloxane chain segment is coordinated on the surface of the surface layer, so that the lubricity of the surface layer is improved, and the frictional resistance can be reduced. As a result, the scratch resistance can be suppressed.

In order to provide the surface layer with a (poly) siloxane segment and/or a polydimethylsiloxane segment, the coating composition for forming the surface layer may contain a resin containing a polydimethylsiloxane segment. In the present invention, as the resin containing a polydimethylsiloxane segment, a copolymer in which a vinyl monomer is copolymerized in a polydimethylsiloxane segment is preferably used.

For the purpose of improving the toughness of the surface layer, the polydimethylsiloxane segment-containing resin is preferably copolymerized with a monomer having a hydroxyl group reactive with an isocyanate group, or the like. In the case where the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, if the surface layer is formed using a coating composition containing a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group, the surface layer having a polydimethylsiloxane segment and a urethane bond can be efficiently formed.

When the resin containing a polydimethylsiloxane segment is a copolymer with a vinyl monomer, the resin 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, the copolymer is referred to as a polydimethylsiloxane-based copolymer. The polydimethylsiloxane-based copolymer can be produced by living polymerization, a polymer initiator method, a polymer chain transfer method, or the like, but in view of productivity, it is preferable to use a polymer initiator method or a polymer chain transfer method.

In the case of using the polymer initiator method, a polymer azo-based radical polymerization initiator represented by chemical formula 11 may be copolymerized with other vinyl monomers.

(m is an integer of 10 to 300, n is an integer of 1 to 50). Further, two-stage polymerization may be performed in which a peroxide monomer and a polydimethylsiloxane having an unsaturated group are copolymerized at a low temperature to synthesize a prepolymer having a peroxide group introduced into a side chain, and the prepolymer and a vinyl monomer are copolymerized.

In the case of using the polymer chain transfer method, HS-CH, for example, can be used₂COOH、HS-CH₂CH₂COOH or the like is added to the silicone oil shown in chemical formula 12 to form a compound having an SH group, and then the silicone compound and a vinyl monomer are copolymerized by chain transfer of the SH group, thereby synthesizing a block copolymer.

(m is an integer of 10 to 300)

In order to synthesize the polydimethylsiloxane-based graft copolymer, the graft copolymer can be easily obtained by copolymerizing a vinyl monomer with a compound represented by chemical formula 13, that is, a methacrylate of polydimethylsiloxane, or the like, for example.

(m is an integer of 10 to 300)

Examples of the vinyl monomer 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, alpha-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N-methylol-acrylic acid, methyl methacrylate, ethyl methacrylate, N-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, N-propyl vinyl ether, styrene, alpha-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl, N, N-dimethylacrylamide, N-dimethylaminoethylmethacrylamide, N-diethylaminoethyl methacrylate, diacetone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol and the like.

The polydimethylsiloxane-based copolymer is preferably produced by solution polymerization in an aromatic hydrocarbon-based solvent such as toluene or xylene, a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone, an ester-based solvent such as ethyl acetate or butyl acetate, or an alcohol-based solvent such as ethanol or isopropyl alcohol, alone or in a mixed solvent.

If necessary, a polymerization initiator such as dibenzoyl peroxide or azobisisobutyronitrile may be used in combination. The polymerization is preferably carried out at 50 to 150 ℃ for 3 to 12 hours.

The amount of the polydimethylsiloxane segment in the polydimethylsiloxane-based copolymer of the present invention is preferably 1 to 30% by mass, based on 100% by mass of the total components of the polydimethylsiloxane-based copolymer, from the viewpoint of lubricity and contamination resistance of the surface layer. The polydimethylsiloxane segment preferably has a weight average molecular weight of 1000 to 30000.

When the polydimethylsiloxane segment is copolymerized or separately added, it is preferable in terms of self-repairing property, stain resistance, weather resistance and heat resistance if the dimethylsiloxane segment is 1 to 20 mass% in 100 mass% of the total components of the coating composition for forming the surface layer. The coating composition does not contain any solvent that does not participate in the reaction, based on 100% by mass of the total components. Comprising a monomer component participating in the reaction.

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

The coating composition used for forming the surface layer may be a copolymer of a (poly) caprolactone segment and a polydimethylsiloxane segment, a copolymer of a (poly) caprolactone segment and a (poly) siloxane segment, a copolymer of a (poly) caprolactone segment and a polydimethylsiloxane segment and a (poly) siloxane segment, or the like. The surface layer obtained using such a coating composition may have (poly) caprolactone segments and polydimethylsiloxane segments and/or (poly) siloxane segments.

In the coating composition used for the surface layer having a (poly) caprolactone segment, a (poly) siloxane segment and a polydimethylsiloxane segment, the reaction of the polydimethylsiloxane-based copolymer, the (poly) caprolactone and the (poly) siloxane may be carried out by adding the (poly) caprolactone segment and the polysiloxane segment as appropriate during the synthesis of the polydimethylsiloxane-based copolymer.

[ (poly) alkylene glycol segments ]

In the present invention, the surface layer preferably has a (poly) alkylene glycol segment. In the present invention, the (poly) alkylene glycol segment means a segment represented by chemical formula 14.

Wherein 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 exceeds 4 or the number of repeating units m of the alkylene glycol exceeds 11, the molecular chain of the alkylene glycol becomes long and the crosslink density of the cured product becomes low, and the hardness thereof becomes low and the coating film strength, scratch resistance, and the like may be lowered. On the other hand, when the number m of repeating units of the alkylene glycol is less than 2, the molecular chain of the alkylene glycol becomes short, the crosslink density of the cured product becomes high, and the cured product loses flexibility, so that the self-repairability and the processability of the cured product may be reduced.

The surface layer may have a (poly) alkylene glycol segment by forming the surface layer using a coating composition containing a resin containing a (poly) alkylene glycol segment.

The (poly) alkylene glycol segment-containing resin preferably has at least 1 or more hydroxyl groups (hydroxyl groups). The hydroxyl group is preferably located at the terminal of the resin containing the (poly) alkylene glycol segment.

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

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

(poly) ethylene glycol (meth) acrylate:

(poly) propylene glycol (meth) acrylate:

(poly) butanediol (meth) acrylate:

in chemical formula 15, chemical formula 16, chemical formula 17, R is hydrogen (H) or methyl (-C)H₃) And m is an integer of 2 to 11.

Among these polyalkylene glycol (meth) acrylates, a (poly) ethylene glycol (meth) acrylate which is an ethylene glycol having an alkylene glycol carbon number m of 2 is particularly preferable. Since the number of carbon atoms n in chemical formula 14 is the smallest, (poly) ethylene glycol (meth) acrylate contributes to the obtained cured product having both cosmetic resistance and scratch resistance.

In the present invention, it is preferable that the urethane (meth) acrylate is used for the surface layer by reacting the isocyanate group-containing compound with the hydroxyl group of the (poly) alkylene glycol (meth) acrylate, and the surface layer can have (2) a urethane bond and (3) a (poly) alkylene glycol segment, as a result, the toughness of the surface layer can be improved and the self-repairability can be improved.

In the urethane-forming reaction between the isocyanate group-containing compound and the (poly) alkylene glycol (meth) acrylate, a hydroxyalkyl (meth) acrylate, a long-chain alcohol, or the like may be added. By blending a hydroxyalkyl (meth) acrylate, the hardness of the surface layer as a cured product can be improved. By blending a long-chain alcohol, the surface sliding property of the surface layer as a cured product can be improved, and as a result, the scratch resistance can be improved. The long-chain alcohol is a compound included in the concept of the long-chain alkyl group-containing compound.

Examples of the hydroxyalkyl (meth) acrylate to be simultaneously blended in the urethanization reaction of the isocyanate group-containing compound and the (poly) alkylene glycol (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like.

Examples of the long-chain alcohol to be added simultaneously in the urethanization reaction of the isocyanate group-containing compound and the (poly) alkylene glycol (meth) acrylate include tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene monostearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and glycerin monostearate. Particularly preferred long-chain alcohols include polyether-modified long-chain alcohols such as polyether-modified cetyl alcohol. This is because the use of a polyether-modified long-chain alcohol can impart an antistatic effect to the surface layer of a cured product.

The urethanization reaction of the isocyanate group-containing compound and the (poly) alkylene glycol (meth) acrylate is carried out in an organic solvent in the presence of a catalyst, a polymerization inhibitor, and the like. The reaction temperature in the carbamation reaction is preferably normal temperature to 100 ℃, and the reaction time is preferably 1 to 10 hours. When the reaction temperature is lower than room temperature or the reaction time is shorter than 1 hour, the reaction may progress slowly, and the yield of the target urethane (meth) acrylate may decrease. On the other hand, when the reaction temperature exceeds 100 ℃ or the reaction time is longer than 10 hours, side reactions are likely to occur in some cases.

Examples of the organic solvent used in the urethanization reaction of the isocyanate group-containing compound and the (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; ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate. Examples of the catalyst include dibutyltin dilaurate, dibutyltin diethylhexanoate, and dibutyltin sulfide. Examples of the polymerization inhibitor include hydroquinone monomethyl ether and the like.

[ solvent, solvent E ]

The coating compositions a and B may contain a solvent. The number of types of the solvent is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6.

