JP6531531B2 - Laminated film, and method of manufacturing laminated film - Google Patents

Description

  The present invention relates to a laminated film which is resistant to scratching even when rubbed with a hard material and repeated, and a method of manufacturing the laminated film.

  In recent years, a plastic film provided with a surface layer made of a synthetic resin or the like has been used for the purpose of protecting an optical material such as a color filter or a flat panel display or surface of an automobile body There is.

  Since these surface layers are required to have scratch resistance as an important characteristic from the viewpoint of surface protection, various prepolymers such as organosilanes and polyfunctional acrylics described in Non-Patent Document 1 are generally used. , A coating composition containing an oligomer, etc., by coating-drying-heating or UV curing, and using an “organic-inorganic hybrid material” or the like in which various high surface density fillers are further combined. The scratch resistance is imparted by using a so-called "hard coat material" having an increased surface hardness.

  On the other hand, a film using a so-called "self-repairing material" is proposed in Patent Documents 1 and 2 which repairs scratches on the surface by deformation of the elastic recovery range of the material of the surface layer to achieve scratch resistance. There is.

  Furthermore, as a method of further improving the scratch resistance of the self-repairing material, Patent Document 3 states that “the at least one resin (A) selected from epoxy resin, oxetane resin and vinyl ether resin, and number average molecular weight is 400 or more A resin composition comprising a polyol (B) and an active energy ray sensitive catalyst (C), wherein the polyol (B) has a main chain consisting of carbon-carbon bonds, a polycarbonate polyol (B2), a polyester An active energy ray curable coating agent characterized by being at least one polyol selected from a polyol (B3) and a polyether polyol (B4).

  Further, as another method of improving the scratch resistance of a self-repairing material, as an invention focusing on a laminated structure, in Patent Document 4, “A stress relieving layer and a self-repairing layer are formed in this order on at least one surface of a resin substrate The self-repairing layer is made of at least a soft synthetic resin, and the hardness H of the stress relaxation layer in contact with the self-repairing layer is the nanoindentation of the self-repairing layer. A laminate with a self-repairing layer characterized by being equal to or lower than the hardness H according to

Plastic hard coat applied technology CMC publication 2004

International Publication No. 2011/136042 brochure JP-A-11-228905 JP 2007-284613 A JP, 2011-5766, A

  However, in spite of the extremely high surface hardness, the molded body using the above-mentioned "hard coat material" for the surface layer is often damaged in daily life and the appearance is impaired. According to the investigation by the present inventors, the “hard coat material” has a high surface hardness, and therefore, although it is characterized by being scratched by rubbing with a high hardness material such as metal or ceramic, It was found that when the surface was repeatedly scratched with a soft cloth etc., fine scratches were generated on the surface and the surface became cloudy.

  On the other hand, the inventors confirmed that the materials proposed in Patent Documents 1 to 4 show that in the daily life, the scratch resistance is equal to or higher than that of the hard coat material because the scratch is recovered by the self-repairing function. Is inherently vulnerable to damage that the surface layer should protect, that is, scratches that are accidentally formed by touching a hard material such as a key or metal fitting, and if examined further, it is repeated with a soft cloth, etc. It was found that when scratched, there was almost no scratch, but there was a problem that it could not recover and the scratch was likely to remain if it was rubbed with a high hardness material such as metal, ceramic, etc. . Therefore, the present invention is to provide a laminated film having abrasion resistance that is effective against both high hardness materials, abrasion under high load conditions and repeated abrasion with low hardness materials.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of repeating earnest research, the present inventors completed the following invention. That is, the present invention is as follows.
1. 5% (hereinafter referred to as position A), 35% (hereinafter referred to as position B) of the surface layer thickness from the surface of the surface layer, in a laminated film in which a surface layer comprising at least one layer is formed on a supporting substrate ), 65% (hereinafter referred to as position C), 95% (hereinafter referred to as position D) elastic modulus E _A , E _B , E _C , E _D by atomic force microscope in the cross section of each position A laminated film characterized by satisfying all of condition 1, condition 2 and condition 3 below.

Condition 1 E _A ≦ E _B ≦ E _C <E _D
Condition 2 E _A is 100 MPa or less Condition 3 E _D is 1 GPa or more The laminated film according to 1, wherein the elastic modulus E _A , E _B , E _C and E _D satisfy the following condition 4.

Condition 4 (E _C -E _B ) <(E _B -E _A )
And (E _D -E _C ) <(E _B -E _A )
3. And the elastic modulus E _D at position D of the surface layer, and satisfies the condition 5 of the elastic modulus E _E of the supporting substrate below, laminated film according to 1 or 2.

Condition 5 | E _D −E _E | <1 GPa
4. The laminated film according to any one of 1 to 3, wherein the surface layer is formed of two or more layers having different elastic moduli.
5. The laminated film according to any one of 1 to 4, wherein the surface layer satisfies condition 6 below.

Condition 6 The indentation elastic modulus E _IT of the surface layer in the nanoindentation measurement in the thickness direction under the maximum load 100 mN condition is 2,000 MPa or more. The production of the laminated film according to any one of 1 to 5, wherein the surface layer is formed by sequentially applying, drying, and curing two or more types of coating compositions on a supporting substrate. Method.
7. The method for producing a laminated film according to any one of 1 to 5, wherein the surface layer is formed by simultaneously applying, drying and curing two or more kinds of coating compositions on a supporting substrate .

  The present invention can provide a laminated film having abrasion resistance that is effective against abrasion by a material of high hardness and repeated abrasion by a material of low hardness.

They are the structure of a laminated film, and the elastic-modulus measurement position in a surface layer. It is a conceptual diagram which shows the relationship of condition 1 to condition 3. FIG. FIG. 6 is a conceptual diagram showing the relationship of condition 4; It is a preferred embodiment of the surface layer of the laminated film (in the case of comprising two layers having different elastic moduli). It is a preferable example of a surface layer of a laminated film (when it consists of four layers having different elastic moduli). It is an example of elastic modulus distribution of the surface layer in a laminated film. It is an example of elastic modulus distribution of the surface layer in a laminated film. It is an example of elastic modulus distribution of the surface layer in a laminated film. It is an example (multilayer slide die coating) of the manufacturing method which forms a surface layer. It is an example (multilayer slot die coating) of the manufacturing method which forms a surface layer. It is an example (wet-on-wet coat) of the manufacturing method which forms a surface layer. It is an example of the data obtained by nanoindentation measurement.

  In order to achieve the above-mentioned subject, the present inventors examined in detail the "scratch mechanism on the surface". As a result, the formation of flaws on the plastic surface is affected by three factors: (1) pressure, (2) hardness of the object to be abraded, and (3) the number of times of abrasion, and the conventional "hard coat material" is (1) Because it is effective for (2) and (2), it is difficult to get scratched under high hardness and high load conditions, but because it is weak against (3), it is easy to get scratched in the actual use environment. 2.) It was found that although it is weak, it is easy to get scratched under high hardness and high load condition, but it is hard to get scratched in actual use environment because it is strong for (3).

  The reason hard coat materials are easily scratched in actual use environment is the condition that the surface is not scratched by a single abrasion because the hardness is high and the hardness of the object to be scratched is low or the pressure is low. It is believed that internal distortion that does not lead to flaws occurs on the surface of the material, which is repeated to accumulate distortion, and eventually flaws will form if the strain tolerance is exceeded.

  In addition, the self-repairing material is effective against the above (3), because the material has elastic recovery power, so it can release the strain even if it is rubbed under the conditions described above, so no scratch should be formed. Conceivable.

  On the other hand, because the self-repairing material is weak against the above (1) and (2) because the surface layer has a low elastic modulus, deformation of the surface layer at the time of abrasion reaches the interface between the surface layer and the substrate As a result of stress concentration between the surface layer and the substrate, peeling was generated at the substrate-surface layer interface, and it was found that flaws were formed by propagating to the surface.

  Therefore, taking advantage of the advantages of both hard coat material and self-healing material, the following structure has scratch resistance that is effective against high hardness materials, abrasion under high load conditions and repeated abrasion with low hardness materials. The laminated film which has a surface layer which it has was found.

First, the laminated film of the present invention has the surface layer 1 on the supporting substrate 2 as shown in FIG. 1, and in the cross section perpendicular to the substrate of the surface layer, the surface layer has a thickness of 5 Positions of% (hereinafter referred to as position A; position 3 in FIG. 1), 35% (hereinafter referred to as position B. position 4 in FIG. 1), 65% (hereinafter referred to as position C). Modulus E _A , E _B , E _C , E by atomic force microscope in the cross section of each position of 5 in 1) and 95% (hereinafter referred to as position D) of 6 in FIG. It is preferable that _D satisfy all the following condition 1, condition 2 and condition 3.
Condition 1 E _A ≦ E _B ≦ E _C <E _D
Condition 2 E _A is 100 MPa or less Condition 3 E _D is 1 GPa or more.

  The "surface layer" in the present invention refers to a layer formed on a supporting substrate. That is, when only one layer is formed on the supporting substrate, the one layer is the "surface layer". Further, for example, when two or more layers are formed on the supporting substrate, all the layers of two or more layers excluding the supporting substrate are referred to as one “surface layer”.

  Here, "layer" refers to a portion which can be distinguished by having a boundary surface and a portion adjacent in the thickness direction from the surface side of the laminated film in the thickness direction, and a portion having a finite thickness.

  More specifically, when cross-sectional observation of the cross section of the laminated film is carried out with an electron microscope (transmission type, scanning type) or an optical microscope, it refers to those distinguished by the presence or absence of a discontinuous interface.

