TWI643743B - Laminate film - Google Patents

Abstract

A laminated film which is a laminated film having a surface layer on at least one side of a support substrate, which is characterized by satisfying the following conditions 1 and 2; Condition 1: the aforementioned surface of a rigid-body pendulum test method The logarithmic decay rate of the layer at 25 ° C is 0.1 or more; Condition 2: the resin contained in the surface layer comprises the following (1) to (4);

(1) Polycaprolactone segment

(2) urethane bond

(3) Polyoxyalkylene segment and / or polydimethyl siloxane chain segment

(4) Tricyclic sulfhydryl chain segments.

The present invention provides a laminated film which is compatible with the moldability required for a molding material and the scratch resistance due to self-healing properties, and also satisfies the adhesion durability and the antifouling property.

Description

Laminate film

The present invention relates to a laminated film which is excellent in adhesion durability and antifouling properties in addition to the moldability and scratch resistance required for a molding material.

In the molding material such as decorative molding, a surface hardness layer is provided in order to prevent scratches during molding or to prevent scratches during use of the molded article. However, since the surface hardness layer is insufficient in the elongation of the follow-up molding, cracking occurs during molding, or in the extreme case, the film is broken, or the surface hardness layer is peeled off, it is generally used to form a surface hardness layer after molding. After molding in a semi-hardened state, it is completely hardened by heating or irradiation with an active wire. However, since the molded article is processed in three dimensions, it is extremely difficult to provide a surface hardness layer after the post-processing, and when it is molded in a semi-hardened state, there is a case where the mold is dirty due to the molding conditions. Based on the above, it is expected that the "self-healing material" which can follow the molded scratch-resistant material and which can repair the slight scratches by the deformation of the elastic recovery range is attracting attention, and is disclosed in Patent Documents 1 and 2. proposal.

On the other hand, when such a molded body is used as a surface material in a smart phone case or a tablet PC case or the like, durability at the time of long-term use is required. Especially due to the penetration of moisture in the air to The inside of the molding material, especially the surface of the molding material, is destroyed, or the surface of the molding material is broken, or the surface layer is peeled off. In order to solve such a problem, there is a material of the patent document 3 proposed as a technique for imparting durability to the surface hardness layer. Moreover, as a technique for forming a layer that achieves both adhesion strength and durability to a substrate, a material of Patent Document 4 is proposed.

Furthermore, in terms of antifouling properties, jeans or clothing or When a natural leather or a synthetic leather containing a dye is in contact with a sheet composed of a general soft resin, there is a problem that the dye is transferred to the surface, and the resistance is imparted thereto (hereinafter, referred to as "dye transfer resistance"). The method has the material of the proposed patent document 5.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2011/136042

Patent Document 2: Japanese Patent No. 3926461

Patent Document 3: Japanese Laid-Open Patent Publication No. 2013-166889

Patent Document 4: Japanese Laid-Open Patent Publication No. 2012-233079

Patent Document 5: Japanese Laid-Open Patent Publication No. 2008-62408

The inventors of the present invention have confirmed the moldability and the self-healing property, but the adhesion durability or the antifouling property are greatly deteriorated. For hard coating materials.

Further, with regard to the technique of the aforementioned Patent Document 3, the present invention As a result, it was confirmed that although the effect of the adhesion durability was confirmed to some extent, it was not a moldability or self-healing property. Moreover, it is impossible to combine with the techniques of Patent Documents 1 and 2 described above, and it is not possible to have self-healing properties.

Furthermore, with regard to the technique of the aforementioned Patent Document 4, It is effective in the adhesion durability, but it does not exhibit moldability or self-healing property, and it is impossible to combine with the techniques of the aforementioned Patent Documents 1 to 3.

Further, the method of the method described in the above Patent Document 5 is It is effective in resistance to dye transfer, but it does not exhibit moldability or self-healing property, and it is impossible to combine it with the techniques of the aforementioned Patent Documents 1 to 4, and it is understood that it does not coexist with self-healing property.

Therefore, the problem to be solved by the present invention is to provide a The laminated film is in addition to the moldability and scratch resistance required for the molding material, and also satisfies the adhesion durability and the antifouling property.

In order to solve the above problems, the inventors of the present invention repeated the intensive research and completed the following invention. That is, the present invention is as follows.

<1> A laminated film which is a laminated film having a surface layer on at least one side of a support substrate, which is characterized by satisfying the following conditions 1 and 2; Condition 1: The aforementioned surface layer of the rigid body pendulum test method is 25 The logarithmic decay rate of °C is 0.1 or more; Condition 2: the resin contained in the surface layer contains (1) to (4) below;

(1) Polycaprolactone segment

(2) urethane bond

(3) Polyoxyalkylene segment and / or polydimethyl siloxane chain segment

(4) Tricyclic sulfhydryl segment

<2> The laminated film according to the above <1>, wherein the laminated film satisfies the following condition 3; Condition 3: The adhesion index of the surface layer in the extension-boil adhesion test method is 3 or more.

<3> The laminated film according to the above <1> or <2>, wherein the laminated film satisfies the following condition 4; Condition 4: Relative storage elastic modulus of the surface layer of the rigid body pendulum test at 100 ° C The number system has a higher relative storage elastic modulus at 25 °C.

The laminated film according to any one of the above-mentioned <1> to <3> wherein the laminated film satisfies the following conditions 5 to 7; Condition 5: The surface layer of the dynamic viscoelastic method is 25 The storage elastic modulus of °C is 10 MPa or more and 1,000 MPa or less; Condition 6: The above-mentioned surface layer of the dynamic viscoelastic method has a storage elastic modulus at 100 ° C higher than the storage elastic modulus at 25 ° C; Condition 7: Dynamic viscoelasticity The loss of the surface layer of the above method at 25 ° C is 0.15 or more.

<5> The laminated thin film according to any one of the above <1> to <4> The film in which the above-mentioned condition 8 is satisfied in the laminated film; Condition 8: The surface layer of the tensile test method has a crack elongation of at least 20% at 23 °C.

The laminated film according to any one of the above-mentioned <1>, wherein the support substrate which forms the surface layer in the laminated film satisfies the following condition 9; Condition 9: swelling of the support substrate The degree index is 0.01 or more.

The laminated film according to any one of the above-mentioned <1>, wherein the laminated film satisfies the following condition 10; Condition 10: The resin contained in the surface layer contains the following (5) (5) a fluorine compound segment.

The laminated film according to any one of the above-mentioned <1>, wherein the laminated film satisfies the following condition 11; Condition 11: the resin contained in the surface layer contains the following (6) (6) polycarbonate segment.

According to the present invention, a laminated film which satisfies moldability, self-healing property, adhesion durability, and antifouling property can be obtained.

1‧‧‧ Temperature (°C)

2‧‧‧Logarithmic decay rate

3‧‧‧ Temperature dependence curve of logarithmic decay rate

4‧‧‧ Temperature (°C)

5‧‧‧ Storage elastic modulus (MPa)

6‧‧‧ Temperature dependence curve of storage elastic modulus

7‧‧‧ Temperature (°C)

8‧‧‧ loss elastic modulus (MPa)

9‧‧‧ Temperature dependence curve of loss elastic modulus

10‧‧‧ Temperature (°C)

11‧‧‧ loss tangent

12‧‧‧The temperature dependence curve of the loss tangent

Fig. 1 is an example of logarithmic decay rate data obtained by the rigid body pendulum test method.

Fig. 2 is an example of storage elastic modulus data obtained by the dynamic viscoelastic method.

Fig. 3 is an example of loss elastic modulus data obtained by the dynamic viscoelastic method.

Fig. 4 is an example of the loss tangent data obtained by the dynamic viscoelastic method.

Before describing the embodiments of the present invention, The technical problem points, that is, moldability, self-healing property, adhesion durability, and antifouling property, are examined from the viewpoint of the inventors.

First, it is described in Patent Document 1 and Patent Document 2. The reason why the self-healing material of the prior art cannot coexist with the adhesion durability is because the self-repairing property is obtained by reducing the density of the crosslinked structure in the coating film in order to make the coating film soft in the prior art. Or formability. However, the effect of side effects is that the amount of penetration of moisture in the air into the coating film is increased, the coating film under long-term use conditions is broken, or the coating film is peeled off from the substrate, and the adhesion durability is insufficient.

Moreover, the techniques of Patent Documents 3 to 5 are due to the improvement of materials. The crosslink density of the surface prevents the penetration of moisture in the air or the penetration of the dye, and exhibits excellent adhesion durability or dye transfer resistance, but on the other hand, it does not exhibit moldability or self-healing property. In addition, even if the material of Patent Document 3 or 4 is combined with the material of Patent Document 1 or 2, the self-healing property and the moldability, the adhesion durability, and the antifouling property are in a trade-off relationship. Furthermore, in the technique of Patent Document 4, the scratch resistance required for the molding material is poor due to the strength of the material. insufficient.

Therefore, the inventors required the molding materials to be required. Moldability and scratch resistance due to self-healing properties, and as a mechanical property of the surface layer, attention is paid to the display of viscoelastic properties, that is, the storage elastic modulus showing the property of elasticity, and the loss elasticity of the property showing viscosity Modulus, the loss tangent divided by the loss elastic modulus divided by the stored elastic modulus. Also, attention is paid to the logarithmic decay rate having the same meaning as the loss tangent.

When the surface layer is subjected to external loads, its mechanics The response is dependent on the aforementioned viscoelastic properties. Due to the loss of the material with low tangent, that is, the material with strong elasticity, the mechanical energy is used to store most of the load. If the load is large, the material exceeding the range of storage can be destroyed. In such a case, scratches and the like occur on the surface layer, and the scratch resistance is insufficient. On the other hand, a material with a high tangent loss, that is, a material having a strong viscous property, has a load as a loss energy, that is, a heat dissipation effect is large, and a stored mechanical energy is relatively small. Therefore, even if the load is large, the possibility of being lower than the range in which it can be stored is high, and the material is not easily destroyed. As a result, it is possible to suppress the occurrence of scratches on the surface layer and the like, and it is excellent in scratch resistance.

Moreover, by making the storage elastic modulus constant In the range, the effect of the loss tangent is further increased. When the storage elastic modulus and the loss tangent of the surface layer are in a specific range, the moldability and self-healing property of the surface layer are improved.

Specifically, it is preferable to make the table of the rigid body pendulum test method The logarithmic decay rate of the top layer becomes a specific range and/or dynamic viscoelasticity The storage elastic modulus and loss tangent of the surface layer of the method become a specific range.

Furthermore, self-healing of the surface layer of the laminated film Sexuality, the reason for focusing on the temperature dependence of the viscoelastic behavior of the surface layer, is based on the following findings: in self-healing materials where the storage elastic modulus at high temperatures is higher than the storage elastic modulus at a certain temperature, As a result of the increase in the storage elastic modulus of the surface layer, the self-healing system is elevated.

The inventors performed the analysis of the above phenomenon, and the result was If scratches occur in the surface layer, the residual stress associated with the displacement is related to the storage elastic modulus. In other words, when the storage elastic modulus of the surface layer is increased, the elastic force inside the surface layer becomes a force for liberating the residual stress accompanying the abrasion, and as a result, the abrasion is repaired.

When the use of this property is envisaged in actual use, The laminated film of the present invention is suitable as a molding material for a smart phone or the like, and when various electronic devices such as smart phones are cooled from the surface of the casing due to heat generated inside, the surface temperature of the self-healing material is also linked. Rise and repair the abrasions that occur at room temperature, so it is expected to increase self-healing.

Specifically, the surface layer of the rigid body pendulum test method is The relative storage elastic modulus at 100 ° C is preferably higher than the relative storage elastic modulus at 25 ° C. Further, the storage elastic modulus of the surface layer of the dynamic viscoelastic method at 100 ° C is preferably higher than the storage elastic modulus at 25 ° C.

