JPWO2015041175A1 - Laminated film - Google Patents

Abstract

Provided is a laminated film that satisfies moldability, self-repairability, fingerprint resistance, and dye transfer resistance. In the laminated film having a surface layer on a supporting substrate, the resin constituting the surface layer has the following (1) to (3). (1) A segment containing at least one selected from the group consisting of (poly) butadiene segments, and / or (poly) isoprene segments (2) tricyclodecyl segments, dicyclopentazinyl segments and isobonyl segments (3) A segment containing at least one selected from the group consisting of a fluorine compound segment, a (poly) siloxane segment, and a (poly) dimethylsiloxane segment

Description

  The present invention relates to a laminated film excellent in fingerprint resistance and dye transfer resistance in addition to compatibility between moldability and scratch resistance required for a molding material.

  In a molding material used for decorative molding or the like, a surface hardened layer is provided in order to prevent scratches during molding and to prevent scratches in the process of using the article after molding. However, since the surface hardened layer has insufficient elongation to follow the molding, cracks occur at the time of molding, and in extreme cases, the film breaks or the surface hardened layer peels off. Means are applied such as forming a surface hardened layer after molding, or molding in a semi-cured state, followed by complete curing by heating or irradiation with actinic radiation. However, since the molded article is processed three-dimensionally, it is very difficult to provide a surface hardened layer by post-processing, and when molding in a semi-cured state, depending on the molding conditions, the mold may become dirty. May be triggered. From the above points, scratch-resistant materials that follow molding are desired, and “self-healing materials” capable of self-repairing minor scratches by deformation of their own elastic recovery range have attracted attention. Patent Documents 1 and 2 have been proposed. ing.

  In addition, as a surface state of the molded body surface, a soft touch film for film insert molding for producing a resin molded product having a so-called “soft touch” surface against a hard, cold, slippery surface of a so-called hard coat material Patent Document 3 has been proposed as a molded body.

  On the other hand, when using these moldings such as the surface of a touch panel in applications where human fingers touch the surface in daily life, the fingerprint (here, the fingerprint is a line in which the opening of the sweat gland in the skin of the fingertip is raised ( There is a problem that the pattern formed by the ridge) and the trace of the pattern attached to the surface of the object are visually recognized, and if it cannot be easily wiped off, it gives an unpleasant impression that it looks dirty. In particular, Patent Document 4 proposes a self-healing material provided with antifouling properties in order to solve the above problems.

  Furthermore, when a sheet made of general soft resin comes into contact with jeans (denim fabric), clothing, or natural leather or synthetic leather containing dye, there is a problem that these dyes migrate to the surface of the sheet. As a method for imparting resistance (hereinafter referred to as dye transfer resistance), the material of Patent Document 5 has been proposed.

International Publication No. 2011/136042 Japanese Patent Laid-Open No. 11-228905 JP2013-35258A JP 2012-196868 A JP 2008-62408 A

  Regarding the techniques of Patent Document 1 and Patent Document 2 proposed as the above-mentioned self-healing materials and Patent Document 3 proposed as a soft touch film molded body, the present inventors confirmed that the moldability and self- Although repairability or soft touch property was recognized, fingerprint resistance and dye transfer resistance were significantly inferior to those of the hard coat material.

  In addition, with regard to the technique of Patent Document 4 described above, the present inventors have confirmed the fingerprint resistance under various conditions. By making the described materials and coating film properties within the described ranges, the fingerprints are not noticeable. The effect of facilitating or wiping off the fingerprint was recognized to some extent, but the dye transfer resistance was not obtained.

  Furthermore, although the method described in Patent Document 5 described above was effective with respect to dye transfer resistance, it does not exhibit moldability or self-healing property, and can be combined with the techniques of Patent Documents 1 to 4 described above. It was impossible and found to be incompatible with self-healing.

  Therefore, the problem to be solved by the present invention is to provide a laminated film satisfying both fingerprint resistance and dye transfer resistance in addition to compatibility between moldability required for molding materials and scratch resistance due to self-healing properties. It is in.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
1) A laminated film having a surface layer on a supporting substrate, wherein the resin constituting the surface layer has the following (1) to (3).
(1) (poly) butadiene segment and / or (poly) isoprene segment (2) segment containing at least one selected from the group consisting of tricyclodecyl segment, dicyclopentazinyl segment and isobonyl segment (3) fluorine A segment comprising at least one selected from the group consisting of a compound segment, a (poly) siloxane segment, and a (poly) dimethylsiloxane segment 2) When measured from the surface layer side, the following condition 1 is satisfied: The laminated film as described in 1).
Condition 1: The maximum displacement in the thickness direction is 1.20 μm or more and the remaining displacement in the thickness direction is 1 in a load-unloading test method using a microhardness meter under conditions of a maximum load of 0.5 mN and a holding time of 10 seconds. 0.001 μm or less 3) The laminated film according to 1) or 2), wherein the surface layer satisfies the following conditions 2 and 3.
Condition 2: The elongation at break of the surface layer at 25 ° C. is 120% or more in the tensile test method. Condition 3: The elastic recovery rate at 25 ° C. of the surface layer is 80 in the tensile test method at a deformation amount of 120%. % Or more 4) The surface layer is formed of at least two layers, and the resin constituting the layer farthest from the support substrate (hereinafter referred to as the first layer) has (1) to (3), The resin constituting the layer (hereinafter referred to as the second layer) adjacent to the first layer on the support base material side has the following (4) and (5), from 1) The laminated film as described in any one of 3).
(4) A segment comprising at least one selected from the group consisting of (poly) caprolactone segment, (poly) carbonate segment and (poly) alkylene glycol segment (5) urethane bond

  According to the present invention, it is possible to obtain a laminated film satisfying moldability, self-repairability, fingerprint resistance, and dye transfer resistance.

This is an example where the surface layer is composed of one layer. This is an example where the surface layer is composed of two layers. The resin constituting the first layer includes resins having (1) to (3) described later, and the resin constituting the second layer includes resins having (4) to (5) described later. This is an example where the surface layer is composed of two layers. The resin constituting the first layer includes resins having (4) to (5) described later, and the resin constituting the second layer includes resins having (1) to (3) to be described later. It is an example of the data obtained by the load-unloading test method. It is an example of the data obtained by the tensile test method.

  In order to satisfy the above-mentioned problems, that is, the moldability, self-repairability, fingerprint resistance, and dye transfer resistance, the inventors of the present invention may have a specific material, layer structure, and physical properties. I found it effective. They are as follows.

First, in the laminated film of the present invention, as shown in FIG. 1, in the laminated film having the surface layer 1 on the support substrate 2, the resin constituting the surface layer may have the following (1) to (3): preferable.
(1) (poly) butadiene segment and / or (poly) isoprene segment (2) segment containing at least one selected from the group consisting of tricyclodecyl segment, dicyclopentazinyl segment and isobonyl segment (3) fluorine A segment comprising at least one selected from the group consisting of a compound segment, a (poly) siloxane segment, and a (poly) dimethylsiloxane segment.

  Details of the structure of the surface layer and the manufacturing method will be described later. Furthermore, the resin refers to a substance containing a polymer compound, and the range includes a range from a polymer to an oligomer.

  Moreover, about each segment which resin which comprises a surface layer contains, it can confirm by TOF-SIMS, FT-IR, etc.

  The (poly) butadiene segment described in (1) is a polymer of 1,3-butadiene, which is represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, 1,2-polybutadiene, trans-1,4 butadiene, cis-1 , 4 Polybutadiene segment, or a segment in which hydrogen is added to the unsaturated bond portion thereof (hereinafter referred to as a hydrogenated product), and a mixture thereof. Here, (poly) butadiene includes both low molecular weight (so-called oligomer) having 8 to 100 repeating units of butadiene and high molecular weight (so-called polymer) having more than 100 repeating units of butadiene. .

  (Poly) isoprene segment is a polymer of 1,3-isoprene, cis-1,4-polyisoprene represented by Chemical Formula 4, Chemical Formula 5, trans-1,4-isoprene segment, or hydrogenated product thereof, and These copolymers and mixtures are pointed out. Here, (poly) isoprene includes both those having a low molecular weight (so-called oligomer) having 40 to 100 isoprene repeating units and those having a high molecular weight having more than 100 isoprene repeating units (so-called polymer). .

  n is an integer from 8 to 370.

  n is an integer from 8 to 370.

  n is an integer from 8 to 370.

  n is an integer from 40 to 400.

  n is an integer from 40 to 400.

  The details of the (poly) butadiene segment and the (poly) isoprene segment will be described later, but the resin constituting the surface layer has these segments to give the surface layer flexibility and make it self-healing. It has both excellent scratch resistance and moldability, and exhibits excellent dye transfer resistance due to a hydrocarbon skeleton that does not contain an easily dyeable part as in the prior art. More preferably, the resin constituting the surface layer is a resin containing a hydrogenated product of a (poly) butadiene segment and / or a (poly) isoprene segment from the viewpoint of dye transfer resistance and weather resistance.

  The tricyclodecyl segment described in (2) above refers to the chemical formula 6, the dicyclopentazinyl segment refers to the chemical formula 7, and the isobonyl segment refers to the chemical formula 8.

  n is an integer of 1 to 50.

  The details of the tricyclodecyl segment, dicyclopentazinyl segment, and isobonyl segment will be described later, but the resin constituting the surface layer has at least one segment selected from these groups, While improving toughness, it can improve self-repairability by combining with said (1). Furthermore, it is more preferable from the surface of the toughness of a coating film to contain a tricyclodecyl segment.