Here, the "solvent" refers to a substance that is liquid at normal temperature and normal pressure and that can evaporate almost the entire amount in the drying step after coating.

Here, the kind of the solvent depends on the molecular structure constituting the solvent. That is, even if the same element composition is used and the types and numbers of functional groups are the same, solvents (structural isomers) having different bonding relationships are treated as solvents having different types, but solvents (stereoisomers) which do not completely overlap in a three-dimensional space regardless of the type of configuration are not the structural isomers. For example, 2-propanol is treated as a different solvent than n-propanol.

When the solvent is contained, the solvent preferably exhibits the following characteristics (condition 1).

Condition 1: when the solvent E is a solvent having the lowest relative evaporation rate based on n-butyl acetate (ASTM D3539-87 (2004)), the relative evaporation rate of the solvent E is 0.3 or less.

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

When the relative evaporation rate of the solvent E is greater than 0.3, the time required for the surface orientation of the fluorine compound D becomes short, and thus the fingerprint resistance may be lowered. The lower limit of the relative evaporation rate of the solvent E is not particularly limited as long as it can be evaporated and removed from the coating film in the drying step, and may be 0.005 or more in the general coating step.

Examples of the solvent E include isobutyl ketone (relative evaporation rate: 0.2), isophorone (relative evaporation rate: 0.026), diethylene glycol monobutyl ether (relative evaporation rate: 0.004), diacetone alcohol (relative evaporation rate: 0.15), oleyl alcohol (relative evaporation rate: 0.003), ethylene glycol monoethyl ether acetate (relative evaporation rate: 0.2), nonylphenoxyethanol (relative evaporation rate: 0.25), and propylene glycol monoethyl ether (relative evaporation rate: 0.1).

[ other additives ]

The coating composition A, B preferably contains a polymerization initiator, a curing agent, or a catalyst. A polymerization initiator and a catalyst are used to accelerate the curing of the surface layer. The polymerization initiator is preferably a substance capable of initiating or accelerating polymerization, condensation, or crosslinking reaction of the components contained in the coating composition by anionic, cationic, or radical polymerization reaction.

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

The photopolymerization initiator is preferably an alkyl benzophenone compound in view of curability. Specific examples of the alkylbenzene ketone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-dimethoxy-1, 2-diphenylethan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, and mixtures thereof, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] -1-butane, 1-cyclohexyl-phenyl-methanone, 2-methyl-1-phenylpropan-1-one, 1- [4- (2-ethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxydiethylene, and a substance obtained by polymerizing these materials with a high molecular weight.

In addition, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like may be added to the coating composition A, B for forming the surface layer, as long as the effects of the present invention are not hindered. 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 acrylic copolymers, siloxane-based leveling agents, and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, diphenylamine oxalate-based, triazine-based and hindered amine-based ultraviolet absorbers. Examples of the antistatic agent include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.

[ method for producing laminated film ]

The surface layer formed on the surface of the laminate film of the present invention is preferably produced by the following method: the coating composition is applied to the supporting substrate, dried, and cured.

The method for producing a laminated film by coating is not particularly limited, but it is preferable to form a surface layer by applying a coating composition to a supporting substrate or the like by dip coating, roll coating, wire bar coating, gravure coating, die coating (U.S. patent No. 2681294), or the like. Among these coating methods, the gravure coating method or die coating method is more preferable as the coating method.

Next, the liquid film applied on the supporting substrate or the like is dried. In addition to completely removing the solvent from the obtained laminated film, it is preferable to heat the liquid film in the drying step in order to move the fluorine compound D in the liquid film formed by coating to the surface and segregate the fluorine compound segment on the outermost surface of the surface layer.

Examples of the drying method include heat transfer drying (adhesion to a high-heat object), convection heat transfer (hot air), radiation heat transfer (infrared ray), and others (microwave and induction heating). Among them, in the manufacturing method of the present invention, since the drying rate must be accurately equalized even in the width direction, a method of convection heat transfer or radiation heat transfer is preferably used.

The drying process is generally divided into (a) a constant-rate drying period in which the drying rate is constant because diffusion of solvent molecules into the atmosphere on the surface of the liquid film is the rate-limiting rate of drying, and (B) a deceleration drying period in which the drying rate is controlled by the partial pressure of the solvent evaporated in the atmosphere, the wind speed, and the temperature, and the film surface temperature is a value determined by the hot air temperature and the partial pressure of the solvent evaporated in the atmosphere and is constant. In the latter, since the solvent diffusion in the liquid film is rate-limiting, the drying rate does not show a constant value in this interval but continuously decreases, and the film surface temperature increases depending on the diffusion coefficient of the solvent in the liquid film. Here, the drying rate is expressed as the amount of solvent evaporated per unit time and per unit area in terms of g.m^-2·s^-1。

The drying rate is preferably within a range of 10 g.m^-2·s^-1Hereinafter, more preferably 5 g.m^-2·s^-1The following. The lower limit value is preferably 0.1 g.m^-2·s^-1The above. By setting the drying rate in the constant-rate drying section within this range, unevenness caused by unevenness in the drying rate can be prevented.

As long as 0.1 g.m can be obtained^-2·s^-1Above 10 g.m^-2·s^-1The drying speed in the following range is not particularly limited to a specific wind speed and temperature.

In the method for producing a laminated film of the present invention, the residual solvent is evaporated during the reduced-speed drying, and the orientation of the fluorine compound D is performed. In this process, since a time for alignment is required, there is a preferable range of the film surface temperature rising rate during the deceleration drying, preferably 5 ℃/sec or less, more preferably 1 ℃/sec or less.

Further, a curing operation (curing step) may be performed by irradiating heat or an energy ray. In the curing step, when the coating composition a is used and cured by heat, it is preferably room temperature to 200 ℃, more preferably 100 ℃ to 200 ℃, and still more preferably 130 ℃ to 200 ℃ from the viewpoint of activation energy of the curing reaction.

In addition, in the case of curing by an active energy ray, electron beam (EB ray) and/or ultraviolet ray (UV ray) are preferable from the viewpoint of versatility. In the case of curing by ultraviolet rays, the oxygen concentration is preferably as low as possible in order to prevent oxygen inhibition, and curing is preferably performed in a nitrogen atmosphere (nitrogen flushing). When the oxygen concentration is high, the curing of the outermost surface is inhibited, and the surface may be insufficiently cured and the fingerprint resistance may be insufficient. Examples of the ultraviolet lamp used for ultraviolet irradiation include a discharge lamp system, a flash system, a laser system, and an electrodeless lamp system. When ultraviolet curing is performed using a high-pressure mercury lamp as a discharge lamp system, the ultraviolet light preferably has an illuminance of 100 to 3000mW/cm²Preferably 200-2000 mW/cm²More preferably 300 to 1500mW/cm²The ultraviolet ray irradiation is performed under the condition(s), and the cumulative quantity of the ultraviolet rays is more preferably 100 to 3000mJ/cm²Preferably 200 to 2000mJ/cm²More preferably 300 to 1500mJ/cm²The ultraviolet irradiation is performed under the conditions of (1). Here, the illuminance of ultraviolet light is the irradiation intensity per unit area, and varies depending on the lamp output, the emission spectral efficiency, the diameter of the light-emitting bulb, the design of the reflector, and the distance from the light source to the irradiation object. However, the illuminance does not change depending on the conveyance speed. The cumulative quantity of ultraviolet light is the irradiation energy received per unit area, and is the total quantity of photons reaching the surface. The cumulative light quantity is inversely proportional to the irradiation speed under the light source and proportional to the number of times of irradiation and the number of lamps.

Examples

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

< fluorine Compound D >

[ fluorine Compound D1]

An acrylate compound containing a fluoropolyether segment ("メガファック" solid content concentration 40 mass% solvent (toluene and methyl ethyl ketone) 60 mass% manufactured by RS-75 DIC) was used as the fluorine compound D1.

[ fluorine Compound D2]

A fluorinated polyether segment-containing siloxane compound (KY-108 shin-Etsu chemical Co., Ltd., solid content concentration 20 mass% solvent (methanol and isopropanol) 80 mass%) was used as the fluorinated compound D2.

[ fluorine Compound D3]

A2-functional acrylate compound containing a fluoropolyether segment (fluoroethylene glycol segment) (FPTM-A oil and fat products Co., Ltd., solid content concentration 100 mass%) was used as the fluorine compound D3.

[ fluorine Compound D4]

An acrylate compound containing a fluoroalkyl segment (a solid content concentration of 100% by mass, manufactured by chemical Co., Ltd., triacryloyl-heptadecafluorononenyl-pentaerythritol) was used as the fluorine compound D4.

[ fluorine Compound D5]

An acrylate compound containing a fluoroalkyl segment (a solid content concentration of 100% by mass, manufactured by Pentacryl-heptadecafluorononenyl-dipentaerythritol Kyoeiski Kaisha) was used as the fluorine compound D5.

< 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 of hydrochloric acid were charged into a 500-ml flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, and after keeping at 85 ℃ for 2 hours, ethanol was recovered while raising the temperature, and kept at 180 ℃ for 3 hours. Then, the mixture was cooled to obtain a viscous polysiloxane (a).

