JP6911648B2 - Laminated film - Google Patents

Description

The present invention relates to a laminated film having excellent flexibility, scratch resistance, and antifouling property.

In molding materials such as decorative molding, a surface hardening layer is provided in order to prevent scratches during molding and to prevent scratches in the process of using the article after molding. However, since the surface-hardened layer does not have sufficient elongation to follow molding, cracks occur during molding, the film breaks in extreme cases, and the surface-hardened layer peels off, which is generally the case. A means such as forming a surface hardening layer after molding, molding in a semi-cured state, and then completely curing by heating or irradiation with active rays is applied. However, since the article after molding is processed three-dimensionally, it is very difficult to provide a surface hardness layer in the post-processing, and when molding in a semi-cured state, depending on the molding conditions, the mold may be used. May induce dirt. From the above points, scratch-resistant materials that follow molding are desired, and "self-healing materials" that can self-repair minor scratches by deforming their own elastic recovery range are attracting attention, and Patent Documents 1 and 2 have been proposed. ing.

On the other hand, from the viewpoint of energy cost reduction and environmental load reduction, it is required that the coating can be performed at room temperature when the coating is performed with a surface protection film for protecting the surface of the article. Therefore, it is important that the surface protection film is sufficiently flexible even at room temperature.

As a surface protection film that is flexible even at room temperature, Patent Document 3 states, "A film used for the exterior of automobiles, a base material of an olefin resin having an adhesive function, and a two-component urethane supported by the base material. An automobile exterior component made of an olefin resin, which comprises a resin topcoat layer, and the base material and the topcoat layer are directly adjacent to each other without interposing another layer. A film for automobile exterior, which is a film to be attached to the base material, and the base material is coated with the top coat layer, and then a carrier film is laminated on the surface of the top coat layer. " , Patent Document 4 states, "A first layer containing a polyurethane, the polyurethane being a polyester-based polyurethane, a polycarbonate-based polyurethane, or a combination thereof, a second layer containing a polycaprolactone-based thermoplastic polyurethane, and A PSA layer containing a pressure sensitive adhesive is included, the first layer is bonded to one main surface of the second layer, and the PSA layer is bonded to the opposite main surface of the second layer. , The paint protective multilayer film in which the second layer is sandwiched between the first layer and the PSA layer and protects the painted surface of the vehicle body portion of the vehicle. "

International Publication No. 2011/136042 Pamphlet Japanese Patent No. 3926461 Japanese Patent No. 4225730 Japanese Patent No. 5426159

As for the techniques of Patent Document 1 and Patent Document 2 proposed as the above-mentioned self-healing materials, the present inventors confirmed that they had self-healing properties, but their antifouling properties were insufficient.

Further, the technique of Patent Document 1 has insufficient flexibility at room temperature and is not suitable for use as a surface protection film at room temperature. Regarding the technique of Patent Document 2, there is no concept used for the surface protection film, and it is not assumed that the film is coated at room temperature.

Regarding the techniques of Patent Document 3 and Patent Document 4, although they showed a certain degree of flexibility at room temperature, their scratch resistance and antifouling property were insufficient.

Therefore, an object of the present invention is to provide a laminated film having excellent flexibility, scratch resistance, and antifouling property.

In order to solve the above problems, the present inventors have completed the following inventions as a result of repeated diligent research. That is, the present invention is as follows.
<1>
A laminated film having a surface layer containing an acrylic resin as a constituent on at least one of a supporting base material containing polyurethane as a constituent, which satisfies the following conditions 1 and 2.
Condition 1: The 100% strain stress F _{100 of the} laminated film is 20 MPa or less.
Condition 2: The receding contact angle of the surface layer in pure water is 75 ° or more.
<2>
The laminated film according to <1>, which satisfies the following condition 3.
Condition 3: The following equations 1 and 2 hold for _{the glass transition temperature T g1} (K) of the surface layer and the glass transition temperature T _{g2 (K) of the supporting base material.}
233 ≤ T _g1 ≤ 313 (Equation 1)
T _g1 / T _g2 ≤ 1.15 (Equation 2)
<3>
The laminated film according to <1> or <2>, which satisfies the following condition 4.
Condition 4: The storage elastic modulus of the surface layer at 298 K is 1,000 MPa or less.
<4>
The laminated film according to any one of <1> to <3>, wherein the adhesive layer is provided on a surface opposite to the surface of the support base material having the surface layer.
<5>
The laminated film according to any one of <1> to <4>, which is used as a surface protective film.

According to the present invention, a laminated film having good flexibility, scratch resistance, and antifouling property can be obtained.

This is an example of a laminated body in the present invention. It is sectional drawing which shows an example of the method of forming a surface layer in this invention. It is sectional drawing which shows an example of the method of forming a surface layer in this invention. It is sectional drawing which shows an example of the method of forming a surface layer in this invention.

Before explaining the embodiment of the present invention, the problems of the prior art, that is, flexibility, scratch resistance, and antifouling property, will be considered from the viewpoint of the present inventor.

[Comparison between the present invention and the prior art]
First, the reason why the self-healing materials of the prior art described in Patent Document 1 and Patent Document 2 cannot achieve both scratch resistance and antifouling property is that the prior art makes the coating film flexible, so that the cross-linking in the coating film is performed. Self-healing is obtained by lowering the density of the structure (hereinafter referred to as the crosslink density). However, as a side effect, it is considered difficult to prevent permeation into the inside when a harsh dirt component adheres to the surface. Further, when combined with a so-called antifouling additive such as a water-repellent additive or an oil-repellent additive, the crosslink density in the coating film is reduced, so that the antifouling additive can be immobilized on the surface. It is probable that it became difficult and it became difficult to impart antifouling properties. Further, since these are not supposed to be coated on the surface of an article at room temperature, there is a problem that they are not flexible enough to be deformed at room temperature and are not suitable for use as a surface protective film at room temperature. rice field.

Further, the techniques described in Patent Documents 3 and 4 show a certain degree of flexibility at room temperature, but since these techniques also reduce the crosslink density in the coating film, they have antifouling properties for the same reason as described above. It is probable that it was difficult to grant. In addition, although it showed a certain effect on scratch resistance, it could not be said to be sufficient. In order to impart flexibility to the laminated film as a whole, a flexible material is used for the supporting base material, but the amount of deformation of the entire laminated film becomes large when a load is applied, and the surface layer and the supporting base material also become large. It is probable that the scratch resistance was insufficient when a harsh load was applied because the deformation behavior of the film was different.

Therefore, the present inventors have considered the optimum configuration in advancing the study of a surface protective film that is preferably used at room temperature. It is effective that the supporting base material contains polyurethane resin as a constituent component in order to impart flexibility at room temperature, and further, in order to achieve both antifouling property, the surface layer should contain acrylic resin as a constituent component. Found to be valid. This is because the entire laminated film has flexibility because the supporting base material is made of a flexible polyurethane resin, and the surface layer is made of an acrylic resin having a relatively high crosslink density, so that the stain component is removed. This is due to the effect of suppressing penetration into the surface layer and improving antifouling properties. In addition, since the cross-linking density of the surface layer is relatively high, when the antifouling additive is combined with the surface layer, the effect of immobilizing the antifouling additive on the surface becomes stronger, and there is an effect of raising the antifouling property. I think it was.

In the surface protective film, which is a suitable application of the laminated film of the present invention, it is important that the laminated film is sufficiently flexible and can be deformed and followed even if the article to be protected has a complicated shape. In particular, from the viewpoint of energy cost reduction and environmental load reduction, when the surface of an article is coated with the laminated film of the present invention, it is preferable that the coating can be performed at room temperature without any special equipment. As a result of verification by the present inventors, it was found that the above coating is possible by making the laminated film more flexible than a certain level.

Specifically, it is preferable that the 100% strain stress of the laminated film is set to a value of a certain value or less.

Furthermore, the present inventors paid attention to the movement of the stain component adhering to the surface layer when examining the antifouling property of the laminated film. Flexible materials, such as self-healing materials, are relatively more susceptible to dirt components such as oil than hard materials, and may have insufficient antifouling properties against harsh dirt. Therefore, it is effective to quickly remove the dirt component from the surface before it penetrates, but simply improving the contact angle (= static contact angle) of the surface does not necessarily correspond to the improvement of antifouling property. There wasn't. Therefore, as a result of focusing on the dynamic behavior of the dirt component, it was found that controlling the dynamic contact angle of the surface is effective in improving the antifouling property. In particular, it was found that by controlling the receding contact angle, the dirt component can be removed before it penetrates into the surface layer, which is effective in improving the antifouling property.

Specifically, it is preferable that the receding contact angle of the surface layer is set to a value equal to or higher than a certain value.