  The fluorine compound segment (fluorine-containing segment) described in (3) above includes at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group. More preferably, the fluorine compound segment is a fluoropolyether segment. The fluoropolyether segment is a segment composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., and has a structure represented by chemical formulas (9) and (10).

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

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

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

  The (poly) siloxane segment (3) is a segment represented by Chemical Formula 11, and the (poly) dimethylsiloxane segment is a segment represented by Chemical Formula 12. Here, the (poly) siloxane includes both low molecular weight (so-called oligomer) having about 100 repeating units of siloxane and high molecular weight (so-called polymer) having more than 100 repeating units of siloxane. Similarly, (poly) dimethylsiloxane includes both low molecular weight dimethylsiloxane repeating units of 10 to 100 (so-called oligomers) and high molecular weight dimethylsiloxane repeating units of more than 100 (so-called polymers). Is included.

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

  m is an integer of 10 to 300.

  The details of the (poly) siloxane segment and (poly) dimethylsiloxane segment will be described later, but the resin constituting the surface layer has these segments to improve heat resistance and weather resistance, and lubricity of the surface layer. Can improve the scratch resistance. More preferably, it contains a (poly) dimethylsiloxane segment represented by Chemical Formula 12 from the viewpoint of lubricity.

  Furthermore, the present inventors pay attention to the viscoelastic behavior of the surface layer of the laminated film, and it is possible to form and self-healing by combining the displacement amount with respect to the load of the surface layer and the displacement amount after releasing the load. It was found to be effective for both. Specifically, as a mechanical characteristic, in the load-unloading test method using a microhardness meter, paying attention to the maximum displacement amount and the residual displacement amount in the thickness direction, these two parameters are set within a specific range, that is, the laminated film. It is preferable to satisfy the following condition 1 when measured from the surface layer side.

  Condition 1: The maximum displacement in the thickness direction is 1.20 μm or more and the remaining displacement in the thickness direction is 1 in a load-unloading test method using a microhardness meter under conditions of a maximum load of 0.5 mN and a holding time of 10 seconds. 0.000 μm or less.

  Here, although details of the load-unloading test using a microhardness meter will be described later, from the viewpoint of moldability and self-repairability, the maximum amount of displacement in the thickness direction is more preferably 1.50 μm or more, Particularly preferably, it is 1.80 μm or more. This is preferable as the maximum amount of displacement in the thickness direction is larger, but if it is too large, the self-repairing property may be incomplete, so the upper limit value is considered to be about 3.00 μm. This is because if the maximum displacement amount is less than 1.20 μm, the moldability may deteriorate.

  Similarly, the residual displacement in the thickness direction is more preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. This is preferably as the residual displacement is smaller, but generally the self-healing material is plastically deformed. Therefore, in this measurement method, the lower limit of the residual displacement is considered to be about 0.3 μm. On the other hand, if the residual displacement in the thickness direction is larger than 1.00 μm, visible scratches may remain even after the surface layer is self-repaired.

In addition, the laminated film preferably satisfies the following condition 2 and condition 3 in order to achieve both moldability and self-repairability.
Condition 2: The elongation at break of the surface layer at 25 ° C. is 120% or more in the tensile test method. Condition 3: The elastic recovery rate at 25 ° C. of the surface layer is 80 in the tensile test method at a deformation amount of 120%. %that's all.

  Here, the tensile test method and the elastic recovery rate measurement method will be described later. From the viewpoint of self-repairability and moldability, the elongation at break of the surface layer at 25 ° C. in the tensile test method is 120% or more. However, 150% or more is more preferable, and 180% or more is more preferable. FIG. 5 is an example of data obtained by the tensile test method.

  If the elongation at break is large, the surface layer is prevented from being destroyed when scratches are generated or deformed during molding, and self-repairability and moldability are improved. The higher the elongation at break, the better, but the self-healing material has a limit because it has a crosslinked network, and the upper limit is considered to be about 500%. On the other hand, if the elongation at break is less than 120%, the surface layer may be destroyed when scratches occur or when it is deformed, and self-repairability and moldability may be reduced.

  Similarly, the elastic recovery rate at 25 ° C. of the surface layer in the tensile test method with a deformation amount of 120% is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.

  This is because when the elastic recovery rate is high, the material recovers when the scratches are generated or when the material is deformed during molding, so that the deformation is recovered and the self-restoring property is improved. The higher the elastic recovery rate, the better. The upper limit is 100%. On the other hand, when the elastic recovery rate is less than 80%, when the scratches are generated or the material is deformed at the time of molding, the material is not restored and the deformation remains, so that the self-repairability may be lowered.

  About these physical properties, resin which comprises the said surface layer has the segment of said (1) to (3), and can be achieved by adjusting the ratio suitably.

Moreover, in order to solve the problem of the present invention by satisfying the above-mentioned more preferable range, the surface layer is composed of at least two layers as shown in FIG. The layer 4 (hereinafter referred to as the first layer) has the above (1) to (3), is further adjacent to the first layer, and is closer to the support substrate than the first layer ( Hereinafter, the resin constituting the second layer preferably has the following (4) and (5).
(4) A segment comprising at least one selected from the group consisting of a (poly) caprolactone segment, a (poly) carbonate segment, and a (poly) alkylene glycol segment (5) urethane bond What is the (poly) caprolactone segment of (4) above? In the chemical formula 13, the (poly) alkylene glycol segment refers to the chemical formula 14 and the (poly) carbonate segment refers to the segment represented by the chemical formula 15. Here, (poly) caprolactone includes those having a repeating unit of caprolactone such as 1 (monomer), 2 (dimer), 3 (trimer), and an oligomer having a repeating unit of caprolactone up to 35. The (poly) alkylene glycol also includes those having an alkylene glycol repeating unit of 2 (dimer) and 3 (trimer), and oligomers having an alkylene glycol repeating unit of up to 11. Similarly, (poly) carbonates include those having 2 (dimer) and 3 (trimer) carbonate repeating units, and oligomers having up to 16 carbonate repeating units.

n is an integer of 1 to 35.

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

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

  By constructing the surface layer with two or more layers, the function of the surface layer as a bulk is self-healing, scratch resistance, moldability, and antifouling, dye transfer that emphasizes the surface function By separately sharing gender functions, trade-offs can be avoided and both functions can be further enhanced.

The details of the (poly) caprolactone segment, (poly) carbonate segment, and (poly) alkylene glycol segment will be described later, but the resin constituting the second layer has these segments, so that the flexibility of the surface layer is increased. , Can improve self-repairability.
Furthermore, here, the urethane bond of (5) refers to a segment represented by Chemical Formula 16.

  Although details of the urethane bond will be described later, the toughness of the entire surface layer can be improved when the resin constituting the second layer has this bond. Hereinafter, embodiments of the present invention will be described in detail.

[Laminated film and surface layer]
As long as the laminated film of the present invention has a surface layer exhibiting the characteristics of the present invention, it may be any one of a flat shape (film, sheet, plate) and a three-dimensional shape (molded product). Here, the surface layer in the present invention is directed from the surface of the laminated film in the thickness direction (in the case of a planar shape) or in the internal direction (in the case of a three-dimensional shape), and the portion and element composition adjacent to the thickness direction or the internal direction. In addition, the shape and physical properties of the inclusions can be distinguished by having a discontinuous boundary surface, and indicate a portion having a finite thickness. More specifically, cross-sectional observation of the laminated film in the thickness direction from the surface with various composition / element analyzers (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscope (transmission type, scanning type) or optical microscope In this case, it is distinguished by the presence or absence of the discontinuous boundary surface.

  Moreover, the structure may be a form in which the surface layer 1 is formed as a single layer on the support base 2 as shown in FIG. 1 described above, or may be formed as two or more layers.

  When the surface layer is formed of a plurality of layers, the resin constituting the first layer has (1) to (3), and the resin constituting the second layer is the above (4) and (5). Preferably, the resin constituting the first layer has (4) and (5) as shown in FIG. 3, and the resin constituting the second layer has (1) to (3). Is also preferable.

  In addition to the moldability, self-healing property, antifouling property, dye transfer resistance, the surface layer is an object of the present invention, antireflection, antistatic, antifouling property, conductivity, heat ray reflection, near infrared absorption, electromagnetic wave You may have other functions, such as shielding and easy adhesion.

  The thickness of the surface layer is not particularly limited, but is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less, and the thickness of each layer when the surface layer is formed of two or more layers as shown in FIG. The thickness of the first layer / second layer is preferably 100 nm or more and 200 μm or less / 5 μm or more and 200 μm or less, and more preferably 200 nm or more and 100 μm or less / 10 μm or more and 100 μm or less.

[Supporting substrate]
The resin constituting the support substrate used in the laminated film of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, or may be a copolymer resin or two or more types of resins. It may be a blend of resins. More preferably, the resin constituting the support substrate is preferably a thermoplastic resin because of good moldability.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins, and polyarylate resins. Fluorine resins such as polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-6 fluoropropylene copolymer, vinylidene fluoride resin, acrylic Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin, or a methacrylic resin from the viewpoint of strength, heat resistance, and transparency, and a polyester resin is particularly preferable.

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

  In addition, for the support substrate, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant for adjusting the refractive index may be added. The support substrate may be either a single layer configuration or a laminated configuration.

  Various surface treatments can be applied to the surface of the support substrate before the surface layer is formed. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

  In addition to the surface layer of the present invention, a functional layer such as an easy-adhesion layer, an antistatic layer, an undercoat layer, a hard coat layer, or an ultraviolet absorbing layer can be provided in advance on the surface of the support substrate. It is preferable to provide an easy adhesion layer.