  In addition, about the elastic modulus of the surface layer mentioned later, it may be a laminated film in which a plurality of layers having different elastic moduli are laminated, or in a layer having different elastic moduli in the thickness direction in one same layer. It may be.

  The measurement of elastic modulus with an atomic force microscope is a compression test with a probe of an extremely small portion, and is a degree of deformation due to the pressing force, so each of the surface layers in the thickness direction using a cantilever with a known spring constant. Measure the modulus of elasticity in the cross section of the position. Specifically, the laminated film is cut, and the elastic modulus in the cross section at each position in the thickness direction of the surface layer is measured by an atomic force microscope. The details will be described in the section of the example, but using an atomic force microscope shown below, the probe at the tip of the cantilever is brought into contact with the cross section of the surface layer, and a cantilever is obtained by measuring a force curve with a pressing force of 55 nN. The amount of deflection of can be measured. Details will be described later.

Atomic force microscope: MFP-3DSA-J manufactured by Asylum Technology
Cantilever: A cantilever “R150-NCL-10 (material Si, spring constant 48 N / m, radius of curvature at the tip 150 nm) made by NANOSENSORS.

Condition 1 is intended to preferably increase the elastic modulus in the thickness direction of the surface layer from the surface side toward the substrate side, and it is more preferable that E _A ≦ E _B <E _C <E _D Preferably, E _A <E _B <E _C <E _D is more preferable.

If this order is reversed, that is, E _A > E _B > E _C > E _D , the outermost surface is not able to release strain due to elastic recovery, so it is vulnerable to repeated abrasion. Since the strain is increased due to the low rate, the scratch resistance may be reduced when scratching with a material having high pressure or high hardness. In addition, if the order changes, that is, E _B > E _A > E _D > E _C, etc., a stress concentration portion is formed in the layer, and peeling occurs in the vicinity, so abrasion is caused by a high pressure or high hardness material. When it does, abrasion resistance may fall.

Condition 2 indicates a preferable range of the elastic modulus (E _A ) on the surface side of the surface layer. The value of E _A is preferably at most 100 MPa, more preferably at most 50 MPa, and particularly preferably 20 MPa. When the value of E _A exceeds 100 MPa, release of strain due to elastic recovery may be insufficient at repeated abrasion. The small value of E _A does not cause any problem in achieving this subject, but when it is 1 MPa or less, the surface may be tacky and may not be practical from the viewpoint of surface protection. is there.

Condition 3 indicates a preferable range of the elastic modulus (E _D ) of the surface layer on the support substrate side. The value of E _D is preferably at least 1 GPa, more preferably at least 2 GPa, more 5GPa is particularly preferred. If the E _D value is less than 1 GPa, the surface hardness may be insufficient, and the durability against abrasion by a hard material may be insufficient. The value of E _D is preferably as high for scratch resistance but, as a material usable as a surface layer on the laminated film from the viewpoint of practical folding and workability is the limit of about 100 GPa.

  The relationship between the conditions 1 to 3 is illustrated in FIG. The vertical axis 8 in FIG. 2 indicates the relative position from the surface side to the thickness of the surface layer, and the horizontal axis 9 in FIG. 2 indicates the elastic modulus according to atomic force microscope from position A to position D described above. There is. According to the condition 1, the elastic modulus is increased as the relative position from the surface to the thickness of the surface layer is increased. 10 and 13 in FIG. 2 correspond to the conditions 2 and 3 and indicate the preferable elastic modulus range of the position A and the position D.

Furthermore, it is preferable that the elastic modulus E _A , E _B , E _C and E _D satisfy the following condition 4.
Condition 4 (E _C -E _B ) <(E _B -E _A )
And (E _D -E _C ) <(E _B -E _A )
Condition 4 is intended to be large on the surface side with respect to elastic modulus change with respect to thickness change in the surface layer, that is, the slope of the elastic modulus, more preferably the following condition 4-1, particularly preferably the condition 4-2 is satisfied. Is that
Condition 4-1 (E _D -E _C ) ≦ (E _C -E _B ) <(E _B -E _A )
Condition 4-2 (E _D -E _C ) <(E _C -E _B ) <(E _B -E _A ).

  In FIG. 3, elastic modulus changes (16, 17 and 18 in FIG. 3) between position A and position B, position B and position C, and position C and position D are smaller as they are closer to the surface (FIG. 3) 16), the larger the substrate side is, the larger (18 in FIG. 3) is shown.

The order is reversed, that is, (E _D -E _C )> (E _C -E _B )> (E _B -E _A ), or replaced, that is, (E _D -E _C ) <(E _B -E _A ) When it becomes <(E _C -E _B ), the durability to pressure and hardness of the object to be scratched may be slightly reduced.

Further, the elastic modulus E _D at the position D of the surface layer, there is preferred relationship between the elastic modulus E _E of the supporting substrate, it is preferable to satisfy the condition 5 below.
Condition 5 | E _D −E _E | <1 GPa
Under condition 5, the value of | E _D −E _E | is preferably smaller than 1 GPa, and more preferably 500 MPa or less. The magnitude relationship between E _D and E _E is not particularly limited as long as the aforementioned condition 3 is satisfied. There is no particular limitation on the portion where the value of | E _D -E _E | is small, and there is no problem even if it is zero.

When the value of | E _D −E _E | is 1 GPa or more, the durability against pressure and the hardness of the object to be rubbed may be slightly lowered.

  Further, in order to solve the problems of the present invention by satisfying the above-mentioned conditions, there is a preferable form of the structure of the surface layer, one of which is that the surface layer has different elastic modulus as shown in FIG. It is a form formed from the above layers (21, 22 in FIG. 4), more preferably 3 or more layers, and particularly preferably 4 or more layers (25 to 28 in FIG. 5) as shown in FIG. . The number of layers is not particularly limited, but may be appropriately selected from the number of steps of the method of forming the surface layer and the effects obtained. Furthermore, the thickness of each layer is not particularly limited as long as the above-mentioned physical properties are satisfied. Here, the definition of layers is as described above.

  Moreover, another preferable form is a form in which the said surface layer has a part to which an elastic modulus changes continuously. Here, the "elastically changing portion" means that the elastic modulus obtained by measuring the elastic modulus of the surface layer continuously in the thickness direction with the force curve of the atomic force microscope is the thickness direction. It is intended to have a part that changes with "finite slope". Details will be described with reference to FIGS. 6 to 8.

  As shown in FIG. 6, the change in the elastic modulus 28 relative to the relative position 27 in the thickness direction of the surface layer indicated by the broken line is extremely large, and the slope of the elastic modulus with respect to the thickness of the surface layer is infinite. As shown in FIG. 7, the modulus of elasticity of the surface layer is not as large as that of the surface layer consisting of only the portions 30 where the change of the modulus of elasticity 28 to thickness is extremely small and the slope of the modulus of elasticity to the thickness of the surface layer is zero. The surface layer has a portion 33 which changes with a finite inclination to the thickness, or the surface layer whose elastic modulus changes with a finite inclination throughout the thickness direction of the surface layer, as shown in FIG.

  More specifically, the “continuously changing part” is a section of 10% of the layer thickness when the force curve of the atomic force microscope is continuously measured in the thickness direction of the surface layer. It refers to the part where the change is 5% or more and 95% or less. That is, the thickness of the entire surface layer is 100%, an arbitrary section which is 10% of the thickness in the thickness direction is selected, and the elastic modulus is measured in each of the cross section on the surface side and the support base side of the section. At that time, assuming that the elastic modulus on the side of the support substrate is 100%, when the elastic modulus on the surface side is in the range of 5% to 95% of the elastic modulus on the side of the support substrate, Judge that there is. In addition, such "continuously changing portion" is determined to be "continuously changing portion" in the surface layer if there is only one corresponding section in the whole surface layer.

  Furthermore, it is preferable that the surface layer satisfy the following condition 6.

Condition 6 The indentation elastic modulus E _IT of the surface layer in the nanoindentation measurement in the thickness direction under the maximum load 100 mN condition is 2,000 MPa or more. Details of the nanoindentation measurement will be described later.

From the viewpoint of indentation resistance, the indentation elastic modulus E _IT is preferably 2,000 MPa or more, more preferably 2,500 MPa or more, and particularly preferably 3,000 MPa or more. The indentation elastic modulus E _IT has a correlation with the mechanical response to the external force, and when the indentation elastic modulus E _IT is large, it becomes possible to suppress so-called resin flow, in which a mark remains after applying the external force for a long time, As a result, the scratch resistance is improved.

The above effect is larger as the indentation elastic modulus E _IT is larger, but when it is excessive, the self-repairing property may be lowered, so about 20,000 MPa is considered to be the upper limit. On the other hand, if the indentation elastic modulus E _IT is less than 2,000 MPa, indentations may occur due to indentation for a long period of time, and the quality may be degraded.

  As a manufacturing method of forming these surface layers, the following two methods are preferable. One such method is to form two or more paint compositions on a support substrate by "sequentially" applying, drying and curing. Here, "apply sequentially" is intended to form a surface layer by applying, drying and curing one kind of coating composition, and then applying, drying and curing different kinds of coating composition. doing.

  Another manufacturing method is a method of forming two or more coating compositions by applying, drying and curing "simultaneously" on a support substrate. The number of types of coating compositions is not particularly limited as long as it is two or more. Here, "simultaneously applying" is intended to dry and cure after forming two or more types of liquid films on the supporting substrate in the application step, and the method is not particularly limited as long as the conditions are satisfied. Typically, “multilayer slide die coating” (FIG. 9) in which liquid films are sequentially laminated and then coated in a state before application, and “multilayer simultaneously laminated on a substrate, as a typical example. There is a "slot-die coat" (FIG. 10), a "wet-on-wet coat" (FIG. 11), etc., in which one layer of liquid film is formed on a supporting substrate and another layer is laminated in an undried state.