[ polysiloxane (b) ]

106 parts by mass of ethanol, 270 parts by mass of methyltrimethoxysilane, 23 parts by mass of γ -methacryloxypropylmethyldimethoxysilane, 100 parts by mass of deionized water, 1 part by mass of 1% by mass of hydrochloric acid and 0.1 part by mass of hydroquinone monomethyl ether were charged into a 500ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube, and reacted at 80 ℃ for 3 hours to synthesize polysiloxane (b). The content was adjusted to 50% by mass with methyl isobutyl ketone.

< Synthesis of Dimethicone Compound >

[ polydimethylsiloxane-based block copolymer (a) ]

Using the same apparatus as that for the synthesis of polysiloxane (a), 50 parts by mass of toluene, 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 and reacted at 180 ℃ for 8 hours to obtain a polydimethylsiloxane-based block copolymer (a). The solid content concentration of the obtained block copolymer was 50 mass% (50 mass% for the solvents (toluene and methyl isobutyl ketone)).

[ polydimethylsiloxane-based graft copolymer (b) ]

Using an apparatus used for the synthesis of polysiloxane (a), 50 parts by mass of toluene and 50 parts by mass of isobutyl acetate were added, and the temperature was raised to 110 ℃. Further, 20 parts by mass of methyl methacrylate, 32 parts by mass of caprolactone methacrylate (プラクセル FM-5, manufactured by ダイセル chemical industries Co., Ltd.), 17 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of polysiloxane (b), 20 parts by mass of single-terminal methacryloyl polydimethylsiloxane (AK-32, manufactured by Toyo Seisaku-Sho Co., Ltd.), 1 part by mass of methacrylic acid, and 2 parts by mass of 1, 1-azobiscyclohexane-1-carbonitrile were mixed. The mixed monomer was added dropwise to the above-mentioned mixed solution of toluene and butyl acetate over 2 hours. Then, the reaction was carried out at 110 ℃ for 8 hours to obtain a polydimethylsiloxane-based graft copolymer (b) having a hydroxyl group at a solid content of 50 mass%. The solid content of the block copolymer (b) thus obtained was 50 mass% (50 mass% for the solvents (toluene and isobutyl acetate)).

[ polydimethylsiloxane-based block copolymer (c) ]

Using the same apparatus as that for the synthesis of polysiloxane (a), 50 parts by mass of toluene, 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 and reacted at 180 ℃ for 8 hours to obtain a polydimethylsiloxane-based block copolymer (c). The solid content of the obtained block copolymer (c) was 50 mass% (50 mass% for the solvents (toluene and methyl isobutyl ketone)).

[ polydimethylsiloxane-based graft copolymer (d) ]

A polydimethylsiloxane-based graft copolymer (d) was synthesized in the same manner as the polydimethylsiloxane-based graft copolymer (b) except that the monomer composition was changed to 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, and 20 parts by mass of single-terminal methacrylic-modified polydimethylsiloxane (X-22-174 DX, manufactured by shin-Etsu chemical Co., Ltd.). The solid content of the graft copolymer (d) was 50 mass% (50 mass% for the solvents (toluene and isobutyl acetate)).

[ polydimethylsiloxane Compound (e) ]

EBECRYL350 (2-functional, silicone acrylate) manufactured by ダイセルサイテック K.K. was used as the polydimethylsiloxane compound (e).

[ polydimethylsiloxane Compound (f) ]

EBECRYL1360 (6-functional, silicone acrylate) manufactured by ダイセルサイテック K.K. was used as the polydimethylsiloxane compound (f).

< Synthesis of urethane (meth) acrylate B >

[ urethane (meth) acrylate B1]

50 parts by mass of toluene, 50 parts by mass of an isocyanurate-modified hexamethylene diisocyanate (タケネート D-170N, manufactured by Mitsui chemical Co., Ltd.), 76 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (プラクセル FA5, manufactured by ダイセル chemical industry Co., Ltd.), 0.02 part by mass of dibutyltin dilaurate, and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ℃ for 5 hours. Then, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate B1 having a solid content concentration of 50% by mass.

[ urethane (meth) acrylate B2]

50 parts by mass of toluene, 25 parts by mass of an isocyanurate-modified hexamethylene diisocyanate (タケネート D-170N, manufactured by Mitsui chemical Co., Ltd.), (162.8 parts by mass of a (poly) caprolactone-modified hydroxyethyl acrylate (プラクセル FA10, manufactured by ダイセル chemical industry Co., Ltd.), (0.02 part by mass) of dibutyltin dilaurate, and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ℃ for 5 hours. Then, 137.8 parts of toluene was added to obtain a toluene solution of urethane (meth) acrylate B2 having a solid content of 50 mass%. In addition, the number of repeating caprolactone units per acrylate monomer residue in the urethane (meth) acrylate is 10.

[ urethane (meth) acrylate B3]

100 parts by mass of toluene, 50 parts by mass of methyl-2, 6-diisocyanate caproate (LDI, manufactured by Kyowa fermentation キリン Co., Ltd.), and 119 parts by mass of polycarbonate diol (プラクセル CD-210HL, manufactured by ダイセル chemical industries Co., Ltd.) were mixed, and the mixture was heated to 40 ℃ and held for 8 hours. Then, 28 parts by mass of 2-hydroxyethyl acrylate (ライトエスレル HOA, product of Kyoeisha chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400, product of Toyo chemical Co., Ltd.), and 0.02 part by mass of hydroquinone monomethyl ether were added thereto, and the mixture was held at 70 ℃ for 30 minutes, then 0.02 part by mass of dibutyltin dilaurate was added thereto, and the mixture was held at 80 ℃ 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% by mass.

[ urethane (meth) acrylate B4]

50 parts by mass of toluene, 50 parts by mass of an isocyanurate-modified hexamethylene diisocyanate (タケネート D-170N, manufactured by Mitsui chemical Co., Ltd.), 70 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (プラクセル FA5, manufactured by ダイセル chemical Co., Ltd.), 0.02 part by mass of dibutyltin dilaurate 8 part (X-22-160 AS, manufactured by shin-Etsu chemical Co., Ltd.), and 0.02 part by mass of hydroquinone monomethyl ether were mixed and the mixture was held at 70 ℃ for 5 hours. Then, 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 hexamethylene diisocyanate (タケネート D-170N, manufactured by Mitsui chemical Co., Ltd.), (poly) caprolactone-modified hydroxyethyl acrylate (プラクセル FA10, manufactured by ダイセル chemical Co., Ltd.), (polycaprolactone-modified hydroxyethyl acrylate (プラクセル FA3, manufactured by ダイセル chemical Co., Ltd.)), 0.02 part by mass of dibutyltin dilaurate, and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ℃ for 5 hours. Then, 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 hexamethylene diisocyanate (デュラネート 24A-90CX manufactured by Asahi Kasei chemical Co., Ltd., nonvolatile matter: 90% by mass, isocyanate content: 21.2% by mass), 92 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (プラクセル FA2D manufactured by ダイセル chemical Co., Ltd.), 0.02 part by mass of dibutyltin dilaurate, and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ℃ for 5 hours. 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. In addition, the number of repeating caprolactone units per acrylate monomer residue in the urethane (meth) acrylate is 2.

[ urethane (meth) acrylate C2]

50 parts by mass of toluene, 50 parts by mass of an isocyanurate-modified hexamethylene diisocyanate (タケネート D-170N, manufactured by Mitsui chemical Co., Ltd.), 114 parts by mass of (poly) caprolactone-modified hydroxyethyl acrylate (プラクセル FA3, manufactured by ダイセル chemical industries, Ltd.), 0.02 part by mass of dibutyltin dilaurate, and 0.02 part by mass of hydroquinone monomethyl ether were added thereto and the mixture was held at 70 ℃ for 3 hours. Then, 118.2 parts by mass of toluene was added to the reaction solution to obtain a toluene solution of urethane (meth) acrylate C2 having a solid content of 50% by mass. In addition, the number of repeating caprolactone units per acrylate monomer residue in the urethane (meth) acrylate is 3.

[ urethane (meth) acrylate C3]

50 parts by mass of an isocyanurate-modified hexamethylene diisocyanate (タケネート D-170N manufactured by Mitsui chemical Co., Ltd., isocyanate group content: 20.9% by mass), 42 parts by mass of polyethylene glycol monoacrylate (ブレンマー AE-90 manufactured by Nichikura, Ltd., hydroxyl value: 332(mgKOH/g)), 0.02 part by mass of dibutyltin dilaurate, and 0.02 part by mass of hydroquinone monomethyl ether were added. Further, the reaction was maintained at 70 ℃ for 5 hours. After the completion of the reaction, 92 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction mixture to obtain a toluene solution of urethane (meth) acrylate C3 having a solid content concentration of 50% by mass.

[ urethane (meth) acrylate C4]

A toluene solution of urethane (meth) acrylate C4 was obtained in the same manner as urethane (meth) acrylate C3 except that the amount of polyethylene glycol monoacrylate was changed to ブレンマー AE-150 (hydroxyl value: 264(mgKOH/g))53 parts by mass and the amount of MEK in the reaction solution was changed to 102 parts by mass in urethane (meth) acrylate C3.