Further, in pursuing improvement in scratch resistance, the present inventors focused on the characteristics of the surface layer. It is effective to apply a self-healing material to the surface layer in order to achieve both flexibility and scratch resistance, but in order to exhibit self-healing property, the glass transition temperature of the surface layer should be kept within a certain range. Is valid. The glass transition temperature shows the temperature dependence of the mechanical properties, and by setting the glass transition temperature within a certain range, it is possible to have good deformability and restoration of the surface layer at daily operating temperatures, and as a result, It becomes possible to develop self-repairing property. The lower the glass transition temperature of the surface layer, the better the deformability and resilience of the surface layer at the daily operating temperature, and therefore the effect of self-healing property is improved. On the other hand, when the glass transition temperature of the surface layer is extremely low, the deformability of the surface layer becomes too large, and the surface layer may be deformed beyond restoration. Further, when the glass transition temperature of the surface layer is extremely low, the surface layer becomes sticky, which may not be preferable as a film for protecting the surface of an article, which is one of the uses of the present invention. Therefore, as a result of detailed verification by the present inventors, it was concluded that it is preferable to keep the glass transition temperature of the surface layer within a certain range as described above.

Here, we focused on the behavior of the surface layer and the supporting base material with respect to deformation. As a result of pursuing the response to each load, it was found that the scratch resistance can be further improved by setting the relationship between the glass transition temperature of the surface layer and the supporting base material within a certain range. Originally, imparting scratch resistance by self-healing is the performance expected of the surface layer, but by suppressing the difference in glass transition temperature between the surface layer and the supporting base material within a certain range, the entire laminated film is deformed with respect to the load. It is thought that the restoration is possible, and as a result, the self-repairing effect can be exhibited in the entire laminated film. Due to this effect, it is possible to significantly improve the scratch resistance as compared with the configuration in which the surface layer is composed of an acrylic resin as a constituent component and the supporting base material is composed of a polyurethane resin as a constituent component.

Specifically, it is preferable that the glass transition temperature of the surface layer and the glass transition temperature of the supporting base material satisfy the formulas described below.

Furthermore, in examining the scratch resistance of the laminated film, the present inventors focused on the response to the load of the surface layer. When the surface layer receives an external load, its mechanical response depends on the viscoelastic properties described above. In a material with low loss tangent, that is, a material with strong elastic properties, most of the load is stored by mechanical energy, so if the load is large, the storage range will be exceeded and the material will be destroyed. In such a case, the surface layer may be scratched and the scratch resistance may be insufficient. On the other hand, in a material having a high loss tangent, that is, a material having a strong viscous property, the effect of releasing the load as loss energy, that is, heat energy is large, and the stored mechanical energy is relatively small. Therefore, even if the load is large, there is a high possibility that the material will fall below the storable range, and the material will not be easily destroyed. As a result, the occurrence of scratches on the surface layer can be suppressed, and the scratch resistance is excellent.

From the above, as a method of increasing the loss tangent of the surface layer, there is a method of lowering the storage elastic modulus, and lowering the storage elastic modulus is preferable because the scratch resistance of the surface layer is improved.

Specifically, it is preferable that the storage elastic modulus of the surface layer is set to a certain value or less.

Further, since the laminated film of the present invention has an adhesive layer on the surface opposite to the surface having the surface layer of the supporting base material, the laminated film can be easily attached to the surface of the article. In other words, having an adhesive layer enables bonding even at room temperature, which is preferable because a special device is not required to protect the surface of the article. Further, since the laminated film of the present invention has sufficient flexibility even at room temperature, it can follow a complicated article shape even at room temperature, and is preferable because it can be applied to various articles.

[Mode of the present invention]
Hereinafter, embodiments of the present invention will be specifically described.

In order to satisfy the above-mentioned problems, that is, flexibility, scratch resistance, and antifouling property, the laminated film of the present invention has a surface layer containing an acrylic resin as a constituent on at least one of a supporting base material containing polyurethane as a constituent. It is a laminated film having, and is characterized by satisfying the following conditions 1 and 2.
Condition 1: 100% strain stress F _{100 of the} laminated film is 20 MPa or less Condition 2: The receding contact angle of the surface layer in pure water is 75 ° or more 100% strain stress F ₁₀₀ and the method of measuring the receding contact angle will be described later.

From the viewpoint of scratch resistance, flexibility, and antifouling property, it is preferable that the surface layer contains an acrylic resin as a constituent component and the supporting base material contains a polyurethane resin as a constituent component.

When the supporting base material contains a polyurethane resin as a constituent component, the flexibility of the laminated film is improved, so that sufficient flexibility can be imparted even at room temperature.

Here, when the supporting base material contains polyurethane as a constituent component, it means that the supporting base material contains polyurethane, and when the entire supporting base material is 100% by mass, it is more preferable to contain 60% by mass or more of polyurethane. It is more preferable to contain 70% by mass or more. Similarly, when the surface layer contains an acrylic resin as a constituent component, it means that the surface layer contains an acrylic resin, and when the entire surface layer is 100% by mass, it is more preferable to contain 60% by mass or more of the acrylic resin. It is more preferable to contain 70% by mass or more.

When the surface layer contains an acrylic resin as a constituent component, the antifouling property of the laminated film can be improved. From the viewpoint of flexibility, the laminated film of the present invention _{preferably has a 100% strain stress F 100} of 20 MPa or less, more preferably 15 MPa or less. Here, the 100% strain stress F ₁₀₀ is an index showing the flexibility of the laminated body, and the smaller the value, the higher the flexibility.

When the 100% strain stress F ₁₀₀ is 20 MPa or less, the flexibility is improved, which is preferable. On the other hand, if F ₁₀₀ is larger than 20 MPa, the flexibility may be insufficient.

In order to make the 100% strain stress F ₁₀₀ 20 MPa or less, for example, it is possible to use a polyurethane resin as a constituent component for the supporting base material.

From the viewpoint of antifouling property, the laminated film of the present invention preferably has a receding contact angle of the surface layer of 75 ° or more, more preferably 80 ° or more, and particularly preferably 85 ° or more. The receding contact angle correlates with the antifouling property, and the antifouling property can be enhanced by setting the receding contact angle to a specific value.

When the receding contact angle takes a constant value, the effect of repelling dirt components such as oil is increased, so that the antifouling property is improved, which is preferable. If the receding contact angle is smaller than 75 °, the antifouling property may be insufficient.

In order to set the receding contact angle to 75 ° or more, for example, it is possible to use an acrylic resin as a constituent component in the surface layer and use a water-repellent additive or an oil-fueling additive.

Further, from the viewpoint of scratch resistance, it is preferable that the laminated film satisfies the following condition 3.
Condition 3: The following equations 1 and 2 hold for _{the glass transition temperature T g1} (K) of the surface layer and the glass transition temperature T _{g2 (K) of the supporting base material.}
233 ≤ T _g1 ≤ 313 (Equation 1)
T _g1 / T _g2 ≤ 1.15 (Equation 2)
The method for measuring the glass transition temperature will be described later.

From the viewpoint of scratch resistance, the glass transition temperature T _g1 of the surface layer, the glass transition temperature T _g2 of the supporting substrate preferably satisfies Equations 1 and 2. Equations 1 and 2 have a correlation with scratch resistance, and the scratch resistance can be enhanced by satisfying these equations.

When the formula 1 is satisfied, as described above, the flexibility of the surface layer is improved and the effect of self-repair is increased, so that the scratch resistance can be improved, which is preferable. If the formula 1 is not satisfied, the above effect may be insufficient and the scratch resistance may be insufficient.

Regarding the formula 1, the _{smaller the glass transition temperature T g1} of the surface layer, the greater the effect of self-repair, which is preferable because the scratch resistance is improved. The _{smaller the T g1, the} greater this effect, but if it is extremely low, the rigidity may be insufficient and the scratch resistance may be lowered, or the surface layer may become sticky, which may be unfavorable. Therefore, _{as a preferable range of T g1} , the upper limit is 313K and the lower limit is 233K.

When the formula 2 is satisfied, as described above, the followability of the surface layer and the supporting base material is improved, so that the scratch resistance can be improved, which is preferable. If the formula 2 is not satisfied, the above effect may be insufficient and the scratch resistance may be insufficient.

In order to satisfy the formulas 1 and 2, for example, it is possible to combine the materials used for the surface layer and the supporting base material according to the target glass transition temperature, or to select a known material.

Further, from the viewpoint of scratch resistance, it is preferable that the laminated film satisfies the following condition 4.

Condition 4: The storage elastic modulus of the surface layer at 298 K is 1,000 MPa or less The method for measuring the storage elastic modulus will be described later.

From the viewpoint of scratch resistance, the laminated film of the present invention preferably has a storage elastic modulus of the surface layer of 1,000 MPa or less, more preferably 500 MPa or less, and particularly preferably 200 MPa or less. The storage elastic modulus has a correlation with the scratch resistance, and the scratch resistance can be enhanced by setting the storage elastic modulus to a value below a certain level.