  By appropriately selecting the type, number, and supporting substrate of the coating composition used in the present manufacturing method, the slope of the elastic modulus on the surface side-substrate side of the surface layer and the magnitude of the elastic modulus of the substrate and the surface layer The continuity of the form of the elastic modulus distribution in the surface layer can be controlled by appropriately selecting the type, composition, drying condition and curing condition of the coating composition. Details of these coating methods will be described later.

Moreover, in order to solve the subject of this invention by satisfy | filling the above-mentioned conditions, it is preferable that resin which comprises the surface side of the said surface layer of this invention has the following (1) to (3).
(1) Segment containing at least one selected from the group consisting of polycaprolactone segment, polycarbonate segment and polyalkylene glycol segment (2) Urethane bond (3) Fluorine compound segment, polysiloxane segment and polydimethylsiloxane segment A segment containing at least one selected.

  About each segment which resin which comprises the surface side of this surface layer contains, TOF-SIMS, FT-IR, etc. can confirm.

  The polycaprolactone segment of the above (1) refers to the chemical formula 1, the polyalkylene glycol segment refers to the chemical formula 2, and the polycarbonate segment refers to the segment shown by the chemical formula 3.

  Here, polycaprolactone includes caprolactone having repeating units of 1 (monomer), 2 (dimer), 3 (trimer) and oligomers having caprolactone having 35 repeating units or less. In addition, polyalkylene glycols include those having a repeating unit of alkylene glycol such as 2 (dimer) or 3 (trimer), or an oligomer having a repeating unit of alkylene glycol of 11 or less. Furthermore, polycarbonates also include those having a repeating unit of carbonate such as 2 (dimer), 3 (trimer), and oligomers having up to 16 repeating units of carbonate.

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 to 16;
R ₄ refers to an alkylene or cycloalkylene group having 1 to 8 carbon atoms.

  Although details of the polycaprolactone segment, polycarbonate segment, and polyalkylene glycol segment will be described later, the resin constituting the surface side of the surface layer has these segments, thereby improving the self-repairing property of the surface layer, Repeated abrasion can be improved.

  Furthermore, here, the urethane bond of (2) refers to a segment represented by Chemical Formula 4.

  Although the detail of the said urethane bond is mentioned later, when the resin which comprises the surface side of the said surface layer has this coupling | bond, the toughness of the whole surface layer can be improved.

  The fluorine compound segment described in the above (3) refers to a segment containing at least one selected from the group consisting of fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoroalkanediyl group and 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 and the like, and is a structure represented by the chemical formula 5 and the chemical formula 6.

  Here, n1 is an integer of 1 to 3, n2 to n5 is an integer 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 exhibiting low surface energy can be present at a high density on the outermost surface, and the repetitive abrasion of the surface is improves.

  The chain length of this fluoropolyether segment has a preferable range, and the number of carbon atoms is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. If the number of carbon atoms is 3 or less, the surface energy is not sufficiently reduced, so the oil repellency may decrease. If the number of carbon atoms is 13 or more, the solubility in the solvent may decrease, and the quality of the surface layer may decrease.

  The polysiloxane segment of (3) above refers to the segment represented by Formula 7, and the polydimethylsiloxane segment refers to the segment represented by Formula 8. Here, the polysiloxane includes both low molecular weight ones (so-called oligomers) in which the repeating units of the siloxane are about 100 and high molecular weight ones (so-called polymers) in which the repeating units of the siloxanes exceed 100. Similarly, polydimethylsiloxanes include both low molecular weight (the so-called oligomers) with 10 to 100 repeating units of dimethylsiloxane and high molecular weight (the so-called polymers) with more than 100 repeating units of dimethylsiloxane. .

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

  m is an integer of 10 to 300.

Although the details of the polysiloxane segment and the polydimethylsiloxane segment will be described later, when the resin constituting the surface layer has these segments, the heat resistance and the weather resistance are improved, and the scratch resistance due to the lubricity of the surface layer Can be improved. It is more preferable from the viewpoint of lubricity to include a polydimethylsiloxane segment represented by the chemical formula 8 more preferably.
Hereinafter, embodiments of the present invention will be described in detail.
[Laminated film and surface layer]
The laminated film of the present invention may be either in a flat state or in a three-dimensional shape after being formed, as long as it has a surface layer exhibiting the aforementioned physical properties. Here, the "surface layer" in the present invention may be formed of one "layer" or may be formed of a plurality of "layers". Here, “layer” can be distinguished by having a boundary surface which is directed from the surface of the laminated film in the thickness direction and has an element composition adjacent to the thickness direction, the element composition, the shape of the inclusion, and the physical characteristics discontinuous. Refers to a portion having a thickness of On the other hand, when the physical properties and the elemental composition in the surface layer are continuously changing, they are handled as one layer.

  The surface layer is an object of the present invention, and in addition to scratch resistance, it has antifouling property, antireflective property, antistatic property, antifouling property, conductivity, heat ray reflectivity, near infrared ray absorbing property, electromagnetic wave shielding property, It may have other functions such as easy adhesion.

The thickness of the surface layer is not particularly limited, but is preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less. The thickness of each layer when the surface layer is formed of a plurality of layers is as described above.
[Supporting base material]
The material constituting the support base used in the laminated film of the present invention may be any of thermoplastic resin and thermosetting resin, may be homo resin, and may be copolymer or blend of two or more types. Good. More preferably, the resin constituting the support base is preferably a thermoplastic resin because the moldability is good.

  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, polyimide resins, polyester resins, polycarbonate resins, Fluorine such as polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochlorinated ethylene resin, tetrafluoroethylene-6fluoropropylene copolymer, vinylidene fluoride resin Resin, acrylic resin, methacrylic resin, polyacetal resin, polyglycolic acid resin, polylactic acid resin, etc. can be used. As an example of a thermosetting resin, a phenol resin, an epoxy resin, a urea resin, a melamine resin, an unsaturated polyester resin, a polyurethane resin, a polyimide resin, a silicone resin etc. can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. From the viewpoint of strength, heat resistance and transparency, the thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin or a methacrylic resin, and a polyester resin is particularly preferable.

  The polyester resin in the present invention is a general term for a polymer having an ester bond as the main bond chain of the main chain, and is obtained by polycondensation of an acid component and its ester and diol component. Specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate. Moreover, what co-polymerized other dicarboxylic acid and its ester and diol component as an acid component and a diol component may be used for these. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in view of transparency, dimensional stability, heat resistance and the like.

  In addition, the supporting substrate includes various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, an inorganic particle, an organic particle, a viscosity reducing agent, a heat stabilizer, a lubricant, an infrared ray absorbent, an ultraviolet ray absorbent, A dopant for adjusting the refractive index may be added. The supporting substrate may have either a single-layer structure or a laminated structure.

  It is also possible to apply various surface treatments to the surface of the supporting substrate before forming the surface layer. Examples of 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 preferable, and glow discharge treatment and ultraviolet treatment are more preferable.

  In addition to the surface layer of the present invention, functional layers such as an adhesive layer, an antistatic layer, an undercoat layer, and an ultraviolet ray absorbing layer can be provided in advance on the surface of the supporting substrate, and in particular, adhesion is easy It is preferable to provide a layer.

[Coating composition]
The laminated film of the present invention can form a surface layer having a structure capable of achieving the above-mentioned physical properties by applying, drying and curing the coating composition on the supporting substrate using the method for manufacturing the laminated film described later. . Here, the "coating composition" is a liquid comprising a solvent and a solute, and is a material that can be applied on the above-mentioned supporting substrate and can form a surface layer by volatilization, removal and curing in the step of drying the solvent. Point to Here, the “type” of the coating composition refers to a liquid in which the types of solutes constituting the coating composition are partially different. The solute is a resin or a material capable of forming them in a coating process (hereinafter referred to as a precursor), particles, and a polymerization initiator, a curing agent, a catalyst, a leveling agent, an ultraviolet absorber, an antioxidant, etc. It consists of various additives.

  The laminated film of the present invention uses at least two types of coating compositions (hereinafter referred to as coating composition A and coating composition B) as described above, and is sequentially applied or simultaneously applied on a supporting substrate as described above It is preferable to form by Here, the coating composition A is applied on a supporting substrate, dried and cured to form the outermost surface side of the surface layer with a liquid capable of forming a material having a low elastic modulus and excellent self-healing properties. Or a suitable resin, or precursor. Coating composition B is a liquid capable of forming a material having a high elastic modulus and a high surface hardness by being applied, dried and cured on a supporting substrate, and a resin suitable for forming the substrate side of the surface layer Or contains a precursor.

  When three or more types of coating compositions are used in the method for producing a laminated film, the coating composition A and the coating composition B can be prepared by appropriately mixing them according to the physical properties of the coating film. The details of these will be described below.

[Coating composition A]
The coating composition A is a liquid containing a material suitable for forming the surface side of the surface layer, or containing a precursor that can be formed, and a resin or a resin containing the above-mentioned segment (1) to (3) as a solute It is preferred to include a precursor.

  Moreover, the mass part of said (1), (2), (3) contained in the coating composition A is (1) / (2) / (3) = 95/5/1-50/50/15. (1) / (2) / (3) = 90/10/1 to 60/40/10 are more preferable. The details of (1), (2) and (3) will be described below.