Furthermore, the inventors analyzed the durability of the adhesion, The eye is the moisture in the air that penetrates into the surface layer. In particular, it has been found that under long-term use conditions, the infiltrated moisture reaches the surface layer-support substrate interface. The reason for the destruction of the interface is that the surface layer is peeled off from the support substrate. In particular, the self-healing material is considered to have a large amount of moisture intruding into the surface layer due to a decrease in the crosslinking density of the surface layer.

Prevent damage to the surface layer-support substrate interface In the method, the density of the crosslinked structure in the surface layer is initially increased and the adhesion durability is increased, but as described above, it does not coexist with moldability or self-healing property.

Therefore, to explore the formability and self-healing and close The method of coexisting with durability found that it was effective to introduce a hydrophobic segment into the resin contained in the surface layer.

The resin contained in the surface layer contains a hydrophobic chain In the segment, the moisture in the air that penetrates into the surface layer is reduced. Further, if attention is paid to the water to be infiltrated, the amount of water reaching the interface is further reduced by repeatedly contacting the hydrophobic segment from the surface of the surface layer to the interface of the surface layer-supporting substrate. Therefore, the destruction of the surface layer-supporting substrate interface due to the infiltrated moisture can be suppressed, and as a result, the adhesion durability can be improved.

Again, the above effects are repeatedly verified, and the results are found to be imported. Hydrophobic segments from alicyclic structures are particularly effective. Since the alicyclic structure has a three-dimensional structure, the mobility is relatively lower than that of the chain from the chain structure. Therefore, even when the surface layer is deformed at the time of molding or due to a load from the outside, the distribution state of the hydrophobic segments in the surface layer can be suppressed from being dense, and the deterioration of the adhesion durability can be prevented. Further, since this effect does not change the crosslinked structure density of the surface layer, the moldability or self-healing property is not easily lowered due to the alicyclic structure.

Specifically, the resin contained in the surface layer is more The best includes a tricyclic sulfhydryl segment.

Furthermore, the inventors analyzed the dye transfer property, Eye dye transfer procedure. Thus, it has been found that the distinction between the dye transfer to the surface layer, the dye infiltration procedure, and the dye fixing procedure are important.

First, the procedure for dye penetration, due to the dye The infiltration of the water system serves as a medium, so that the penetration of the dye can be suppressed by preventing the penetration of water into the surface layer. By suppressing the penetration of the dye, the chance of fixing the dye described later can be reduced, and as a result, the dye transfer resistance can be improved. As such a method, introduction of a hydrophobic segment into the resin contained in the surface layer, in particular, introduction of a hydrophobic segment derived from an alicyclic structure is effective.

Specifically, for the penetration of the dye, the aforementioned surface layer The resin contained in the resin preferably contains a tricyclic fluorenyl group.

Second, the procedure for dye fixation, if in the surface layer When the affinity between the resin and the dye contained is high, the probability of fixing the dye becomes high. Therefore, by reducing the affinity of the resin contained in the surface layer and the dye, the fixation of the dye can be suppressed, and as a result, the dye transfer resistance can be improved. As such a method, it is effective to introduce a segment having a low affinity for a resin contained in the surface layer and a dye.

Specifically, the resin contained in the surface layer is more Preferably, it comprises a tricyclic sulfhydryl segment, a polycaprolactone segment, and a polycarbonate segment.

Furthermore, the inventors focused on the load at the time of molding or The load occurring at the interface of the surface layer-supporting substrate under long-term use conditions. Found in the molding, will be at the interface of the surface layer - support substrate The mechanical load, that is, the stress or deformation, causes local adhesion failure at the interface of the surface layer-supporting substrate, which causes the formability to decrease. Further, it has been found that under long-term use conditions, since moisture in the air penetrates into the surface layer and breaks the interface between the surface layer and the support substrate, the surface layer is peeled off from the support substrate, which causes the adhesion durability to be lowered. Therefore, a method of preventing the adhesion of the surface layer-support substrate at the interface of the support layer was examined, and as a result, it was found that it is effective to select a support substrate having a surface having a certain affinity with a solvent or more.

If the affinity of the surface of the support substrate with the solvent is high, then When the surface layer is formed on the support substrate, since the components of the surface layer penetrate into the support substrate, the adhesion of the surface layer-support substrate interface can be improved. This is because it is effective for suppressing local adhesion failure of the surface layer-supporting substrate interface or suppressing peeling of the surface layer from the substrate, thereby improving moldability or adhesion durability. Specifically, it is preferred that the swelling index of the support substrate be within a specific range.

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

In order to satisfy the above problems, that is, moldability, self-healing property, adhesion durability, and antifouling property, the laminated film of the present invention is a laminated film having a surface layer on at least one side of a support substrate, and preferably satisfies the following conditions. 1 to 3.

Condition 1: The logarithmic decay rate of the aforementioned surface layer at 25 ° C in the rigid body pendulum test method was 0.1 or more.

Condition 2: The resin contained in the surface layer described above contains the following (1) to (4).

(1) Polycaprolactone segment

(2) urethane bond

(3) Polyoxyalkylene segment and / or polydimethyl siloxane chain segment

(4) Tricyclic sulfhydryl segment

Furthermore, the rigid body pendulum test method will be described later.

Here, the term "resin" means a substance containing a polymer compound.

From the viewpoint of moldability and self-healing property, the laminated film of the present invention is in the rigid body pendulum test method, and the logarithmic decay rate of the surface layer at 25 ° C is preferably 0.1 or more, more preferably 0.2 or more. It is 0.4 or more. The logarithmic decay rate indicates the responsiveness when subjected to a mechanical load, and by making the logarithmic decay rate a specific value, moldability and self-healing property can be improved.

If the logarithmic decay rate is large, the effect of the above-described load from the outside as heat energy is increased, and the moldability and self-healing property are preferably improved. The larger the logarithmic decay rate, the greater the effect, but since the self-healing material has a crosslinked network and has a limit, the upper limit is judged to be about 1.0. On the other hand, when the logarithmic decay rate is less than 0.1, the surface layer may be damaged by external load, and moldability and self-healing property may be lowered.

In order to make the logarithmic decay rate of the surface layer of the rigid body pendulum test method at 25 ° C 0.1 or more, the resin contained in the surface layer can satisfy the condition 2 described above.

The above (1) polycaprolactone segment means a segment represented by Chemical Formula 1, (2) a urethane bond refers to a bond represented by Chemical Formula 2, and (3) a polyoxyalkylene segment refers to a segment. Segment shown by Chemical Formula 3, polydimethyl oxime The alkyl segment means a segment represented by Chemical Formula 4, and the (4) tricyclodecyl segment refers to a segment represented by Chemical Formula 5. The details of these are as follows.

(n is an integer from 1 to 35);

(R ₁ , R ₂ is OH or an alkyl group having 1 to 8 carbon atoms, and each of the formulas has at least one or more, and n is an integer of 100 to 300);

(m is an integer from 10 to 300);

(n is an integer from 1 to 50).

When the resin contained in the surface layer has (1) a polycaprolactone segment, the surface layer obtained by self-repairability is preferably improved.

The resin contained in the surface layer has (2) an amine The urethane bond improves the toughness of the resulting surface layer while improving self-healing properties.

The resin contained in the surface layer has (3) poly The siloxane chain segment and/or the polydimethyl siloxane chain segment can improve the heat resistance and weather resistance of the obtained surface layer or improve the scratch resistance due to the lubricity of the surface layer.

The resin contained in the surface layer contains (4) three The cyclodecyl group segment can improve the moldability, adhesion durability, dye transfer resistance, and toughness of the coating film of the obtained surface layer.

Furthermore, from the viewpoint of adhesion durability, the foregoing In the laminated film, it is preferred to satisfy the following condition 3.

Condition 3: The aforementioned surface of the extension-boil tight test method The adhesion index of the layer is 3 or more.

Further, the extension-boil adhesion test method will be described later.

From the standpoint of adhesion durability, in extension-boil In the adhesion test method, the adhesion index of the surface layer is preferably 3 or more, more preferably 4 or more, and particularly preferably 5. The adhesion index indicates the surface layer and support The adhesion of the layer, the height of the adhesion index indicates the height of the adhesion and the durability of the adhesion.

If the adhesion index is high, especially in the long-term use Further, it is also possible to suppress the peeling of the surface layer from the support substrate, and it is preferable that the adhesion durability is increased. On the other hand, if the adhesion index is less than 3, the surface layer may be peeled off from the support substrate especially under long-term use conditions, and the adhesion durability may be lowered.

In the extension-boil tight test method, in order to The adhesion index of the surface layer is 3 or more, and the resin contained in the surface layer can satisfy the above condition 2.

Furthermore, from the point of view of self-healing and formability It is preferable to satisfy the following condition 4 in the above laminated film.

Condition 4: The aforementioned surface layer of the rigid body pendulum test method is The relative storage elastic modulus at 100 ° C is higher than the relative storage elastic modulus at 25 ° C.

Furthermore, the rigid body pendulum test method will be described later.

From the standpoint of self-healing and formability, rigid body The relative storage elastic modulus of the aforementioned surface layer of the pendulum test method at 100 ° C is preferably higher than the relative storage elastic modulus at 25 ° C. The relative storage elastic modulus indicates how much the material system can be restored when a load is applied, and the increase in the relative storage elastic modulus indicates an improvement in self-healing property.

Relative storage elastic modulus of the aforementioned surface layer at 100 ° C If the relative storage elastic modulus at 25 ° C is higher, the self-healing property is improved by the aforementioned effects.

In order to make the relative surface elastic modulus ratio of the aforementioned surface layer at 100 ° C The relative storage elastic modulus at 25 ° C is high, so that the resin contained in the surface layer can satisfy the condition 2.

Furthermore, from the point of view of self-healing and formability It is preferable to satisfy the following conditions 5 to 7 in the above laminated film.

Condition 5: The aforementioned surface layer of the dynamic viscoelastic method is The storage elastic modulus at 25 ° C is 10 MPa or more and 1,000 MPa or less.

Condition 6: The aforementioned surface layer of the dynamic viscoelastic method is The storage elastic modulus at 100 ° C is higher than the storage elastic modulus at 25 ° C.

Condition 7: The aforementioned surface layer of the dynamic viscoelastic method is The loss tangent at 25 ° C is 0.15 or more.

Furthermore, the dynamic viscoelasticity method will be described later.

From the point of view of self-healing and formability, In the state viscoelasticity method, the storage elastic modulus of the surface layer at 25 ° C is preferably 10 MPa or more and 1,000 MPa or less, more preferably 10 MPa or more and 800 MPa or less, and particularly preferably 150 MPa or more and 500 MPa or less. The storage elastic modulus indicates the elasticity responsiveness under a mechanical load, and the storage modulus and self-healing property can be improved by making the storage elastic modulus a specific value.

If the storage elastic modulus is small to some extent, The effect of the aforementioned loss tangent is enhanced, and the effect from the external load as the heat energy dissipation is increased, and the moldability and self-healing property are improved. The smaller the storage elastic modulus is, the larger the effect is. However, if the storage layer is too small, the toughness of the surface layer is lowered, so the lower limit is determined to be about 10 MPa. On the other hand, if the storage elastic modulus is larger than 1,000 MPa, there is a load from the outside. The surface layer is destroyed, and the formability and self-healing property are lowered.

In order to make the aforementioned surface layer of the dynamic viscoelastic method When the storage elastic modulus at 25 ° C is 10 MPa or more and 1,000 MPa or less, the resin contained in the surface layer can satisfy the above condition 2.