[Coating composition A, coating composition B]
The laminated film of the present invention can be provided with a surface layer by applying, drying and curing the coating composition on the support substrate by using a method for producing a laminated film described later. Further, even when the surface layer is composed of a plurality of layers, a surface layer composed of a plurality of layers can be provided by sequential coating, simultaneous coating, or a combination thereof.

  The coating composition for providing the surface layer when the surface layer is one layer and the coating composition for providing the first layer when there are a plurality of layers (hereinafter referred to as coating composition A) are described above. It is preferable to include a resin containing the segments (1) to (3) or a material capable of forming them in the coating process (hereinafter referred to as a precursor). By using the product A, the resin contained in the surface layer in the case where the surface layer is one layer and the first layer in the case where the surface layer is a plurality of layers can have these segments. The coating composition A contains various additives such as a solvent, a polymerization initiator, a curing agent, a crosslinking agent, a gelling agent, a catalyst, a leveling agent, a surfactant, and an antistatic agent in addition to the resin or the precursor. But you can. The mass parts of (1), (2) and (3) contained in the coating composition A are (1) / (2) / (3) = 95/5/1 to 50/50/15. Preferably, (1) / (2) / (3) = 90/10/1 to 60/40/10 is more preferable.

  When the surface layer has a plurality of layers, the coating composition for providing the second layer (hereinafter referred to as coating composition B) is the above-mentioned (4) (poly) caprolactone segment, ( It is preferable to include a segment containing at least one selected from the group consisting of a poly) carbonate segment and a (poly) alkylene glycol segment, (5) a resin containing a urethane bond, or a precursor capable of forming them in a coating process. In the method for producing a laminated film described later, by using the coating composition B, the resin contained in the second layer in the case of a plurality of layers can have these segments. The coating composition B may contain various additives in the same manner as the coating composition A. Moreover, (4) / (5) = 95 / 5-50 / 50 is preferable, and the mass part of (4) and (5) contained in the coating composition B is (4) / (5) = 90/10. -70/30 is more preferable.

[(Poly) butadiene segment, (Poly) isoprene segment]
In the laminated film of the present invention, the resin constituting the surface layer or the first layer of the surface layer preferably has a (poly) butadiene segment and / or a (poly) isoprene segment. Furthermore, by forming a surface layer using a resin containing a (poly) butadiene segment and / or a (poly) isoprene segment, or a coating composition A containing the precursor, the surface layer or the first layer of the surface layer Can have (poly) butadiene segments and / or (poly) isoprene segments.

  The structures of the (poly) butadiene segment and the (poly) isoprene segment are as described in the above chemical formulas 1 to 5, but the number average molecular weight is preferably 500 to 20,000, 1,000 More preferred are those of ˜5,000. When the number average molecular weight is less than 500, suitable flexibility may be difficult to obtain, and when the number average molecular weight exceeds 20,000, the solubility may be lowered. . The (poly) butadiene segment and (poly) isoprene segment may have double bonds in the molecule or hydrogenated double bonds in the molecule. If a bond remains, a crosslinking reaction may occur and flexibility may be lowered. Therefore, it is preferable to include a hydrogenated (poly) butadiene segment in which an intramolecular double bond is hydrogenated.

  A preferable compound as the coating composition A is a resin containing a (poly) butadiene segment, a (poly) isoprene segment, or a precursor represented by chemical formulas 17 and 18.

Here, l, m and n are integers of 0 or more, the sum of l, m and n is an integer of 1 or more, p is an integer of 1 or more, R ₅ is an alkanediyl group, alkane A triyl group, an oxyalkanediyl group, an oxyalkanetoluyl group, and an ester structure, a urethane structure, an ether structure, or a triazine structure derived therefrom are shown, and D ₁ represents a reactive site.

Here, m and n are integers of 0 or more, the sum of m and n is an integer of 1 or more, p is an integer of 1 or more, and R ₅ is an alkanediyl group, alkanetriyl group, oxyalkane. A diyl group, an oxyalcantoluyl group, and an ester structure, a urethane structure, an ether structure, and a triazine structure derived from them are shown, and D ₁ represents a reactive site.

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

More preferably, R ₅ is an alkanediyl group, a urethane bond or an ester structure, and D ₁ is an acryloyl (methacryloyl) group or a hydroxyl group.

  By using these, a necessary amount of (poly) butadiene segment and / or (poly) isoprene segment can be introduced into the resin constituting the surface layer, and the viscosity can be adjusted to a suitable viscosity region in the surface layer production method described later. it can.

In a resin or precursor containing a (poly) butadiene segment or a (poly) isoprene segment that is preferable for the coating composition A, a material in which D ₁ is a hydroxyl group in the above-described chemical formulas 17 and 18, that is, (poly) butadiene polyol, (poly) Examples of commercially available materials for isoprene polyol include G-1000, G-2000, G-3000, GI-1000, GI-2000, GI-3000 (Nippon Soda Co., Ltd.), Poly Bd R-45HT R-15HT. , Poly iP, Epaul (Idemitsu Kosan Co., Ltd.) and the like can be preferably mentioned.

Examples of commercially available materials of the above-described chemical formulas 17 and 18 in which D ₁ is an acryloyl (methacryloyl) group, that is, (meth) acryl-modified (poly) butadiene and (meth) acryl-modified (poly) isoprene. , BAC45, SPBDA-S30 (Osaka Organic Co., Ltd.), TEAI-1000, TE-2000, EMA-3000 (Nippon Soda Co., Ltd.), CN307 (Sartomer Japan Co., Ltd.), Claprene UC203, UC102 (Kuraray Co., Ltd.), etc. Can be preferably mentioned.

[Tricyclodecyl segment, dicyclopentazinyl segment, isobonyl segment]
In the laminated film of the present invention, the surface layer or the resin constituting the first layer of the surface layer includes a segment containing at least one selected from the group consisting of a tricyclodecyl segment, a dicyclopentazinyl segment, and an isobonyl segment. It is preferable to have.

  Further, a surface layer is formed using a resin containing a segment containing at least one selected from the group consisting of a tricyclodecyl segment, a dicyclopentazinyl segment and an isobonyl segment, or a coating composition A containing the precursor. Thus, the surface layer or the resin constituting the first layer of the surface layer may have a segment containing at least one selected from the group consisting of a tricyclodecyl segment, a dicyclopentazinyl segment, and an isobornyl segment. it can.

  The structures of the tricyclodecyl segment, dicyclopentazinyl segment, and isobonyl segment are as described in the above chemical formulas 6 to 8. However, as a preferable compound as the coating composition A, the tricyclodecyl segment is preferable. , Dicyclopentazinyl segment, resin containing isobornyl segment, or precursor is a compound represented by Chemical Formula 19, Chemical Formula 20, and Chemical Formula 21.

R ₆ represents an alkanediyl group, alkanetriyl group, oxyalkanediyl group, oxyalkanetoluyl group, and an ester structure, urethane structure, ether structure or triazine structure derived therefrom, and D ₁ represents a reactive site.

  This reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such reactive sites include alkoxysilyl groups and silanol groups in which alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. Can be mentioned. Of these, vinyl groups, allyl groups, alkoxysilyl groups, silyl ether groups, silanol groups, epoxy groups, and acryloyl (methacryloyl) groups are preferred from the viewpoints of reactivity and handling properties.

More preferably, R ₆ is an alkanediyl group, a urethane bond or an ester structure, and D ₁ is an acryloyl (methacryloyl) group or a hydroxyl group.

Preferred tricyclodecylacrylate segment containing resin as described above in the coating composition A or as a precursor, and is commercially available (meth) acrylate having the D ₁ in Formula 19 described above acryloyl (methacryloyl) groups, i.e. a tricyclodecyl segment Examples of materials include IRR214-K (Daicel Ornex Co., Ltd.), SR833S (Sartomer), FA-513AS, FA-513M (Hitachi Chemical Co., Ltd.), A-DCP, DCP (Shin Nakamura Chemical Co., Ltd.), Light acrylate. DCP-A (Kyoeisha Chemical Co., Ltd.) etc. are mentioned.

Similarly, examples of commercially available materials of (meth) acrylates in which D ₁ contains a dicyclopentazinyl segment in the above chemical formula 20 include FA-511AS, FA-512AS, FA-512M (Hitachi Chemical Co., Ltd.) Company).

Similarly, examples of commercially available materials of (meth) acrylates in which D ₁ includes an isobonyl segment in the above chemical formula 21 include light ester IB-X, light acrylate IB-XA (Kyoeisha Chemical Co., Ltd.) and the like. Is mentioned.

[Fluorine compound segment, (poly) siloxane segment, (poly) dimethylsiloxane segment]
In the laminated film of the present invention, the resin contained in the surface layer or the first layer of the surface layer contains at least one selected from the group consisting of a fluorine compound segment, a (poly) siloxane segment, and a (poly) dimethylsiloxane segment. It preferably has a segment.

  Further, a surface layer or surface using a coating composition A containing a resin containing a segment containing at least one selected from the group consisting of a fluorine compound segment, a (poly) siloxane segment and a (poly) dimethylsiloxane segment, or a precursor By forming the first layer, the surface layer or the resin constituting the first layer of the surface layer can have these.

  Hereinafter, these fluorine compound segments, (poly) siloxane segments, and (poly) dimethylsiloxane segments will be described.

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

  Here, a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group are alkyl groups, oxyalkyl groups, alkenyl groups, alkanediyl groups, and oxyalkanediyl groups. A part or all of the substituents are replaced by fluorine, both of which are mainly composed of fluorine atoms and carbon atoms, and there may be branching in the structure. A plurality of linked dimers, trimers, oligomers, and polymer structures may be formed.