[ urethane (meth) acrylate C5]

A toluene solution of urethane (meth) acrylate C5 was obtained in the same manner as urethane (meth) acrylate C3 except that the amount of polyethylene glycol monoacrylate in urethane (meth) acrylate C3 was changed to ブレンマー AE-200 (hydroxyl value: 205(mgKOH/g))68 parts by mass and the amount of MEK in the reaction solution was changed to 118 parts by mass.

[ urethane (meth) acrylate C6]

A toluene solution of urethane (meth) acrylate C6 was obtained in the same manner as urethane (meth) acrylate C3 except that the amount of polyethylene glycol monoacrylate was changed to ブレンマー AE-400 (hydroxyl value: 98(mgKOH/g))142 parts and the amount of MEK in the reaction solution was changed to 192 parts by mass in urethane (meth) acrylate C3.

[ urethane (mesityl) acrylate C7]

50 parts by mass of 1, 3-diisocyanate methylcyclohexane, 100 parts by mass of hydroxyalkyl acrylate, 0.05 part by mass of dibutyltin dilaurate, and 2 parts by mass of hydrogen roller were added thereto, and the mixture was held at 70 ℃ for 3 hours. Then, the mixture was aged at 85 ℃ for 2 hours to obtain a toluene solution of urethane (meth) acrylate C7.

< formulation 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 mass%.

6 parts by mass of a solution of the fluorine compound D1 (solid content concentration: 40% by mass)

15 parts by mass of polycaprolactone polyol (プラクセル 308, weight-average molecular weight 850, manufactured by polycaprolactone triol ダイセル chemical Co., Ltd.)

15 parts by mass of a compound having an isocyanate group (タケネート D-170N manufactured by hexamethylene diisocyanate Mitsui chemical Co., Ltd.)

75 parts by mass of a polydimethylsiloxane-based block copolymer (a) solution (solid content concentration 50% by mass)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

1 part by mass of a photo-radical polymerization initiator (イルガキュア 184, manufactured by チバ & スペシャルティ & ケミカルズ K.).

[ 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 mass%.

2 parts by mass of a solution of the fluorine compound D1 (solid content concentration: 40% by mass)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

10 parts by mass of a fluorine compound D1 solution (solid content concentration: 40% by mass)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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%.

12 parts by mass of a solution (solid content concentration: 20% by mass) of the fluorine compound D2

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

32.4 parts by mass of fluorine Compound D

Polycaprolactone polyol (polycaprolactone triol ダイセル, プラクセル 308, weight average molecular weight 850) 15 parts by mass

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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.

42.4 parts by mass of fluorine Compound D

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

52.4 parts by mass of fluorine Compound D

15 parts by mass of polycaprolactone polyol (プラクセル 308 weight-average molecular weight 850, manufactured by polycaprolactone triol ダイセル chemical industries Co., Ltd.)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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%.

10 parts by mass of polysiloxane (a)

10 parts by mass of propylene glycol monoethyl ether

[ 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 mass%.

10 parts by mass of polysiloxane (a)

[ 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 mass%.

17 parts by mass of a compound having an isocyanate group (タケネート D-170N manufactured by hexamethylene diisocyanate Mitsui chemical Co., Ltd.)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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%.

15 parts by mass of polycaprolactone polyol (Pacce 1308, weight-average molecular weight 850, product of polycaprolactone triol ダイセル chemical industries, Ltd.)

8 parts by mass of a compound having an isocyanate group (タケネート D-170N manufactured by hexamethylene diisocyanate Mitsui chemical Co., Ltd.)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

100 parts by mass of polydimethylsiloxane-based graft copolymer (b)

12 parts by mass of a compound having an isocyanate group (タケネート D-170N made by Hexane methylene diisocyanate Kaisha)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

15 parts by mass of polycaprolactone polyol (プラクセル 312 weight-average molecular weight 1250 manufactured by polycaprolactone triol ダイセル chemical Co., Ltd.)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

75 parts by mass of a polydimethylsiloxane-based block copolymer (c) solution (solid content concentration 50% by mass)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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%.

15 parts by mass of a compound having an isocyanate group (デスモジュール N3200 manufactured by hexamethylene diisocyanate biuret バイエル Co., Ltd.)

10 parts by mass of polysiloxane (a)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

10 parts by mass of polysiloxane (a).

[ coating composition A9]

< blending 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%.

36 parts by mass of a compound having an isocyanate group (タケネート D-170N manufactured by hexamethylene diisocyanate Mitsui chemical Co., Ltd.)

10 parts by mass of polysiloxane (a)

[ coating composition A10]

< blending 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 mass%.

25 parts by mass of a compound having an isocyanate group (タケネート D-170N manufactured by hexamethylene diisocyanate Mitsui chemical Co., Ltd.)

10 parts by mass of polysiloxane (a)

[ coating composition A11]

< blending 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%.

12 parts by mass of a compound having an isocyanate group (trimethylolpropane adduct of hexamethylene diisocyanate, manufactured by DIC バーノック DN-950, solid content concentration: 75% by mass)

100 parts by mass of a polydimethylsiloxane-based graft copolymer (d) solution (solid content concentration 50% by mass)

[ coating composition A12]

< blending 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 mass%.

100 parts by mass of polydimethylsiloxane-based graft copolymer (b)

25 parts by mass of a compound having an isocyanate group (タケネート D-170N made by Hexane methylene diisocyanate Kaisha)

< formulation 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 mass%.

3.8 parts by mass of a solution of fluorine compound D1 (solid content concentration: 40% by mass)

50 parts by mass of a urethane (meth) acrylate B1 solution (solid content concentration 50% by mass)

50 parts by mass of a urethane (meth) acrylate C1 solution (solid content concentration 50% by mass)

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

10 parts by mass of toluene

10 parts by mass of diethylene glycol monobutyl ether

3 parts by mass of a photoradical polymerization initiator (イルガキュア 184, manufactured by チバ & スペシャルティ & ケミカルズ 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 mass%.

50 parts by mass of a urethane (meth) acrylate B2 solution (solid content concentration 50% by mass)

50 parts by mass of a urethane (meth) acrylate C2 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

1.5 parts by mass of a photoradical polymerization initiator (イルガキュア I84, manufactured by チバ, スペシャルティ, ケミカルズ Co., Ltd.).

[ 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 mass%.

70 parts by mass of a urethane (meth) acrylate B2 solution (solid content concentration 50% by mass)

30 parts by mass of a urethane (meth) acrylate C2 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

1.5 parts by mass of a photoradical polymerization initiator (イルガキュア 184, manufactured by チバ & スペシャルティ & ケミカルズ K.).

[ 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%.

30 parts by mass of a urethane (meth) acrylate B3 solution (solid content concentration 50% by mass)

70 parts by mass of a urethane (meth) acrylate C2 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B5 having a solid content concentration of 40 mass%.

50 parts by mass of a urethane (meth) acrylate B3 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ 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 mass%.

50 parts by mass of a urethane (meth) acrylate C3 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-1]

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

3.6 parts by mass of a solution of fluorine compound D1 (solid content concentration: 40% by mass)

50 parts by mass of a urethane (meth) acrylate C4 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-2]

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

1.3 parts by mass of a solution of fluorine compound D1 (solid content concentration: 40% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-3]

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

6.3 parts by mass of a solution of fluorine compound D1 (solid content concentration: 40% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-4]

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

7.5 parts by mass of a solution of fluorine compound D2 (solid content concentration: 20% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-5]

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

31.5 parts by mass of fluorine Compound D

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-6]

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

Fluorine Compound D41.5 parts by mass

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-7]

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

51.5 parts by mass of fluorine Compound D

10 parts by mass of diethylene glycol monobutyl ether

[ coating composition B7-8]

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

10 parts by mass of propylene glycol monoethyl ether

[ coating composition B7-9]

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

50 parts by mass of a solution of the fluorine compound D1 (solid content concentration: 40% by mass)

[ coating composition B7-10]

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

3 parts by mass of polydimethylsiloxane Compound (e)

[ coating compositions B7-11]

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

3 parts by mass of polydimethylsiloxane Compound (f)

[ coating composition B7-12]

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

10 parts by mass of the polydimethylsiloxane Compound (e)

[ coating compositions B7-13]

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

25 parts by mass of the polydimethylsiloxane Compound (e)

[ 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%.

50 parts by mass of a urethane (meth) acrylate C5 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ 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%.

50 parts by mass of a urethane (meth) acrylate C6 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ 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%.

50 parts by mass of a urethane (meth) acrylate B4 solution (solid content concentration 50% by mass)

10 parts by mass of diethylene glycol monobutyl ether

[ 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%.

[ coating composition B12]

100 parts by mass of a urethane (meth) acrylate B1 solution (solid content concentration 50% by mass)

[ 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%.

100 parts by mass of a urethane (meth) acrylate B2 solution (solid content concentration 50% by mass)

[ 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%.

[ 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%.

80 parts by mass of a urethane (meth) acrylate B3 solution (solid content concentration: 50% by mass)

20 parts by mass of a urethane (meth) acrylate C2 solution (solid content concentration 50% by mass)

[ 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%.

20 parts by mass of a urethane (meth) acrylate B2 solution (solid content concentration 50% by mass)

[ 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%.