When the storage elastic modulus takes a value of a certain value or less, the effect of self-repair is increased, so that the scratch resistance is improved, which is preferable. If the storage elastic modulus is larger than 1,000 MPa, the self-repairing effect may be insufficient and the scratch resistance may be insufficient.

In order to reduce the storage elastic modulus to 1,000 MPa or less, for example, (Equation 1) can be satisfied.

Further, from the viewpoint of using the laminated film of the present invention as a surface protective film, it is preferable that the laminated film has an adhesive layer on a surface opposite to the surface of the supporting base material having the surface layer. Details of the adhesive layer will be described later.

When the laminated film of the present invention has an adhesive layer on the surface opposite to the surface having the surface layer of the supporting base material, the laminated film can be easily attached to the surface of the article. In other words, having an adhesive layer enables bonding even at room temperature, which is preferable because a special device is not required to protect the surface of the article. Further, since the laminated film of the present invention has sufficient flexibility even at room temperature, it can follow a complicated article shape even at room temperature, and is preferable because it can be applied to various articles.

[Laminated film and surface layer]
The laminated film of the present invention may be in a flat state or in a three-dimensional shape after being molded as long as it has a surface layer exhibiting the above-mentioned physical characteristics. The number of layers of the surface layer is not particularly limited, and may be formed from one layer or may be formed from two or more layers.

The thickness of the surface layer is not particularly limited, but the lower limit thereof is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more. The upper limit thereof is preferably 100 μm or less, more preferably 50 μm or less, further preferably 40 μm or less, and particularly preferably 30 μm or less. The thickness of the surface layer can be selected according to the other functions described above.

In the present invention, from the viewpoint of flexibility, scratch resistance and antifouling property, it is preferable that the surface layer contains an acrylic resin as a constituent component. In order for the surface layer to contain an acrylic resin as a constituent component, for example, the coating composition used to form the surface layer contains an acrylic resin or is a precursor of an acrylic resin typified by acrylate / methacrylate. It is possible by including the substance that becomes.

In addition to the self-healing property, scratch resistance, and antifouling property, which are the subjects of the present invention, the surface layer has gloss, fingerprint resistance, moldability, design property, adhesion durability, antireflection, antistatic property, and conductivity. , Heat ray reflection, near infrared ray absorption, electromagnetic wave shielding, easy adhesion and the like.

[Supporting base material]
The supporting base material in the present invention preferably contains a polyurethane resin as a constituent component. When the resin constituting the supporting base material is a polyurethane resin, it has good flexibility and can be sufficiently deformed even at room temperature. Further, the polyurethane resin is more preferably a thermoplastic polyurethane resin from the viewpoint of strength, heat resistance and transparency. Further, since the polyurethane resin has thermoplasticity, the deformability is further improved by heating, so that it is possible to deform even a very complicated shape, which is preferable.

Further, the support base material may contain a resin other than the polyurethane resin as a constituent resin, and the resin constituting the support base material may be either a thermoplastic resin or a thermosetting resin, or may be a homo resin. It may be copolymerized or a blend of two or more kinds. The resin constituting the support base material is more preferably a thermoplastic resin because it has good moldability.

Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyimide resins, polyester resins, and polycarbonate resins. Fluorine such as polyallylate resin, polyacetal resin, polyphenylene sulfide resin, ethylene tetrafluoride resin, ethylene trifluoride resin, ethylene trifluoride chloride resin, ethylene tetrafluoride-6 fluoride copolymer, vinylidene fluoride resin, etc. Resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins and the like can be used. As an example of the thermosetting resin, a phenol resin, an epoxy resin, a urea resin, a melamine resin, an unsaturated polyester resin, a polyimide resin, a silicone resin and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability.

The method for forming the support base material is not particularly limited, but as a method for forming the support base material containing a polyurethane resin as a constituent component, a melt film forming method in which a urethane resin is melted into a film shape, or a urethane resin is dissolved in a solvent. Examples thereof include a solution film forming method in which the solvent is volatilized after forming the film into a film shape, and a coating method in which the polyol and isocyanate are dissolved in a solvent, coated on another film and polymerized to form a film shape. Further, in the case of the solution film forming method or the coating method, the supporting base material and the surface layer can be formed at once in one manufacturing process by combining with the multi-layer slide die coat, the multi-layer slot die coat and the wet-on-wet coat described later. Is also possible.

In addition, various additives such as antioxidants, antioxidants, crystal nucleating agents, inorganic particles, organic particles, thickeners, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, etc. A dope for adjusting the refractive index or the like may be added. The supporting base material 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 base material before forming the surface layer. Examples of surface treatments include chemical treatments, mechanical treatments, corona discharge treatments, flame treatments, ultraviolet irradiation treatments, high frequency treatments, glow discharge treatments, active plasma treatments, laser treatments, acid mixture treatments and ozone oxidation treatments. 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.

The supporting base material A used in the present invention includes "Silklon" (registered trademark) series (Okura Industrial Co., Ltd.), "Higres" (registered trademark) series (Seadam Kasei Co., Ltd.), and "Esmer" (registered trademark) series. A product such as (Nihon Matai Co., Ltd.) can be preferably exemplified.

[Paint composition]
The method for producing the laminated film of the present invention is not particularly limited, but the laminated film of the present invention has a step of applying a coating composition to at least one of the above-mentioned supporting substrates, a step of drying and a step of curing as necessary. Can be obtained through. Here, the "paint composition" is a liquid composed of a solvent and a solute, and is a material capable of forming a surface layer by applying it on the above-mentioned supporting base material and volatilizing, removing, and curing the solvent in a drying step. 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 solutes are resins or materials (hereinafter referred to as precursors), particles, and polymerization initiators, hardeners, catalysts, leveling agents, UV absorbers, antioxidants, etc. that can form them in the coating process. It consists of various additives.

Further, in the laminated film of the present invention, it is preferable to use the coating composition A and apply it on a supporting base material to form a surface layer.

[Paint composition A]
The coating composition A is a liquid containing a material suitable for forming the surface layer of the present invention or containing a precursor that can be formed, and is a liquid containing a precursor of an acrylic resin typified by an acrylic resin or acrylate / methacrylate. It is preferable to contain the above-mentioned substance.

Further, from the viewpoint of scratch resistance, antifouling property and flexibility, the coating composition A preferably contains a resin or a precursor containing the following segments (1) to (3) as a solute.
(1) A segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment and a polyalkylene glycol segment (2) A urethane bond (3) A group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment. A segment containing at least one selected.

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

Further, the mass parts of the above (1), (2) and (3) contained in the coating composition A are (1) / (2) / (3) = 95/5/1 to 50/50/15. Is preferable, and (1) / (2) / (3) = 90/10/1 to 60/40/10 is more preferable. Hereinafter, details of (1), (2), and (3) will be described.

The acrylic resin and the resin constituting the precursor of the acrylic resin may exist independently of the above (1), (2) and (3), or may be copolymerized. In the case of copolymerization, as described later, polycaprolactone-modified hydroxyethyl (meth) acrylate may be used, polyalkylene glycol (meth) acrylate having an acrylate group at the terminal may be used, or a compound containing an isocyanate group and a polycarbonate may be used. It can be exemplified that the hydroxyl group of the diol is reacted and used as a urethane (meth) acrylate.

Details of the (1) polycaprolactone segment, polycarbonate segment, and polyalkylene glycol segment will be described later, but the resin constituting the A layer on the surface of the surface layer has these segments, so that the surface layer has self-healing properties. The scratch resistance can be improved, and the repeated scratch resistance can be improved.

The details of the urethane bond will be described later, but when the resin constituting the A layer on the surface of the surface layer has this bond, the toughness of the entire surface layer can be improved.

The details of the fluorine compound segment will be described later, but 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 scratch resistance of the surface is improved. ..

[Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]
First, the polycaprolactone segment refers to the segment represented by Chemical Formula 1. Polycaprolactone also includes oligomers with caprolactone repeating units such as 1 (monomer), 2 (dimer) and 3 (trimer), and caprolactone repeating units up to 35.

n is an integer from 1 to 35.

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

As the resin containing the polycaprolactone segment, polycaprolactone having a 2-3 functional hydroxyl group is particularly preferable. Specifically, the polycaprolactone diol represented by Chemical Formula 2

Here, m + n is an integer of 4 to 35, m and n are integers of 1 to 34, respectively, and R is C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ or C (CH ₃ ) ₃ (CH ₂ ) _2.
Or the polycaprolactone triol represented by Chemical Formula 3,

Here, l + m + n is an integer of 3 to 30, l, m, and n are integers of 1 to 28, respectively, and R is CH ₂ CHCH ₂ , CH ₃ C (CH ₂ ) ₃ or CH ₃ CH ₂ C (CH ₂ ). ₃
Polycaprolactone polyol such as, or polycaprolactone-modified hydroxyethyl (meth) acrylate represented by Chemical Formula 4.