  The fluorine compound segment is preferably a fluoropolyether segment, which is a site comprising a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group or the like, and more preferably in the chemical formulas (9) and (10). As described above, it is a representative fluoropolyether segment.

  In order for the resin contained in the surface layer to contain a fluorine compound segment, the coating composition A described above preferably contains the following fluorine compound D. This fluorine compound D is a compound represented by the chemical formula 22.

Here, R ^f1 represents a fluorine compound segment, R ₇ represents an alkanediyl group, an alkanetriyl group, and an ester structure, urethane structure, ether structure, or triazine structure derived therefrom, D ¹ represents a reactive site, n Is 1 or 2.

  This reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such reactive sites include alkoxysilyl groups and silanol groups in which alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. Can be mentioned. Of these, vinyl groups, allyl groups, alkoxysilyl groups, silyl ether groups, silanol groups, epoxy groups, and acryloyl (methacryloyl) groups are preferred from the viewpoints of reactivity and handling properties.

  An example of the fluorine compound D is a compound shown below. 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanate silane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltri Chlorosilane, 2-perfluorooctyl isocyanate silane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluoro Butyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2- Perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro -5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate Octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-par Fluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro- 3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methyl Hexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoro Examples include pentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol.

The fluorine compound D may have a plurality of fluoropolyether moieties per molecule.
Examples of commercially available fluorine compounds D include RS-75 (DIC Corporation), OPTOOL DAC-HP (Daikin Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Co., Ltd.), and the like. Can be used.

  Next, the (poly) siloxane segment will be described. In the present invention, the (poly) siloxane segment refers to a segment represented by the above chemical formula 11. In the present invention, a partially hydrolyzed product of a silane compound containing a hydrolyzable silyl group, an organosilica sol, or a coating composition in which a hydrolyzable silane compound having a radical polymer is added to the organosilica sol, (poly) siloxane It can be used as a resin containing segments.

  Resins containing (poly) siloxane segments are tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxy Hydrolyzable on the surface of organosilica sol dispersed in organic solvent with complete or partial hydrolysates of silane compounds with hydrolyzable silyl groups such as propyltrialkoxysilane and γ-methacryloxypropylalkyldialkoxysilane The thing etc. which added the hydrolysis silane compound of the silyl group can be illustrated.

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

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

  Next, the (poly) dimethylsiloxane segment will be described. In the present invention, the (poly) dimethylsiloxane segment refers to a segment represented by the above chemical formula 12.

  When the resin contained in the surface layer or the first layer of the surface layer has a (poly) dimethylsiloxane segment, the (poly) dimethylsiloxane segment is coordinated to the surface of the surface layer. When the (poly) dimethylsiloxane segment is coordinated on the surface of the surface layer, the lubricity of the surface layer surface is improved, and the frictional resistance can be reduced. As a result, scratch resistance and blocking resistance can be imparted.

  In the present invention, as the resin containing the (poly) dimethylsiloxane segment, it is preferable to use a copolymer obtained by copolymerizing a vinyl monomer with the (poly) dimethylsiloxane segment.

  For the purpose of improving the toughness of the surface layer, the resin containing the (poly) dimethylsiloxane segment is preferably copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group. When the resin containing a (poly) dimethylsiloxane segment is a copolymer having a hydroxyl group, a paint comprising a resin (copolymer) containing a (poly) dimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group When the surface layer is formed using the composition, the surface layer having a (poly) dimethylsiloxane segment and a urethane bond can be efficiently formed.

  When the resin containing the (poly) dimethylsiloxane segment is a copolymer with a vinyl monomer, it may be any of a block copolymer, a graft copolymer, and a random copolymer. When the resin containing the (poly) dimethylsiloxane segment is a copolymer with a vinyl monomer, this is referred to as a (poly) dimethylsiloxane copolymer. (Poly) dimethylsiloxane copolymer can be produced by living polymerization method, polymer initiator method, polymer chain transfer method, etc., but considering the productivity, polymer initiator method, polymer chain transfer The method is preferably used.

  When the polymer initiator method is used, it can be copolymerized with other vinyl monomers using a polymer azo radical polymerization initiator represented by Chemical Formula 23. In addition, a two-stage synthesis of a prepolymer in which a peroxy monomer and (poly) dimethylsiloxane having an unsaturated group are copolymerized at a low temperature to introduce a peroxide group into a side chain, and the prepolymer is copolymerized with a vinyl monomer The polymerization can also be carried out.

m is an integer of 10 to 300, and n is an integer of 1 to 50.
In the case of using the polymer chain transfer method, for example, after adding HS—CH ₂ COOH or HS—CH ₂ CH ₂ COOH to the silicone oil represented by Chemical Formula 24 to obtain a compound having an SH group, the SH group A block copolymer can be synthesized by copolymerizing the silicone compound and vinyl monomer using chain transfer.

m is an integer of 10 to 300.
In order to synthesize a (poly) dimethylsiloxane graft copolymer, for example, a graft copolymer can be easily prepared by copolymerizing a compound represented by the chemical formula 25, that is, a methacrylic ester of (poly) dimethylsiloxane and a vinyl monomer. Can be obtained.

m is an integer of 10 to 300.

  Examples of vinyl monomers used in the copolymer with (poly) dimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, and ethyl methacrylate. , N-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, Vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acrylate Glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethyl Examples thereof include aminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, diacetylone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and allyl alcohol.

  In addition, (poly) dimethylsiloxane copolymers include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, isopropyl It is preferable to produce an alcohol solvent such as alcohol by a solution polymerization method alone or in a mixed solvent.

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

  The amount of the (poly) dimethylsiloxane segment in the (poly) dimethylsiloxane copolymer in the present invention is 100% of all components of the (poly) dimethylsiloxane copolymer in terms of lubricity and contamination resistance of the surface layer. It is preferable that it is 1-30 mass% in mass%. The weight average molecular weight of the (poly) dimethylsiloxane segment is preferably 1,000 to 30,000.

  Whether the (poly) dimethylsiloxane segment is copolymerized or added separately, the (poly) dimethylsiloxane is used in 100% by mass of the total components of the coating composition used to form the surface layer. When the segment is 1 to 20% by mass, it is preferable in terms of self-repairing property, contamination resistance, weather resistance, and heat resistance. The solvent which does not participate in the reaction is not included in 100% by mass of all components of the coating composition. The monomer component involved in the reaction is included.

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

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

  (Poly) dimethylsiloxane-based copolymer, (poly) caprolactone, and (poly) caprolactone in a coating composition used to form a surface layer having a (poly) caprolactone segment, a (poly) siloxane segment, and a (poly) dimethylsiloxane segment, and The reaction of (poly) siloxane can be copolymerized by adding a (poly) caprolactone segment and a (poly) siloxane segment as appropriate during the synthesis of the polydimethylsiloxane copolymer.

[(Poly) caprolactone segment, (poly) carbonate segment, (poly) alkylene glycol segment]
In the laminated film of the present invention, when the surface layer is composed of a plurality of layers, the resin constituting the second layer is selected from the group consisting of (poly) caprolactone segments, (poly) carbonate segments, and (poly) alkylene glycol segments. It is preferable to have a segment containing at least one selected.

  Further, a surface using a resin containing a segment containing at least one selected from the group consisting of a (poly) caprolactone segment, a (poly) carbonate segment and a (poly) alkylene glycol segment, or a coating composition B containing the precursor These can be included by forming a second layer of layers.

  Hereinafter, the details of the (poly) caprolactone segment, the (poly) carbonate segment, and the (poly) alkylene glycol segment will be described.

First, the (poly) caprolactone segment refers to the segment represented by Chemical Formula 13 described above.
The resin containing a (poly) caprolactone segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the (poly) caprolactone segment.

  As the resin containing a (poly) caprolactone segment, (poly) caprolactone having 2 to 3 functional hydroxyl groups is particularly preferable. Specifically, (poly) caprolactone diol represented by Chemical Formula 26,

(Here, m + n is an integer of 4 to 35, and R is C ₂ H ₄ or C ₂ H ₄ OC ₂ H _4. )
Or (poly) caprolactone triol represented by Chemical Formula 27,

(Here, l + m + n is an integer of 3 to 30, and R is either CH ₂ CHCH ₂ , CH ₃ C (CH ₂ ) ₃ , or CH ₃ CH ₂ C (CH ₂ ) ₃ ).
(Poly) caprolactone polyol such as (poly) caprolactone modified hydroxyethyl (meth) acrylate represented by Chemical Formula 28

(Wherein n is an integer of 1 to 25 and R is H or CH ₃ ) or the like, active energy ray-polymerizable caprolactone can be used. Examples of other active energy ray polymerizable caprolactones include (poly) caprolactone-modified hydroxypropyl (meth) acrylate, (poly) caprolactone-modified hydroxybutyl (meth) acrylate, and the like.

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

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

  Next, the (poly) alkylene glycol segment refers to the segment represented by Chemical Formula 14 described above. The resin containing a (poly) alkylene glycol segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the (poly) alkylene glycol segment.

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

Examples of the (poly) alkylene glycol (meth) acrylate contained in the coating composition used to form the surface layer include (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, (poly ) Butylene glycol (meth) acrylate. The structures are represented by the following chemical formula 29, chemical formula 30, and chemical formula 31, respectively.
(Poly) ethylene glycol (meth) acrylate:

(Poly) propylene glycol (meth) acrylate:

(Poly) butylene glycol (meth) acrylate:

In Chemical Formula 29, Chemical Formula 30, and Chemical Formula 31, R is hydrogen (H) or a methyl group (—CH ₃ ), and m is an integer from 2 to 11.