[ 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%.

100 parts by mass of a urethane (meth) acrylate C7 solution (solid content concentration 50% by mass)

[ coating composition X and coating composition Y ]

The compositions of urethane (meth) acrylate B (B1 to B5) and urethane (meth) acrylate C (C1 to C7) were mixed in the following ratios, and diluted with methyl ethyl ketone to obtain coating compositions X (X1 to X5) and Y (Y1 to Y7) having a solid content concentration of 40 mass%.

100 parts by mass of a solution of urethane (meth) acrylate B or C (solid content concentration 50% by mass)

< method for producing laminated film >

[ production of laminated film A ]

"ルミラー" (registered trademark) U46 (manufactured by Toray corporation) having a thickness of 100 μm, on which an easily adhesive coating is applied, was used as a supporting base material, the resin film being a polyethylene terephthalate (hereinafter, sometimes referred to as "PET"). The coating composition A (A1-1 to A12) was applied by using a continuous coating apparatus equipped with a die-gap coater, and adjusting the discharge flow rate from the die gap so that the thickness after drying was 30 μm. The conditions of the drying step and the curing step in which the liquid film is contacted during the period from the application to the drying and curing are as follows.

1 st drying step

Air supply temperature and humidity: temperature: 80 deg.C

Wind speed: coating surface side: 5 m/sec, opposite side of coated side: 5 m/s

Wind direction: coating surface side: parallel to the surface of the substrate, the opposite side to the coated surface: perpendicular to the plane of the substrate

Residence time: 1 minute

2 nd drying step

Air supply temperature and humidity: temperature: 160 deg.C

Wind speed: coating surface side: 10 m/sec, opposite side of coated side: 10 m/s

Wind direction: coating surface side: relative to the perpendicular to the surface of the substrate, the opposite side of the coated surface: perpendicular to the plane of the substrate

Residence time: 2 minutes

Curing step

Irradiation output: 400W/cm²Accumulated light amount: 120mJ/cm²

Oxygen concentration: 0.1% by volume.

The wind speed and the temperature and humidity were measured by a hot-wire anemometer (アネモマスター wind speed and anemometer MODEL6034, japan カノマックス ltd.). Then, the films were stored (aged) at 20 ℃ for 14 days to obtain multilayer films of examples A1-1 to A7 and comparative examples A1 to A5.

[ production of laminated film B ]

"ルミラー" (registered trademark) U46 (manufactured by Toray corporation) having a thickness of 100 μm and having an easily adhesive coating material applied to a PET resin film was used as a supporting substrate. The coating compositions B (B1 to B18), X (X1 to X5), and Y (Y1 to Y7) were applied using a continuous coating apparatus equipped with a die-gap coater, with the discharge flow rate from the die gap adjusted so that the thickness after drying was 30 μm. The conditions of the drying air contacting the liquid film during the period from the application to the drying and curing are as follows.

Drying step

Air supply temperature and humidity: temperature: 80 ℃ and relative humidity: less than 1%

Wind speed: coating surface side: 5 m/sec, opposite side of coated side: 5 m/s

Residence time: 2 minutes

Curing step

Irradiation output: 400W/cm²Accumulated light amount: 120mJ/cm²

Oxygen concentration: 0.1% by volume.

The wind speed and the temperature and humidity were measured by a hot-wire anemometer (アネモマスター wind speed and anemometer MODEL6034 manufactured by japan カノマックス co., ltd.). In the above manner, laminated films X (X1 to X5) for evaluating the characteristics of examples B1 to B10, comparative examples B1 to B8, and urethane (meth) acrylate B (B1 to B5), and laminated films Y (Y1 to Y7) for evaluating the characteristics of urethane (meth) acrylate C (C1 to C17) were prepared.

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

[ Mass increase rate in oleic acid coating ]

The laminated films X and Y obtained by coating a coating composition containing urethane (meth) acrylate B and urethane (meth) acrylate C on a support base material by the above-described method were cut into a length of 200mm × 200mm, and the mass of the laminated film was defined as a. Fixed to an electric wooden board, oleic acid was applied to the X layer or the Y layer side 100mm wide by 100mm long. The coating was performed by forming a fence with plastic so that oleic acid did not flow out (i.e., applying oleic acid in an amount larger than the amount absorbed by the laminated film). It was stored in an oven heated to 60 ℃ for 1 hour. After storage, the laminated film was wiped with a sanitary gauze until it was transparent, and stored at 23 ℃ for 24 hours (i.e., the coating composition not absorbed into the laminated film was wiped off). The mass of the film measured thereafter was designated as B. The mass increase rate of oleic acid at this time was determined by the following equation. The measurement was performed 3 times, and the average value was used.

(B-A)/(100×t×d)×100

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

d: specific gravity (g/cm) of X layer or Y layer before oleic acid coating²)。

Here, the specific gravities of the X layer and the Y layer were measured by a density gradient tube method (JIS K7112 (1999)) using an aqueous sodium bromide solution as a medium, by cutting out a slice of the X layer and the Y layer from the laminated film with a single blade. At this time, 5 samples were measured, and the average value thereof was used.

The obtained results are shown in tables 1 and 2.

< evaluation of laminated film >

The following performance evaluations were carried out on the produced laminated film, and the results are shown in tables 3-1, 3-2, 4-1, 4-2, 5-1, and 5-2. Except for the case described above, the measurement was carried out 3 times for 1 sample change position in each example and comparative example, and the average value was used.

[ 60 degree specular gloss of surface layer ]

The gloss of the surface layer of the laminated film was measured using VG7000, manufactured by japan electrochromism, and the 60 ° specular gloss of the surface of the laminated film was measured according to JIS Z8741 (1997), and 60% or more was defined as a pass.

[ advancing contact angle and receding contact angle of oleic acid on the surface layer ]

Measurement of advancing contact angle and receding contact angle was performed by the expansion-contraction method. The handbook was measured by the expansion-contraction method using a Drop Master DM-501 contact angle meter, manufactured by Council interfacial science, in accordance with the same apparatus. Specifically, oleic acid (manufactured by ナカライ -standard first-class ナカライテクス) was continuously discharged from a syringe at a liquid discharge speed of 8.5 μ L/sec until the final liquid volume of 50 μ L, the shape of the droplet was photographed 30 times every 0.5 seconds from the start of discharge to the end of discharge, and the respective contact angles were obtained from the image using integrated analysis software "FAMAS" attached to the same apparatus. Since the contact angle during the expansion of the liquid droplet shows a behavior that initially changes with the expansion and then becomes substantially constant, when the contact angle data are arranged in the order of measurement and 5 consecutive points are selected in this order, the average value of the standard deviation of 5 consecutive points that initially becomes 1 ° or less is taken as the advancing contact angle of the measurement, and the measurement is performed 5 times on 1 sample and the average value is taken as the advancing contact angle of the sample. Further, although the imaging is performed for a certain time period before the start of the discharge and after the end of the discharge, the imaging data before the start of the discharge and after the end of the discharge are excluded from the 5-point data for calculating the contact angle in the analysis software.

The receding contact angle was obtained by continuously sucking a liquid droplet at an initial liquid droplet volume of 50 μ L and a liquid discharge speed of 8.5 μ L/sec, taking an image of the shape of the liquid droplet during the contraction from before the start of suction to after the end of suction, and obtaining the respective contact angles in the same manner. Although the image pickup is performed for a certain period of time before the start of the suction and after the end of the suction, the image pickup data before the start of the suction and after the end of the suction are excluded from the data of 5 points for calculating the contact angle in the analysis software. Since the contact angle during the contraction of the liquid droplet shows a behavior that changes first with the contraction and then becomes almost constant, when the contact angles are arranged in the direction in which the liquid droplet contracts and 5 consecutive points are selected in this order, the average value of the standard deviation of 5 consecutive points that initially becomes 1 ° or less is taken as the receding contact angle of the measurement, and the measurement is performed 5 times for 1 sample, and the average value is taken as the receding contact angle of the sample. Further, depending on the sample, the contact angle in the contraction process of the liquid droplet may not be constant and may continuously decrease, and in this case, the receding contact angle is set to 0 °.

[ absorption coefficient of oleic acid ]

In the measurement of the volume of oleic acid dropped on the surface layer and the area of the attached region in the values required for calculating the absorption coefficient of oleic acid, Drop Master DM-501, a contact angle meter by synechia interface science co. Specifically, a droplet of oleic acid (ナカライテクス, ナカライ standard) of 2 μ L was formed at the tip of the syringe, and the droplet was dropped on the surface of the molding material, and then an image of the adhesion state was taken, and the volume and the contact area were calculated using the integrated analysis software "FAMAS" attached to the same apparatus. In addition, the volume is approximated by a shape of the deposited oil droplets as a spherical cut, and the contact area is calculated as an area of a perfect circle assuming that the length of the contact line is the diameter of the perfect circle. The adhered oil droplets were allowed to stand at 25 ℃ for 10 hours in an airless state, and then the volume was measured by the same measurement.

The thickness T of the surface layer was calculated based on the coating thickness when the molding material was prepared. On the other hand, when the coating thickness is unknown, as described above, the thickness can be estimated from the presence of the discontinuous boundary surface when the cross-sectional observation is performed by an electron microscope (transmission type, scanning type) or an optical microscope.