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

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

Further, 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 the more preferable weight average molecular weight is 1,000 to 1,500. .. When the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, the self-healing effect is more exhibited, the scratch resistance is improved, and the repeated scratch resistance is further improved, which is preferable.

Next, the polyalkylene glycol segment refers to the segment represented by Chemical Formula 5. The polyalkylene glycol also includes oligomers having a repeating unit of alkylene glycol up to 2 (dimer) and 3 (trimer), and an oligomer having a repeating unit of alkylene glycol up to 11.

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

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

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

Examples of the polyalkylene glycol (meth) acrylate contained in the coating composition used for forming 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 formulas 6, 7, and 8, respectively.

Polyethylene glycol (meth) acrylate:

Polypropylene glycol (meth) acrylate:

Polybutylene glycol (meth) acrylate:

In Chemical Formula 6, Chemical Formula 7, and Chemical Formula 8, R is _{an integer such that hydrogen (H) or a methyl group (-CH 3} ), and m is 2-11.

In the present invention, a resin constituting the surface layer is preferably used as a urethane (meth) acrylate by reacting a compound containing an isocyanate group, which will be described later, with a hydroxyl group of (poly) alkylene glycol (meth) acrylate. However, it is preferable because it can have (2) urethane bond and (3) (poly) alkylene glycol segment, and as a result, the toughness of the surface layer can be improved and the self-healing property can be improved.

Hydroxyalkyl (meth) acrylates that are simultaneously blended during the urethanization reaction between the isocyanate group-containing compound and the polyalkylene glycol (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl. (Meta) acrylate and the like are exemplified.

Next, the polycarbonate segment refers to the segment represented by Chemical Formula 9. Polycarbonate also includes oligomers with carbonate repeating units such as 2 (dimer) and 3 (trimer), and carbonate repeating units up to 16.

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

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

As the resin containing the polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferable. Specifically, it is represented by the chemical formula 10.
Polycarbonate diol:

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

The number of repetitions of the carbonate unit may be any number for the polycarbonate diol, but if the number of repetitions of the carbonate unit is too large, the strength of the cured product of urethane (meth) acrylate decreases, so the number of repetitions should be 10 or less. Is preferable. The polycarbonate diol may be a mixture of two or more kinds of polycarbonate diols having different numbers of repetitions of the carbonate unit.

The polycarbonate diol preferably has a number average molecular weight of 500 to 10,000, and more preferably 1,000 to 5,000. If the number average molecular weight is less than 500, it may be difficult to obtain suitable flexibility, and if the number average molecular weight exceeds 10,000, heat resistance and solvent resistance may decrease. Is.

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

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

In the present invention, preferably, the resin constituting the surface layer is prepared by reacting a compound containing an isocyanate group, which will be described later, with a hydroxyl group of a polycarbonate diol and using it as a urethane (meth) acrylate in the surface layer (2). It can have urethane bonds and (1) polycarbonate diol segments, and as a result, the toughness of the surface layer can be improved and the self-healing property can be improved.

[Compounds containing urethane bonds and isocyanate groups]
In the present invention, the "urethane bond" refers to the bond represented by the chemical formula 11.

When the resin constituting the surface layer has this bond, the toughness of the entire surface layer can be improved.

When the coating composition A contains a commercially available urethane-modified resin, the resin constituting the surface layer can have a urethane bond. Further, when forming 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 generate a urethane bond to form a surface layer. Can also contain a urethane bond.

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

Further, a resin containing the above-mentioned polycaprolactone segment, polycarbonate segment, and polyalkylene glycol segment, or when having a hydroxyl group, a urethane bond is formed between these resin and a compound containing an isocyanate group as a precursor by heat or the like. It is also possible to let it.

When a surface layer is formed using a compound containing an isocyanate group, a resin containing a polysiloxane segment having a hydroxyl group, which will be described later, or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the toughness and self-repair of the surface layer are achieved. In addition to the property, the slipperiness of the surface can be enhanced, and it is more preferable from the viewpoint of resistance to repeated scratching.

In the present invention, the isocyanate group-containing compound refers to a resin containing an isocyanate group, a monomer or an oligomer containing an isocyanate group. Compounds containing an isocyanate group include, for example, methylenebis-4-cyclohexylisocyanate, trimethylalopropane adduct of tolylene diisocyanate, trimethylalopropane adduct of hexamethylene diisocyanate, trimethylalopropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Examples thereof include an isocyanurate form, an isocyanurate form of hexamethylene diisocyanate, a (poly) isocyanate such as a burette form of hexamethylene isocyanate, and a block form of the above-mentioned isocyanate.

Among these isocyanate group-containing compounds, aliphatic isocyanates are preferable because they have high self-healing properties, as compared with alicyclic and aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. As the compound containing an isocyanate group, an isocyanate having an isocyanurate ring is particularly preferable in terms of heat resistance, and an isocyanurate form of hexamethylene diisocyanate is most preferable. The isocyanate having an isocyanurate ring forms a surface layer having both self-healing properties and heat resistance properties.

[Fluorine compound segment, polysiloxane segment, polydimethylsiloxane segment]
In the laminated film of the present invention, it is preferable that the resin constituting the surface layer has a segment containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment.

Further, a coating composition A containing a resin containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment, or a precursor, is used as a coating material for forming a surface layer. By using one, the resin constituting the surface layer can have these.

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

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

Here, the fluoroalkyl group, the fluorooxyalkyl group, the fluoroalkenyl group, the fluoroalkanediyl group, and the fluorooxyalkandyl group are the hydrogens of the alkyl group, the oxyalkyl group, the alkenyl group, the alkanediyl group, and the oxyalkanediyl group. Substituents in which some or all of them are replaced with fluorine, all of which are substituents mainly composed of fluorine atoms and carbon atoms, and may have branches in the structure, and the structure having these sites A plurality of linked dimers, trimmers, 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 and the like, and more preferably represented by chemical formula 5 and chemical formula 6. As already mentioned, it is a fluoropolyether segment.

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

Here, n1 is an integer of 1 to 3, n2 to n5 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 is an integer of 1 or 2, and more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.
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. When the number of carbon atoms is 3 or less, the surface energy is not sufficiently lowered, so that the oil repellency may be lowered, and when the carbon number is 13 or more, the solubility in a solvent is lowered, so that the quality of the surface layer may be deteriorated.

When the resin contained in the surface layer contains a fluorine compound segment, it is preferable that the above-mentioned coating composition A contains the following fluorine compound. This fluorine compound is a compound represented by Chemical Formula 14.

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

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

An example of a fluorine compound is the compound shown below. 3,3-Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-Trifluoropropyltriisocyanatesilane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltri Chlorosilane, 2-perfluorooctyl isocyanatesilane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluorobutyl -2-Hydroxypropyl acrylate, 2-perfluorohexyl ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctyl ethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-per Fluorodecylethyl 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, hexafluoro Butyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2 -Perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2- Hydroxypropyl methacrylate, 2-perfluoro-5-methyl Hexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoro Examples thereof include pentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacrylloyl-heptadecafluorononenyl-pentaerythritol and the like.

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

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

Here, the polysiloxane includes both a low molecular weight siloxane having a repeating unit of about 100 (so-called oligomer) and a high molecular weight siloxane having a repeating unit of more than 100 (so-called polymer).

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

The details of the polysiloxane segment and the polydimethylsiloxane segment will be described later, but the resin constituting the surface layer has these segments to improve heat resistance and weather resistance, and to improve the scratch resistance due to the lubricity of the surface layer. Can be improved. More preferably, it contains a polydimethylsiloxane segment represented by the chemical formula 16 described later from the viewpoint of lubricity.

In the present invention, a polysiloxane segment is used as a coating composition obtained by adding a partially hydrolyzed product of a silane compound containing a hydrolyzable silyl group, an organosilice sol, or a hydrolyzable silane compound having a radical polymer to the organosilice sol. It can be used as a resin to be contained.

Resins containing polysiloxane segments include tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxypropyltri. Fully or partially hydrolyzed silane compounds having a hydrolyzable silyl group such as alkoxysilane and γ-methacryloxypropylalkyldialkoxysilane, organosilica sol dispersed in an organic solvent, and hydrolyzable silyl group on the surface of the organosilica sol. Examples thereof include those to which the hydrolyzed silane compound of the above is added.

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

When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, a coating composition containing a resin containing a polysiloxane segment having a hydroxyl group (copolymer) and a compound containing an isocyanate group is used on the surface. When the layer is formed, it can be efficiently formed into a surface layer having a polysiloxane segment and a urethane bond.