From the point of view of self-healing, dynamic viscoelastic method The storage elastic modulus of the aforementioned surface layer at 100 ° C is preferably higher than the storage elastic modulus at 25 ° C. The storage elastic modulus indicates how much the material system can be restored when a load is applied, and the rise in the storage elastic modulus indicates an improvement in self-healing property.

The storage modulus of the aforementioned surface layer at 100 ° C When the storage elastic modulus at 25 ° C is high, the self-healing property is improved by the aforementioned effects. In order to make the storage elastic modulus of the surface layer at 100 ° C higher than the storage elastic modulus at 25 ° C, the resin contained in the surface layer described above can satisfy the aforementioned condition 2.

From the point of view of formability and self-repairability, this issue The laminated film of Ming is in the dynamic viscoelastic method, and the loss tangent of the surface layer at 25 ° C is preferably 0.15 or more, more preferably 0.20 or more, and particularly preferably 0.30 or more. The loss tangent indicates the responsiveness when subjected to a mechanical load, and the moldability and self-healing property can be improved by making the loss tangent a specific value.

If the loss tangent is large, the aforementioned load from the outside is made. The effect of dissipating heat energy is increased, and the formability and self-healing property are improved. The larger the loss tangent is, the larger the effect is. However, since the self-healing material has a crosslinked network and has a limit, the upper limit value is judged to be about 1.00. On the other hand, if the loss tangent is less than 0.15, there is a load from the outside. Destroy the surface layer, and reduce the formability and self-healing properties.

In order to make the aforementioned surface layer of the dynamic viscoelastic method The loss tangent at 25 ° C is 0.15 or more, and the resin contained in the surface layer can satisfy the above condition 2.

Furthermore, from the viewpoint of formability, the above laminate In the film, it is preferred to satisfy the following condition 8.

Condition 8: The aforementioned surface layer of the tensile test method is at 23 ° C The crack elongation is 20% or more.

Further, the tensile test method will be described later.

From the viewpoint of moldability, the aforementioned tensile test method The crack elongation of the surface layer at 23 ° C is preferably 20% or more, more preferably 30%, and particularly preferably 40% or more. The crack elongation indicates the followability at the time of molding, and the magnitude of the crack elongation indicates the height of the moldability.

If the crack elongation at 25 ° C is large, the above product The layer film can follow the shape of the formed article, so the moldability is increased. The larger the crack elongation at 23 ° C, the better, but the difference between the surface layer and the supporting substrate at the time of molding is different, so the upper limit is determined to be about 500%. On the other hand, when the crack elongation at 25 ° C is less than 20%, the film is introduced into the surface layer during the molding process to cause molding failure, and the moldability may be lowered.

In order to make the crack elongation at 25 ° C 20% or more, the resin contained in the surface layer described above can satisfy the above condition 2.

Further, from the viewpoint of moldability and adhesion durability, it is preferable that the laminated film satisfies the following condition 9 as follows.

Condition 9: The swelling index of the support substrate is 0.01 on.

In addition, the measuring method of the swelling degree index is mentioned later.

The swelling index of the support substrate is preferably 0.01 or more, more preferably 0.05 or more, and still more preferably 0.10 or more. The swelling index indicates the affinity with the solvent and the coating composition, and the degree of the swelling index indicates the height of the adhesion between the supporting substrate and the surface layer, that is, the height of the moldability or the adhesion durability.

When the swelling index of the support substrate is large, the adhesion between the surface layer and the support substrate is increased, and the moldability or the adhesion durability is increased. The larger the swelling index, the better, but when it is too large, the support substrate is destroyed when the surface layer is formed, so the upper limit is judged to be about 10. On the other hand, when the degree of swelling index is less than 0.01, the interface between the surface layer and the supporting substrate may be broken at the time of deformation due to molding or deterioration over a long period of use, and the moldability or the adhesion durability may be lowered.

In order to make the swelling index of the support substrate 0.01 or more, a support substrate having specific surface physical properties may be selected.

Further, from the viewpoint of the antifouling property, it is preferable that the laminated film 10 satisfies the following condition 10.

Condition 10: The resin contained in the surface layer contains the following (5).

(5) Fluorine compound segment

The term "resin" as used herein refers to a substance containing a polymer compound, and the range thereof ranges from the polymer to the oligomer.

The fluorochemical segment described in the above (5) is selected from the group consisting of fluoroalkyl, fluoroalkyl, fluoroalkenyl, fluoroalkanediyl and fluoroalkoxy. The segment of at least one of the groups consisting of the alkanediyl groups is more preferably the fluorochemical segment-based fluoropolyether segment. The fluoropolyether segment is a segment composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group or the like, and is represented by a chemical formula (6) or a chemical formula (7).

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

The details of the fluoropolyether segment will be described later, and the resin constituting the surface layer is such that the molecules exhibiting low surface energy are present on the outermost surface at a high density.

The chain length of the fluoropolyether segment has a preferred range, carbon number It 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 carbon number is 3 or less, the oil repellency may be lowered because the surface energy is not sufficiently lowered, and when the solubility is 13 or more, the solubility of the solvent may be lowered, and the grade of the surface layer may be lowered.

The resin contained in the surface layer contains (5) fluorine The compound segment can improve the adhesion durability and resistance of the obtained surface layer. Dye transfer is preferred.

Further, from the viewpoint of self-healing property and moldability, it is preferable that the laminated film as described above satisfy the following condition 11.

Condition 11: The resin contained in the surface layer contains the following (6).

(6) polycarbonate segment

The term "resin" as used herein refers to a substance containing a polymer compound, and the range thereof ranges from the polymer to the oligomer.

The above (6) polycarbonate segment means a segment represented by Chemical Formula 8. The details of these are as follows.

(n is an integer of 2 to 16; R _{3 is} an alkylene group or a cycloalkyl group having 1 to 8 carbon atoms).

When the resin contained in the surface layer has (6) a polycarbonate segment, the surface layer obtained by self-repairability and moldability can be preferably improved.

Hereinafter, embodiments of the present invention will be described in detail.

[Laminated film and surface layer]

The laminated film of the present invention has a surface layer exhibiting specific characteristics and can be planar (film, sheet, plate). Here, the surface layer which exhibits a specific characteristic means the surface layer which satisfies the conditions 1 and 2 mentioned above.

The surface layer is formed in addition to the subject of the present invention. Sex, self-healing, adhesion durability, anti-fouling, but also gloss, fingerprint resistance, design, anti-reflection, anti-static, electrical conductivity, hot wire reflection, near-infrared absorption, electromagnetic wave shielding, easy to follow, etc. Other functions.

The thickness of the aforementioned surface layer is not particularly limited, but It is preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less, and the thickness can be selected in accordance with the other functions described above.

[support substrate]

The resin constituting the support substrate used for the laminated film of the present invention may be either a thermoplastic resin or a thermosetting resin, and may be a homopolymer resin or a copolymer or a blend of two or more types. The resin constituting the support substrate is preferably a thermoplastic resin for good moldability.

As an example of a thermoplastic resin, polyethylene can be used. Gather Propylene. Polystyrene. Polyolefin resin such as polymethylpentene, alicyclic polyolefin resin, nylon 6. Polyamide resin such as nylon 66, aromatic polyamide resin, polyester resin, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin. Trifluoroethylene resin. Chlorofluoroethylene resin. Tetrafluoroethylene-6 fluoropropylene copolymer. A fluororesin such as a vinylidene fluoride resin, an acrylic resin, a methacrylic resin, a polyacetal resin, a polyglycolic acid resin, or a polylactic acid resin. The thermoplastic resin is preferably a resin having sufficient elongation and followability. From strength. Heat resistance. From the viewpoint of transparency, the thermoplastic resin is particularly preferably a polyester resin, a polycarbonate resin, an acrylic resin or a methacrylic resin.

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

Moreover, various additions can be added to the support substrate. Agents such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, thermal stabilizers, slip agents, infrared absorbers, ultraviolet absorbers, dopants for refractive index adjustment, and the like. The support substrate may be either a single layer structure or a laminate structure.

On the surface of the support substrate, the aforementioned table may also be formed Various surface treatments are applied before the top layer. Examples of the surface treatment include pharmaceutical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. . Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment, and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

Moreover, the support substrate used in the laminated film of the present invention, As described above, it is preferred to use a support substrate having a degree of swelling index of 0.01 or more (hereinafter, support substrate A). When the support substrate A is used, the adhesion between the surface layer and the support substrate is increased as described above, and as a result, moldability or adhesion durability is improved.

As the support substrate A used in the present invention, suitably Products such as "Cosmoshine" (registered trademark) A4300, A4100 (Toyobo Co., Ltd.), "Panlite" (registered trademark) PC-2151 (Teijin Chemicals Co., Ltd.), and the like are 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 may be subjected to a step of applying a coating composition on at least one side of the supporting substrate, and a drying step or a hardening step as necessary. And got it. Preferably, the coating composition comprises (1) a polycaprolactone segment, (2) a urethane bond, (3) a polyoxyalkylene segment, and/or a polydimethyl siloxane. a resin of a segment, (4) a tricyclic fluorenyl group, or a material (hereinafter referred to as a precursor) which can be formed in a coating process, which is used in a surface layer by a manufacturing method described later. The resin contained may have such segments and bonds.

Furthermore, the coating composition preferably contains (5) A resin or precursor of a fluorochemical segment. Further, a resin or a precursor containing the (6) polycarbonate segment may be contained instead of the resin or precursor containing the (5) fluorochemical segment, or may contain a resin or precursor containing the (5) fluorochemical segment. Both the resin and the precursor containing the (6) polycarbonate segment.

Further, the coating composition may contain a solvent or other components described later.

[polycaprolactone segment]

In the laminated film of the present invention, the resin contained in the surface layer preferably contains (1) a polycaprolactone segment. The so-called polycaprolactone segment here, It means the segment shown in the above Chemical Formula 1. When the resin contained in the surface layer contains the (1) polycaprolactone segment, it is preferable because the surface layer can be improved in self-healing property and moldability.

The coating composition used to form the surface layer can have a polycaprolactone segment in the resin contained in the surface layer by including a resin or a precursor containing a polycaprolactone segment.

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

As the resin containing a polycaprolactone segment, polycaprolactone having a hydroxy group having 2 to 3 functions is particularly preferred. Specific examples of the polycaprolactone having a hydroxy group having a 2-3 function include polycaprolactone diol represented by Chemical Formula 9, polycaprolactone triol represented by Chemical Formula 10, or polycondensation represented by Chemical Formula 11. Caprolactone modified hydroxyethyl (meth)acrylate. Here, the polycaprolactone diol represented by Chemical Formula 9 and the polycaprolactone triol represented by Chemical Formula 10 are generally referred to as polycaprolactone polyol.

The polycaprolactone diol represented by Chemical Formula 9 is represented by the following.

Here, m+n is an integer of 4 to 35, and R ₄ is any one of C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ , C(CH ₃ ) ₃ or (CH ₂ ) ₂ .

Further, the polycaprolactone triol represented by Chemical Formula 10 is represented by the following.

Here, l+m+n is an integer of 3 to 30, and R ₅ is any one of CH ₂ CHCH ₂ , CH ₃ C(CH ₂ ) ₃ or CH ₃ CH ₂ C(CH ₂ ) ₃ .

Further, polycaprolactone-modified (hydroxy)ethyl methacrylate is represented by the following.

Here, n is an integer of 1 to 25, and R ₆ is either H or CH ₃ . Further, when R ₆ is either H or CH ₃ , these are referred to as active energy ray-polymerizable caprolactone. Further, the so-called (meth) acrylate means methacrylate or acrylate.