  In the present invention, the resin constituting the surface layer is preferably formed by reacting a compound containing an isocyanate group, which will be described later, with the hydroxyl group of (poly) alkylene glycol (meth) acrylate and using it as the urethane (meth) acrylate in the surface layer. However, it can have (5) a urethane bond and (4) (poly) alkylene glycol segment, and as a result, it can improve the toughness of the surface layer and improve the self-repairability, which is preferable.

  As hydroxyalkyl (meth) acrylate compounded at the same time during the urethanization reaction between the compound containing an isocyanate group and (poly) alkylene glycol (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Examples thereof include hydroxybutyl (meth) acrylate.

  Next, the (poly) carbonate segment refers to the segment represented by Formula 15 above.

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

As the resin containing a (poly) carbonate segment, a (poly) carbonate diol having a bifunctional hydroxyl group is particularly preferable. Specifically, it is represented by Chemical Formula 32.
(Poly) carbonate diol:

n is an integer of 2-16.
R represents an alkylene group having 1 to 8 carbon atoms or a cycloalkylene group.

  (Poly) carbonate diol may have any number of carbonate unit repeats, but if the number of carbonate unit repeats is too large, the strength of the cured urethane (meth) acrylate is reduced, so the number of repeats is 10 or less. It is preferable that The (poly) carbonate diol may be a mixture of two or more (poly) carbonate diols having different numbers of carbonate units.

  The (poly) carbonate diol preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. When the number average molecular weight is less than 500, suitable flexibility may be difficult to obtain, and when the number average molecular weight exceeds 10,000, the heat resistance and solvent resistance may be deteriorated. It is.

  The (poly) carbonate diol used in the present invention includes UH-CARB, UD-CARB, UC-CARB (Ube Industries Co., Ltd.), PACCEL CD-PL, PLACEL CD-H (Daicel Chemical Industries, Ltd.), Products such as Kuraray polyol C series (Kuraray Co., Ltd.) and Duranol series (Asahi Kasei Chemicals Co., Ltd.) can be suitably exemplified. These (poly) carbonate diols may be used alone or in combination of two or more.

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

  In the present invention, the second layer of the surface layer is preferably used by reacting a compound containing an isocyanate group, which will be described later, with the hydroxyl group of (poly) carbonate diol and using it as the urethane (meth) acrylate in the second layer of the surface layer. Is preferable because it can have (5) a urethane bond and (4) a (poly) carbonate diol segment, thereby improving the toughness of the surface layer and improving the self-healing property.

[Compound containing urethane bond and isocyanate group]
In the present invention, the urethane bond refers to the bond represented by Chemical Formula 16 described above. When the coating composition B used for forming the second layer of the surface layer contains a commercially available urethane-modified resin, the resin contained in the second layer of the surface layer can have a urethane bond. . Moreover, when forming the said 2nd layer of a surface layer, a urethane bond is produced | generated in the application | coating process by apply | coating the coating composition B containing the compound containing an isocyanate group as a precursor, and the compound containing a hydroxyl group. Then, the second layer of the surface layer can contain a urethane bond.

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

  In addition, when the resin contains the above-mentioned (poly) caprolactone segment, (poly) carbonate segment, (poly) alkylene glycol segment, or has a hydroxyl group, these resins and a compound containing an isocyanate group as a precursor by heat, etc. It is also possible to form urethane bonds between the two. When a 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 (poly) dimethylsiloxane segment having a hydroxyl group, the toughness and elasticity of the surface layer It is preferable because the recoverability (self-repairability) and the surface slipperiness can be improved.

  In the present invention, the compound containing an isocyanate group refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Examples include isocyanurate bodies, isocyanurate bodies of hexamethylene diisocyanate, (poly) isocyanates such as a burette body of hexamethylene isocyanate, and block bodies of the above isocyanates.

  Of these isocyanate group-containing compounds, aliphatic isocyanates are preferred because of their high self-healing properties compared to alicyclic and aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. The isocyanate group-containing compound is particularly preferably an isocyanate having an isocyanurate ring from the viewpoint of heat resistance, and most preferably an isocyanurate of hexamethylene diisocyanate. Isocyanates having an isocyanurate ring form a surface layer having both self-healing properties and heat resistance.

[solvent]
The coating composition A and the coating composition B may contain a solvent. The number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less. Here, the “solvent” refers to a substance that is liquid at room temperature and normal pressure, which can be evaporated in substantially the entire amount in the drying step after application.

  Here, the kind of solvent is determined by the molecular structure constituting the solvent. That is, the same elemental composition and the same type and number of functional groups have different bond relationships (structural isomers), which are not structural isomers, but what conformations are in three-dimensional space Those that do not overlap exactly even if they are removed (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are handled as different solvents.

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

  Various polymerization initiators, curing agents and catalysts can be used. In addition, the polymerization initiator, the curing agent, and the catalyst may be used alone, or a plurality of polymerization initiators, curing agents, and catalysts may be used simultaneously. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like.

  As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropane-1-o , 1- [4- (2-Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and materials thereof And the like having a high molecular weight.

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

[Production method of laminated film]
The surface layer formed on the surface of the laminated film of the present invention preferably uses a production method in which the coating composition A is formed by applying, drying and curing the coating composition A on the supporting substrate.
When the surface layer is composed of two or more layers, the coating composition B is applied to the supporting base material side, dried, cured, and the second layer is formed. The first layer may be formed by coating-drying-curing, or coating-drying-coating the coating composition A in an uncured state after coating-drying the coating composition B described above on the support substrate side. Then, the first layer and the second layer may be formed, or after the coating composition B is applied to the support substrate side, the coating composition A is applied in an undried state-dried-cured to form a first layer. One layer and a second layer may be formed, or the above-mentioned coating composition B is applied to the supporting substrate side, and the coating composition A is simultaneously applied to the first substrate and the second layer. May be formed.

  The production method of the laminated film by coating is not particularly limited, but the coating composition is supported by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Pat. No. 2,681,294). It is preferable to form a surface layer by applying to the surface. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.

  Next, the liquid film applied on the support substrate or the like is dried. In addition to completely removing the solvent from the laminated film obtained, from the viewpoint of moving the fluorine compound D in the liquid film formed by coating to the surface and segregating the fluorine compound segment to the outermost surface of the surface layer, In the drying step, it is preferable to involve heating of the liquid film.

  Examples of the drying method include heat transfer drying (adherence to a high-temperature object), convection heat transfer (hot air), radiant heat transfer (infrared ray), and others (microwave, induction heating). Among these, in the manufacturing method of the present invention, a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to make the drying speed uniform even in the width direction.

The drying process is generally divided into (A) a constant rate drying period and (B) a decreasing rate drying period. Since the former is the rate of drying, diffusion of solvent molecules into the atmosphere on the liquid film surface is The drying speed is constant in this section, the drying speed is governed by the partial pressure of the solvent to be evaporated in the atmosphere, the wind speed and the temperature, and the film surface temperature is constant at a value determined by the hot air temperature and the partial pressure of the solvent to be evaporated in the atmosphere. Become. In the latter, since the diffusion of the solvent in the liquid film is rate-limiting, the drying rate does not show a constant value in this section and continues to decrease, and is governed by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature is To rise. Here, the drying rate represents the amount of solvent evaporation per unit time and unit area, and has a dimension of g · m ⁻² · s ⁻¹ .

The drying speed has a preferred range, preferably 10 g · m ⁻² · s ⁻¹ or less, and more preferably 5 g · m ⁻² · s ⁻¹ or less. The lower limit is preferably 0.1 g · m ⁻² · s ⁻¹ or more. By setting the drying speed in the constant rate drying section within this range, unevenness due to nonuniform drying speed can be prevented. As long as a drying speed in the range of 0.1 g · m ⁻² · s ⁻¹ or more and 10 g · m ⁻² · s ⁻¹ or less can be obtained, the wind speed and temperature are not particularly limited.

  In the method for producing a laminated film of the present invention, the fluorine compound D is oriented along with the evaporation of the remaining solvent during the reduced rate drying period. In this process, since time for alignment is required, there is a preferable range for the film surface temperature increase rate during the decreasing drying period, preferably 5 ° C./second or less, preferably 1 ° C./second or less. More preferably.

  Furthermore, you may perform the further hardening operation (hardening process) by irradiating a heat | fever or an energy ray. In the curing step, when the coating composition A is used and cured with heat, it is preferably from room temperature to 200 ° C., and more preferably from 100 ° C. to 200 ° C. from the viewpoint of the activation energy of the curing reaction. More preferably, the temperature is 130 ° C. or higher and 200 ° C. or lower.

Moreover, when hardening with an active energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. In the case of curing with ultraviolet rays, the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable. When the oxygen concentration is high, the hardening of the outermost surface is hindered, the hardening of the surface becomes insufficient, and the fingerprint resistance may be insufficient. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. Case of UV cured using a high pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays 100~3,000mW / cm ^2, preferably 200~2,000mW / cm ^2, more preferably 300~1,500mW / cm ² performing the ultraviolet irradiation is preferred, the accumulated light quantity of ultraviolet 100~3,000mJ / cm ^2, preferably 200~2,000mJ / cm ^2, more preferably a 300~1,500mJ / cm ² under the condition that the It is more preferable to perform ultraviolet irradiation under conditions. Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

[Application example]
The laminated film of the present invention is excellent in moldability, self-repairability, scratch resistance, fingerprint resistance, and dye transfer resistance, and thus can be widely used for, for example, electrical appliances, automobile interior members, and building members. .