Next, the polydimethylsiloxane segment will be described. In the present invention, the polydimethylsiloxane segment refers to the segment represented by Chemical Formula 16. Polydimethylsiloxane includes both low molecular weight dimethylsiloxane having a repeating unit of 10 to 100 (so-called oligomer) and high molecular weight dimethylsiloxane having a repeating unit of more than 100 (so-called polymer).

m is an integer of 10 to 300.

When the resin constituting 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 layer surface can be improved and the frictional resistance can be reduced. As a result, scratch resistance can be improved.

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

For the purpose of improving the toughness of the surface layer, it is preferable that the resin containing the polydimethylsiloxane segment is copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group.

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

When the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, it may be a block copolymer, a graft copolymer, or a random copolymer. When the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, this is referred to as a polydimethylsiloxane-based copolymer. The polydimethylsiloxane-based copolymer can be produced by a living polymerization method, a polymer initiator method, a polymer chain transfer method, etc., but in consideration of productivity, the polymer initiator method and the polymer chain transfer method are used. It is preferable to use it.

When the polymer initiator method is used, the polymer azo radical polymerization initiator represented by Chemical Formula 17 can be used for copolymerization with other vinyl monomers. Further, a peroxy monomer and a polydimethylsiloxane having an unsaturated group are copolymerized at a low temperature to synthesize a prepolymer in which a peroxide group is introduced into a side chain, and the prepolymer is copolymerized with a vinyl monomer in a two-step polymerization. Can also be done.

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

When the polymer chain transfer method is used, for example, HS-CH ₂ COOH, HS-CH ₂ CH ₂ COOH, or the like is added to the silicone oil represented by the chemical formula 18 to obtain a compound having an SH group, and then the SH group is added. 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-based graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound represented by chemical formula 19, that is, a methacrylic ester of polydimethylsiloxane, and a vinyl monomer. can.

m is an integer of 10 to 300.

Examples of the vinyl monomer used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, and 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, methacrylicamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, diacetitone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , Allyl alcohol and the like.

The polydimethylsiloxane-based copolymer includes aromatic hydrocarbon-based solvents such as toluene and xylene, ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester-based solvents such as ethyl acetate and butyl acetate, ethanol and isopropyl alcohol. It is preferable that the alcohol-based solvent or the like is produced by a solution polymerization method alone or in a mixed solvent.

If necessary, a polymerization initiator such as benzoyl peroxide or azobisisobutynitrile 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-based copolymer in the present invention is 1 to 1 in 100% by mass of all the components of the polydimethylsiloxane-based copolymer in terms of the lubricity and 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 the coating composition used to form the surface layer, other segments and the like are contained (copolymerized) in addition to the polydimethylsiloxane segment. You may. For example, a polycaprolactone segment or a polysiloxane segment may be contained (copolymerized).

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

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

[solvent]
The coating composition may contain a solvent. The number of types of the solvent is preferably 1 type or more and 20 types or less, more preferably 1 type or more and 10 types or less, further preferably 1 type or more and 6 types or less, and particularly preferably 1 type or more and 4 types or less.

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

Here, the type of solvent is determined by the molecular structure constituting the solvent. That is, those having the same element composition and having the same type and number of functional groups but different bonding relationships (structural isomers) are not the structural isomers, but what kind of conformation is used in the three-dimensional space. Those that do not exactly overlap even if they are taken (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are treated as different solvents.

Further, when a solvent is contained, it is preferable that the solvent exhibits the following characteristics.

Condition 1 When the solvent having the lowest relative evaporation rate (ASTM D3539-87 (2004)) based on n-butyl acetate is used as the solvent B, the relative evaporation rate of the solvent B is 0.4 or less.

Here, the relative evaporation rate based on the solvent n-butyl acetate is the evaporation rate measured according to ASTMD3539-87 (2004). Specifically, it is a value defined as a relative value of the evaporation rate based on the time required for 90% by mass of n-butyl acetate to evaporate under dry air.

When the relative evaporation rate of the solvent is greater than 0.4, the time required for the above-mentioned polysiloxane segment and / or polydimethylsiloxane segment and the fluorine compound segment to be oriented to the outermost surface in the surface layer is shortened. Therefore, the self-healing property and antifouling property of the obtained laminated film may be deteriorated. Further, the lower limit of the relative evaporation rate of the solvent is no problem as long as it is a solvent that can be evaporated and removed from the coating film in the drying step, and may be 0.005 or more in the general coating step.

As the solvent, isobutyl ketone (relative evaporation rate: 0.2), isophorone (relative evaporation rate: 0.026), diethylene glycol monobutyl ether (relative evaporation rate: 0.004,), diacetone alcohol (relative evaporation rate: 0). .15), oleyl alcohol (relative evaporation rate: 0.003), ethylene glycol monoethyl ether acetate (relative evaporation rate: 0.2), nonylphenoxyethanol (relative evaporation rate: 0.25), propylene glycol monoethyl ether (relative evaporation rate: 0.25). Relative evaporation rate: 0.1), cyclohexanone (relative evaporation rate: 0.32), etc.

[Other components in the paint composition]
Further, the coating composition A preferably contains 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 polymerization, condensation or cross-linking reaction of the components contained in the coating composition by an anion, cation, radical polymerization reaction or the like 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 individually, or a plurality of polymerization initiators, the curing agent and the catalyst may be used at the same time. Further, an acidic catalyst or a thermal polymerization initiator may be used in combination. Examples of acidic catalysts include hydrochloric acid aqueous solution, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone-based compounds, sulfur-containing compounds, acylphosphine oxide-based compounds, and amine-based compounds. Examples of the cross-linking catalyst that promotes the urethane bond formation reaction include dibutyltin dilaurate and dibutyltin diethylhexoate.

Further, the coating composition contains other cross-linking agents such as a melamine cross-linking agent such as alkoxymethylol melamine, an acid anhydride-based cross-linking agent such as 3-methyl-hexahydrophthalic anhydride, and an amine-based cross-linking agent such as diethylaminopropylamine. It can also be included.

As the photopolymerization initiator, an alkylphenone-based compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone-type compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)-. 2-Morphorinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenylketone, 2-methyl-1-phenylpropan-1-one, 1- [4- (2-ethoxy) ) -Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and high-molecular-weight materials thereof. ..

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

[Manufacturing method of laminated film]
The surface layer formed on the surface of the laminated film of the present invention is preferably formed by applying the above-mentioned coating composition for a surface layer on the above-mentioned supporting base material, drying, and curing. Hereinafter, the step of applying the coating composition will be referred to as a coating step, the step of drying will be referred to as a drying step, and the step of curing will be referred to as a curing step. As the coating composition for the surface layer, two or more kinds of coating compositions may be applied sequentially or simultaneously to form a surface layer composed of two or more layers.

Here, "sequentially applied" means that one kind of coating composition is applied onto a supporting base material, dried, and cured, and then another coating composition is applied and dried. It means that a surface layer composed of two or more layers is formed by curing. By appropriately selecting the type of coating composition to be used, it is possible to control the magnitude and gradient of the contact rigidity between the surface layer side and the supporting substrate side of the surface layer, the magnitude of the contact rigidity between the supporting substrate and the surface layer, and the like. .. Further, by appropriately selecting the type, composition, drying condition and curing condition of the coating composition, the form of the contact rigidity distribution in the surface layer can be controlled stepwise or continuously.

Further, "applying at the same time" means that in the coating step, two or more kinds of coating compositions are simultaneously applied onto the supporting base material, and then dried and cured.

In the coating step, the method of applying the coating composition is not particularly limited, but the coating composition is coated with a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method (US Pat. No. 2,681294) and the like. It is preferable to apply the coating to the supporting substrate. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.

When two or more kinds of coating compositions are applied at the same time, a method such as a multilayer slide die coating, a multilayer slot die coating, and a wet-on-wet coating can be used without particular limitation.

An example of the multi-layer slide die coat is shown in FIG. In the multilayer slide die coat, a liquid film composed of two or more kinds of coating compositions is laminated in order using the multilayer slide die 3, and then applied onto a supporting base material.

An example of a multi-layer slot die coat is shown in FIG. In the multi-layer slot die coat, a liquid film composed of two or more kinds of coating compositions is laminated on a supporting base material at the same time as being applied using the multi-layer slot die 4.

An example of a wet-on-wet coat is shown in FIG. In the wet-on-wet coat, a one-layer liquid film composed of the coating composition discharged from the single-layer slot die 5 is formed on the supporting base material, and then the liquid film is undried. A liquid film composed of another coating composition discharged from the single-layer slot die 5 of No. 1 is laminated.

Following the coating step, the liquid film coated on the supporting substrate is dried by a drying step. From the viewpoint of completely removing the solvent from the obtained laminated film, the drying step preferably involves heating the liquid film.

Examples of the heating method in the drying step include heat transfer drying (adhesion to a high heat object), convection heat transfer (hot air), radiant heat transfer (infrared ray), and others (microwave, induction heating). Among these, a method using convection heat transfer or radiant heat transfer is preferable because it is necessary to precisely make the drying rate uniform in the width direction.