The so-called active energy ray polymerization is by A property of crosslinking with an active energy ray such as an ultraviolet ray (UV line) or an electron beam (EB line), and a compound having a functional group such as a (meth) acrylate group is compatible. Examples of the other active energy ray-polymerizable caprolactone include polycaprolactone-modified (hydroxy) methacrylate, polycaprolactone-modified (hydroxy) hydroxybutyl acrylate, and the like.

Furthermore, in the present invention, the polycaprolactone containing segment The resin, in addition to the polycaprolactone segment, may also contain (or copolymerize) other segments or monomers. For example, a compound containing a tricyclodecyl chain segment, a polydimethylsiloxane chain segment or a polyoxyalkylene segment, a polycarbonate segment, or an isocyanate compound to be described later may be contained (or copolymerized).

Further, in the present invention, a tree containing a polycaprolactone segment The polycaprolactone segment in the fat preferably has a weight average molecular weight of 500 to 2,500 and a weight average molecular weight of preferably 1,000 to 1,500. When the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, it is preferable because the effect of self-healing property is further exhibited and the scratch resistance is further increased.

Even when the polycaprolactone segments are copolymerized, or In the case of adding 100% by mass of the total solid content of the coating composition for forming the surface layer, the content of the polycaprolactone segment is 5 to 50% by mass, and the self-healing property, design property, and moldability are The point is better.

[urethane bond]

In the laminated film of the present invention, the resin contained in the surface layer preferably contains (2) a urethane bond. Here, the urethane bond is a segment represented by the above Chemical Formula 2. When the resin contained in the surface layer contains (2) a urethane bond, the toughness of the surface layer can be improved and self-healing property can be improved.

a coating composition used to form a surface layer The resin contained in the surface layer can have a urethane bond by containing a commercially available urethane-modified resin. Further, at the time of forming the surface layer, by coating a coating composition containing the difference as a precursor The cyanate group-containing compound and the hydroxyl group-containing compound form a urethane bond in the coating step, and the surface layer may also contain a urethane bond.

In the present invention, it is preferred to have an isocyanate group and The hydroxyl group reacts to form a urethane bond, and the resin contained in the surface layer has a urethane bond. By reacting an isocyanate group with a hydroxyl group to form a urethane bond, the toughness of the surface layer can be improved while improving self-healing properties.

Further, when the above-mentioned resin containing polycaprolactone segments or contains When a resin having a tricyclic fluorenyl group segment, a resin containing a polycarbonate segment, a resin containing a polyoxyalkylene segment described later, or a resin containing a polydimethylsiloxane chain segment has a hydroxyl group, A urethane bond is formed between the resin and the isocyanate group-containing compound as a precursor due to heat or the like. When a surface layer is formed by using a compound containing an isocyanate group and a resin having a polyoxyalkylene segment having a hydroxyl group or a resin having a polydimethylsiloxane chain having a hydroxyl group, the surface layer can be improved in toughness. And elastic recovery (self-healing) and surface slipperiness are preferred.

In the present invention, the so-called isocyanate group-containing compound The substance refers to a resin containing an isocyanate group or a monomer or oligomer containing a cyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, a trimethylolpropane adduct of toluene diisocyanate, and a trimethylolpropane adduct of hexamethylene diisocyanate. Trimethylolpropane adduct of isophorone diisocyanate, isomeric cyanurate of toluene diisocyanate, isomeric cyanurate of hexamethylene diisocyanate, hexamethylene isocyanate A polyisocyanate such as a diurea or a terminal block of the above isocyanate.

Such isocyanate group-containing compounds Among them, aliphatic isocyanates are more self-healing than alicyclic or aromatic isocyanates, and are preferred. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Further, the isocyanate group-containing compound is particularly preferably an isocyanate having an isomeric cyanate ring, and is preferably a hexamethylene diisocyanate isocyanurate. An isocyanate having an isomeric cyanate ring forms a surface layer having both self-healing properties and heat resistance properties.

[Polyoxyalkylene segment and / or polydimethyl siloxane chain segment]

In the laminated film of the present invention, the resin contained in the surface layer preferably contains (3) a polyoxyalkylene segment and/or a polydimethylsiloxane chain segment. Here, the polyoxyalkylene segment refers to the segment shown in the above Chemical Formula 3, and the polydimethylsiloxane chain segment refers to the segment shown in the above Chemical Formula 4. If the resin contained in the surface layer contains (3) a polyoxyalkylene segment and/or a polydimethylsiloxane chain, the polydimethylsiloxane chain is disposed in the surface layer. On the surface side, since the lubricity of the surface layer is improved, there is an effect of dissipating the load, and since the occurrence of scratches that cannot be repaired in the surface layer is suppressed, the self-healing property of the surface layer can be improved.

The coating composition used to form the surface layer can be made by containing a resin or a precursor containing a polyoxyalkylene segment and/or a polydimethylsiloxane chain segment. It has a polyoxyalkylene segment and/or a polydimethyloxyalkylene segment.

Further, the resin or precursor containing a polyoxyalkylene segment and/or a polydimethylsiloxane chain segment preferably contains a reactive site. This reaction A sexual site refers to a site that reacts with other components due to external energy such as heat or light. Examples of such a reactive site include a stanol group in which alkoxyalkylene group and alkoxyalkylene group are hydrolyzed, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allylic group, from the viewpoint of reactivity. Base, propylene sulfhydryl, methacryl fluorenyl and the like. Among them, from the viewpoint of reactivity and handleability, a vinyl group, an allyl group, an alkoxyalkyl group, a decyl ether group or a stanol group, or an epoxy group, an acryl group or a methacryl group is preferred.醯基.

Hereinafter, the polyoxyalkylene segment and the polydimethyloxyalkylene segment are sequentially described in detail.

[polyoxyalkylene segment]

In the present invention, the term "polyoxyalkylene chain segment" means the segment shown in the above Chemical Formula 3.

In the present invention, a hydrazine containing a hydrolyzable decyl group can be used. A partial hydrolyzate of an alkane compound, an organic cerium sol or a composition in which a hydrolyzable decane compound having a radical polymer is added to the organic cerium sol is used as a compound having a polyoxyalkylene segment.

a compound having a polyoxyalkylene segment, which can be exemplified by tetraalkane Oxydecane, methyltrialkoxydecane, dimethyldialkoxydecane, γ-glycidoxypropyltrialkoxydecane, γ-glycidoxypropylalkyldide Full or partial decane compound having a hydrolyzable decyl group such as decane, γ-methacryloxypropyltrialkoxy decane or γ-methacryloxypropylalkyl dialkoxy decane The hydrolyzate or an organic cerium sol dispersed in an organic solvent, or a hydrolyzed decane compound having a hydrolyzable decyl group added to the surface of the organic cerium sol.

Further, in the present invention, a tree containing a polyoxyalkylene segment The fat may contain (copolymerize) other segments or the like in addition to the polyoxyalkylene segment. For example, a monomer component having a polycaprolactone segment, a tricyclodecanyl segment, a polycarbonate segment, or a polydimethylsiloxane chain segment may be contained (copolymerized).

In the present invention, as a tree containing a polyoxyalkylene segment The lipid is preferably a monomer which copolymerizes a hydroxyl group which reacts with an isocyanate group. In the resin containing a polyoxyalkylene segment, when a monomer having a hydroxyl group reactive with an isocyanate group is copolymerized, the toughness of the surface layer is increased.

When the resin containing a polyoxyalkylene segment has a hydroxyl group In the case of a copolymer, if a coating layer comprising a resin (copolymer) containing a polyoxyalkylene segment having a hydroxyl group and a compound containing an isocyanate group is used to form a surface layer, it is possible to efficiently form a polysiloxane. a surface layer of an alkane segment and a urethane bond.

[polydimethyl siloxane chain segment]

In the present invention, the polydimethyl siloxane chain segment means the segment shown in the above Chemical Formula 4.

In the present invention, as having a polydimethyl siloxane chain The compound of the segment is preferably a copolymer obtained by copolymerizing a vinyl monomer in a polydimethylsiloxane chain segment.

When the compound having a polydimethyl siloxane chain segment is When it is a copolymer with a vinyl monomer, it may be any of a block copolymer, a graft copolymer, and a random copolymer. When the compound of the polydimethylsiloxane chain segment is a copolymer with a vinyl monomer, this is called a polydimethylsiloxane derivative.

As a compound having a polydimethylsiloxane chain segment (Polydimethylsiloxane-based copolymer), the synthetic polydimethylsiloxane-based block copolymer can be produced by a living polymerization method, a polymer initiator method, a polymer chain transfer method, or the like, but When productivity is considered, it is preferable to use a polymer initiator method or a polymer chain transfer method.

Polydimethyl hydrazine when using a polymer starter method The compound of the oxyalkylene chain (polydimethyl siloxane) is a polymer azo-based radical polymerization initiator represented by Chemical Formula 12, which is copolymerized with other vinyl monomers. And got it.

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

Moreover, it is also possible to carry out the peroxymonomer and the unsaturated group. The polydimethylsiloxane is copolymerized at a low temperature to synthesize a two-stage polymerization in which a peroxide-based prepolymer is introduced into a side chain to copolymerize the prepolymer with a vinyl monomer.

When a polymer chain transfer method is used, a compound having a polydimethylsiloxane chain (polydimethylsiloxane) copolymer, for example, a polyfluorene oxide represented by Chemical Formula 13 may be added to the HS-CH. ₂ COOH or HS-CH ₂ CH ₂ COOH or the like to form a compound having an SH group, and then obtained by copolymerization of the SH group with a vinyl monomer by chain transfer of the SH group.

(m is an integer from 10 to 300).

As a compound having a polydimethylsiloxane chain segment (polydimethylsiloxane) copolymer, a synthetic polydimethylsiloxane coupled graft copolymer can be obtained, for example, by a compound represented by Chemical Formula 14 , that is, a methacrylate of polydimethyl methoxy alkane or the like is copolymerized with a vinyl monomer, and is easily obtained.

(m is an integer from 10 to 300).

As a compound with a polydimethylsiloxane chain segment Examples of the vinyl monomer used for the copolymer of the copolymer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, and A. Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, octadecyl 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 epoxypropyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, propylene Indoleamine, methacrylamide, N-methylol acrylamide, N,N-dimethyl decylamine, N,N-dimethylaminoethyl methacrylate, N,N methacrylate -diethylaminoethyl ester, diethyl propylene decylamine, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, olefin Propanol and the like.

Further, the polydimethyl siloxane derivative is preferably in the form of An aromatic hydrocarbon solvent such as benzene or xylene; a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate or butyl acetate; or ethanol or isopropyl alcohol; The alcohol-based solvent or the like is produced by a solution polymerization method alone or in a mixed solvent. Further, it is preferred to use a polymerization initiator such as benzamidine peroxide or azobisisobutylcarbonitrile in combination. The polymerization reaction is preferably carried out at 50 to 150 ° C for 3 to 12 hours.

In the polydimethyl siloxane series copolymer of the present invention The amount of the polydimethylsiloxane chain segment is preferably from 1 to 30 mass in 100% by mass of all components of the polydimethylsiloxane derivative in terms of lubricity or stain resistance of the surface layer. %. Further, the polydimethylsiloxane chain segment preferably has a weight average molecular weight of 1,000 to 30,000.

Even if the polydimethylsiloxane chain is copolymerized In the case of 100% by mass of all the components of the coating composition used for forming the surface layer, the dimethyl siloxane chain segment is 1 to 20% by mass, and is self-healing and resistant to contamination. The point of properties, weather resistance and heat resistance is preferred. 100% by mass of the entire composition of the coating composition Contains solvents that are not involved in the reaction. Contains the monomer components involved in the reaction.