[Polycaprolactone Segment, Polycarbonate Segment, Polyalkylene Glycol Segment]
First, the polycaprolactone segment refers to the segment represented by the above-mentioned chemical formula 1.
It is preferable that the resin containing a polycaprolactone segment has at least one or more hydroxyl groups (hydroxyl groups). The hydroxyl group is preferably at the end of the resin containing a polycaprolactone segment.

  As a resin containing a polycaprolactone segment, polycaprolactone having a 2- to 3-functional hydroxyl group is particularly preferable. Specifically, polycaprolactone diol represented by the chemical formula 9,

Here, m + n is an integer of 4 to 35, m and n each is an integer of 1 to 34, R is C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ , C (CH ₃ ) ₃ (CH ₂ ) ₂
Or polycaprolactone triol represented by the formula 10

Here, l + m + n is an integer of 3 to 30, l, m and n each is an integer of 1 to 28, R is CH ₂ CHCH ₂ , CH ₃ C (CH ₂ ) ₃ and CH ₃ CH ₂ C (CH ₂ ) ₃
And polycaprolactone-modified hydroxyethyl (meth) acrylates represented by the chemical formula 11

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

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

  In the present invention, the weight average molecular weight of the polycaprolactone segment in the resin containing the polycaprolactone segment is preferably 500 to 2,500, and more preferably 1,000 to 1,500. . When the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, the self-repairing effect is more exhibited, and the repetitive abrasion is further improved, which is preferable.

  Next, a polyalkylene glycol segment refers to the segment represented by the above-mentioned chemical formula 2. It is preferable that the resin containing the polyalkylene glycol segment has at least one or more hydroxyl groups (hydroxyl groups). The hydroxyl group is preferably at the end of the resin containing a polyalkylene glycol segment.

  The resin containing a polyalkylene glycol segment is preferably a polyalkylene 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 polyalkylene glycol (meth) acrylate is not limited, but is most preferably monofunctional from the viewpoint of the self-healing property of the cured product.

  Examples of polyalkylene glycol (meth) acrylate contained in the coating composition used to form the surface layer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and polybutylene glycol (meth) acrylate . The structures are represented by the following chemical formula 12, chemical formula 13, and chemical formula 14, respectively.

  Polyethylene glycol (meth) acrylate:

  Polypropylene glycol (meth) acrylate:

  Polybutylene glycol (meth) acrylate:

Formula 12, Formula 13, is R in the chemical formula 14 hydrogen (H) or methyl group _(-CH 3), m is an integer comprised between 2 to 11.

  In the present invention, preferably, a resin constituting a surface layer is produced by reacting a compound having an isocyanate group to be described later with a hydroxyl group of (poly) alkylene glycol (meth) acrylate to use as a urethane (meth) acrylate in the surface layer. (2) urethane bond and (3) (poly) alkylene glycol segment, which is preferable because it can improve the toughness of the surface layer and improve the self-repairing property.

  Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl as hydroxyalkyl (meth) acrylate simultaneously compounded in the urethanization reaction of a compound containing an isocyanate group and a polyalkylene glycol (meth) acrylate Examples are (meth) acrylates and the like.

  Next, the polycarbonate segment refers to the segment represented by the above-mentioned chemical formula 3.

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

As a resin containing a polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferable. Specifically, it is represented by Chemical Formula 15.
Polycarbonate diol:

n is an integer of 2 to 16;
R refers to an alkylene or cycloalkylene group having 1 to 8 carbon atoms.

  The polycarbonate diol may have any number of repeating carbonate units, but if the number of repeating carbonate units is too large, the strength of the cured urethane (meth) acrylate decreases, so the number of repeating is 10 or less. Is preferred. The polycarbonate diol may be a mixture of two or more polycarbonate diols having different numbers of repeating carbonate units.

  The polycarbonate diol preferably has a number average molecular weight of 500 to 10,000, and more preferably 1,000 to 5,000. When the number average molecular weight is less than 500, it may be difficult to obtain suitable flexibility, and when the number average molecular weight exceeds 10,000, the heat resistance and the solvent resistance may decrease, so the above-mentioned material is preferable. It is.

  Moreover, as polycarbonate diol used by this invention, UH-CARB, UD-CARB, PLACCEL CD-PL of UC-CARB (Ube Industries, Ltd.), PLACCEL CD-H (Daicel Chemical Industries, Ltd.), Kuraray polyol C Products such as series (Kuraray Co., Ltd.) and Duranol series (Asahi Kasei Chemicals Co., Ltd.) can be suitably exemplified. These polycarbonate diols can also be used alone or in combination of two or more.

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

In the present invention, preferably, the surface side of the surface layer is constituted by reacting a compound containing an isocyanate group to be described later with the hydroxyl group of polycarbonate diol and using it as a urethane (meth) acrylate on the surface side of the surface layer. The resin can have the aforementioned (2) urethane bond and (1) polycarbonate diol segment, and as a result can improve the toughness of the surface layer and improve the self-repairing property, and improve the repetitive abrasion. be able to.
[A compound containing a urethane bond and an isocyanate group]
In the present invention, "urethane bond" refers to the bond represented by the above-mentioned chemical formula 4. By the coating composition A containing a commercially available urethane-modified resin, the resin constituting the surface side of the surface layer can have a urethane bond. Further, when forming the surface side of the surface layer, a coating composition A containing a compound containing an isocyanate group and a compound containing a hydroxyl group as a precursor is applied, dried and cured to form a urethane bond. Also, urethane bonds can be contained on the surface side of the surface layer.

  In the present invention, it is preferable to introduce a urethane bond into the resin constituting the surface side of the surface layer by reacting an isocyanate group and a hydroxyl group to form a urethane bond. By reacting the isocyanate group and the hydroxyl group to form a urethane bond, the toughness of the surface layer can be improved and the self-repairing property can be improved, whereby the repetitive abrasion can be improved.

  In addition, a resin containing a polycaprolactone segment, a polycarbonate segment, or a polyalkylene glycol segment as described above, or, if having a hydroxyl group, generates a urethane bond between these resin and a compound containing an isocyanate group as a precursor by heat or the like. It is also possible to

  When the surface layer is formed using a compound containing an isocyanate group, a resin containing a polysiloxane segment having a hydroxyl group described later, or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the toughness and self-repairing of the surface layer In addition to the nature, the slipperiness of the surface can be enhanced, which is more preferable from the viewpoint of repeated abrasion.

  In the present invention, a compound containing an isocyanate group refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. The compound containing an isocyanate group is, for example, methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, tolylene diisocyanate. An isocyanurate body, an isocyanurate body of hexamethylene diisocyanate, a (poly) isocyanate such as a biuret body of hexamethylene isocyanate, and a block body of the above isocyanate can be mentioned.

Among these isocyanate group-containing compounds, aliphatic isocyanates are preferable because they have high self-healing properties compared to alicyclic or aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Further, as the compound having an isocyanate group, an isocyanate having an isocyanurate ring is particularly preferable in terms of heat resistance, and an isocyanurate of hexamethylene diisocyanate is most preferable. An isocyanate having an isocyanurate ring forms a surface layer having both self-healing properties and heat resistance properties.
[Fluorinated compound segment, polysiloxane segment, polydimethylsiloxane segment]
In the laminated film of the present invention, the surface layer or the resin constituting the surface side of the surface layer has a segment including at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment Is preferred.

  Further, a paint composition for forming a surface layer is a paint composition A containing a resin containing a segment containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment, or a precursor The resin which comprises the surface side of a surface layer can have these by using one.

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

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

  Here, fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoroalkanediyl group, fluorooxyalkanediyl group means hydrogen of alkyl group, oxyalkyl group, alkenyl group, alkanediyl group, oxyalkanediyl group. Part or all is a substituent substituted with fluorine, and each is a substituent mainly composed of a fluorine atom and a carbon atom, and there may be a branch in the structure, and a structure having these portions is A plurality of linked dimers, trimers, oligomers, and polymer structures may be formed.

  Further, as the fluorine compound segment, a fluoropolyether segment is preferable, and this is a site composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., more preferably represented by the chemical formula 5 and the chemical formula 6 It is as already stated that it is a 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. The fluorine compound D is a compound represented by the chemical formula 16.

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

  The reactive site refers to a site that reacts with other components by external energy such as heat or light. As such a reactive site, a silanol group in which an alkoxysilyl group and an alkoxysilyl group are hydrolyzed from the viewpoint of reactivity, a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, etc. It can be mentioned. Among them, vinyl, allyl, alkoxysilyl, silyl ether or silanol, an epoxy and acryloyl (methacryloyl) are preferable from the viewpoint of reactivity and handling.

  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-perfluorooctylethyltrichloride Chlorosilane, 2-perfluorooctylisocyanate 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-permer 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 methacrylate Hexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoro And pentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyl trifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol and the like.

The fluorine compound D may have a plurality of fluoropolyether moieties per molecule.
Examples of the commercially available fluorine compound D include RS-75 (DIC Corporation), Optool DAC-HP (Daikin Industries, Ltd.), C10GACRY, C8HGOL (oil and fat product corporation), and the like. You can use the products of

  Next, the polysiloxane segment will be described. In the present invention, the polysiloxane segment refers to the segment represented by the above-mentioned chemical formula 7. In the present invention, a coating composition obtained by adding a hydrolyzable silane compound having a radical polymer to a partial hydrolyzate of a silane compound containing a hydrolyzable silyl group, an organosilica sol, or the organosilica sol is used as a polysiloxane segment. It can be used as a resin to be contained.