  Examples include plastic products such as glasses / sunglasses, cosmetic boxes, food containers, smartphone housings, touch panels, keyboards, home appliances such as remote controls for TVs and air conditioners, buildings, dashboards, car navigation systems, touch panels, and rooms. It can be suitably used for vehicle interior parts such as mirrors, and the surfaces of various printed materials.

  In particular, since the laminated film of the present invention is excellent in dye transfer resistance, it is particularly suitably used for decorative items such as denim and other clothes that easily transfer colors and which are expected to come into contact with a high frequency. be able to.

  Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.

<Fluorine compound D>
[Fluorine compound D1]
As the fluorine compound D1, a methyl ethyl ketone / methyl isobutyl ketone solution of acrylate compound containing a fluoropolyether moiety (fluorotetraethylene glycol moiety) (solid concentration 40% by mass manufactured by MegaFac RS75 DIC Corporation) was used.

[Fluorine compound D2]
An acrylate compound containing a fluoroalkyl moiety (triacryloyl-heptadecafluorononenyl-pentaerythritol, Kyoeisha Chemical Co., Ltd. solid content concentration of 100% by mass) was used as the fluorine compound D2.

[Fluorine compound D3]
A hydrofluoroether solution of a siloxane compound containing a fluoropolyether moiety (KY-108, Shin-Etsu Chemical Co., Ltd., solid content concentration 20% by mass) was used as the fluorine compound D3.

<Synthesis of polysiloxane compound>
[Polysiloxane (a)]
A 500 ml flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube was charged with 106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1% by mass hydrochloric acid, 85 After maintaining at 2 ° C. for 2 hours, ethanol was recovered while the temperature was raised and maintained at 180 ° C. for 3 hours. Then, it cooled and obtained viscous polysiloxane (a) (solid content concentration of 100 mass%).

<Synthesis of polydimethylsiloxane compound>
[Polydimethylsiloxane block copolymer (a)]
Using the same apparatus as the synthesis of polysiloxane (a), 50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, polydimethylsiloxane polymer polymerization initiator (VPS-0501 manufactured by Wako Pure Chemical Industries, Ltd., solid content concentration 100) (Mass%) 20 parts by weight, 18 parts by weight of methyl methacrylate, 38 parts by weight of butyl methacrylate, 23 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid and 0.5 parts by weight of 1-thioglycerin were charged at 180 ° C. For 8 hours to obtain a toluene / methyl isobutyl ketone solution of the polydimethylsiloxane block copolymer (a). The obtained block copolymer had a solid content concentration of 50% by mass.

[Polydimethylsiloxane compound (b)]
As the polydimethylsiloxane compound (b), EBECRYL350 (bifunctional, silicone acrylate solid concentration 100 mass%) manufactured by Daicel Cytec Co., Ltd. was used.

<Synthesis of urethane (meth) acrylate B>
[Urethane acrylate B1]
50 parts by mass of toluene, isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N, solid content concentration 100% by mass, manufactured by Mitsui Chemicals, Inc.), polycaprolactone-modified hydroxyethyl acrylate (Dacel Chemical Industries, Ltd. PLACCEL FA5 solid) (Minute concentration 100% by mass) 76 parts by mass, 0.02 part by mass of dibutyltin laurate, and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a urethane acrylate B1 solution having a solid content concentration of 50% by mass.

[Urethane acrylate B2]
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI solid content concentration: 100% by mass, manufactured by Kyowa Hakko Kirin Co., Ltd.) and polycarbonate diol (Placcel CD-210HL, solid content concentration manufactured by Daicel Chemical Industries, Ltd.) 100 mass%) 119 mass parts were mixed, heated to 40 ° C. and held for 8 hours. Then, 2-hydroxyethyl acrylate (Kyoeisha Chemical Co., Ltd. light ester HOA solid content concentration 100% by mass) 28 parts by mass, dipentaerystol hexaacrylate (Toagosei Co., Ltd. M-400 solid content concentration 100% by mass) 5 After adding part by mass and 0.02 part by mass of hydroquinone monomethyl ether and maintaining at 70 ° C. for 30 minutes, 0.02 part by mass of dibutyltin laurate was added and maintained at 80 ° C. for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate B2 having a solid content concentration of 50% by mass.

<Synthesis of urethane (meth) acrylate C>
[Urethane acrylate C1]
50 parts by weight of toluene, biuret-modified type of hexamethylene diisocyanate (Duranate 24A-90CX, manufactured by Asahi Kasei Chemicals Corporation, solid content concentration 90% by weight, isocyanate content: 21.2% by weight), polycaprolactone-modified hydroxyethyl acrylate (Dacel Chemical Industries, Ltd. PLACCEL FA2D solid content concentration: 100% by mass) 92 parts by mass, dibutyltin laurate 0.02 parts by mass, and hydroquinone monomethyl ether 0.02 parts by mass were mixed and held at 70 ° C. for 5 hours. Thereafter, 82 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate C1 having a solid content concentration of 50% by mass. The number of repeating caprolactone units per acrylate monomer residue in this urethane acrylate is 2.

[Urethane methacrylate C2]
Isocyanurate modified form of hexamethylene diisocyanate (Mitsui Chemicals, Takenate D-170N, isocyanate group content: 20.9 mass%, solid content concentration 100 mass%) 50 parts by mass, polyethylene glycol monoacrylate (manufactured by NOF Corporation) BLEMMER AE-150, hydroxyl value: 264 (mg KOH / g) solid content concentration 100% by mass) 53 parts by mass, dibutyltin laurate 0.02 parts by mass and hydroquinone monomethyl ether 0.02 parts by mass were charged. And it reacted by hold | maintaining at 70 degreeC for 5 hours. After completion of the reaction, 118 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction solution to obtain a methyl ethyl ketone solution of urethane acrylate C2 having a solid content concentration of 50% by mass.

<Preparation of coating composition A>
[Coating composition A1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 having a solid concentration of 30% by mass.
・ 80 parts by weight of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd.
(Solid content concentration: 100% by mass)
・ 20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd.)
(Solid content concentration: 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid content concentration of 30% by mass.
・ 80 parts by mass of polybutadiene methacrylate oligomer (NISSO-PB EMA-3000 Nippon Soda Co., Ltd., solid content concentration: 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A3]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid concentration of 30% by mass.
・ 80 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Fluorine compound D2 1 part by mass-Ethylene glycol monobutyl ether 10 parts by mass-Photo radical polymerization initiator 3 parts by mass (Irgacure 184 BASF Japan Ltd.).

[Coating composition A4]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid content concentration of 30% by mass.
・ 80 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
・ 20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd.)
(Solid content concentration: 100% by mass)
-Fluorine compound D3 solution (solid content concentration 20 mass%) 5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid concentration of 30% by mass.
・ 80 parts by mass of polyisoprene methacrylate oligomer (Kuraprene UC102 Kuraray Co., Ltd. solid content concentration: 100% by mass)
・ 20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd.)
(Solid content concentration: 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[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 30% by mass.
・ Hydrogenated polybutadiene acrylate oligomer 80 parts by mass (SPBDA Osaka Organic Chemical Industry Co., Ltd. solid content concentration 100% by mass)
・ 20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd.)
(Solid content concentration: 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A7]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 having a solid concentration of 30% by mass.
・ Hydrogenated polybutadiene acrylate oligomer 80 parts by mass (SPBDA Osaka Organic Chemical Industry Co., Ltd. solid content concentration 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A8]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 having a solid concentration of 30% by mass.
・ Hydrogenated polybutadiene acrylate oligomer 80 parts by mass (SPBDA Osaka Organic Chemical Industry Co., Ltd. solid content concentration 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A9]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 having a solid concentration of 30% by mass.
・ Hydrogenated polybutadiene acrylate oligomer 80 parts by mass (SPBDA Osaka Organic Chemical Industry Co., Ltd. solid content concentration 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A10]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A10 having a solid content concentration of 30% by mass.
・ Hydrogenated polybutadiene acrylate oligomer 80 parts by mass (SPBDA Osaka Organic Chemical Industry Co., Ltd. solid content concentration 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A11]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A11 having a solid concentration of 30% by mass.
・ 80 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
・ Isobonyl acrylate 20 parts by mass (IBXA Osaka Organic Chemical Industry Co., Ltd., solid content concentration 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A12]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A12 having a solid concentration of 30% by mass.
・ 80 parts by mass of polybutadiene methacrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
・ Dicyclopentenyl acrylate 20 parts by mass (Fancryl FA-511AS Hitachi Chemical Co., Ltd.
(Solid content concentration: 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A13]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A13 having a solid concentration of 30% by mass.
・ 80 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Polydimethylsiloxane block copolymer (a) 10 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A14]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A14 having a solid content concentration of 30% by mass.
・ 80 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Polydimethylsiloxane block copolymer (b) 5 parts by mass-Ethylene glycol monobutyl ether 10 parts by mass-Photo radical polymerization initiator 3 parts by mass (Irgacure 184 BASF Japan Ltd.).