In the present invention, used as a surface layer for forming The coating composition, when a resin containing a polydimethylsiloxane chain segment is used, may contain (copolymerization) other segments or the like in addition to the polydimethylsiloxane chain segment. For example, it is also possible to contain (copolymerization) a polycaprolactone segment, a tricyclodecanyl segment, a polycarbonate segment or a polyoxyalkylene segment.

a coating composition used to form a surface layer, Using a copolymer of a polycaprolactone segment and a polydimethyl siloxane chain, a copolymer of a polycaprolactone segment and a polyoxyalkylene segment, a polycaprolactone segment and a polydimethyl hydrazine a copolymer of an oxyalkylene segment and a polyoxyalkylene segment, and the like. The surface layer obtained by using such a coating composition may have a polycaprolactone segment and a polydimethylsiloxane chain segment and/or a polyoxyalkylene segment.

In order to form a polycaprolactone segment, polyoxyalkylene In the coating composition used for the surface layer of the segment and the polydimethylsiloxane chain segment, the reaction of the polydimethylsiloxane derivative, the polycaprolactone, and the polyoxyalkylene can be polymerized. When the dimethyloxane-based copolymer is synthesized, a polycaprolactone segment and a polyoxyalkylene segment are appropriately added to carry out copolymerization.

[Tricyclic sulfhydryl segment]

In the laminated film of the present invention, the resin contained in the surface layer preferably contains a (4) tricyclononyl group segment. Here, the term "tricyclic fluorenyl group" means the segment shown in the above Chemical Formula 5. When the resin contained in the surface layer contains the (4) tricyclononyl group segment, the antifouling property and the adhesion durability of the surface layer can be improved.

The coating composition used to form the surface layer can be made in the surface layer by including a resin or a precursor containing a tricyclononyl group segment. The resin contained has a tricyclic fluorenyl segment.

The structure of the tricyclic fluorenyl group is as described above. The resin or precursor containing a tricyclononyl group segment is preferably a compound represented by the formula 15 in the above coating composition.

R ₇ represents an alkanediyl group, an alkanetriyl group, an oxyalkyldiyl group, an oxyalkylene group, and an ester structure derived therefrom, a urethane structure, an ether structure, and three In either of the structures, D ₁ represents a reactive site.

The reactive site refers to external energy due to heat or light. The amount of the part that reacts with other ingredients. Examples of such a reactive site include a stanol group in which alkoxyalkylene group and alkoxyalkylene group are hydrolyzed, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allylic group, from the viewpoint of reactivity. Base, propylene sulfhydryl, methacryl fluorenyl and the like. Among them, from the viewpoint of reactivity and handleability, a vinyl group, an allyl group, an alkoxyalkyl group, a decyl ether group or a stanol group, or an epoxy group or a propylene group (methacryl oxime) is preferred. )base.

More preferably, it is any one of an R ₇ -based alkanediyl group, a urethane structure or an ester structure, and D ₁ is a propylene (methacryl oxime) group or a hydroxyl group.

As a preferred resin or precursor containing a tricyclic fluorenyl group for the aforementioned coating composition, in the above Chemical Formula 15, D ₁ is an acrylonitrile (methacryl oxime) group, that is, a tricyclic fluorenyl group Examples of commercially available materials of (meth) acrylate include IRR214-K (Daicel-Allnex Co., Ltd.), SR833S (Sartomer), FA-513AS, and FA-513M (Hitachi Kasei Co., Ltd.). A-DCP, DCP (Xinzhongcun Chemical Co., Ltd.), Light Acrylate DCP-A (Kyoeisha Chemical Co., Ltd.).

[fluorochemical segment]

In the laminated film of the present invention, the resin contained in the surface layer preferably contains (5) a fluorine compound segment. When the resin contained in the surface layer contains the (5) fluorine compound segment, the antifouling property and the fingerprint resistance of the surface layer can be improved.

a coating composition used to form a surface layer The resin contained in the surface layer can have a fluorine compound segment by including a resin or a precursor containing a fluorine compound segment.

Fluorine compound segment means comprising selected from fluoroalkyl, fluorine A segment of at least one of the group consisting of an oxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluoroaloxanediyl group.

Here, the so-called fluoroalkyl, fluoroalkyl, fluoroolefin a fluoroalkanediyl group or a fluoroalkanediyl group, which is a substituent which is partially or wholly substituted with a fluorine of an alkyl group, an oxyalkyl group, an alkenyl group, an alkanediyl group or an oxyalkanediyl group. All of them are substituents mainly composed of a fluorine atom and a carbon atom, and may have a branch in the structure, and may also form a dimer, a trimer, an oligomer, a polymer structure in which a plurality of structures having such a structure are linked. .

Further, as the fluorine compound segment, fluoropolymer is preferred An ether segment, which is a moiety composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., and more preferably represented by a chemical formula (6) or a chemical formula (7). The fluoropolyether segment is as described above.

The resin contained in the surface layer contains a fluoride compound In the case of the article segment, the aforementioned coating composition preferably contains the following fluorine compound. This fluorine compound is a compound represented by Chemical Formula 16.

R ^f1 -R _B -D ¹ . . . Chemical formula 16

Here, R ^f1 represents a fluorine compound segment, R ₈ represents an alkanediyl group, an alkanetriyl group, and an ester structure derived therefrom, a urethane structure, an ether structure, and three Structure, D ¹ represents a reactive site.

This reactive site refers to a site that reacts with other components due to external energy such as heat or light. Examples of such a reactive site include a stanol group in which alkoxyalkylene group and alkoxyalkylene group are hydrolyzed, or a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allylic group, from the viewpoint of reactivity. Base, propylene sulfhydryl, methacryl fluorenyl and the like. Among them, from the viewpoint of reactivity and handleability, a vinyl group, an allyl group, an alkoxyalkyl group, a decyl ether group or a stanol group, or an epoxy group or a propylene group (methacryl oxime) is preferred. )base.

One of the fluorine compounds is exemplified by the compounds shown below. 3,3-trifluoropropyltrimethoxydecane, 3,3,3-trifluoropropyltriethoxydecane, 3,3,3-trifluoropropyltriisopropoxydecane, 3,3, 3-trifluoropropyltrichloromethane, 3,3,3-trifluoropropyltriisocyanate decane, 2-perfluorooctyltrimethoxydecane, 2-perfluorooctylethyltriethoxydecane, 2 -Perfluorooctylethyltriisopropoxydecane, 2-perfluorooctylethyltrichlorodecane, 2-perfluorooctyl isocyanate decane, 2,2,2-trifluoroethyl acrylate, propylene Acid 2,2,3,3,3-pentafluoropropyl ester, 2-perfluorobutyl ethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, acrylic acid 3-perfluorohexyl-2-hydroxypropyl ester, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecyl acrylate, 2-all of acrylic acid Fluoro-3-methylbutylethyl ester, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoroacrylate -5-Methylhexyl-2-hydroxypropyl ester, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate , hexadecafluorodecyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, methacrylic acid 2 -Perfluorobutylethyl ester, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctyl methacrylate, 3-perfluorooctyl-2-hydroxypropane methacrylate Ester, 2-perfluorodecyl methacrylate, 2-perfluoro-3-methylbutyl methacrylate, 3-perfluoro-3-methyl methacrylate Butyl-2-hydroxypropyl ester, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, methacrylic acid 2 -Perfluoro-7-methyloctylethyl ester, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate Ester, dodecafluoroheptyl methacrylate, hexadecafluorodecyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, tripropylene decyl-heptadecafluoro Decenyl-pentaerythritol and the like.

Furthermore, the fluorine compound may have a plurality of molecules per molecule. Fluoropolyether site.

As a commercially available example of the above fluorine compound, RS-75 (DIC stock) is exemplified. Ltd.), Optool DAC-HP (DAIKIN Industries Co., Ltd.), C10GACRY, C8HGOL (Oil Products Co., Ltd.), etc., and can use such products.

[polycarbonate segment]

In the laminated film of the present invention, the resin contained in the surface layer preferably contains (6) a polycarbonate segment. The polycarbonate segment referred to herein means the segment shown in the above Chemical Formula 8. When the resin contained in the surface layer contains (6) a polycarbonate segment, it is preferable to improve the toughness and self-healing property of the surface layer.

The coating composition used to form the surface layer can have a polycarbonate segment in the resin contained in the surface layer by including a resin or a precursor containing a polycarbonate segment.

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

As the resin containing a polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferred. Specifically, it is a polycarbonate diol represented by the chemical formula (17).

(R ₉ is any one of alkyl groups having 1 to 8 carbon atoms, and n is an integer of 1 or more).

The number of repetitions of the polycarbonate diol-based carbonate unit may be any, but if the number of repetitions of the carbonate unit is too large, the urethane (methyl) Since the strength of the cured acrylate is lowered, the number of repetitions n is preferably 10 or less. Further, the polycarbonate diol may be a mixture of two or more kinds of polycarbonate diols having different numbers of repeating carbonate units.

The polycarbonate diol coefficient amount average molecular weight is preferably 500~10,000, more preferably 1,000~5,000. When the number average molecular weight is less than 500, it may be difficult to obtain appropriate flexibility, and if the number average molecular weight exceeds 10,000, heat resistance or solvent resistance may be lowered.

Further, as the polycarbonate diol used in the present invention, Suitably exemplified UH-CARB, UD-CARB, UC-CARB (Ube Industries Co., Ltd.), PLACCEL CD-PL, PLACCEL CD-H (DAICEL Chemical Industry Co., Ltd.), KURARAY Polyol C Series (KURARAY Limited Shares) Company), Duranol series (Asahi Kasei Chemical Co., Ltd.) and other products. These polycarbonate diols can be used singly or in combination of two or more kinds.

Furthermore, in the present invention, the polycarbonate segment is included The resin or precursor, in addition to the polycarbonate segment, may also contain (or copolymerize) other segments or monomers. For example, a compound containing the aforementioned polycaprolactone segment, tricyclodecyl segment, polydimethylsiloxane chain segment or polyoxyalkylene segment, or isocyanate compound may be contained (or copolymerized).

In the present invention, it is preferred that the aforementioned isocyanic acid is contained The ester group compound reacts with the hydroxyl group of the polycarbonate diol, and is used as a urethane (meth) acrylate for the coating composition, and the surface layer can have (6) a polycarbonate segment and (2) The urethane bond results in an increase in the toughness of the surface layer while improving self-healing properties.

[solvent]

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

The term "solvent" as used herein refers to after coating. In the drying step, almost all of the evaporation can be carried out, and it is a liquid substance at normal temperature and normal pressure.

Here, the type of solvent is a molecular knot constituting a solvent. The structure decided. That is, even if the same element composition and the type and number of functional groups are the same, the binding relationship is different (structural isomers); and although not the structural isomers described above, what configuration is adopted in the 3-dimensional space Those that cannot be closely overlapped (stereoisomers) are handled as solvents of different types. For example, 2-propanol and n-propanol are operated as dissimilar solvents.

Further, when a solvent is contained, it is preferred to exhibit the following characteristics Solvent.

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

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

When the relative evaporation rate of the aforementioned solvent is greater than 0.4, Since the time required for the alignment of the polyoxyalkylene segment and/or the polydimethylsiloxane chain segment and the fluorine compound segment with respect to the outermost surface in the surface layer is shortened, the resulting laminated film occurs. Reduced self-healing and anti-fouling properties. Further, the lower limit of the relative evaporation rate of the solvent B is not particularly limited as long as it is a solvent which can be removed from the coating film by evaporation in the drying step, and may be 0.005 or more in a general coating step.

As solvent B, there is isobutyrone (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: 0.1), cyclohexyl Ketone (relative evaporation rate: 0.32) and the like.

[Other ingredients in the coating composition]

Further, the coating composition preferably contains a polymerization initiator or a hardener or a catalyst. The polymerization initiator and the catalyst are used to promote the hardening of the surface layer. As the polymerization initiator, it is preferred that the component contained in the coating composition can initiate or promote polymerization, condensation or crosslinking reaction due to anion, cation, radical polymerization or the like.