  Resins containing a polysiloxane segment include tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxypropyltritriol. Organo silica sol dispersed in a completely or partially hydrolyzate of a silane compound having a hydrolyzable silyl group such as alkoxysilane, γ-methacryloxypropyl alkyl dialkoxysilane, or an organic solvent, hydrolyzable silyl group on the surface of organosilica sol The thing etc. which added the hydrolysis silane compound of these can be illustrated.

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

  When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, the surface is obtained using a coating composition containing a resin (copolymer) containing a polysiloxane segment having a hydroxyl group and a compound containing an isocyanate group. By forming the layer, it is possible to efficiently form a surface layer having a polysiloxane segment and a urethane bond.

  Next, the polydimethylsiloxane segment is described. In the present invention, the polydimethylsiloxane segment refers to the segment represented by the above-mentioned chemical formula 8.

  When the resin constituting the surface side of the surface layer has a polydimethylsiloxane segment, the polydimethylsiloxane segment is coordinated to the surface of the surface layer. By coordinating the polydimethylsiloxane segment to the surface of the surface layer, the lubricity of the surface of the surface layer can be improved and the frictional resistance can be reduced. As a result, repetitive abrasion can be improved.

  In the present invention, as the resin containing a polydimethylsiloxane segment, it is preferable to use a copolymer in which a vinyl monomer is copolymerized with the polydimethylsiloxane segment.

  In order to improve the toughness of the surface layer, it is preferable that the resin containing a polydimethylsiloxane segment is copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group.

  When the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, a paint composition containing a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group is used Once the surface layer is formed, the surface layer can be efficiently provided with the polydimethylsiloxane segment and the urethane bond.

  When the resin containing a polydimethylsiloxane 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 a polydimethylsiloxane segment is a copolymer with a vinyl monomer, this is referred to as a polydimethylsiloxane copolymer. The polydimethylsiloxane copolymer can be produced by living polymerization method, polymer initiator method, polymer chain transfer method, etc., but considering the productivity, the polymer initiator method, polymer chain transfer method It is preferred to use.

  When the polymer initiator method is used, the polymer azo radical polymerization initiator represented by the chemical formula 17 can be used to copolymerize with other vinyl monomers. Also, a two-step polymerization is carried out by copolymerizing a peroxy monomer and a polydimethylsiloxane having an unsaturated group at low temperature to introduce a peroxide group into a side chain, and copolymerizing the prepolymer with a vinyl monomer. You can also do

m is an integer of 10 to 300 and n is an integer of 1 to 50.
In the case of using a polymer chain transfer method, for example, after adding HS-CH ₂ COOH, HS-CH ₂ CH ₂ COOH, etc. to a silicone oil represented by the chemical formula 18 to obtain a compound having an SH group, A block copolymer can be synthesized by copolymerizing the silicone compound and a vinyl monomer using chain transfer.

m is an integer of 10 to 300.

  In order to synthesize a polydimethylsiloxane graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound represented by the chemical formula 19, that is, a methacrylic ester of polydimethylsiloxane with a vinyl monomer. it can.

m is an integer of 10 to 300.

  As a vinyl monomer used for a copolymer with polydimethylsiloxane, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, 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-methylol acrylamide, N, N-dimethyl acrylamide, N, N-dimethylaminoethyl ester Methacrylates, N, N-diethylaminoethyl methacrylate, diacetotone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol and the like can be mentioned.

  In addition, polydimethylsiloxane-based 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 alcohol and the like It is preferable to manufacture by the solution-polymerizing method in alcohol solvent etc. of this in an individual or mixed solvent.

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

  The amount of the polydimethylsiloxane segment in the polydimethylsiloxane copolymer in the present invention is 1 to 10% by mass of all components of the polydimethylsiloxane copolymer in terms of the lubricity and the stain resistance of the surface layer. It is preferably 30% by mass. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

  In the present invention, when a resin containing a polydimethylsiloxane segment is used as a paint composition used to form a surface layer, other segments etc. are contained (copolymerized) in addition to the polydimethylsiloxane segment. May be For example, polycaprolactone segments and polysiloxane segments may be contained (copolymerized).

  Coating compositions used to form the surface layer include copolymers of polycaprolactone segments and polydimethylsiloxane segments, copolymers of polycaprolactone segments and polysiloxane segments, polycaprolactone segments and polydimethylsiloxane segments, and poly It is possible to use a copolymer with a siloxane segment or the like. The surface layer obtained using such a coating composition can have a polycaprolactone segment and a polydimethylsiloxane segment and / or a polysiloxane segment.

  The reaction of polydimethylsiloxane-based copolymer, polycaprolactone, and polysiloxane in a coating composition used to form a surface layer having a polycaprolactone segment, a polysiloxane segment and a polydimethylsiloxane segment is a polydimethylsiloxane-based At the time of copolymer synthesis, a polycaprolactone segment and a polysiloxane segment can be appropriately added and copolymerized.

[Coating composition B]
Coating composition B is a liquid capable of forming a material having a high elastic modulus and a high surface hardness by being applied, dried and cured on a supporting substrate, and a resin suitable for forming the substrate side of the surface layer Or contains a precursor.

  Specific examples of materials having high elastic modulus and high surface hardness include polyfunctional acrylate monomers, oligomers, alkoxysilanes, alkoxysilane hydrolysates, alkoxysilane oligomers and the like, and polyfunctional acrylate monomers and oligomers are more preferable.

  Examples of polyfunctional acrylate monomers include polyfunctional acrylates having three or more (meth) acryloyloxy groups in one molecule and modified polymers thereof, and specific examples thereof include pentaerythritol tri (meth) acrylate and pentaerythritol Tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate And pentaerythritol triacrylate hexane methylene diisocyanate urethane polymer can be used. These monomers can be used alone or in combination of two or more.

  Further, examples of polyfunctional acrylate oligomers include epoxy acrylate, urethane acrylate, polyester acrylate and the like, and can also be used in combination with polyfunctional acrylate monomers and the like.

  Moreover, as a polyfunctional acrylic composition marketed, Mitsubishi Rayon Co., Ltd .; (trade name "Dia Beam" (registered trademark) series etc.), Nagase & Co., Ltd .; (trade name "Denacol" (registered trademark) series Etc.), Shin-Nakamura Chemical Co., Ltd .; (trade name “NK Ester” series etc.), DIC Inc .; (trade name “UNIDIC” (registered trademark) etc.), Toagosei Co., Ltd .; (“ALONIX” (registered trademark) Series, etc., NOF Corporation; (“Blenmar” (registered trademark) series etc.), Nippon Kayaku Co., Ltd .; (brand name “KAYARAD” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd. (brand name “ These products can be used, for example, Light Ester "series" and the like.

  In order to further increase the elastic modulus, it is also preferable to introduce particle components into these materials. Details of the particle component will be described later.

[Particle component]
The surface layer of the laminate film of the present invention, and the paint composition A or the paint composition B may contain a particle component, and the substrate side of the surface layer of the laminate film and the paint composition B contain a particle component preferable. Here, the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of durability.

  Here, "inorganic particles" also include those subjected to surface treatment. This surface treatment means introducing a compound onto the particle surface by chemical bond (including covalent bond, hydrogen bond, ionic bond, van der Waals bond, hydrophobic bond, etc.) or adsorption (including physical adsorption, chemical adsorption) Even when the compound introduced by the surface treatment is an organic compound, if the particles to be the base are inorganic particles, the particles are inorganic particles.

As a kind of inorganic particle contained, 1 type or more and 20 types or less are preferable. The number of kinds of inorganic particles is more preferably one or more and ten or less, and particularly preferably two or more and four or less. Here, the type of the inorganic particle is determined by the type of the element constituting the inorganic particle, and in the case of performing any surface treatment, it is determined by the type of the element constituting the particle before the surface treatment. For example, since titanium oxide (TiO ₂ ) and nitrogen-doped titanium oxide (TiO ₂ -xN _x ) in which a part of oxygen of titanium oxide is replaced with nitrogen which is an anion, the elements constituting the inorganic particles are different, Suppose that they are different types of inorganic particles. Further, in the case of particles (ZnO) consisting only of the same element, for example, Zn or O, even if there are a plurality of particles different in the number average particle diameter, or the composition ratio of Zn to O is different, These are particles of the same type. Further, even if a plurality of Zn particles having different oxidation numbers are present, they are particles of the same type as long as the elements constituting the particles are the same (in this example, as long as all elements other than Zn are the same) I assume.

  In addition, the particles contained in the coating composition of the present invention are included in the surface layer in a form in which the surface state is changed by heat, ionizing radiation or the like in the treatment such as coating, drying, curing treatment or vapor deposition. There is also.

  The inorganic particles are not particularly limited, but are preferably oxides of metals and metalloids, nitrides, borides, chlorides, carbonates and sulfates, and complex oxides containing two metals and metalloids, A different element may be introduced between the lattices, a lattice point may be replaced with a different element, or a lattice defect may be introduced.

  The inorganic particles are oxide particles in which at least one metal or metalloid selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba and Ce is oxidized. Is more preferred.

Specifically, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide It is preferable that it is at least one metal oxide or semimetal oxide selected from the group consisting of (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ) and indium tin oxide (In ₂ O ₃ · SnO ₂ ). Particularly preferred is silica (SiO ₂ ).