Time-of-flight type 2-order ion mass spectrometry: f of TOF-SIMS^-Fragment ion (M/Z ═ 19) and Si (CH) derived from dimethylsiloxane₃)⁺In-plane distribution determination of fragment ions]

F was measured by 2-fold ION mass spectrometry on the outermost SURFACE of the laminated film using 2-fold ION mass spectrometer TOF-SIMSV manufactured by ION TOF corporation and SURFACACE LAB 6 software^-Fragment ion (M/Z ═ 19) and Si (CH) derived from dimethylsiloxane₃)⁺The fragment ions were distributed in the plane. The measurement conditions were as follows.

Measurement conditions

Primary ion species: bi⁺

Primary ion current: 1.000pA

Acceleration voltage: 25kV

Detecting the polarity of ions: negative (F)^-)、positive(Si(CH₃)⁺)

Measurement range: 100 μm × 100 μm

Decomposition energy: 128 x 128

The scanning times are as follows: and 36 times.

For analysis of measurement data, two-dimensional positional information on the outermost surface of the laminated film and information on the 2 nd order ion intensity of each fragment ion at the corresponding position are extracted using software incorporated in a2 nd order ion mass spectrometer. The position information is output as a grid point of orthogonal coordinates by equally dividing the measurement range set in the measurement conditions by the value of the resolution energy. The coefficient of variation of the 2-fold ion intensity can be calculated based on the extracted 2-fold ion intensity value. That is, the standard deviation and the average value of the ion intensity of 2 times were calculated using the extracted values of all the ion intensities of 2 times, and the value of (standard deviation)/(average value) was defined as the coefficient of variation.

Next, using software incorporated in the 2-order ion mass spectrometer, three-dimensional information obtained by adding 2-order ion intensities to the above-described planar position information is converted into a planar distribution image (mapping image) as shown in fig. 2 to 4 for each fragment ion. At this time, the scale of the 2-fold ion intensity was automatically set from the maximum value and the minimum value in the measurement region by the software described above. On the other hand, since the oil repellency and the oil repellency expected from each chemical species originating from the fragment ions are not sufficiently obtained for the portion with the low detection intensity, specifically, 20% of the maximum value is regarded as a critical value in the ion intensity for 2 times, and a region not satisfying the critical value is regarded as a region not substantially affected by the chemical species of interest, and is regarded as a region lower than the critical value.

F to be obtained from the result^-Fragment ion (M/Z ═ 19) and Si (CH) derived from dimethylsiloxane₃)⁺The planar distribution image and scale of fragment ions were converted into gray scale by image processing software Easy Access Ver6.7.1.23, white balance was adjusted so that the brightest part and the darkest part were within the tone curve of 8bit, and the contrast was adjusted while referring to the scale so that the above-mentioned threshold value in 2-time ion distribution could be clearly identified. Next, using Image analysis software Image j1.45s, 2-valued pixels were generated with the above-described boundary as a boundary, and after only planar distribution images were extracted, the areas formed by the distribution regions of the respective fragment ions were calculated. Further, the occupancy ratio, which is the ratio of the region in which the fragment ions exist, is obtained by dividing the area of the region by the area of the entire measurement range.

Further, with a time-of-flight type 2-th-order ion mass spectrometer, if the coefficient of variation of the 2-order ion intensity is within 0.4 at all measurement points in the range of 100 μm × 100 μm measured at 128 points in the vertical direction × and at 128 points in the horizontal direction, it is judged that F is a positive ion intensity, and F is a negative ion intensity^－The fragment ions are "uniformly present".

Further, as a result of observing the image, as shown in fig. 2, Si (CH) at the measurement point to be measured₃)⁺2 times ofWhen the ion intensity is plotted, if the periphery is surrounded by a portion that does not satisfy the critical value corresponding to 20% of the maximum intensity (except for the case where the portion falls on the outer periphery of the graph), Si (CH) is determined₃)⁺Fragment ions are "present in islands".

On the other hand, as a result of observing the image, Si (CH) was added as shown in FIG. 3₃)⁺When the 2 nd order ion intensity of the fragment is plotted, when the region lower than the critical value is present in an island shape, it is judged that Si (CH)₃)⁺The fragment ions are "present in a mesh shape".

Alternatively, as a result of observing the image, Si (CH) is added as shown in FIG. 4₃)⁺When the ion intensity of the fragment 2 times is plotted, Si (CH) is judged in the case where the island-shaped region and the mesh-shaped region coexist in the measurement range₃)⁺Fragment ions are "present in island and mesh shapes".

Further, information of an arbitrary column or line parallel or perpendicular to the orthogonal coordinate of the position information is extracted from the plane distribution image, and the following spectral line profile analysis is performed. First, the extracted row or column is divided into 2 types, i.e., "a line segment in which each fragment ion exists" and "a line segment below the critical value" based on the critical value of the ion intensity of 2 times described above. Then, the lengths of the respective line segments are calculated, and the average value is obtained.

[ elongation at Break of surface layer ]

The laminated film was cut into a width of 10mm × 200mm, held by a jig so as to extend in the longitudinal direction, and stretched at a stretching speed of 100 mm/min by an インストロン -type tensile testing machine (MODEL 5848, manufactured by インストロン). The measurement environment at this time was 23 ℃ 65 RH%. During the drawing, the specimen under drawing was observed, and the specimen was stopped when the occurrence of cracks (cracks) was visually observed (the elongation at the time of stopping was adjusted to be an integral multiple of 5 (%). From the next measurement sample, samples in which the tensile elongation was decreased by 5% from the elongation at the time of stop were collected in order until the elongation without cracks was finally observed visually.

The surface layer was observed on the observation screen of a transmission electron microscope at a magnification of 30mm or more in the thickness of the observed surface layer, and a case where a crack of 50% or more of the average thickness of the surface layer occurred was regarded as a crack (breakage of the surface layer), and the elongation value of the sample having the lowest elongation among the samples regarded as cracked was regarded as the elongation at break. The same measurements were carried out 3 times in total, and the average of the elongation at break was taken as the elongation at break of the surface layer, and 30% or more was taken as a pass.

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

A smooth metal plate (die steel: SKD-11) was coated with 1g of "high vacuum grease" manufactured by Toray ダウコーニング K.K., and the support base side of the laminated film was attached to the high vacuum grease coated portion, and a filter paper was placed on the surface layer side of the laminated film, and the laminated film was pressed with a hand press so as not to allow air to enter. The press-in load/release test was performed on the stationary sample obtained in this way using a triangular pyramid, and a weight-press-in depth map (see fig. 1) was obtained.

From this graph, the displacement amount in the thickness direction (maximum displacement amount) from the application of the load to the release of the load, the displacement amount in the thickness direction (creep displacement amount) when the load is kept for 10 seconds after reaching 0.5mN, and the displacement amount in the thickness direction (permanent displacement amount) when the load is released to 0mN after being kept for 10 seconds were obtained.

The device comprises the following steps: dynamic ultramicro hardness tester "DUH-201" (manufactured by Shimadzu Kaisha)

Using a pressure head: diamond regular triangle cone pressure head (115 degree between edges)

Measurement mode: 2

Maximum load: retention time when 0.5mN reached 0.5mN load: 10 seconds

Load speed, load removal speed: 0.1 mN/second, 422 mN/second.

[ self-repairability of surface layer ]

After leaving at 20 ℃ for 12 hours, the surface layer surface was scratched horizontally 5 times under the same atmosphere with the following load applied to a copper brush (manufactured by TRUSCO), and the recovery state of the scratch after leaving for 5 minutes was visually judged according to the following criteria, and 4 points or more was regarded as a pass.

10, point: no damage remained under a load of 9.8N (1kg weight).

And 7, point: although a flaw remained under a load of 9.8N (1kg weight), no flaw remained under 6.9N (700g weight).

And 4, point: although a flaw remained under a load of 6.9N (700g weight), no flaw remained under 4.9N (500g weight).

Point 1: a flaw remained under a load of 4.9N (500g weight).

[ design of surface layer ]

After leaving at 20 ℃ for 12 hours, the surface layer was scratched horizontally 5 times with a 500g load on a copper brush (manufactured by TRUSCO) under the same environment, and the recovery state of the scratch was visually judged according to the following criteria, and 4 points or more was regarded as being acceptable.

10, point: all wounds recovered in less than 3 seconds.

And 7, point: all wounds recovered in 3 seconds or more and less than 10 seconds.

And 4, point: all wounds recovered in more than 10 seconds and less than 30 seconds.

Point 1: others (recovery of total injury takes more than 30 seconds, or there is no injury recovered, etc.).

[ method of applying simulated fingerprint ]

The attachment of the simulated fingerprint to the object side of the laminated film of the present invention was performed in 3 steps as follows: 1. manufacturing an analog fingerprint sheet, 2, transferring the analog fingerprint to silicon rubber, and 3, adhering the analog fingerprint to the surface of the laminated film.

1. Making of simulated fingerprint sheet

The following materials were weighed at the following ratios and stirred with an electromagnetic stirrer for 30 minutes to obtain a coating material for preparing an artificial fingerprint sheet.