Various polymerization initiators, hardeners and catalysts can be used. By. Further, the polymerization initiator, the curing agent, and the catalyst may be used singly or in combination with a plurality of polymerization initiators, hardeners, and catalysts. Further, an acid catalyst or a thermal polymerization initiator may be used in combination. Examples of the acidic catalyst include an aqueous hydrochloric acid solution, formic acid, acetic acid, and the like. Examples of the thermal polymerization initiator include a peroxide and an azo compound. In addition, as Examples of the photopolymerization initiator include an alkylphenone compound, a sulfur-containing compound, a mercaptophosphine oxide compound, and an amine compound. Further, examples of the crosslinking catalyst that promotes the formation reaction of the urethane bond include dibutyltin dilaurate and dibutyltin diethylhexanoate.

Further, the coating composition may also contain an alkoxyl group Other crosslinking agents such as a melamine crosslinking agent such as melamine, an acid anhydride crosslinking agent such as 3-methyl-hexahydrophthalic anhydride, or an amine crosslinking agent such as diethylaminopropylamine.

As a photopolymerization initiator, from the viewpoint of hardenability, An alkylphenone-based compound is preferred. Specific examples of the alkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and 2- Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-phenyl)-1- Butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-phenyl)-1-butane, 2-benzyl-2-di Methylamino-1-(4-morpholinophenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-morpholinyl)phenyl]-1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1-[4-(2- Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxydiethylene, and the materials thereof Polymer quantifiers.

Moreover, as long as it does not impair the effect of the present invention, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, or the like may be added to the coating composition for forming the surface layer. Thereby, the surface layer may contain a leveling agent, an ultraviolet absorber, a slip agent, an antistatic agent, or the like. Examples of the leveling agent include an acrylic copolymer, a fluorene-based, and a fluorine-based leveling agent. Specific examples of the ultraviolet absorber include diphenylketone, benzotriazole, oxalic acid, and And a hindered amine-based UV absorber. Examples of the antistatic agent include metal salts such as a lithium salt, a sodium salt, a potassium salt, a phosphonium salt, a phosphonium salt, a magnesium salt, and a calcium salt.

[Manufacturing method of laminated film]

The surface layer formed on the surface of the laminated film of the present invention is preferably a production method formed by coating-drying-hardening the above-mentioned coating composition on the above-mentioned supporting substrate. Hereinafter, the step of coating is described as a coating step, the step of drying is described as a drying step, and the step of curing is described as a curing step.

In the coating step, the method of applying the coating composition is There is no particular limitation, but it is preferred to apply the coating composition to the support substrate by dip coating, roll coating, wire bar coating, gravure coating or die coating (U.S. Patent No. 2,681,294). Form a surface layer. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.

After the coating step, drying is performed by a drying step A liquid film coated on the support substrate. From the viewpoint of completely removing the solvent from the obtained laminated film, it is preferred to carry out heating with the liquid film in the drying step.

Regarding the drying method of the drying step, heat transfer can be mentioned Dry (close to high heat objects), convective heat transfer (hot air), radiation heat transfer (infrared), other (microwave, induction heating), etc. Among them, in the production method of the present invention, it is preferable to use convection heat transfer or radiation heat transfer from the viewpoint of precisely making the drying speed uniform in the width direction.

The drying process in the drying step is generally divided into (A) constant rate drying period, (B) decrement drying period, the former is due to the rate of drying of the solvent molecules in the atmosphere on the surface of the liquid film, so the drying speed is The interval is fixed, and the drying speed is governed by the partial pressure of the evaporating solvent in the atmosphere, the wind speed, and the temperature. The film surface temperature is fixed by the value determined by the hot air temperature and the partial pressure of the evaporated solvent in the atmosphere. In the latter case, since the diffusion of the solvent in the liquid film is rate-limiting, the drying rate does not show a fixed value in this section and continues to decrease, and is controlled by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature rises. The so-called drying speed here means the amount of solvent evaporation per unit time and unit area, by g. m ^-2 . The s ^-1 is composed of dimensions.

The aforementioned drying speed has a preferred range, preferably 0.1 g. m ^-2 . s ^-1 or more 10g. m ^-2 . s ^-1 or less, more preferably 0.1g. m ^-2 . s ^-1 or more 5g. m ^-2 . s ^-1 or less. By making the drying speed in the constant-rate drying section into this range, it is possible to prevent unevenness due to unevenness in drying speed. Just get 0.1g. m ^-2 . s ^-1 or more 10g. m ^-2 . The drying speed in the range of s ^-1 or less is not particularly limited by the specific wind speed and temperature.

In the method for producing a laminated film of the present invention, The evaporation of the residual solvent is carried out during the drying, and the alignment of the polyoxyalkylene segment and/or the polydimethyloxyalkylene segment and the fluorine compound segment is carried out simultaneously. In this process, since the time required for the alignment is required, the film surface temperature rising rate during the decrement drying period is preferably in the range of preferably 5 ° C / sec or less, more preferably 1 ° C / sec or less.

Furthermore, it can also be carried out by illuminating heat or energy rays. One-step hardening operation (hardening step).

Further, when hardened by the active energy ray, it is preferably an EB line and/or an UV line from the viewpoint of versatility. Further, when curing by ultraviolet rays, it is preferable that the oxygen concentration is as low as possible from the viewpoint of preventing oxygen barrier, and it is more preferable to perform hardening in a nitrogen atmosphere (nitrogen flushing). When the oxygen concentration is high, the hardening of the outermost surface is inhibited, the hardening of the surface is insufficient, and the self-healing property and the adhesion durability are insufficient. Moreover, examples of the type of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash mode, a laser method, and an electrodeless lamp method. When ultraviolet ray hardening is performed by a high-pressure mercury lamp of a discharge lamp type, the illuminance of ultraviolet rays is 100 to 3,000 mW/cm ² , preferably 200 to 2,000 mW/cm ² , more preferably 300 to 1,500 mW/cm ² . under ultraviolet irradiation conditions, the cumulative light quantity of ultraviolet light is 100 ~ 3,000mJ / cm ^2, preferably 200 ~ 2,000mJ / cm ^2, more preferably ultraviolet irradiation at 300 ~ 1,500mJ / cm ² of conditions. Here, the illuminance of the ultraviolet ray is the intensity of the illumination per unit area, which varies depending on the lamp output, the luminescence spectral efficiency, the diameter of the illuminating bulb, the design of the mirror, and the distance from the light source of the object to be irradiated. However, the illuminance does not vary with the transport rate. Further, the amount of ultraviolet light accumulated is the amount of photons received per unit area, and is the total amount of photons reaching the surface. The cumulative amount of light is inversely proportional to the illumination rate through the light source, and is proportional to the number of illuminations and the number of lamps.

[Example of use]

The laminated film of the present invention has the advantages of moldability, self-healing property, adhesion durability, and antifouling property, and is molded into various types by molding. Among the uses of the molded article, it is particularly applicable to applications requiring high scratch resistance and desirability of scarring.

For example, it can be applied to glasses. Sunglasses, makeup Plastic molded products such as boxes and food containers, smart phone cases, touch panels, keyboards, and televisions. Home appliances, buildings, dashboards, and navigation navigators for remote controls such as air conditioners. Vehicle interiors such as touch panels and interior mirrors, and the respective surfaces of various printed materials.

[Examples]

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

[urethane (meth) acrylate A]

[Synthesis of urethane (meth) acrylate A1]

50 parts by mass of toluene, 50 parts by mass of hexamethylene diisocyanate modified type of isocyanurate ("Takenate" (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc.), 76 parts by mass Polycaprolactone-modified hydroxyethyl acrylate ("Placcel" (registered trademark) FA5 manufactured by DAICEL Chemical Industry Co., Ltd.), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether. Hold 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 concentration of 50% by mass.

[Synthesis of urethane (meth) acrylate A2]

50 parts by mass of toluene, 67 parts by mass of H6XDI Nurate (D-127N manufactured by Mitsui Chemicals, Inc., NCO content 13.5 mass%), and 76 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (DAICEL Chemical Industry Co., Ltd.) Limited "Placcel" (Registrar) Standard) FA5), 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were kept at 70 ° C for 5 hours. Then, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate A 2 having a solid concentration of 50% by mass.

[Synthesis of urethane (meth) acrylate A3]

a biuret modified type of 50 parts by mass of toluene and 50 parts by mass of hexamethylene diisocyanate (Duranate (registered trademark) 24A-90CX manufactured by Asahi Kasei Chemicals Co., Ltd., nonvolatile matter: 90% by mass, Isocyanate content: 21.2% by mass), 92 parts by mass of polycaprolactone-modified hydroxyethyl acrylate ("Placcel" (registered trademark) FA2D manufactured by DAICEL Chemical Industry Co., Ltd.), 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether was kept at 70 ° C for 5 hours. Then, 82 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate A3 having a solid concentration of 50% by mass.

[urethane (meth) acrylate B]

[Synthesis of urethane (meth) acrylate B1]

100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Fermentation Kylin Co., Ltd.), and 119 parts by mass of polycarbonate diol (DAICEL Chemical Industry Co., Ltd.) "Placcel" (registered trademark) CD-210HL, which was heated to 40 ° C for 8 hours, and then added 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 Toagosei Co., Ltd.) and 0.02 parts by mass of hydroquinone monomethyl ether were added at 0.02 ° C for 30 minutes, and then 0.02 parts by mass of dibutyltin laurate was added. Keep at 80 ° C 6 hours. Further, 97 parts by mass of toluene was finally added to obtain a toluene solution of urethane (meth)acrylate B1 having a solid concentration of 50% by mass.

[Synthesis of urethane (meth) acrylate B2]

100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Ukrainian Kirin Co., Ltd.), and 150 parts by mass of polycarbonate diol (DAICEL Chemical Industry Co., Ltd.) "Placcel" (registered trademark) CD-220) was heated to 40 ° C for 8 hours. Then, 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 Toagosei Co., Ltd.), and 0.02 mass were added. The hydroquinone monomethyl ether was kept at 70 ° C for 30 minutes, and then 0.02 parts by mass of dibutyltin laurate was added and kept at 80 ° C for 6 hours. Further, 97 parts by mass of toluene was finally added to obtain a toluene solution of urethane (meth)acrylate B2 having a solid concentration of 50% by mass.

[urethane (meth) acrylate C]

[Synthesis of urethane (meth) acrylate C1]

50 parts by mass of a modified isocyanurate modified from hexamethylene diisocyanate (Takenate (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc., isocyanate group content: 20.09% by mass), 53 mass Polyethylene glycol monoacrylate ("Blemmer" (registered trademark) AE-150, Nippon Oil Co., Ltd., hydroxyl value: 264 (mgKOH/g)), 0.02 parts by mass of dibutyltin laurate and 0.02 mass A portion of hydroquinone monomethyl ether. Then, the reaction was carried out by maintaining at 70 ° C for 5 hours. After the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction liquid to obtain a urethane (meth) acrylate C1 having a solid concentration of 50% by mass.

[矽 oxane compound]

[矽 oxane compound 1]

As the decane compound 1, a decane diacrylate compound (solid content concentration: 100% by mass manufactured by EBECRYL350 DAICEL. CYTEC Co., Ltd.) was used.

[矽 oxane compound 2]

As the decane compound 2, a hexa hexaacrylate compound (solid content concentration: 100% by mass manufactured by EBECRYL 1360 DAICEL. CYTEC Co., Ltd.) was used.