  Here, the number average particle diameter of the inorganic particles means the number-based arithmetic average length diameter described in JIS Z 8819-2: 2001, and primary particles are measured using a scanning electron microscope (SEM), a transmission electron microscope, etc. It observes, diameter of the circumscribed circle of each primary particle is made equivalent particle diameter, and it points out the value calculated from the number-based average value. In the case of a molding material, it is possible to determine the number average particle size by observing the surface or cross section, and in the case of a paint composition, the paint composition diluted with a solvent is dropped and dried. It is possible to prepare and observe a sample.

[solvent]
The paint composition A and the paint composition B preferably contain a solvent. The number of types of solvent is preferably one or more and 20 or less, more preferably one or more and ten or less, and still more preferably one or more and six or less. Here, the term "solvent" refers to a substance that is liquid at normal temperature and normal pressure and can be removed from the coating film by evaporating substantially the entire amount in the drying step after application.

Here, the type of solvent is determined by the molecular structure constituting the solvent. That is, those having the same elemental composition and different bonding relations even if the number and type of functional groups are the same (structural isomers), which are not the above-mentioned structural isomers but in any three-dimensional space Those that do not overlap properly (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are treated as different solvents.
[Other additives]
The paint composition A and the paint composition B preferably contain a polymerization initiator, a curing agent, and a catalyst. Polymerization initiators and catalysts are used to accelerate the curing of the surface layer. As the polymerization initiator, those capable of initiating or promoting the polymerization, condensation or crosslinking reaction of the components contained in the paint composition by anion, cation or radical polymerization reaction are preferable.

  Various polymerization initiators, curing agents and catalysts can be used. Further, the polymerization initiator, the curing agent and the catalyst may be used alone, respectively, or a plurality of polymerization initiators, curing agents and catalysts may be used simultaneously. Furthermore, an acidic catalyst, a thermal polymerization initiator or a photopolymerization initiator may be used in combination. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of thermal polymerization initiators include peroxides and azo compounds. Moreover, as an example of a photoinitiator, an alkyl phenone type compound, a sulfur-containing type compound, an acyl phosphine oxide type compound, an amine type compound etc. are mentioned.

  From the viewpoint of curability, the photopolymerization initiator is preferably an alkylphenone compound. Specific examples of the alkylphenone compound 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-cyclohyxyl-phenyl ketone, 2-methyl-1-phenylpropan-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.

  Moreover, if it is a range which does not inhibit the effect of the present invention, you may add a leveling agent, a ultraviolet absorber, a lubricant, an antistatic agent etc. to paint composition A and paint composition B which are used in order to form a surface layer. . Thus, the surface layer can contain a leveling agent, an ultraviolet light absorber, a lubricant, an antistatic agent, and the like. As an example of a leveling agent, an acrylic copolymer or silicone type and a fluorine type leveling agent are mentioned. Specific examples of the ultraviolet absorber include ultraviolet absorbers of benzophenone type, benzotriazole type, anilide oxalate type, triazine type and hindered amine type. Examples of antistatic agents include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts and the like.

[Method of producing laminated film]
The method for producing the laminated film of the present invention is to use a production method in which at least the coating composition A and the coating composition B described above are formed by applying, drying and curing on the supporting substrate mentioned above sequentially or simultaneously. More preferable.

  Here, "apply sequentially" is intended to form a surface layer by applying, drying and curing one kind of coating composition, and then applying, drying and curing different kinds of coating composition. doing. By appropriately selecting the type and the number of coating compositions used in the present manufacturing method, the magnitude and gradient of the elastic modulus of the surface side to the substrate side of the surface layer and the magnitude of the elastic modulus of the substrate and the surface layer are controlled. The form of the elastic modulus distribution in the surface layer can be controlled stepwise or continuously by appropriately selecting the type, composition, drying conditions and curing conditions of the coating composition.

  Another manufacturing method is a method of forming two or more coating compositions by applying, drying and curing "simultaneously" on a support substrate. The number of types of coating compositions is not particularly limited as long as it is two or more. Here, "simultaneously applying" is intended to dry and cure after applying two or more types of liquid films on the support substrate in the application step.

In the present manufacturing method, when the coating composition described above is applied sequentially, 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 a supporting substrate etc. by the above) etc. Moreover, when applying two or more kinds of the above-mentioned paint composition simultaneously, after laminating a liquid film in order in the state before application, "Multilayer slide die coat" to be applied (Fig. 9), "Multilayer slot die coat" to be laminated simultaneously with application on a substrate (Fig. 10), undried state after forming one layer of liquid film on supporting substrate And any one of "wet-on-wet coat" (FIG. 11) or the like in which another layer is laminated.

  Then, the liquid film applied on the support substrate or the like is dried. In addition to completely removing the solvent from the resulting laminated film, it is preferable that the drying step be accompanied by heating of the liquid film.

  As a drying method, heat transfer drying (adhesion to high heat object), convective heat transfer (hot air), radiant heat transfer (infrared ray), others (microwave, induction heating), etc. may be mentioned. 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 precisely make the drying speed uniform even in the width direction.

  Furthermore, a further curing operation (curing step) may be performed by irradiating heat or energy rays. In the curing step, when the coating composition A is cured by heat, the temperature is preferably from room temperature to 200 ° C. or less, more preferably 100 ° C. or more and 200 ° C. or less from the viewpoint of activation energy of the curing reaction More preferably, the temperature is 130 ° C. or more and 200 ° C. or less.

  Moreover, when it hardens | cures with an active energy ray, it is preferable from an versatility point that it is an electron beam (EB beam) and / or an ultraviolet-ray (UV ray). In the case of curing by ultraviolet light, the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing under a nitrogen atmosphere (nitrogen purge) is more preferred. When the oxygen concentration is high, the curing of the outermost surface may be inhibited, the curing of the surface may be insufficient, and the fingerprint resistance may be insufficient.

Moreover, as a kind of ultraviolet ray lamp used when irradiating an ultraviolet-ray, a discharge lamp system, a flash system, a laser system, an electrodeless lamp system etc. are mentioned, for example. 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 the conditions. Here, the illuminance of the ultraviolet light is the irradiation intensity received per unit area, and changes depending on the lamp output, the luminous spectrum efficiency, the diameter of the luminous bulb, the design of the reflecting mirror and the light source distance to the object to be irradiated. However, the illuminance does not change depending on the transport speed. Further, the ultraviolet integrated light quantity is the 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 proportional to the number of times of irradiation and the number of lamp lights.

[Application example]
Since the laminated film of the present invention is excellent in abrasion resistance, it can be widely used, for example, as an interior member of an electric appliance or a car, a building member, and the like.

  For example, glasses / sunglasses, cosmetic boxes, plastic molded articles such as food containers, housings for smartphones, touch panels, keyboards, home appliances such as remote controls for TVs and air conditioners, buildings, dashboards, car navigation / touch panels, rooms The present invention can be suitably used for vehicle interior parts such as mirrors, and surfaces of various printed materials.

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

<Fluorine compound D>
[Fluorine compound D1 methyl ethyl ketone / methyl isobutyl ketone solution]
As the fluorine compound D1, an acrylate compound containing a fluoropolyether moiety ("Megafuck" (registered trademark) RS-75 manufactured by DIC Corporation, a methyl ethyl ketone / methyl isobutyl ketone solution having a solid content concentration of 40% by mass) was used.

<Synthesis of Polysiloxane Compound>
[Polysiloxane (a)]
106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1 mass% hydrochloric acid are introduced into a 500 ml flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet pipe, After holding at ° C for 2 hours, ethanol was recovered while raising the temperature, and held at 180 ° C for 3 hours. Thereafter, it was cooled to obtain a viscous (poly) siloxane (a).

<Synthesis of Polydimethylsiloxane Compound>
[Polydimethyl siloxane block copolymer (a) toluene solution]
50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, (poly) dimethylsiloxane-based high molecular weight polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd. VPS-0501) 20 using the same apparatus as in the synthesis of the polysiloxane (a) Parts by mass, 18 parts by mass of methyl methacrylate, 38 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, 1 part by mass of methacrylic acid and 0.5 parts by mass of 1-thioglycerin are charged and reacted at 180 ° C. for 8 hours As a result, a toluene solution having a solid content concentration of 50% by mass of the polydimethylsiloxane block copolymer (a) was obtained.

[Polydimethyl siloxane compound (b)]
As the polydimethylsiloxane compound (b), EBECRYL 350 (bifunctional silicone acrylate) manufactured by Daicel-Cytec Co., Ltd. was used.

<Synthesis of Urethane Acrylate>
[Toluene solution of urethane acrylate 1]
50 parts by mass of toluene, 50 parts by mass of isocyanurate modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals, Inc.), 76 parts by mass of polycaprolactone modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.), dibutyl tin 0.02 parts by mass of laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and maintained at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate 1 having a solid content concentration of 50% by mass.

[Toluene solution of urethane acrylate 2]
Mix 100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanatohexanoate, and 119 parts by mass of polycarbonate diol (Plaxel CD-210HL, manufactured by Daicel Chemical Industries, Ltd.), and raise the temperature to 40 ° C. I kept it for a while. Then, 28 parts by mass of 2-hydroxyethyl acrylate, 5 parts by mass of dipentaerythritol hexaacrylate and 0.02 parts by mass of hydroquinone monomethyl ether are added and maintained at 70 ° C. for 30 minutes, and then 0.02 parts by mass of dibutyltin laurate In addition, it was kept at 80 ° C. for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate 2 having a solid content of 50% by mass.