Oleic acid 14 parts by mass

6 parts by mass of silica particles (number average particle diameter 2 μm)

80 parts by mass of isopropyl alcohol

The number average particle diameter of the silica particles was observed and measured by a Scanning Electron Microscope (SEM). The observation sample was prepared by mixing the silica particles in a dispersion medium (isopropyl alcohol) at a solid content concentration of 5 mass%, dispersing the mixture with ultrasonic waves, dropping the dispersion onto a conductive tape, and drying the dispersion. The number average particle diameter is observed at a magnification of 10 to 50 as the number of primary particle aggregates per 1 field of view, the diameter of the circumscribed circle of the primary particles is determined from the obtained image and is taken as the particle diameter, the observed number is increased, and the number average particle diameter is determined from the values measured for 100 primary particles.

This "coating material for preparing a pseudo-fingerprint sheet" was applied to "ルミラー" (registered trademark) U46 (manufactured by tokyo corporation) as a support base material, which was a PET resin film coated with an easily adhesive coating material, using a wire bar (#7), and dried at 50 ℃ for 2 minutes to remove isopropyl alcohol, thereby obtaining a pseudo-fingerprint sheet in which a pseudo-fingerprint liquid (a dispersion containing 70 mass% of oleic acid and 30 mass% of silica) was uniformly spread on the film.

2. Transfer printing of simulated fingerprint to silicon rubber

A silicone rubber having a rubber hardness of 50 specified in JIS K6253 (1997) was ground with a #250 water-resistant paperThe surface of the rubber was adjusted to have an Ra of 3 μm as defined in JIS B0601 (2001). Next, the ground silicone rubber was pressed against the fingerprint simulating sheet with the above water-resistant paper at 30 kPa. Adhesion amount (g/m) of simulated fingerprint liquid to silicone rubber²) The values obtained from the area of the silicone rubber and the mass difference before and after adhesion were 1.0g/m in each case as a result of the above-described method²。

3. Simulating the attachment of fingerprints to the surface of a laminate

The silicone rubber transferred with the analog fingerprint liquid in 2 was pressed to the surface of the laminated film at 30kPa, and the trace formed on the surface of the laminated film was used as an analog fingerprint.

[ simulated wiping method for simulated fingerprint ]

The laminate film having the analog fingerprint attached to the surface to be measured by the above method was fixed to a flat plate, and the a point and the B point were determined on the laminate film so that the interval was 10 cm. Then, a cellulose long fiber nonwoven cloth gauze ("ハイゼ" ガーゼ NT-4 manufactured by Kagaku Kogyo Co., Ltd.) having a folded size of 12.5X 12.5cm was placed on the laminated film, a weight was placed thereon so as to apply a pressure of 30kPa, and the cellulose long fiber nonwoven cloth gauze on which the weight was placed was reciprocated 3 times between the points A and B at a speed of 5 cm/sec, thereby wiping the laminated film.

[ color difference between the front and back sides of the fingerprint containing regular reflection light and the fingerprint containing no regular reflection light ]

A black polyvinyl chloride insulating tape was attached to the opposite surface of the object to be molded, and the reflected color not including the normal reflected light was captured as (de: 8) S using the specular reflected light according to JIS Z8722(2009) using a spectrocolorimeter CM-3600A manufactured by コニカミノルタ K.K. (DE: 8 ℃ C.)_bUnder the condition of 10W10, the reflected color including the regular reflection light is captured as S (di: 8 DEG) without using the specular reflection light_bUnder the condition of 10W10, the reflected colors of the simulated fingerprints before and after attachment were measured by CIE1976(L a b) described in JIS Z8730 (2009). Measurement after attachment of the simulated fingerprint for 3 hours immediately after attachment, 30 minutes after attachment, and 10 hours after attachmentAnd (4) planting.

Then, from the reflected color before the attachment of the simulated fingerprint and the reflected color after the attachment of the simulated fingerprint, a value (△ E ab (di: 8 °) S was obtained by the calculation method described in JISZ8730 (2009)_b10W10) and (△ E @_ab(de：8°)S_b10W10)。

The color difference (△ E) of the simulated fingerprint before and after attachment_ab(di：8°)S_b10W10) is 0.4 or less, and the color difference (△ E) before and after the attachment of the simulated fingerprint is free of the regular reflection light_ab(de：8°)S_b10W10) is 4 or less.

Next, (△ E) was obtained from the reflected colors before and 30 minutes after the attachment by the calculation method described in JIS Z8730(2009)_ab(di：8°)S_b10W10、△E_SCI-0.5) And (△ E)_ab(de：8°)S_b10W10、△E_SCE-0.5). Then, based on the measured value, the parameter K defined by the above formula (5) is calculated_0.5The following 2 was defined as pass.

Further, (△ E) was obtained from the reflected color before and after 10 hours of attachment by the calculation method described in JIS Z8730(2009)_ab(di：8°)S_b10WI0、△E_SCI-10) And (△ E)_ab(de：8°)S_b10W10、△E_SCE-10). Then, based on the measured value, the parameter K defined by the above formula (6) is calculated₁₀As shown in the above formula (4), the parameter K is compared with_0.5The difference of (A) is 1 or less.

[ color difference containing regular reflection light and no regular reflection light before attachment of the simulated fingerprint and after erasure of the simulated fingerprint ]

A black polyvinyl chloride insulating tape was attached to the surface opposite to the surface to be laminated, and the reflected color not containing the specular reflection light was captured as (de: 8) S without using the specular reflection light according to JIS Z8722(2009) using a spectrocolorimeter CM-3600A manufactured by コニカミノルタ K_bCondition of 10W10, and normal reflection lightS captured at (di: 8 °) without using specular reflection light_bUnder the condition of 10W10, the reflected color before the attachment and after the wiping of the above-described simulated fingerprint was measured by CIE1976(L a b) described in JIS Z8730 (2009).

Then, from the reflected colors before the attachment of the simulated fingerprint and after the erasure of the simulated fingerprint, the reflected colors before the attachment of the simulated fingerprint and after the erasure of the simulated fingerprint were obtained (△ E ×) by the calculation method described in JIS Z8730(2009)_ab(di：8°)S_b10W10) and (△ E @_ab(de：8°)S_b10W10), the former was △ E_SCL-2The latter was referred to as △ E_SCE-2。

[ measurement of oil droplet diameter ]

The simulated fingerprint attached to the surface of the molding material by the same method as the above-mentioned simulated fingerprint attachment was used as an object, the molding material was stored at 25 ℃ for 24 hours, a surface projection image of the oil droplets was taken by a differential interference microscope, and the diameter d of the oil droplets was obtained from the obtained image by using image processing software_pThe area-based frequency distribution and the transition of the cumulative frequency are obtained based on the result.

The oil droplet diameter d is described below_pThe specific measurement sequence of (1).

First, the surface of the fingerprint-proof molding material to which the simulated fingerprint is attached is imaged at a magnification of 100 times by a differential interference microscope. Then, the image is converted into gray scale by image processing software Easy Access Ver6.7.l.23, white balance is adjusted so that the brightest part and the darkest part are in a tone curve of 8bit, and contrast is further adjusted so that the boundary of oil drops can be clearly identified. Next, using Image analysis software Image j1.45s, 2-valued pixels are formed with the above-described boundary as a boundary, the area of each oil drop is calculated, and then the diameter at which the area of the area is approximated to a circle is obtained as the oil drop diameter.

[ area-based frequency distribution of oil droplets ]

At the area reference frequency of the oil dropIn the calculation of the rate distribution, the oil droplet diameter d obtained by the above-described processing is used first_pA histogram is made for the reference. The oil droplet diameters at this time were divided every 5 μm, and the layering was performed according to this using the histogram function of Microsoft Excel 2003. Next, in order to weight the obtained histogram according to the surface projection image area, a representative area of each layer of the histogram is obtained by assuming a circle having the center value of each base as a representative diameter, and the representative area is multiplied by the frequency of each layer and divided by the total area again, thereby obtaining an area reference frequency distribution. In the area reference frequency distribution, the frequency is plotted on the vertical axis and the oil droplet diameter is plotted on the horizontal axis, the cumulative frequency is plotted, and the median diameter D is obtained from the value of the oil droplet diameter at the cumulative frequency of 50%_P. Specifically, 2 layers sandwiching a point having a cumulative frequency of 50% are identified from the histogram, the center value of the oil droplet diameter of the layer and 2 coordinates specified by the cumulative frequency are connected by a straight line, and the oil droplet diameter of the point having the cumulative frequency of 50% on the straight line is calculated as the median diameter D_P。

[ Change in area-based frequency distribution with time ]

After the simulated fingerprint was attached to the surface of the molding material in the same manner as the above-mentioned simulated fingerprint attachment, the molding material was left to stand at 25 ℃ for 30 minutes and 10 hours, respectively, under a windless condition. Next, the oil droplet diameter after 30 minutes and the oil droplet diameter after 10 hours were measured by the measurement of the oil droplet diameter. Further, the median diameter D after 30 minutes was calculated by analysis described in the area standard frequency distribution_P0.5And median diameter D after 10 hours_P10。

[ fingerprint resistance (fingerprint adherence) ]

The fingerprint resistance (fingerprint adherence) was evaluated by placing the evaluation surface of the laminated film on a black picture paper as an upper side, rubbing a finger (index finger) to which a fingerprint was applied with a thumb 3 times, slowly pressing the finger (index finger) on the surface of the surface layer, and evaluating the discriminativity of the adhered fingerprint by the following evaluation criteria, and taking 5 points or more as a pass.