The drying process of the liquid film in the drying step is generally divided into (A) constant drying period and (B) lapse rate drying period. In the former, since the diffusion of solvent molecules into the atmosphere on the surface of the liquid film is the rate-determining factor for drying, the drying rate is constant in this section, and the drying rate is the partial pressure of the solvent to be vaporized in the atmosphere, the wind speed, and the temperature. The film surface temperature is constant at a value determined by the hot air temperature and the partial pressure of the solvent to be evaporated in the atmosphere. In the latter case, since the diffusion of the solvent in the liquid film is rate-determining, the drying rate does not show a constant value in this section and continues to decrease, and is dominated by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature gradually increases. Rise. Here, the drying rate represents the amount of solvent evaporation per unit time and unit area, and is composed of the dimensions of ^{g, m-2,} and s- ^1.

The drying rate is preferably 0.1 g · m ^-2 · s ^-1 or more and 10 g · m ^-2 · s ^-1 or less, and 0.1 g · m ^-2 · s ^-1 or more and 5 g · m ^-2 ·. More preferably, it is s ^{-1 or less.} By setting the drying rate in the constant drying section within this range, unevenness due to non-uniformity of the drying rate can be prevented.

The drying speed is not particularly limited as long as it can be obtained, but in order to obtain the drying speed, the temperature is preferably 15 ° C. to 129 ° C., more preferably 50 ° C. to 129 ° C., and 50 ° C. It is particularly preferable that the temperature is from 99 ° C.

During the rate-reducing drying period, the above-mentioned polysiloxane segment and / or polydimethylsiloxane segment or fluorine compound segment is oriented along with the evaporation of the residual solvent. Since time for orientation is required in this process, the rate of increase in film surface temperature during the rate-reducing drying period is preferably 5 ° C./sec or less, and more preferably 1 ° C./sec or less.

Following the drying step, a further curing operation (curing step) may be performed by irradiating with heat or active energy rays.

As the active energy ray, an electron beam (EB ray) and / or an ultraviolet ray (UV ray) is preferable from the viewpoint of versatility. When curing by ultraviolet rays, it is preferable that the oxygen concentration is as low as possible because oxygen inhibition can be prevented, and it is more preferable to cure in a nitrogen atmosphere (nitrogen purge). When the oxygen concentration is high, the hardening of the outermost surface may be inhibited, the hardening of the surface may be weakened, and the self-healing property and the scratch resistance may be lowered. Further, examples of the type of ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp type, a flash type, a laser type, and an electrodeless lamp type. When using a high-pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays is preferably 100~3,000mW / cm ^2, more preferably 200~2,000mW / cm ^2, more preferably the 300~1,500mW / cm ² It is preferable to irradiate ultraviolet rays under the above conditions. Integrated quantity of ultraviolet light is preferably 100~3,000mJ / cm ^2, more preferably 200~2,000mJ / cm ^2, is further preferably irradiated with ultraviolet rays under the condition that the 300~1,500mJ / cm ² preferable. Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectrum efficiency, the diameter of the emission valve, the design of the reflecting mirror, and the light source distance from the object to be irradiated. However, the illuminance does not change depending on the transport speed. The integrated ultraviolet light amount is the irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light intensity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

[Adhesive layer]
In the present invention, it is preferable that the laminated film has an adhesive layer on the surface opposite to the surface having the surface layer of the supporting base material. When the laminated film has an adhesive layer, the laminated film can be easily attached to the surface of an article as described above. In other words, having an adhesive layer enables bonding even at room temperature, which is preferable because a special device is not required to protect the surface of the article. Further, since the laminated film of the present invention has sufficient flexibility even at room temperature, for example, it can follow a complicated article shape even at room temperature, and is preferable because it can be applied to various articles.

The adhesive layer is a layer containing a so-called pressure-sensitive adhesive, and is preferably adhesive at room temperature.

As a method of forming the pressure-sensitive adhesive layer, a method of dissolving a pressure-sensitive adhesive or a substance that is a precursor of the pressure-sensitive adhesive in a solvent, applying it to a support base material and curing it, or attaching a transparent optical pressure-sensitive adhesive sheet or a double-sided pressure-sensitive adhesive sheet to the support base material. The method of doing this can be exemplified.

As the pressure-sensitive adhesive and the precursor of the pressure-sensitive adhesive, various pressure-sensitive adhesives are preferably used. For example, acrylic resin, terpene resin, phenol resin, terpene phenol resin, silicone resin, kumaron resin, rosin compound (rosin or rosin ester, hydrogenated rosin ester), petroleum resin, xylene resin, etc. Alternatively, a styrene resin or the like can be mentioned. Among these, an acrylic pressure-sensitive adhesive is preferably used.

As the acrylic pressure-sensitive adhesive, for example, an acrylic pressure-sensitive adhesive obtained by copolymerizing a monomer component mainly composed of an acrylic acid ester with a monomer component having a functional group such as a carboxyl group can be used.

An acrylic pressure-sensitive adhesive in which a carboxyl group-containing ethylenically unsaturated monomer is copolymerized as an acrylic acid ester-based monomer component can be used.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 10 μm or more and 200 μm or less, more preferably 20 μm or more and 100 μm or less, and particularly preferably 30 μm or more and 70 μm or less. Further, from the viewpoint of weather resistance, the adhesive layer is preferably non-yellowing.

Examples of the acrylic acid ester-based monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isononyl ( Meta) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate and the like can be mentioned. Among them, (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms in the alkyl ester portion is preferable, for example. It is preferable to use methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamideN-glycolic acid, and silicic acid. Etc., and among them, it is preferable to use (meth) acrylic acid.

[Application example]
The laminated film of the present invention takes advantage of excellent flexibility, scratch resistance, and antifouling property, and is particularly required to have high scratch resistance, and can be suitably used for applications in which scratches and cracks are less noticeable. In particular, the laminated film of the present invention can be suitably used as a film (surface protection film) for protecting the surface of an article.

For example, plastic molded products such as glasses / sunglasses, cosmetic boxes, food containers, water tanks, showcases for exhibitions, smartphone housings, touch panels, color filters, flat panel displays, keyboards, remote controls for TVs and air conditioners. Home appliances such as mirrors, windowpanes, buildings, dashboards, car navigation systems, touch panels, vehicle parts such as room mirrors and windows, interior and exterior of aircraft, ships, automobiles, bikes, bicycles, and various printed materials. It can be suitably used on the surface or inside.

Next, the present invention will be described based on examples, but the present invention is not necessarily limited thereto. In the following, Example 8 will be read as Reference Example 8.

[Urethane (meth) acrylate a]
[Synthesis of urethane (meth) acrylate a1]
50 parts by mass of toluene, isocyanurate-modified type of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.) 50 parts by mass, polycaprolactone-modified hydroxyethyl acrylate (Pluxel FA5 manufactured by Daicel Chemical Industries, Ltd.) 76 parts by mass, 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Then, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate a1 having a solid content concentration of 50% by mass.

[Urethane (meth) acrylate b]
[Synthesis of urethane (meth) acrylate b1]
Isocyanurate modified product of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals Co., Ltd., isocyanate group content: 20.9% by mass), 50 parts by mass, polyethylene glycol monoacrylate (manufactured by Nichiyu Co., Ltd.) "Blemmer" (registered trademark) AE-150, hydroxyl value: 264 (mgKOH / g)) 53 parts by mass, dibutyltin laurate 0.02 parts by mass and hydroquinone monomethyl ether 0.02 parts by mass were charged. Then, the reaction was carried out by holding at 70 ° C. for 5 hours. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter sometimes referred to as MEK) was added to the reaction solution to obtain urethane (meth) acrylate b1 having a solid content concentration of 50% by mass.

[Synthesis of urethane (meth) acrylate b2]
Isocyanurate modified product of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals Co., Ltd., isocyanate group content: 20.9% by mass), 50 parts by mass, polyethylene glycol monoacrylate (manufactured by Nichiyu Co., Ltd.) "Blemmer" (registered trademark) AE-400, hydroxyl value: 98 (mgKOH / g)) 142 parts by mass, dibutyltin laurate 0.02 parts by mass and hydroquinone monomethyl ether 0.02 parts by mass were charged. Then, the reaction was carried out by holding at 70 ° C. for 5 hours. After completion of the reaction, 192 parts by mass of methyl ethyl ketone (hereinafter, also referred to as MEK) was added to the reaction solution to obtain urethane (meth) acrylate b2 having a solid content concentration of 50% by mass.