[Synthesis of polyoxyalkylene (a)]

In a 500 ml-capacity flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen introduction tube, 106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1 mass were charged. After maintaining hydrochloric acid at 85 ° C for 2 hours, ethanol was recovered and the temperature was maintained at 180 ° C for 3 hours. Then, it was cooled to obtain a viscous polyoxyalkylene (a).

[Polydimethyl siloxane series block copolymer (a)]

Using the same apparatus as the synthesis of polyoxyalkylene (a), 50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, and 20 parts by mass of polydimethyl siloxane-based polymer polymerization start were added. Agent (VPS-0501, manufactured by Wako Pure Chemical Co., Ltd.), 30 parts by mass of methyl methacrylate, 26 parts by mass of butyl methacrylate, and 23 parts by mass of methacrylic acid 2- Hydroxyethyl ester, 1 part by mass of methacrylic acid, and 0.5 part by mass of 1-thioglycerol were reacted at 80 ° C for 8 hours to obtain a polydimethylsiloxane-based block copolymer (a). The ratio of the block copolymer (a) in the obtained solution was 50% by mass in a 100% by mass solution.

[Polydimethylsiloxane-based graft copolymer (b)]

Using a device used for the synthesis of polyoxyalkylene (a), 50 parts by mass of toluene and 50 parts by mass of isobutyl acetate were added, and the temperature was raised to 110 °C. Further, 20 parts by mass of methyl methacrylate, 20 parts by mass of butyl methacrylate, and 32 parts by mass of caprolactone methacrylate ("Placcel" (registered trademark) FM manufactured by DAICEL Chemical Industry Co., Ltd. were mixed. -5), 23 parts by mass of 2-hydroxyethyl methacrylate, 10 parts by mass of polyoxyalkylene (a), 20 parts by mass of a terminal methacrylic acid modified polydimethyl siloxane (East Asia Synthesis) Chemical Industry Co., Ltd., X-22-174DX) and 1 part by mass of methacrylic acid and 2 parts by mass of 1,1-azobiscyclohexane-1-carbonitrile. This mixed monomer was dropped to the above-mentioned mixed solution of toluene and butyl acetate for 2 hours. Then, the mixture was reacted at 110 ° C for 8 hours to obtain a polydimethylsiloxane-based graft copolymer (b) having a hydroxyl group concentration of 50% by mass. The ratio of the graft copolymer (b) in the obtained solution was 50% by mass in a 100% by mass solution.

[tricyclic fluorenyl compound]

[tricyclic fluorenyl compound 1]

As the tricyclic mercapto compound 1, an acrylate compound containing a tricyclodecyl group (solid content concentration: 100% by mass manufactured by IRR214-K Daicel-Allnex Co., Ltd.) was used.

[tricyclic fluorenyl compound 2]

As the tricyclic mercapto compound 2, an acrylate compound (a solid content concentration of 100% by mass of FA-513AS Hitachi Chemical Co., Ltd.) containing a tricyclodecyl group was used.

[tricyclic fluorenyl compound 3]

As the tricyclic mercapto compound 3, an acrylate compound containing a tricyclodecyl group (solid content: 100 mass% manufactured by SR833S Sartomer Co., Ltd.) was used.

[fluorine compound]

[Fluorochemical 1]

As the fluorine compound 1, an acrylate compound containing a fluoropolyether segment ("Megafac" (registered trademark) RS-75 DIC Co., Ltd. solid content concentration 40% by mass solvent (toluene and methyl ethyl ketone) 60 mass was used. %).

[fluorine compound 2]

As the fluorine compound 2, a fluoropolyether compound containing a fluoropolyether segment (KY-108 Shin-Etsu Chemical Co., Ltd. solid content concentration: 20% by mass solvent (methanol and isopropyl alcohol) 80% by mass) was used.

[Photoradical polymerization initiator]

[Photoradical polymerization initiator 1]

As the photoradical polymerization initiator 1, "Irgacure" (registered trademark) 184 (solid content concentration: 100% by mass by BASF Japan Co., Ltd.) was used.

[Material Composition A Preparation]

[Coating composition A1]

Mix the following materials and dilute with methyl ethyl ketone to obtain a solid A coating composition A1 having a body component concentration of 30% by mass.

[Coating composition A2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid concentration of 30% by mass.

[Coating composition A3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid concentration of 30% by mass.

[Coating composition A4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid concentration of 30% by mass.

[Coating composition A5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid concentration of 30% by mass.

[Coating composition A6]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid concentration of 30% by mass.

[Coating composition A7]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 having a solid concentration of 30% by mass.

[Coating composition A8]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 having a solid concentration of 30% by mass.

[Coating composition A9]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 having a solid concentration of 30% by mass.

[Coating composition A10]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A10 having a solid concentration of 30% by mass.

[Coating composition A11]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A11 having a solid concentration of 30% by mass.

[Coating composition A12]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A12 having a solid concentration of 30% by mass.

[Coating composition A13]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A13 having a solid concentration of 30% by mass.

[Coating composition A14]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A14 having a solid concentration of 30% by mass.

[Material Composition B Preparation]

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

. Polycaprolactone triol 15 parts by mass

("Placcel" (registered trademark) 308 DAICEL Chemical Industry Co., Ltd.)

. Hexamethylene diisocyanate 15 parts by mass

("Takenate" (registered trademark) D-170 Mitsui Chemicals Co., Ltd.)

. Polydimethyloxane block copolymer (a) solution 75 mass

Share

(solid content concentration: 50% by mass)

. Polyoxyalkylene (a) 10 parts by mass.

[Coating composition B2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition B2 having a solid concentration of 40% by mass.

. Polydimethylsiloxane coupled graft copolymer (b) solution 100 parts by mass

(solid content concentration: 50% by mass)

. Hexamethylene diisocyanate 12 parts by mass

("Burnock" (registered trademark) DN-950, manufactured by DIC Corporation).

[Preparation of Coating Composition C]

[Coating composition C1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C1 having a solid concentration of 30% by mass.

[Coating composition C2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C2 having a solid concentration of 30% by mass.

[Coating composition C3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C3 having a solid concentration of 30% by mass.

[Coating composition C4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C4 having a solid concentration of 30% by mass.

[Coating composition C5]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition C5 having a solid concentration of 30% by mass.

[Material Composition D Preparation]

[Coating composition D1]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D1 having a solid concentration of 40% by mass.

[Coating composition D2]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D2 having a solid concentration of 40% by mass.

. Urethane (meth) acrylate B2 solution (solid content

[Coating composition D3]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D3 having a solid concentration of 30% by mass.

[Coating composition D4]

The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition D4 having a solid concentration of 30% by mass.

[support substrate]

[Support substrate A1]

"Cosmoshine" (registered trademark) A4300 (thickness: 125 μm, manufactured by Toyobo Co., Ltd.) was used as the support substrate A1.

[Support substrate A2]

As the support substrate A2, use "Panlite" (Registrar) Standard) PC-2151 (thickness 125 μm, manufactured by Teijin Chemicals Co., Ltd.).

[Support substrate B1]

As the support substrate 1, "Lumirror" (registered trademark) U48 (thickness: 125 μm, manufactured by Toray Industries, Inc.) was used.

[Evaluation of support substrate]

For the support substrate, the performance evaluation shown below was carried out, and the results obtained are shown in Table 1. The measurement was performed three times for each sample except for the case where it was specified in advance, and the average value was used.

[Swelling index of support substrate]

The swelling index of the support substrate was calculated by the following method. First, the haze value h ₁ of the support substrate was measured. Next, on the support substrate, methyl ethyl ketone was applied using a bar coater (#10), and allowed to stand at a temperature of 40 ° C for 1 minute to dry the methyl ethyl ketone. Then, the haze value h ₂ (%) of the support substrate after drying was measured. Using these two values, the swelling index was calculated from the following formula.

Swelling index: h=| h ₂ -h ₁ |

In addition, the haze measurement was carried out by using a haze meter manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7136 (2000), and transmitting light from the side of the self-supporting substrate coated with methyl ethyl ketone. Determined on the device.

The evaluation results of the support substrate obtained in Table 1 are summarized.

[Manufacturing method of laminated film]

[Production of laminated film 1]

On the support substrate, a continuous coating apparatus using a slit die coater is used to adjust the discharge flow rate from the slit so that the thickness of the dried surface layer becomes a predetermined film thickness, and the coating composition A is applied ( A1~A14), coating composition C (C1~C5), and coating composition D (D1~D4). The conditions of the dry air blown to the liquid film from the time of coating to drying and hardening are as follows.

[Drying step]

Supply air temperature and humidity: temperature: 80 ° C, relative humidity: 1% or less

Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec

Wind direction: coated side: parallel to the surface of the substrate, side of the reverse coated side: vertical to the side of the substrate

Residence time: 2 minutes

[hardening step]

Irradiation output: 400W/cm2

Cumulative amount of light: 120mJ/cm2

Oxygen concentration: 0.1% by volume.

[Production of laminated film 2]

Continuous coating using a slot die coater on a support substrate In the apparatus, the discharge flow rate from the slit is adjusted so that the thickness of the dried surface layer becomes a predetermined film thickness, and the coating composition B (B1 to B2) is applied. The conditions of the dry air blown to the liquid film from the time of coating to drying and hardening are as follows.

[Drying step]

Supply air temperature and humidity: temperature: 80 ° C, relative humidity: 1% or less

Wind speed: coated side: 5 m / sec, reverse coated side: 5 m / sec

Wind direction: coated side: parallel to the surface of the substrate, side of the reverse coated side: vertical to the side of the substrate

Residence time: 1 minute

[hardening step]

Supply air temperature and humidity: temperature: 160 ° C, relative humidity: 1% or less

Wind speed: coated side: 10 m / sec, reverse coated side: 10 m / sec

Wind direction: coated side: vertical to the surface of the substrate, coated side: vertical to the side of the substrate

Residence time: 2 minutes

In addition, the wind speed, the temperature and humidity are measured values of a hot wire type anemometer (Anemomaster wind speed air flow meter MODEL6034 manufactured by KANOMAX Co., Ltd., Japan).

The laminate films of Examples 1 to 16 and Comparative Examples 1 to 11 were produced by the above methods. The method for producing the laminated film corresponding to each of the examples and the comparative examples and the film thickness of each layer are described in Tables 2 and 3 to be described later.

[Evaluation of laminated film]

For the laminated film produced, perform the performance evaluation shown below The price, the results obtained in Tables 2 and 3. Unless otherwise specified in advance, the assay is in each embodiment. In the comparative example, for one sample, the position was changed three times, and the average value was used.

[Logarithmic decay rate of surface layer, relative storage elastic modulus (rigid body pendulum test method)]

Based on the free-attenuation vibration method of the rigid body pendulum (this is taken as the rigid body pendulum test method), the logarithmic decay rate and relative of the surface layer are measured using the rigid body pendulum type physical property testing machine RPT-3000 manufactured by A&D Co., Ltd. Store the elastic modulus. The test machine was previously tempered to 15 ° C, and after the sample and the pendulum were attached, the temperature was raised to 150 ° C at a rate of 10 ° C / min, and the measurement was performed while raising the temperature. The measurement system was carried out 5 times each and evaluated by the average value thereof. Furthermore, the pendulum system uses the following.

Edge: Round bar type edge (RBP-040, manufactured by A&D Co., Ltd.) Knife shape edge (RBE-160, A&D Co., Ltd.)

Pendulum mass / moment of inertia: 15g / 640g. Cm (FRB-100, A&D company)

Further, the relative storage elastic modulus at a measurement temperature of 25 ° C was taken as Gr' 25, and the relative storage elastic modulus at a measurement temperature of 100 ° C was taken as Gr'100. The magnitude of each value is compared, and when Gr'25<Gr'100 is established, it is regarded as Y, and when it is not established, it is regarded as N.