10, point: no fingerprint is recognized or the difference from the unattached portion cannot be distinguished.

And 7, point: the fingerprint is hardly recognized or unrecognizable.

And 5, point: fingerprints are slightly recognized, but are hardly noticeable at all.

And 3, point: a fingerprint is identified.

Point 1: clearly identifying a fingerprint is very interesting.

The evaluation was performed on 10 subjects, and the average value was obtained. Rounding is performed below the decimal point.

[ fingerprint resistance (fingerprint disappearance) ]

The fingerprint discrimination performance after transferring a fingerprint and leaving it for 10 hours at 25 ℃ in a windless state as in the evaluation of fingerprint resistance was observed while enlarging the observation angle from the vicinity of 0 ° (from the lateral observation sample) to 90 ° (from the direct upward observation) relative to the evaluation "fingerprint resistance (fingerprint adhesion)", and evaluated at 10 dots as a full mark. The fingerprint after leaving was evaluated for the visibility by the following evaluation criteria, and 7 points or more were regarded as passed.

And 7, point: the fingerprint is hardly recognized or unrecognizable.

And 3, point: a fingerprint is identified.

Point 1: clearly identifying a fingerprint is very interesting.

[ fingerprint resistance (fingerprint erasability) ]

After the fingerprint was attached by the above-mentioned method, the paper was wiped with a nonwoven cloth of cellulose long fiber (manufactured by "ハイゼ" ガーゼ NT-4 Chuanyuan Co., Ltd.) folded into a size of 12.5X 12.5 cm. The fingerprint erasure was evaluated by the following evaluation criteria for the visibility after wiping with this wiping method, and 5 points or more were regarded as a pass.

10, point: wiping 1 time was almost unrecognizable.

And 7, point: wiping 1 time becomes almost unnoticeable.

And 5, point: dirt remained after only 1 or 2 wipes, but was barely recognized after 3 wipes.

And 3, point: if the wiping is performed 5 times, the wiping is almost unnoticed.

Point 1: even if the wiping is performed more than 5 times, dirt remains.

[ cosmetic resistance ]

A5 cm square sample was applied with 0.5g of アトリックス "hand cream A" (NO413) manufactured by Kao corporation, and left to stand at 60 ℃ and 95% relative humidity for 6 hours, and then left to stand at 25 ℃ and 65% relative humidity for 30 minutes, and the surface was wiped with gauze. After the plate was left to stand at 25 ℃ and 65% relative humidity for 24 hours, the surface state was observed and judged according to the following criteria, and 4 points or more were judged as passed.

10, point: no white spots occurred.

And 7, point: almost no white spots occurred at all.

And 4, point: white spots occurred, but became clean if wiped.

Point 1: white spots occur. Even if the wiping was performed, the wiping occurred again after being left for 24 hours in an environment of 25 ℃ and 65% relative humidity.

The physical properties of the laminated film X, Y having X and Y layers formed in tables 1 and 2 for evaluating the physical properties of the urethane acrylate B, C are summarized in tables 3-1, 3-2, 4-1, 4-2, 5-1, and 5-2, as evaluation results of the finally obtained laminated film. Evaluation items (60 ℃ specular gloss, elongation at break, self-repairability, design, cosmetic resistance, color difference before and after attachment of pseudo fingerprint, K)_0.5、K_0.5-K₁₀And fingerprint resistance (fingerprint adhesion), fingerprint resistance (fingerprint disappearance), and fingerprint resistance (fingerprint erasure), it was determined that the problem was not achieved if only 1 item failed.

[ 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 ]

Description of the reference numerals

1 maximum displacement

2 creep displacement

3 permanent displacement

4 Displacement h (μm) in the thickness direction

5 load P (mN)

6 weighting procedure

7 holding step

8 load relieving step

9. 11, 13 Si (CH) from Dimethicone₃)⁺Region where fragment ion (M/Z-43) exists

10. 12, 14 Si (CH) from Dimethicone₃)⁺Region where fragment ion (M/Z43) is less than critical value

Industrial applicability

The laminated film of the present invention can be used for plastic molded products, home electric appliances, buildings, and the like, or for imparting similar functions to the surfaces of vehicle interior parts and various printed matters.

Claims

1. A laminated film characterized by having a surface layer on at least one surface of a support base, the surface layer satisfying the following conditions 1 to 3,

condition 2: receding contact Angle θ of oleic acid_rIs more than 50 degrees;

condition 3: when a load of 0.5mN is applied for 10 seconds in a micro hardness measurement, the maximum displacement amount of the surface layer in the thickness direction is 1.0 μm or more and 3.0 μm or less,

the creep displacement amount of the surface layer in the thickness direction is 0.05 [ mu ] m or more and 0.5 [ mu ] m or less,

when the load is removed to 0mN, the permanent displacement amount of the surface layer in the thickness direction is 0.2 μm or more and 0.7 μm or less,

the resin contained in the surface layer has the following (1) to (3):

(1) (poly) caprolactone segments,

(2) A urethane bond,

(3) A fluoropolyether segment.

2. The laminate film as claimed in claim 1, wherein the surface layer has an advancing contact angle θ of oleic acid_aReceding contact Angle θ_rSatisfies the following formula (1):

(θ_a-θ_r) Formula (1) is less than or equal to 15 degrees.

3. The laminate film as claimed in claim 1 or 2, wherein the oleic acid absorption coefficient A of the surface layer_bThe content of the organic acid is more than 30,

wherein, the absorption coefficient of oleic acid is A_bThe volume (V) determined from the shape of the droplets at the time of discharge from a syringe was determined by dropping 2. mu.l of oleic acid on the surface layer₁) And the area of the drop part during dropping (S)₁) Volume (V) after 10 hours at 25 ℃ in the absence of wind₂) And a thickness (T) of the surface layer, which is a value obtained by the following formula (2):

A_b＝(V₁-V₂)/(S₁× T) formula (2).

4. The laminate film as claimed in claim 1 or 2, wherein in the surface layer, F derived from fluorine measured by time-of-flight type 2-time ion mass spectrometer (TOF-SIMS)^-Fragment ions exist uniformly in plane, F^-M/Z of the fragment ion is 19 and is derived from Si (CH) of dimethyl siloxane₃)⁺The fragment ions are present in any of the ways described belowSi(CH₃)⁺M/Z of fragment ion 43:

is present in an island shape,

Is in a mesh shape,

In the form of islands and meshes.

5. The laminate film according to claim 4,

in the surface layer, the dimethylsiloxane-derived Si (CH)₃)⁺The occupancy rate of the region in which the fragment ions are present is 30% to 70%.

6. The laminate film according to claim 1 or 2,

color difference △ E containing specular reflection light defined in JIS Z8730(2009) and JIS Z8722(2009) before and after the surface layer is attached with the simulated fingerprint under the following conditions_ab(di: 8 ℃) Sb10W10 is 0.4 or less, and does not contain the color difference △ E of the regular reflection light_ab(de: 8 ℃) Sb10W10 is 4 or less,

7. The laminate film according to claim 1 or 2,

the surface layer satisfies the following formulae (3) and (4):

K_0.5less than or equal to 3 type (3)

K_0.5-K₁₀More than or equal to 1 type (4)

Wherein,

K_0.5＝[(△E_SCI-0.5)²+(△E_SCE-0.5)²]^1/2formula (5)

K₁₀＝[(△E_SCI-10)²+(△E_SCE-10)²]^1/2Formula (6)

△E_SCI-0.5、△E_SCE-0.5Respectively means that:

△E_SCI-10、△E_SCE-10Respectively means that:

8. The laminate film according to claim 1 or 2,

D_P0.5less than or equal to 80 mu m type (7)

(D_P0.5-D_P10)/D_P0.5More than or equal to 0.5 type (8)

D_P10: area reference frequency point of oil droplets constituting the simulated fingerprint measured 10 hours after the simulated fingerprint was attachedThe median diameter is calculated and distributed over the entire length of the pipe,

9. The laminate film according to claim 1 or 2,

((△E_SCI-2)²+(△E_SCE-2)²)^1/2less than or equal to 2.0 type (9)

simulating a fingerprint attachment condition: a dispersion of 70% by mass of oleic acid and 30% by mass of silica having a number average particle size of 2 μm was made to be 1.0g/m²Adhered to a silicone rubber having Ra of 3 μm as defined in JIS B0601 (2001) and a rubber hardness of 50 as defined in JIS K6253 (1997), and adhered to a surface to be treated at 30kPa,

simulating a fingerprint erasing condition: the simulated fingerprint attached under the above conditions was wiped 3 times with a nonwoven fabric at a pressure of 30kPa and a speed of 5 cm/sec.

10. The laminate film according to claim 1 or 2,

the resin contained in the surface layer has a (4) (poly) siloxane segment.

11. The laminate film according to claim 1 or 2,

the resin contained in the surface layer has a polydimethylsiloxane segment.