[Urethane (meth) acrylate c]
[Synthesis of urethane (meth) acrylate c1]
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Hakko Kirin Co., Ltd.) and 119 parts by mass of polycarbonate diol ("Plaxel" (registered trademark) CD-210HL manufactured by Daicel Chemical Industry Co., Ltd.) The parts were mixed, the temperature was raised to 40 ° C., and the temperature was maintained for 8 hours. Then, add 28 parts by mass of 2-hydroxyethyl acrylate (light ester HOA manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400 manufactured by Toa Synthetic Co., Ltd.), and 0.02 parts by mass of hydroquinone monomethyl ether. After holding at 70 ° C. for 30 minutes, 0.02 parts by mass of dibutyltin laurate was added and the mixture was held at 80 ° C. for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate c1 having a solid content concentration of 50% by mass.

[Acrylate compound]
[Acrylate compound 1]
As the acrylate compound 1, an acrylate compound containing a tricyclodecyl segment (IRR214-K, manufactured by Daicel Ornex Co., Ltd., solid content concentration: 100% by mass) was used.

[Polyol compound]
[Polyol compound 1]
As the polyol compound 1, a polyol compound containing polycaprolactone triol (“Placcel” (registered trademark) 308, manufactured by Daicel Chemical Industries, Ltd., solid content concentration: 100% by mass) was used.

[Isocyanate compound]
[Isocyanate compound 1]
An isocyanate compound containing hexamethylene diisocyanate (“Takenate” (registered trademark) D-170, manufactured by Mitsui Chemicals, Inc.) was used as the isocyanate compound 1.

[Polysiloxane (a)]
A 500 ml volumetric flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube was charged with 106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1% by mass hydrochloric acid. After holding at ° C. for 2 hours, ethanol was recovered while raising the temperature, and the mixture was held at 180 ° C. for 3 hours. Then, it cooled and obtained viscous polysiloxane (a).

[Polydimethylsiloxane-based block copolymer (a)]
Using the same equipment as for the synthesis of polysiloxane (a), 50 parts by mass of toluene, 50 parts by mass of methylisobutylketone, and 20 parts by mass of a polydimethylsiloxane-based polymer polymerization initiator (VPS-0501, manufactured by Wako Pure Chemical Industries, Ltd.). Parts, 30 parts by mass of methyl methacrylate, 26 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, 1 part by mass of methacrylate and 0.5 part by mass of 1-thioglycerin were charged and reacted at 80 ° C. for 8 hours. Obtained a polydimethylsiloxane-based block copolymer (a). The proportion of the block copolymer (a) in the obtained solution was 50% by mass in 100% by mass of the solution.

[Fluorine compound]
[Fluorine compound 1]
As the fluorine compound 1, an acrylate compound containing a fluoropolyether segment (“Megafuck” (registered trademark) RS-75 DIC Corporation, solid content concentration 40% by mass, solvent (toluene and methyl ethyl ketone) 60% by mass) was used.

[Photoradical polymerization initiator]
[Photoradical polymerization initiator 1]
"Irgacure" (registered trademark) 184 (manufactured by BASF Japan Ltd., solid content concentration 100% by mass) was used as the photoradical polymerization initiator 1.

[Preparation of paint composition A]
[Paint 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 30% by mass.
・ Urethane (meth) acrylate a1 solution (solid content concentration 50% by mass) 100 parts by mass ・ Fluorine compound 1 solution (solid content concentration 40% by mass) 0.6 parts by mass ・ Photoradical polymerization initiator 1 1.5 parts by mass ・Ethylene glycol monobutyl ether 10 parts by mass.

[Paint composition A2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate b1 solution (solid content concentration 50% by mass) 100 parts by mass ・ Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass ・ Photoradical polymerization initiator 1 1.5 parts by mass ・Ethylene glycol monobutyl ether 10 parts by mass.

[Paint 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 30% by mass.
・ Urethane (meth) acrylate c1 solution (solid content concentration 50% by mass) 100 parts by mass ・ Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass ・ Photoradical polymerization initiator 1 1.5 parts by mass ・Ethylene glycol monobutyl ether 10 parts by mass.

[Paint composition A4]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid content concentration of 30% by mass.
・ Urethane (meth) acrylate b2 solution (solid content concentration 50% by mass) 100 parts by mass ・ Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass ・ Photoradical polymerization initiator 1 1.5 parts by mass ・Ethylene glycol monobutyl ether 10 parts by mass.

[Paint composition A5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid content concentration of 30% by mass.
-Urethane (meth) acrylate b1 solution (solid content concentration 50% by mass) 50 parts by mass-Urethane (meth) acrylate c1 solution (solid content concentration 50% by mass) 50 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) ) 3.8 parts by mass, photoradical polymerization initiator 1 1.5 parts by mass, ethylene glycol monobutyl ether 10 parts by mass.

[Paint composition A6]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid content concentration of 30% by mass.
-Urethane (meth) acrylate b1 solution (solid content concentration 50% by mass) 90 parts by mass-acrylate compound 15 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass-Photoradical polymerization initiator 1 1.5 parts by mass ・ Ethylene glycol monobutyl ether 10 parts by mass.

[Preparation of paint composition B]
[Paint 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 30% by mass.
-Urethane (meth) acrylate b1 solution (solid content concentration 50% by mass) 80 parts by mass-acrylate compound 1 10 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 3.8 parts by mass-Photoradical polymerization initiator 1 1.5 parts by mass ・ Ethylene glycol monobutyl ether 10 parts by mass.

[Preparation of paint composition C]
[Paint composition C1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C1 having a solid content concentration of 40% by mass.
-Polyol compound 1 15 parts by mass-Isocyanate compound 1 15 parts by mass-Polydimethylsiloxane-based block copolymer (a) solution 75 parts by mass (solid content concentration 50% by mass)
-Polysiloxane (a) 10 parts by mass.

[Paint composition C2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C2 having a solid content concentration of 40% by mass.
-Polyol compound 1 15 parts by mass-Isocyanate compound 1 15 parts by mass-Polydimethylsiloxane-based block copolymer (a) solution 75 parts by mass (solid content concentration 50% by mass)
-Polysiloxane (a) 10 parts by mass-Fluorine compound 1 solution (solid content concentration 40% by mass) 5.8 parts by mass-Photoradical polymerization initiator 1 2.3 parts by mass.

[Supporting base material]
[Supporting base material X1]
As the supporting base material X1, "Esmer" (registered trademark) URS PX (thickness 150 μm, manufactured by Nihon Matai Co., Ltd.) was used. This product contains polyurethane resin as a constituent component.

[Supporting base material X2]
As the supporting base material X2, "Higres" (registered trademark) DUS605-CER (thickness 100 μm, manufactured by Seadam Co., Ltd.) was used. This product contains polyurethane resin as a constituent component.

[Supporting base material Y1]
As the supporting base material Y1, "Lumirror" (registered trademark) U48 (thickness 125 μm, manufactured by Toray Industries, Inc.) was used. This product contains polyethylene terephthalate resin as a constituent component.

[Manufacturing method of laminated film]
[Preparation of laminated film 1]
Using a continuous coating device using a slot die coater to apply the coating composition A and the coating composition B on the supporting base material, the discharge flow rate from the slots is adjusted so that the thickness of the surface layer after drying becomes a specified film thickness. And applied. The conditions of the dry air that hits the liquid film from application to drying and curing are as follows.

[Drying process]
Blower temperature / humidity: Temperature: 80 ° C, Relative humidity: 1% or less Wind speed: Coating surface side: 5m / sec, Anti-coating surface side: 5m / sec Wind direction: Coating surface side: Parallel to the surface of the substrate, anti-coating Surface side: Vertical to the surface of the base material Dwelling time: 2 minutes [Curing step]
Irradiation output: 400 W / cm ²
Integrated light intensity: 120mJ / cm ²
Oxygen concentration: 0.1% by volume.

[Preparation of laminated film 2]
Using a continuous coating device using a slot die coater to apply the coating composition C (C1) onto the supporting base material, the discharge flow rate from the slots is adjusted so that the thickness of the surface layer after drying becomes a specified film thickness. It was applied. The conditions of the dry air that hits the liquid film from application to drying and curing are as follows.

[Drying process]
Blower temperature / humidity: Temperature: 80 ° C, Relative humidity: 1% or less Wind speed: Coating surface side: 5m / sec, Anti-coating surface side: 5m / sec Wind direction: Coating surface side: Parallel to the surface of the substrate, anti-coating Surface side: Vertical to the surface of the base material Dwelling time: 1 minute [Curing step]
Blower temperature / humidity: Temperature: 100 ° C, Relative humidity: 1% or less Wind speed: Coating surface side: 10m / sec, Anti-coating surface side: 10m / sec Wind direction: Coating surface side: Vertical to the surface of the base material, anti-coating Surface side: Vertical to the surface of the base material Dwelling time: 2 minutes Further, the prepared laminated film was allowed to stand at room temperature for 1 week for aging treatment.

The wind speed and temperature / humidity were measured by a hot wire anemometer (Anemomaster anemometer MODEL6034 manufactured by Kanomax Japan Incorporated Co., Ltd.).