[Toluene solution of urethane acrylate 3]
50 parts by mass of an isocyanurate modified product of hexamethylene diisocyanate (Takenate D-170N, manufactured by Mitsui Chemicals, Inc., content of isocyanate group: 20.9 mass%), polyethylene glycol monoacrylate (manufactured by NOF Corporation, Blenmer AE-150 (hydroxyl group A charge of 53 parts by mass of 264 (mg KOH / g), 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were charged, and the reaction was carried out by maintaining at 70 ° C. for 5 hours. After completion, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction liquid to obtain a toluene solution of urethane acrylate 3 having a solid 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 content concentration of 40% by mass.
-Solid concentration 40% by mass of fluorine compound D1-methyl ethyl ketone / methyl isobutyl ketone solution
3.8 parts by mass Solid content concentration of 50% by mass of urethane acrylate 1-50 parts by mass of toluene solution Solid content concentration of 50% by mass of urethane acrylate 3-50 parts by mass of ethylene glycol monobutyl ether-10 parts by mass of light radical 1.5 parts by mass of a polymerization initiator ("IRGACURE" (registered trademark) 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 40% by mass.
Solid content 40% by mass of fluorine compound D1-3.8 parts by mass of methyl ethyl ketone / methyl isobutyl ketone solution-Solid content 50% by mass of urethane acrylate 1-25 parts by mass of toluene solution-Solid content 50 of urethane acrylate 3 % By mass-toluene solution 75 parts by mass-ethylene glycol monobutyl ether 10 parts by mass-photoradical polymerization initiator 1.5 parts by mass ("IRGACURE" (registered trademark) 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 content concentration of 40% by mass.
-Solid concentration 40% by mass of fluorine compound D1-methyl ethyl ketone / methyl isobutyl ketone solution
3.8 parts by mass Solid content concentration of 50% by mass of urethane acrylate 2-75 parts by mass of toluene solution Solid content concentration of 50% by mass of urethane acrylate 3-25 parts by mass of toluene solution-10 parts by mass of ethylene glycol monobutyl ether-Photoradical 1.5 parts by mass of a polymerization initiator ("IRGACURE" (registered trademark) 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 40% by mass.
・ Polycaprolactone polyol 15 parts by mass (Polycaprolactone triol, manufactured by Daicel Chemical Industries, Ltd. Plaxel 308, weight average molecular weight 850)
-Compound having isocyanate group 15 parts by mass (isocyanurate of hexamethylene diisocyanate manufactured by Mitsui Chemicals, Inc. Takenate D-170N)
· Toluene solution with solid content concentration of 50% by mass of polydimethylsiloxane block copolymer (a)
75 parts by mass · Polysiloxane (a) 10 parts by mass · Ethylene glycol monobutyl ether 10 parts by mass.

[Coating composition A5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 having a solid content concentration of 40% by mass.
Polydimethylsiloxane compound (b) 3.8 parts by mass solid content concentration of urethane acrylate 1 50% by mass toluene solution 50 parts by mass solid content concentration of urethane acrylate 3 50% by mass toluene solution 50 parts by mass ethylene glycol 10 parts by mass of monobutyl ether 1.5 parts by mass of a radical photopolymerization initiator ("IRGACURE" (registered trademark) 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 content concentration of 40% by mass.
-Multifunctional urethane acrylate oligomer 100 parts by mass ("SHIKOU" (registered trademark) UV-1700B Nippon Synthetic Chemical Industry Co., Ltd.)
Ethylene glycol monobutyl ether 10 parts by mass Photoradical polymerization initiator 3.0 parts by mass ("IRGACURE" (registered trademark) 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 concentration of 40% by mass.
-Multifunctional urethane acrylate oligomer 50 parts by mass ("purple light" (registered trademark) UV-1700B Nippon Synthetic Chemical Industry Co., Ltd.)
Solid content 50% by mass of urethane acrylate 1 50 parts by mass of toluene solution Solid content 50% by mass of urethane acrylate 3 50 parts by mass of toluene solution 10 parts by mass of ethylene glycol monobutyl ether Photoradical polymerization initiator 1. 5 parts by mass ("IRGACURE" (registered trademark) 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 content concentration of 40% by mass.
-Multifunctional urethane acrylate oligomer 30 parts by mass ("purple light" (registered trademark) UV-1700B Nippon Synthetic Chemical Industry Co., Ltd.)
Solid content 50% by mass of urethane acrylate 1 35 parts by mass of toluene solution Solid content 50% by mass of urethane acrylate 3 35 parts by mass of ethylene glycol monobutyl ether 10 parts by mass photoradical polymerization initiator 5 parts by mass ("IRGACURE" (registered trademark) 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 40% by mass.
-Multifunctional urethane acrylate oligomer 70 parts by mass ("purple light" (registered trademark) UV-1700B Nippon Synthetic Chemical Industry Co., Ltd.)
Solid content concentration of 50% by mass of urethane acrylate 1-15 parts by mass of toluene solution Solid content concentration of 50% by mass of urethane acrylate 3-15 parts by mass of toluene solution-10 parts by mass of ethylene glycol monobutyl ether-Photoradical polymerization initiator 5 parts by mass ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B4 having a solid content concentration of 40% by mass.
・ Multifunctional urethane acrylate oligomer 15 parts by mass (“SHIPO” (registered trademark) UV-1700B Nippon Synthetic Chemical Industry Co., Ltd.)
Solid content 50% by mass of urethane acrylate 1 42.5 parts by mass of toluene solution Solid content 50% by mass of urethane acrylate 3 42.5 parts by mass of toluene solution 10 parts by mass of ethylene glycol monobutyl ether Photoradical polymerization Initiator 1.5 parts by mass ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B6]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B6 having a solid content concentration of 40% by mass.
・ 10-functional urethane acrylate oligomer 70 parts by mass (“purple light” (registered trademark) UV-1700B Nippon Synthetic Chemical Industry Co., Ltd.)
· Surface-modified silica MEK dispersion 37.5 parts by mass (MEK-AC-2140Z solid concentration 40% by mass)
-Ethylene glycol monobutyl ether 10 parts by mass-Photoradical polymerization initiator 1.5 parts by mass ("IRGACURE" (registered trademark) 184 BASF Japan Ltd.).

<Method of manufacturing laminated film>
[Method 1 of forming laminated film by sequential application (two-layer configuration)]
As a supporting substrate, "Lumirror" (registered trademark) U48 (made by Toray Industries, Inc.) having a thickness of 100 μm in which an easily adhesive coating is applied on a PET resin film was used. The paint composition of the lowermost layer is coated by using a continuous coating apparatus with a slot die coater, adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes a specified film thickness, and then under the following conditions A drying step and a curing step were performed to form the lowermost layer.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: Atmosphere.

Furthermore, using the same apparatus, instead of the paint composition of the outermost layer, the discharge flow rate from the slot is adjusted and applied so that the thickness of the surface layer after drying becomes the specified film thickness, and then under the following conditions The drying step and the curing step were performed to obtain a laminated film.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: 200 ppm or less.

[Method 2 for forming a laminated film by sequential application (in the case of a three-layer configuration to a six-layer configuration)]
As a supporting substrate, "Lumirror" (registered trademark) U48 (made by Toray Industries, Inc.) having a thickness of 100 μm in which an easily adhesive coating is applied on a PET resin film was used. The paint composition of the lowermost layer is coated by using a continuous coating apparatus with a slot die coater, adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying becomes a specified film thickness, and then under the following conditions A drying step and a curing step were performed to form the lowermost layer.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: Atmosphere%.

  Next, using the same device, change the layer from the lower second layer to the lowermost layer to the coating composition of each layer so that the thickness of the surface layer after drying becomes the specified thickness. The discharge flow rate from the slot was adjusted and applied, and then the drying step and the curing step were performed under the above conditions.

Furthermore, the outermost layer is changed to the outermost layer paint composition using the same device, and the discharge flow rate from the slot is adjusted and applied so that the thickness of the surface layer after drying becomes the specified thickness, and then The drying step and the curing step were performed under the following conditions to obtain a final laminated film.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: 200 ppm or less.

[Method 3 for forming a laminated film by simultaneous application of multiple layers (application by multilayer slide die coater)]
As a supporting substrate, "Lumirror" (registered trademark) U48 (made by Toray Industries, Inc.) having a thickness of 100 μm in which an easily adhesive coating is applied on a PET resin film was used. The multilayer slide die coater shown in FIG. 9 was used.

  In the multilayer slide die coater shown in FIG. 9, it is necessary to supply the coating composition applied on the side closest to the support base to the upstream side (42 in FIG. 9) in the transport direction in the application step. Discharge from the most upstream slot 38 in the transport direction (= the lowermost slot of the die). On the other hand, the coating composition to be applied on the most surface side needs to be supplied to the most downstream side of the transport direction on the contrary, and is discharged from the most downstream slot 41 (= uppermost slot of die). . The coating composition to be applied to the middle part of the coating composition follows the above order.

Although FIG. 9 shows an example of a device capable of simultaneous application of up to 4 layers, the number of layers is not limited to this. In this preparation method, the designated paint composition is applied from each slot of the multilayer slide die coater by adjusting the discharge flow rate so that the ratio of the designated discharge amount is achieved, and then the drying process and curing are performed under the following conditions The process was carried out to obtain a laminated film.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Irradiation power: 400 W / cm ²
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: 200 ppm or less.