[Adhesion index of surface layer (extension-boil tight test method)]

The evaluation of the adhesion index of the surface layer was carried out in three stages of elongation treatment, boiling treatment, and adhesion test as described below. Furthermore, This series of processes was used as an extension-boil tight test.

[Extension processing]

The laminate film was cut to a length of 20 mm × 200 mm, and was grasped by a chuck so as to extend in the longitudinal direction, and was passed through an Instron type tensile tester (Instron type ultra-precision material testing machine MODEL 5848) at 100 mm/min. Stretching speed to stretch. The measurement environment at this time was 23 °C. The extension treatment was performed until the strain amount became 20%, and the test piece was collected.

Furthermore, the distance between the initial stretching chucks is 50mm, pulling The distance between the stretching chucks is a (mm), and the strain x (%) is calculated by the following formula.

The dependent variable: x = ((a-50) / 50) × 100.

[Boiled treatment]

Next, the test piece which had been subjected to the elongation treatment was immersed in the boiling hot water (100 ° C) composed of pure water for 6 hours. Then, the test piece was taken out and dried.

[Close test]

Further, 100 pieces of 1 mm2 cross-cut were introduced into the surface layer of the test piece after the boiling treatment. The operation is carried out in accordance with seven steps of JIS K5600-5-6 (1999) except for the following.

Test conditions and number of tests: The test conditions were 23 ° C and a relative humidity of 65%. Also, the number of tests is one.

The aging of the test plate: the ripening conditions were a temperature of 23 ° C, a relative humidity of 65%, and a ripening time of 1 hour.

Number of cuts: The number of cuts is 11.

Interval of cutting: The interval between cuts is 1 mm.

Cutting and removal of the laminated film by a manual step: brushing using a brush was not performed. In addition, JIS K5600-5-6 (1999) 7.2.6 only refers to the provisions of paragraph 2 ("the center of the tape, as shown in Figure 3, in a direction parallel to the square cut group, Place it on the square and use the finger to make the tape flat with a length of more than 20mm from the part applied to the square. Other rules are not used. In addition, a scotch tape (Cellotape (registered trademark) CT405AP by NICHIBAN Co., Ltd.) was used for the tape.

Also, the tape is attached using a hand roller ((HP) 515 manufactured by Audio-technica) was carried out by pushing back and forth three times with a load of 19.6 N/m and a roll moving speed of 5 cm/sec. Next, the tape was peeled off at a speed of 10 cm/sec. at a speed of 10 cm/sec with respect to the surface direction of the surface layer, and the rating was evaluated based on the number of remaining squares provided on the surface layer.

Bonding index 5: The number of remaining layers of the surface layer is 100.

Bonding index 4: The number of remaining layers of the surface layer is 90 or more and less than 100.

Bonding index 3: The number of remaining layers of the surface layer is 80 or more and less than 90.

Bonding index 2: The number of remaining layers of the surface layer is 50 or more and less than 80.

Bonding index 1: The number of remaining layers of the surface layer is less than 50.

[Anti-dye transferability]

6 cm × 6 cm of water-wet jeans (containing dye) were adhered to the surface layer of the laminated film of a size of 9 cm × 6 cm. A 6 cm x 6 cm glass plate was sandwiched. In a manner that moisture does not evaporate, it is wrapped in a polyethylene film, and a 3 kg weight is placed on the glass plate, and placed in an oven at 70 ° C. After 24 hours, the laminated film was placed on a white paper equivalent to the white portion of the gray scale for pollution described later, and the gray scale for pollution (JIS L0805 (2005)) was used to rank 1 to 5 (Grade 1). For the pollution, the gray scale No. 1 or the extent of exceeding it (dirty and deep residue), the second-grade system is the pollution level with the gray scale No. 2 (the amount of dirty residue is quite large), and the third-grade system is dirty. In the case of the gray level No. 3 (slightly left), the fourth grade is the pollution, the gray level is 4 (the dirt is almost not left), and the 5th is the pollution. (dirty is not left)), and the degree of contamination of the surface of the surface layer is judged. Further, according to JIS L0805 (2005), when it is between the levels, for example, between the first level and the second level, it is described as "1-2".

[Crack extension of surface layer]

The laminate film was cut to a length of 10 mm wide by 200 mm, and was grasped by a chuck in the longitudinal direction, and was stretched at a stretching speed of 100 mm/min by an Instron type tensile tester (Instron-made ultra-precision material testing machine MODEL 5848). . The measurement was carried out at a measurement temperature of 23 °C. When extending, the sample in the extension is observed, and when cracks (cracks) are visually observed, the sample is stopped (the amount of the strain at the time of the stop is adjusted to be an integer of 5). Thereafter, the sample to be measured is subjected to a sample in which the amount of strain is reduced by 5% in accordance with the strain at the time of stopping, and the sample is subjected to the strain until the final visual observation is not introduced.

Further, the distance between the initial stretching chucks was 50 mm, the distance between the stretching chucks was a (mm), and the strain x (%) was calculated by the following formula.

The dependent variable: x = ((a-50) / 50) × 100.

Cut out the film section of the cracked part of the collected sample The surface was observed to have a magnification of 30 mm or more on the observation screen of the transmission electron microscope, and the surface layer was observed, and cracks of 50% or more of the average thickness of the surface layer were regarded as cracks (surface). The layer is damaged. Among the samples considered to be cracked, the strain value of the sample with the lowest strain is taken as the crack elongation. Further, the same measurement was performed three times in total, and the average value of the crack elongations was taken as the crack elongation of the surface layer.

[Separation of surface layer]

As a pre-treatment by the dynamic viscoelastic method, the self-laminated film was only peeled off from the surface layer by the following method, and it was used as a test sample.

First, the laminated film is immersed in ethanol at 25 ° C. Leave under conditions for 10 minutes. Then, the surface of the laminated film was peeled off from the support substrate, and a sample was taken.

[Storage modulus of the surface layer, loss tangent (dynamic Viscoelastic method)]

Based on the tensile vibration-non-resonance method of JIS K7244 (1998) (this is regarded as the dynamic viscoelastic method), the surface layer storage was obtained using the dynamic viscoelasticity measuring device "DMS6100" manufactured by SEIKO Instruments Co., Ltd. Elastic modulus and loss elastic modulus.

Measurement mode: stretching

Distance between chucks: 20mm

Test piece width: 10mm

Frequency: 1Hz

Strain amplitude: 10μm

Initial amplitude of force amplitude: 400mN

Measuring temperature: from -150 ° C to 250 ° C

Heating rate: 5 ° C / min

Further, the storage elastic modulus at a measurement temperature of 25 ° C was taken as G' ₂₅ , and the storage elastic modulus at a measurement temperature of 100 ° C was taken as G' ₁₀₀ . Compare the magnitude of each value, treat G' ₂₅ <G' ₁₀₀ as Y when it is established, and treat it as N when it is not established.

Further, the loss elastic modulus at a measurement temperature of 25 ° C was taken as G" ₂₅ , and tan δ ₂₅ indicating the loss tangent at a measurement temperature of 25 ° C was obtained by the following formula.

Tanδ ₂₅ =G" ₂₅ /G' ₂₅ .

[self-healing of surface layer]

After standing at a temperature of 20 ° C for 12 hours, the following load was applied to a brass brush (manufactured by TRUSCO) on the surface of the surface layer in the same environment, and scratched five times horizontally, and visually judged for 5 minutes in accordance with the following criteria. The recovery state of the scar after placement is considered to be 4 or more points.

10 points: no damage remains when the load is 9.8N (1kg weight)

7 points: the residue remains when the load is 9.8N (1kg weight), but the scar does not remain when it is 6.9N (700g weight)

4 points: the residue remains when the load is 6.9N (700g weight), but the scar does not remain when it is 4.9N (500g weight)

1 point: The residue remains when the load is 4.9N (500g weight).

[Formability of surface layer]

The moldability of the surface layer is determined based on the following criteria regarding the crack elongation of the surface layer.

10 points: The crack extension of the surface layer is 40% or more.

7 points: The crack elongation of the surface layer is 30% or more and less than 40%.

4 points: The crack elongation of the surface layer is 20% or more and less than 30%.

1 point: The crack elongation of the surface layer is less than 20%.

[Sealing durability of surface layer]

The adhesion durability of the surface layer is judged by the following criteria based on the adhesion index of the surface layer.

10 points: The adhesion index of the surface layer is 5.

9 points: The adhesion index of the surface layer is 4.

7 points: The adhesion index of the surface layer is 3.

4 points: The adhesion index of the surface layer is 2.

1 point: The adhesion index of the surface layer is 1.

[Antifouling properties of surface layer]

The antifouling property of the surface layer was judged based on the following criteria against the dye transfer resistance of the surface layer.

10 points: The surface layer has an anti-dye transferability of 5 grades.

7 points: The anti-dye transfer property of the surface layer is 4 or more and less than 5.

4 points: The anti-dye transfer property of the surface layer is 3 or more and less than 4.

1 point: The surface layer has an anti-dye transferability lower than Grade 3.

The evaluation results of the finally obtained laminated film are summarized in Table 3.

[Industrial availability]

The laminated film of the invention has the advantages of moldability, self-healing property, antifouling property and adhesion durability, and can be applied to glasses. Plastic molded products such as sunglasses, cosmetic cases, food containers, smart phone cases, touch panels, keyboards, and televisions. Home appliances, buildings, dashboards, and navigation navigators for remote controls such as air conditioners. Vehicle interiors such as touch panels and interior mirrors, and the respective surfaces of various printed materials.

Claims (8)

A laminated film which is a laminated film having a surface layer on at least one side of a support substrate, which is characterized by satisfying the following conditions 1 and 2; Condition 1: Logarithm of the surface layer of the rigid body pendulum test at 25 ° C The attenuation rate is 0.1 or more; Condition 2: The resin contained in the surface layer contains the following (1) to (4); (1) a polycaprolactone segment, (2) a urethane bond, (3) a polyoxyalkylene segment and/or a polydimethylsiloxane chain segment, and (4) a tricyclic fluorenyl segment. The laminated film according to claim 1, wherein in the laminated film, the following condition 3 is satisfied; Condition 3: the surface layer of the extension-boil adhesion test has an adhesion index of 3 or more. The laminated film of claim 1 or 2, wherein in the laminated film, the following condition 4 is satisfied; Condition 4: the relative storage elastic modulus of the surface layer at 100 ° C of the rigid body pendulum test method is at 25 ° C The relative storage elastic modulus is high. The laminated film according to claim 1 or 2, wherein in the laminated film, the following conditions 5 to 7 are satisfied; Condition 5: the storage elastic modulus of the surface layer at 25 ° C of the dynamic viscoelastic method is 10 MPa or more and 1,000 MPa. The condition 6 is that the surface elastic layer of the dynamic viscoelastic method has a storage elastic modulus at 100 ° C higher than a storage elastic modulus at 25 ° C; Condition 7: The loss tangent of the surface layer at 25 ° C of the dynamic viscoelastic method was 0.15 or more. The laminated film according to claim 1 or 2, wherein in the laminated film, the following condition 8 is satisfied; Condition 8: the surface layer of the tensile test method has a crack elongation of at least 20% at 23 °C. The laminated film according to claim 1 or 2, wherein in the laminated film, the supporting substrate forming the surface layer satisfies the following condition 9; Condition 9: The swelling index of the supporting substrate is 0.01 or more. The laminated film according to claim 1 or 2, wherein in the laminated film, the following condition 10 is satisfied; Condition 10: the resin contained in the surface layer contains the following (5); (5) a fluorine compound segment. The laminated film according to claim 1 or 2, wherein in the laminated film, the following condition 11 is satisfied; Condition 11: the resin contained in the surface layer comprises the following (6); (6) a polycarbonate segment.