Laminated films of Examples 1 to 8 and Comparative Examples 1 to 4 were prepared by the above method. Examples and Comparative Examples using the coating compositions A1 to A6 and B1 contain an acrylic resin as a constituent component in the surface layer. Further, a laminated film using the untreated supporting base material X1 was designated as Comparative Example 5. The method for producing the laminated film corresponding to each example and comparative example, and the film thickness of each layer are shown in Tables 1 and 2 described later.

[Evaluation of supporting base material and laminated film]
The following performance evaluations were carried out on the supporting base material and the produced laminated film, and the results obtained are shown in Tables 1 and 2. Unless otherwise specified, in each Example / Comparative Example, one sample was measured three times at different locations, and the average value was used.

[Support base material, thickness of surface layer]
The thickness of the support substrate and the surface layer on the support substrate was measured by observing the cross section using an electron microscope (SEM). The thickness of each layer was measured according to the following method. The thickness of each layer was read by software (image processing software ImageJ) from an image of a cross-sectional section of the laminated film taken by SEM at a magnification of 3,000 times. The average value obtained by measuring the layer thickness at 30 points in total was used as the measured value.

[100% strain stress F ₁₀₀ ]
The laminated film was cut into a rectangle having a width of 10 mm and a length of 150 mm and used as a test piece. The direction of 150 mm length was aligned with the longitudinal direction of the laminated film. Using a tensile tester (Tencilon UCT-100 manufactured by Orientec), the initial tensile chuck distance was set to 50 mm, the tensile speed was set to 300 mm / min, and the tensile test was performed at a measurement temperature of 23 ° C.

The load b (N) applied to the sample when the distance between the chucks was a (mm) was read, and the strain amount x (%) and the stress y (MPa) were calculated from the following equations. However, the sample thickness before the test is k (mm).
Strain amount: x = ((a-50) / 50) x 100
Stress: y = b / (k × 10)
When cutting out the test piece from the laminated film, in order to average the influence of the cutting direction of the test piece, the direction of the test piece cut out first is regarded as an angle of 0 °, and the test piece is tilted by an angle of 45 ° in the plane direction. A total of four test pieces, a test piece tilted at an angle of 90 ° in the plane direction and a test piece tilted at an angle of 135 ° in the plane direction, were evaluated in the same manner, and the stress at 100% strain was measured for each test piece. .. Averaging these four specimens stress obtained strain amount of 100% for, was 100% strain stress _{F 100.}

[Backward contact angle]
The receding contact angle was measured by the expansion-contraction method, and the contact angle meter Drop Master DM-501 manufactured by Kyowa Interface Science was used, and the expansion-contraction method measurement manual of the same device was followed.

As for the receding contact angle, pure water is continuously sucked from the syringe at an initial droplet volume of 50 μL and a liquid discharge rate of 8.5 μL / sec, and the shape of the shrinking process of the droplet is sucked from before the start of suction to the end. The images were taken 30 times every 0.5 seconds until later, and the contact angle was determined from the same image using the integrated analysis software "FAMAS" attached to the device.

Although the images are taken for a certain period of time before the start of suction and after the end of suction, the analysis software excludes the shooting data before the start of suction and after the end of suction from the five points of data for calculating the contact angle. It has become. Since the contact angle during the shrinkage process of the droplet first changes as it shrinks and then behaves to be almost constant, when the contact angles are arranged in the direction in which the droplet shrinks and five consecutive points are selected in that order. The average value when the standard deviation of 5 consecutive points first becomes 1 ° or less is the receding contact angle of the measurement, and this measurement is performed 5 times for one sample, and the average value is defined as the receding contact angle of the sample. did. Depending on the sample, the contact angle during the shrinkage process of the droplet may not be constant and may continue to decrease, but for this, the receding contact angle was set to 0 °.

〔Glass-transition temperature〕
The surface layer and the supporting base material were scraped from the laminated film with a blade knife to obtain a test piece, which was then sealed in an aluminum pan to prepare a measurement sample. A differential scanning calorimeter (DSC6220 manufactured by Seiko Instruments Inc.) was used for the measurement, and the measurement and calculation were performed according to JIS-K-7121 (1987). However, the measured temperature and the rate of temperature rise were as follows.
Measurement temperature: From 173K to 373K Temperature rise rate: 10K / min
Sample mass: 5 mg.

[Storage modulus of surface layer]
Only the surface layer was peeled from the laminated film with reference to the cross-sectional SEM image observed when evaluating the thickness of the surface layer, and used as a test piece.

Based on the tensile vibration-non-resonant method of JIS K7244 (1998) (this is referred to as the dynamic viscoelasticity method), the storage elastic modulus of the surface layer is used using the dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Co., Ltd. Asked.
Measurement mode: Distance between tension chucks: 20 mm
Width of test piece: 10 mm
Frequency: 1Hz
Strain amplitude: 10 μm
Initial force amplitude: 50 mN
Measurement temperature: From 123K to 523K Temperature rise rate: 5K / min.

[Flexibility of laminated film]
After leaving the film at a temperature of 23 ° C. for 12 hours, the laminated film was cut into a rectangle having a width of 10 mm and a length of 150 mm to form a test piece, and the direction having a length of 150 mm was defined as the longitudinal direction. The test piece was manually pulled in the longitudinal direction, and the judgment was made according to the following criteria.
10 points: Can be deformed with a very light force 7 points: Can be deformed by applying a light force 4 points: Can be deformed by applying a slightly stronger force 1 point: Other (deforms) Requires strong force, hardly deforms, etc.).

When cutting out the test piece from the laminated film, in order to average the influence of the cutting direction of the test piece, the direction of the test piece cut out first is regarded as an angle of 0 °, and the test piece is tilted by an angle of 45 ° in the plane direction. , A test piece tilted at an angle of 90 ° in the plane direction, a test piece tilted at an angle of 135 ° in the plane direction, and a total of the above four test pieces were evaluated in the same manner, and the average thereof was used as the evaluation result.

[Scratch resistance of laminated film]
After leaving it at a temperature of 23 ° C for 12 hours, the surface layer surface was scratched horizontally 5 times by applying the following load to a brass brush (manufactured by TRUSCO) in the same environment, and then the scratches were healed within 10 seconds. , The judgment was made visually according to the following criteria.
10 points: No scratches left at load 9.8N (1kg weight) 7 points: No scratches left at load 9.8N (1kg weight) 4 points: No scratches left at 6.9N (700g weight) 4 points: Load 6 At 9.9N (700g weight), scratches remain, but at 4.9N (500g weight), no scratches remain. One point: A load of 4.9N (500g weight) leaves scratches.

[Anti-fouling property of laminated film]
After being left at a temperature of 23 ° C. for 12 hours, the laminated film was cut into a 50 mm width × 100 mm and used as a test piece. The test piece was fixed to the glass plate with tape so that the surface layer was face up, and then the glass plate was tilted and fixed so that the test piece was tilted at an inclination of 30 ° with respect to the ground.

Next, water droplets were continuously dropped on the test piece from above, the behavior of the water droplets on the test piece was visually observed, and a judgment was made according to the following criteria.
10 points: Water droplets are repelled vigorously.
7 points: Water droplets are repelled.
4 points: Water droplets are repelled a little, but some water droplets remain.
1 point: Others (water droplets are not repelled, etc.).

Table 2 summarizes the evaluation results of the finally obtained laminated film.

1 Surface layer 2 Support base material 3 Multi-layer slide die 4 Multi-layer slot die 5 Single-layer slot die

The laminated film of the present invention takes advantage of excellent flexibility, scratch resistance, and antifouling property, and can be suitably used for applications in which particularly high scratch resistance and antifouling property are required and scratches and cracks are less noticeable.

Claims (4)

A laminated film having a surface layer containing an acrylic resin as a constituent on at least one of a supporting base material containing a polyurethane resin as a constituent, which satisfies the following conditions 1, 2 and 3. Laminated film.
Condition 1: 100% strain stress F _{100 of the} laminated film is 20 MPa or less Condition 2: The receding contact angle of the surface layer in pure water is 75 ° or more.
Condition 3: The following equations 1 and 2 hold for _{the glass transition temperature T g1} (K) of the surface layer and the glass transition temperature T _{g2 (K) of the supporting base material.}
233 ≤ T _g1 ≤ 313 (Equation 1)
T _g1 / T _g2 ≤ 1.15 (Equation 2) The laminated film according to claim 1, wherein the laminated film satisfies the following condition 4.
Condition 4: The storage elastic modulus of the surface layer at 298 K is 1,000 MPa or less. The laminated film according to claim 1 or 2, wherein the adhesive layer is provided on a surface opposite to the surface of the support base material having the surface layer. The laminated film according to any one of claims 1 to 3 , wherein the laminated film is used as a surface protective film.

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