[Method 4 of forming laminated film by simultaneous application of multiple layers (application by multi-layer slot die coater)]
As a supporting substrate, "Lumirror" (registered trademark) U48 (made by Toray Industries, Inc.) having a thickness of 100 μm in which an easily adhesive coating is applied on a PET resin film was used. Using the multi-layered slot die coater shown in FIG. 10, the coating composition B is applied from the slot 45 on the upstream side 47 of the support base of the apparatus in the transport direction and the paint composition from the slot 46 on the downstream side 48 of the support base in the transport direction. The material A was coated by adjusting the discharge flow rate such that the ratio of the discharge amount was specified, and then the drying step and the curing step were performed under the following conditions to obtain a laminated film.
"Drying process"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coated side: 5 m / sec, anti coated side: 5 m / sec Wind direction: coated side: parallel to the surface of the substrate, anti coated side: residence time perpendicular to the surface of the substrate: 2 Minute "hardening process"
Irradiation power: 400 W / cm ²
Integrated light quantity: 120mJ / cm ²
Oxygen concentration: 200 ppm or less.

  The laminated film of Examples 1-17 and Comparative Examples 1-4 was created by the above method. The method for producing the above-mentioned laminated film corresponding to each example and comparative example, the paint composition to be used, and the film thickness of each layer are described in Table 1.

<Evaluation of laminated film>
The performance evaluation shown next was implemented about the produced lamination film, and the obtained result is shown in Table 2, Table 3. Unless otherwise specified, measurement was carried out three times at different locations for one sample in each example and comparative example, and the average value was used.

[Measurement of elastic modulus by atomic force microscope]
Cross sections of the laminated films of Examples 1 to 17 and Comparative Examples 1 to 4 are cut out by a freezing microtome method, and the cross sections are fixed as a measurement surface to a dedicated sample fixing base, AFM manufactured by Asylum Technology "MFP-3DSA-J". Using a cantilever “R150-NCL-10 (material Si, spring constant 48 N / m, radius of curvature at the tip 150 nm)” made by NANOSENSORS and force curve in the contact mode perpendicular to the thickness direction of the surface layer 2 μm / s, maximum indentation load 2 μN) was measured.

  From the Force-Ind curve obtained from the force curve, the software based on the Hertz's theory attached to the software “IgorPro 6.22A MFP3D101010 + 1313” attached to the AFM device is used to obtain the elastic modulus distribution in the thickness direction From the distribution shape, the presence or absence of "a portion where the elastic modulus changes continuously" was determined.

  Note that Tip Geometry = Sphere, Radius = 150 nm, Select = Fused Silica, Tip Tip = 0.17, ETip = 74.9 GPa, Sample Sample = 0.33, Force tab Low = 10%, Force tab High = 90%. Calculated.

Further with respect to the thickness direction, the elastic modulus of 5% from the surface (position A) _(E A), the elastic modulus of 35% position (position _{B) (E B), 65} % of the position (position C) rate _(E C), the modulus of elasticity of 95% position (D) _(E D), calculated modulus of elasticity of the supporting base material _{(E E).} Specifically, the laminated film was cut, and the elastic modulus was measured on the laminated film cross section at each position in the thickness direction.

[Measurement of indentation elastic modulus by nano indenter]
For measurement, a nano indenter “ENT-2100” manufactured by Elionix Co., Ltd. was used. Apply one drop of “Aron Alpha” (trademark) professional shock resistance manufactured by Toho Synthetic Co., Ltd. on the supporting substrate side of the laminated film, and fix the laminated film to a dedicated sample fixing base via the instant adhesive. The measurement was performed with the surface layer side as the measurement surface. For measurement, a triangular pyramidal diamond indenter (Berkovich indenter) having a ridge angle of 115 ° was used. The measurement data were processed by the dedicated analysis software (version 6.18) of "ENT-2100", and the indentation modulus E _IT (MPa) was measured.

Measurement mode: Load-unloading test Maximum load: 100 mN
Holding time when maximum load reached: 1 second Loading speed, unloading speed: 10 mN / sec
[Surface hardness measurement by pencil hardness test method of surface layer]
After the laminated film was left to stand at a temperature of 20 ° C. for 12 hours, the surface hardness of the surface layer was measured in accordance with the scratch hardness (pencil method) described in JIS K 5600-5-4 (1999) in the same environment.

Repeated abrasion resistance due to low hardness material of surface layer
After leaving the laminated film to stand at a temperature of 20 ° C for 12 hours, attach the whitenel cloth (made by No. 600 Kowa Co., Ltd.) to the tip (tip area of 1 cm ² ) of the eraser abrasion tester manufactured by KOKO SEIKO in the same environment. Apply a load of 4.9 N (500 g) on the antireflective member 5 cm, 5,000 cycles, and a load of 9.8 N (1,000 g) on the laminated film 5 cm, 200 cycles of friction The following classifications were made. The evaluation was performed five times for each sample, and the average point was rounded to one decimal place.
10 points: no scratch 7 points: 1 to 10 flaws 4 points: 11 to 20 flaws 1 point: The surface layer of the test part is completely peeled off.

Self-healing property of surface layer
After leaving the laminated film to stand at a temperature of 20 ° C. for 12 hours, the surface of the surface layer is scratched horizontally five times under the same load with a brass brush (made by TRUSCO) in the same environment, and then left to stand for 5 minutes Wound recovery was visually judged according to the following criteria. The evaluation was performed five times for each sample, and the average point was rounded to one decimal place.
10 points: no load remains at a load of 9.8 N (1 kg) 7 points: a scratch remains at a load of 9.8 N (1 kg), but no damage remains at 6.9 N (700 g) 4 points: a load of 6.9 N ( Wounds remain at 700 g) but not at 4.9 N (500 g). One point: Wounds remain at a load of 4.9 N (500 g).

[Seal resistance of surface layer]
After leaving the laminated film to stand at a temperature of 20 ° C. for 12 hours, put the following weight on the surface of the surface layer in a brass brush (made by TRUSCO) in the same environment, and let it stand for 1 minute. Judgment was made by visual inspection. The evaluation was performed five times for each sample, and the average point was rounded to one decimal place.
10 points: weight 9.8 N (1 kg) and no marks are left 7 points: weight 9.8 N (1 kg) leaves marks but 6.9 N (750 g) marks no marks 4 points: weight 6 .9 N (750 g) remains an indentation, but 4.9 N (500 g) does not leave an indentation 1 point: A weight remains 4.9 N (500 g) and an indentation remains.

  The evaluation results of the finally obtained laminated film are summarized in the table.

1, 19, 24: surface layer 2, 20, 23: support substrate 21, 22, 25, 26, 27, 28: layer 3, 10: measurement position of elastic modulus (position A)
4, 11: Measurement position of elastic modulus (position B)
5, 12: Measurement position of elastic modulus (position C)
6, 13: Measurement position of elastic modulus (position D)
7: Measurement position of elastic modulus (position E)
16: Difference in elastic modulus between position A and position B (E _B -E _A )
17: Difference in elastic modulus between position B and position C (E _C -E _B )
18: Difference in elastic modulus between position C and position D (E _D −E _C )
29: a portion 30 where the slope of the elastic modulus with respect to the surface layer thickness is infinite 30: a portion where the slope of the elastic modulus with respect to the surface layer thickness is 0 33: a portion where the elastic modulus changes with a finite slope 36: the elastic modulus is finite over the entire area Varying part 37: Multilayer slide die 38, 45: most upstream slot 39, 46: second from the upstream slot 40: third from the upstream slot 41: most downstream slot 42 47, 51: Upstream side 43, 48, 52 of the transport direction of the support substrate: Downstream side 44 of the transport direction of the support substrate: Multilayer slot die 49, 50: Single layer slot die 53: Loading step 54: Unloading Process

  The laminated film according to the present invention can also be used to impart the same function to the surfaces of plastic molded articles, home appliances, buildings, vehicle interiors and various printed materials.

Claims (7)

In a laminated film in which a surface layer consisting of at least one or more layers is formed on a supporting substrate,
From the surface of the surface layer to the surface layer thickness 5% (hereinafter referred to as position A), 35% (hereinafter referred to as position B), 65% (hereinafter referred to as position C), 95% (hereinafter referred to as position D and in the cross section of each position of that), the elastic modulus _E a by atomic force _{microscopy, E B, E C, E} D the following conditions 1 and 2, meets all the conditions 3,
The surface layer is a layer obtained by curing urethane acrylate,
The resin constituting the surface side of said surface layer is characterized Succoth satisfy the condition 7 below, the laminated film.
Condition 1 E _A ≦ E _B ≦ E _C <E _D
Condition 2 E _A is 100 MPa or less Condition 3 E _D is 1 GPa or more
Condition 7 A segment having at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment is included. The laminated film according to claim 1, wherein the elastic modulus E _A , E _B , E _C , E _D satisfy the following condition 4:
Condition 4 (E _C -E _B ) <(E _B -E _A )
And (E _D -E _C ) <(E _B -E _A ) And the elastic modulus E _D at position D of the surface layer, and satisfies the condition 5 of the elastic modulus E _E of the supporting substrate below, laminated film according to claim 1 or claim 2.
Condition 5 | E _D −E _E | <1 GPa The laminated film according to any one of claims 1 to 3, wherein the surface layer is formed of two or more layers having different elastic moduli. The laminated film according to any one of claims 1 to 4, wherein the surface layer satisfies the following condition 6.
Condition 6 The indentation elastic modulus E _IT of the surface layer in the nanoindentation measurement in the thickness direction under the condition of maximum load 100 mN: 2,000 MPa or more The surface layer is formed by sequentially applying, drying and curing two or more types of coating compositions on a supporting substrate, according to any one of claims 1 to 5, Method of manufacturing laminated film. The laminate according to any one of claims 1 to 5, wherein the surface layer is formed by simultaneously applying, drying and curing two or more paint compositions on a support substrate. How to make a film.