[Coating composition A15]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A15 having a solid content concentration of 30% by mass.
・ 80 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Polysiloxane (a) 5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A16]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A16 having a solid content concentration of 30% by mass.
・ 100 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd. solid content concentration: 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A17]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A17 having a solid concentration of 30% by mass.
・ Tricyclodecane dimethanol diacrylate 100 parts by mass (IRR214-K Daicel Ornex Co., Ltd., solid content concentration 100% by mass)
-Fluorine compound D1 solution (solid content concentration 40 mass%) 2.5 mass parts-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A18]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A18 having a solid concentration of 30% by mass.
・ 80 parts by mass of polybutadiene acrylate oligomer (BAC-45 Osaka Organic Chemical Industry Co., Ltd., solid content concentration: 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A19]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A19 having a solid concentration of 30% by mass.
・ Fluorine compound D1 solution (solid content concentration 40% by mass) 2.5 parts by mass ・ Polycaprolactone polyol 15 mass parts (polycaprolactone triol, manufactured by Daicel Chemical Industries, Ltd. Plaxel 308, weight average molecular weight 850, solid content concentration 100% by mass)
・ Isocyanate group-containing compound 15 parts by mass (Isocyanurate of hexamethylene diisocyanate Takenate D-170N, solid content concentration 100% by mass, Mitsui Chemicals, Inc.)
-Polydimethylsiloxane block copolymer (a) 75 parts by mass-Polysiloxane (a) 10 parts by mass-Ethylene glycol monobutyl ether 10 parts by mass-Photoradical polymerization initiator 1 part by mass (Irgacure 184 BASF Japan Ltd.).

[Coating composition A20]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A20 having a solid concentration of 30% by mass.
・ Fluorine compound D1 solution (solid content concentration: 40 mass%) 2.5 mass parts ・ Urethane acrylate B1 solution (solid content concentration: 50 mass%) 50 mass parts ・ Urethane acrylate C1 solution (solid content concentration: 50 mass%) 50 mass parts -Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 1.5 mass parts (Irgacure 184 BASF Japan Ltd.).

[Coating composition A21]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A21 having a solid content of 30% by mass.
・ Fluorine compound D1 solution (solid content concentration: 40 mass%) 2.5 mass parts ・ Urethane acrylate B1 solution (solid content concentration: 50 mass%) 50 mass parts ・ Urethane acrylate C2 solution (solid content concentration: 50 mass%) 50 mass parts -Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 1.5 mass parts (Irgacure 184 BASF Japan Ltd.).

<Preparation 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 concentration of 40% by mass.
-15 parts by mass of polycaprolactone polyol (polycaprolactone triol, Daicel Chemical Industries, Ltd. PLACCEL 308, weight average molecular weight 850)
・ Isocyanate group-containing compound 15 parts by mass (Isocyanurate of hexamethylene diisocyanate
Takenate D-170N manufactured by Mitsui Chemicals, Inc.)
・ Polydimethylsiloxane block copolymer (a) solution (solid content: 50% by mass)
75 parts by mass-polysiloxane (a) 10 parts by mass-ethylene glycol monobutyl ether 10 parts by mass-photoradical polymerization initiator 1 part by mass (Irgacure 184 BASF Japan Ltd.).

[Coating composition B2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B2 having a solid content of 50% by mass.
・ Urethane acrylate B2 solution (solid content concentration 50 mass%) 50 mass parts ・ Urethane acrylate C1 solution (solid content concentration 50 mass%) 50 mass parts ・ Ethylene glycol monobutyl ether 10 mass parts ・ Photoradical polymerization initiator 1.5 mass Department (Irgacure 184 BASF Japan Ltd.).

[Coating composition B3]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B3 having a solid concentration of 50% by mass.
・ Urethane acrylate B1 solution (solid content concentration 50 mass%) 50 mass parts ・ Urethane acrylate C2 solution (solid content concentration 50 mass%) 50 mass parts ・ Ethylene glycol monobutyl ether 10 mass parts ・ Photoradical polymerization initiator 1.5 mass Department (Irgacure 184 BASF Japan Ltd.).

[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 30% by mass.
・ Hydrogenated polybutadiene acrylate oligomer 80 parts by mass (SPBDA Osaka Organic Chemical Industry Co., Ltd. solid content concentration 100% by mass)
-20 parts by mass of tricyclodecane dimethanol diacrylate (IRR214-K Daicel Ornex Co., Ltd. solid content concentration 100% by mass)
-Ethylene glycol monobutyl ether 10 mass parts-Photoradical polymerization initiator 3 mass parts (Irgacure 184 BASF Japan Ltd.).

<Method for producing laminated film>
[Method 1 for producing laminated film]
“Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm, in which an easy-adhesive paint is applied on a PET (polyethylene terephthalate) resin film, was used as a supporting substrate. The coating composition A was applied onto the support substrate by using a continuous coating apparatus using a slot die coater and adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying became a specified film thickness. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying process air temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the surface of the substrate, Anti-coating surface side: Base material surface
Vertical residence time: 2 minutes Curing process irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1% by volume.

[Method 2 for creating laminated film]
As a supporting substrate, “Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm in which an easy-adhesive paint is applied on a PET resin film was used. The coating composition A was applied onto the support substrate by using a continuous coating apparatus using a slot die coater and adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying became a specified film thickness. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying process air temperature and humidity: Temperature: 140 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the surface of the substrate, Anti-coating surface side: Base material surface
Vertical residence time: 2 minutes Curing process irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1% by volume.

[Method 3 for creating laminated film]
As a supporting substrate, “Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm in which an easy-adhesive paint is applied on a PET resin film was used. The coating composition B is applied onto the supporting base material using a continuous coating apparatus using a slot die coater, and the discharge flow rate from the slot is adjusted so that the thickness of the second layer of the surface layer after drying becomes a specified film thickness. And applied. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying process air temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the surface of the substrate, Anti-coating surface side: Base material surface
Vertical residence time: 2 minutes Curing process irradiation output: 200 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: the same as the atmosphere Next, using the same apparatus, the coating composition A is applied to the laminated film on which the second layer of the surface layer is formed (that is, on the second layer) of the first layer after drying. Coating was performed by adjusting the discharge flow rate from the slot so that the thickness would be the specified film thickness. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying process air temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the surface of the substrate, Anti-coating surface side: Vertical residence time with respect to the surface of the substrate: 2 minutes Curing process irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1% by volume.

[Method 4 for making laminated film]
As a supporting substrate, “Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm in which an easy-adhesive paint is applied on a PET resin film was used. The coating composition B is applied onto the supporting base material using a continuous coating apparatus using a slot die coater, and the discharge flow rate from the slot is adjusted so that the thickness of the second layer of the surface layer after drying becomes a specified film thickness. And applied. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying and curing process Blowing temperature and humidity: Temperature: 140 ° C, Relative humidity: 1% or less Wind speed: Application side: 5m / sec, Anti-application side: 5m / sec Air direction: Application side: With respect to the substrate surface Parallel, anti-coating surface side: Base material surface
Vertical residence time: 2 minutes Next, using the same apparatus, the coating composition A was dried on the laminated film on which the second layer of the surface layer was formed (that is, on the second layer). The coating was carried out by adjusting the discharge flow rate from the slot so that the thickness of one layer was a specified film thickness. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying process air temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the surface of the substrate, Anti-coating surface side: Base material surface
Vertical residence time: 2 minutes Curing process irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1% by volume.

[Method 5 for making laminated film]
As a supporting substrate, “Lumirror” (registered trademark) U46 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm in which an easy-adhesive paint is applied on a PET resin film was used. The coating composition B is applied onto the supporting base material using a continuous coating apparatus using a slot die coater, and the discharge flow rate from the slot is adjusted so that the thickness of the second layer of the surface layer after drying becomes a specified film thickness. And applied. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying process air temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the surface of the substrate, Anti-coating surface side: Base material surface
Vertical residence time: 2 minutes Curing process irradiation output: 200 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: the same as the atmosphere Next, using the same apparatus, the coating composition A is applied to the laminated film on which the second layer of the surface layer is formed (that is, on the second layer) of the first layer after drying. Coating was performed by adjusting the discharge flow rate from the slot so that the thickness would be the specified film thickness. The conditions of the drying air which hits the liquid film from the application to drying and curing are as follows.
Drying process air temperature and humidity: Temperature: 140 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the surface of the substrate, Anti-coating surface side: Base material surface
Vertical residence time: 2 minutes Curing process irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1% by volume
In addition, the said wind speed and temperature / humidity used the measured value by a hot-wire type | formula anemometer (Nippon Kanomax Co., Ltd. Anemomaster anemometer and air volume meter MODEL6034).

  The laminated film of Examples 1-25 and Comparative Examples 1-8 was created by the above method. The production method of the laminated film corresponding to each example / comparative example and the film thickness of each layer are shown in the table.

<Evaluation of laminated film>
About the produced laminated | multilayer film, the following performance evaluation was implemented and the obtained result is shown to a table | surface. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

[Maximum displacement and remaining displacement in the thickness direction of the surface layer]
Apply 1g of “High Vacuum Grease” manufactured by Toray Dow Corning Co., Ltd. to a smooth metal plate (die steel: SKD-11), and paste the support film side of the laminated film on the high vacuum grease application part. Then, the filter paper was sandwiched between the surfaces and pressed by a hand press so that air was not bitten. For the stationary sample obtained by such a method, measurement was performed from the surface layer side under the following conditions, and the indentation depth diagram (Fig. 4).

From this diagram, the amount of displacement in the thickness direction (maximum displacement amount) from when the load was applied to when it was unloaded, and the amount of displacement in the thickness direction at the end of the test (residual displacement amount) were determined.
Apparatus: Dynamic ultra micro hardness tester “DUH-201” (manufactured by Shimadzu Corporation)
Working indenter: Diamond regular triangular pyramid indenter (edge angle 115 °)
Measurement mode: 2 (load-unloading test method)
Initial load: 0.5mN
Holding time when 10 mN load is reached: 10 second load (load) speed, unload speed: 0.1422 mN / second.

[Surface elongation of surface layer]
Each value and the value required for evaluation were obtained by the following tensile test method.

[Preparation of test specimen for measurement]
Using the above-mentioned laminated film production methods 1 to 5 and using a PET resin film (“Lumirror” (registered trademark) T60 (manufactured by Toray Industries, Inc.) having a thickness of 100 μm) as a supporting substrate, Examples 1 to 25 described above and comparison The laminated films of Examples 1 to 8 were prepared, this laminated film was immersed in ethanol and allowed to stand for 10 minutes at 25 ° C., and then the surface layer of the laminated film was peeled off from the supporting substrate, and a sample was collected.

[Tensile test method]
The surface layer was cut into a rectangle having a length of 150 mm and a width of 10 mm in the longitudinal direction and the width direction to obtain a test piece. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec Co., Ltd.), the distance between the initial tensile chucks was set to 50 mm, a specific tensile speed was set, and the test piece was placed in a constant temperature layer set to a specific measurement temperature in advance. A tensile test was performed after 90 seconds of preheating. Since the tensile speed and measurement temperature differ depending on the evaluation items, describe them by item.

The load b (N) applied to the sample when the distance between chucks was a (mm) was read, and the strain amount x (%) and the stress y (MPa) were calculated from the following equations. However, the sample (test piece) thickness before the test was set to k (mm).
Strain amount: x = (a-50) / 50) × 100
Stress: y = b / (k × 10).

[Elongation at break]
In the tensile test method at a tensile speed of 50 mm / min and a measurement temperature of 25 ° C., the elongation at which the test piece broke was defined as the breaking elongation. The measurement was performed 5 times for each sample, and the average value was evaluated.

[Elastic recovery rate]
Two marks were put on the surface of the sample (test piece) before measurement. These two marks were attached along the length direction of the sample, and the distance between one mark and the other mark was 20 mm. The length of this distance was the initial test length (20 mm).

  Next, in a tensile test method at a tensile speed of 50 mm / min and a measurement temperature of 25 ° C., the sample (test piece) was stretched to a strain amount of 20%, and then the tensile load on the sample (test piece) was released. (This was the tensile test method with a deformation of 120%).

Thereafter, the distance between the two marks on the sample surface was measured to obtain l (mm), and the elastic recovery rate z (%) was calculated from the following equation. In the measurement, a value obtained by measuring to 1/10 mm and rounding off to the nearest 1/10 mm was used.
Elastic recovery rate: z = (1 − ((1−50) / 100)) × 100.

  In addition, because of the measurement conditions described above, a sample (test piece) having a breaking elongation of less than 120% breaks, and the elastic recovery rate could not be measured.

[Formability of surface layer (crack elongation)]
The laminated film was cut into a length of 10 mm × 200 mm, held with a chuck in the longitudinal direction, and stretched with an Instron type tensile tester (ultra precision material tester MODEL 5848 manufactured by Instron) at a pulling rate of 100 mm / min. The measurement temperature was 23 ° C. When the sample is stretched, the sample being stretched is observed, and is stopped when a crack is visually observed (the elongation at the time of stopping is adjusted to be an integer of 5). The samples to be measured from the next were sequentially sampled with the elongation decreased by 5% from the elongation at the time of stopping, and finally the elongation was such that no cracks were visually observed.

  The test was conducted within a range of 10% minimum and 100% maximum, and “10% or less” was given for cracks at 10% or less, and “100% or more” was given for cracks not exceeding 100%.

  Cut out the thin film cross-section of the cracked portion of the collected sample, distinguish the base material portion and the surface layer from the difference in contrast of the transmission electron microscope image, measure the thickness of 5 portions where there is no abnormality such as cracks, and measure the surface layer The average thickness was determined. When the surface layer is observed at a magnification such that the thickness of the surface layer to be observed is 30 mm or more on the observation screen of the transmission electron microscope, and cracks of 50% or more of the thickness of the surface layer are generated The crack elongation was defined as the elongation value of the sample having the lowest elongation among the samples with cracks. And the same measurement was performed 3 times in total and the average value of those crack elongation was made into the crack elongation of a surface layer.

[Surface layer self-healing]
After leaving the laminated film at a temperature of 20 ° C. for 12 hours, the surface layer surface was scratched five times horizontally by applying the following load to a brass brush (manufactured by TRUSCO) in the same environment, and then leaving scratches after leaving for 5 minutes. The recovery state was visually determined according to the following criteria.
10 points: No scratches left at 1 kg load 7 Scratches remain at 1 kg load, but no scratches left at 700 g 4 points: No scratches left at 700 g load, but no scratches left at 500 g 1 point: At 500 g load The wound remains.

[Fingerprint resistance (fingerprint adhesion)]
Fingerprint resistance (fingerprint adhesion) is determined by placing the evaluation surface (surface layer) of the laminated film on black paper, rubbing the finger (index finger) pressing the fingerprint and the thumb three times, The surface was slowly pressed against the surface, and the visibility of the attached fingerprint was evaluated according to the following evaluation criteria.
10 points: The fingerprint is not visually recognized or the difference from the non-attached part is not recognized. 7 points: The fingerprint is hardly visible or not recognized as the fingerprint. 5 points: The fingerprint is slightly visible, but hardly noticed. Points: Fingerprints are visually recognized. 1 point: Fingerprints are clearly visually recognized and very worrisome. The above evaluation was performed on 10 subjects, and the average value was obtained. The numbers after the decimal point were rounded off.

[Fingerprint resistance (fingerprint wiping)]
After attaching the fingerprint by the above-mentioned method, next, wipe using a cellulose long fiber nonwoven fabric gauze ("Hize" gauze NT-4 manufactured by Kawamoto Sangyo Co., Ltd.) having a folded dimension of 12.5 cm x 12.5 cm. went. For fingerprint wiping, the visibility after wiping by this wiping method was evaluated according to the following evaluation criteria.
10 points: almost unrecognizable after wiping once 7 points: almost unrecognizable after wiping once 5 points: Dirt remains after wiping once or twice, but almost visible after wiping three times 3 points: When wiped 5 times, it becomes almost unnoticeable 1 point: Dirt remains even after wiping 5 times or more The above evaluation was performed on 10 subjects, and the average value was obtained. The numbers after the decimal point were rounded off.

[Dye transfer resistance]
Jeans (containing a dye) wetted with water of 6 cm × 6 cm was brought into close contact with the surface layer of the laminated film cut out to a size of 9 cm × 6 cm, and sandwiched between 6 cm × 6 cm glass plates. It was wrapped in a polyethylene film so that the water did not evaporate, and a 3 kg weight was placed on the glass plate and left in an oven at 70 ° C. After 24 hours, the laminated film was placed on a white paper equivalent to the white part of the contamination gray scale described later, and the contamination degree of the surface layer surface was changed to 1 to 5 on the contamination gray scale (JIS L0805 (2005)). Grade 1 (Grade 1 is dirty gray scale No. 1 or more than that level (dirt remains dark), Grade 2 is gray scale No. 2 for stain (significantly dirty), 3 The grade is for gray scale No. 3 for contamination (slightly remains), the grade 4 is for gray scale No. 4 for contamination (almost no dirt is left), and the grade 5 is for gray stain for contamination Judgment was made with a scale of No. 5 (no dirt remained). In addition, according to the notation of JIS L0805 (2005), when it is between each class, for example, between the 1st class and the 2nd class, it is described as “1-2”.

  The table summarizes the evaluation results of the finally obtained laminated film.

1, 3, 7: Layers 2, 5, 8 including segments (1) to (3): Support base material 4, 6: Layer including resin having segments (4) and (5) 9: Maximum displacement Amount 10: Creep displacement 11: Remaining displacement 12: Thickness displacement h (μm)
13: Load P (mN)
14: Weighting process 15: Holding process 16: Unloading process 17: Strain amount (%)
18: Stress (MPa)
19: Elongation at break (%)
20: Fracture energy (MPa)
21: Stress-strain curve

  The laminated film according to the present invention can also be used for imparting similar functions to the surfaces of plastic molded products, home appliances, buildings, vehicle interiors, and various printed materials.

Claims (4)

The laminated film which has a surface layer on a support base material, The resin which comprises the said surface layer has the following (1) to (3), The laminated film characterized by the above-mentioned.
(1) (poly) butadiene segment and / or (poly) isoprene segment (2) segment containing at least one selected from the group consisting of tricyclodecyl segment, dicyclopentazinyl segment and isobonyl segment (3) fluorine A segment containing at least one selected from the group consisting of a compound segment, a (poly) siloxane segment, and a (poly) dimethylsiloxane segment The laminated film according to claim 1, wherein the following condition 1 is satisfied when measured from the surface layer side.
Condition 1: The maximum displacement in the thickness direction is 1.20 μm or more and the remaining displacement in the thickness direction is 1 in a load-unloading test method using a microhardness meter under conditions of a maximum load of 0.5 mN and a holding time of 10 seconds. .00μm or less The laminated film according to claim 1 or 2, wherein the surface layer satisfies the following conditions 2 and 3.
Condition 2: The elongation at break of the surface layer at 25 ° C. is 120% or more in the tensile test method. Condition 3: The elastic recovery rate at 25 ° C. of the surface layer is 80 in the tensile test method at a deformation amount of 120%. %that's all The surface layer is formed of at least two layers, and a resin constituting a layer (hereinafter referred to as a first layer) farthest from the support base has the above (1) to (3), and the first layer The resin constituting the layer (hereinafter referred to as the second layer) on the side of the supporting substrate adjacent to the substrate has the following (4) and (5): The laminated film of crab.
(4) A segment comprising at least one selected from the group consisting of (poly) caprolactone segment, (poly) carbonate segment and (poly) alkylene glycol segment (5) urethane bond