KR102314335B1 - Multilayer film - Google Patents

Abstract

It is a laminated|multilayer film which has a surface layer on at least one of a support base material, Comprising: The following conditions 1 and 2 are satisfy|filled, The laminated|multilayer film characterized by the above-mentioned.
Condition 1: The logarithmic damping factor at 25°C of the surface layer in the rigid pendulum test method is 0.1 or more.
Condition 2: The resin contained in the surface layer contains the following (1) to (4).
(1) polycaprolactone segment
(2) urethane bond
(3) polysiloxane segments and/or polydimethylsiloxane segments
(4) tricyclodecyl segment
Provided is a laminated film that satisfies adhesion durability and antifouling properties in addition to coexistence of moldability required for molding materials and scratch resistance due to self-healing properties.

Description

Laminated film {MULTILAYER FILM}

The present invention relates to a laminated film excellent in adhesion durability and antifouling properties in addition to coexistence of moldability and scratch resistance required for molding materials.

In molding materials such as decorative molding, a surface hardening layer is formed in order to prevent scratches during molding and scratches in the process of using the article after molding. However, since the surface-hardened layer lacks elongation to follow molding, cracks occur during molding, or in extreme cases, the film breaks or the surface-hardened layer peels off. In general, a surface-hardened layer is formed after molding. Or, after molding in a semi-hardened state, means such as complete curing by heating or irradiation with actinic rays, etc. are applied. However, since the article after molding is processed in three dimensions, it is very difficult to form a hardened surface layer in the post processing, and when molded in a semi-hardened state, contamination of the mold may be caused depending on the molding conditions. From the above points, abrasion-resistant materials that follow molding are promising, and "self-healing materials" that can self-repair a hardness scratch by deformation within its elastic recovery range are attracting attention, and Patent Documents 1 and 2 have been proposed. .

On the other hand, when these molded objects, such as a smartphone housing and a tablet PC housing, are used as a surface material, the durability at the time of long-term use is calculated|required. In particular, there is a problem in that the surface of the molding material is destroyed or the surface layer is peeled off because moisture present in the air penetrates inside the molding material and attacks a particularly surface of the molding material. The material of patent document 3 is proposed as a technique of providing durability to a surface hardening layer with respect to such a problem. Moreover, the material of patent document 4 is proposed as a technique of forming the layer which made the adhesive strength to a base material compatible with durability.

In addition, as one aspect of antifouling properties, there is a problem that these dyes migrate to the surface when a sheet made of a general soft resin comes in contact with jeans, clothing, or natural or synthetic leather containing dyes, The material of Patent Document 5 has been proposed as a method of imparting transferability).

International Publication No. 2011/136042 Japanese Patent No. 3926461 Japanese Patent Laid-Open No. 2013-166889 Japanese Patent Laid-Open No. 2012-233079 Japanese Patent Laid-Open No. 2008-62408

Regarding the techniques of Patent Document 1 and Patent Document 2 proposed as the self-healing material described above, the present inventors confirmed that the moldability and self-healing properties were confirmed, but the adhesion durability and antifouling properties were significantly inferior to that of the hard coat material.

Moreover, as a result of confirming the technique of patent document 3 mentioned above about the technique of the present inventors, although the effect of close_contact|adherence durability was confirmed to some extent, it did not show moldability or self-healing property. Moreover, it was impossible to combine with the technique of patent documents 1 and 2 mentioned above, and it was not compatible with self-healing property.

In addition, although the technique of patent document 4 mentioned above was effective about adhesion durability, it did not show moldability or self-healing property, and it was impossible to combine with the technique of patent documents 1 - 3 mentioned above.

In addition, although the method described in Patent Document 5 described above was effective for dye migration resistance, it does not exhibit moldability or self-healing properties, and cannot be combined with the techniques of Patent Documents 1 to 4 described above. was found to be incompatible.

Then, the subject which this invention is going to solve is providing the laminated|multilayer film which satisfy|fills adhesion durability and antifouling property in addition to coexistence of the abrasion resistance by the moldability and self-healing property required for a molding material.

In order to solve the said subject, the present inventors completed the following invention as a result of repeating earnest research. That is, the present invention is as follows.

<1> Laminated|multilayer film which satisfy|fills the following conditions 1 and 2 as a laminated|multilayer film which has a surface layer on at least one side of a support base material, The laminated|multilayer film characterized by the above-mentioned.

Condition 1: The logarithmic damping factor at 25°C of the surface layer in the rigid pendulum test method is 0.1 or more.

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

(1) polycaprolactone segment

(2) urethane bond

(3) polysiloxane segments and/or polydimethylsiloxane segments

(4) tricyclodecyl segment

<2> The laminated film according to <1>, wherein the following condition 3 is satisfied.

Condition 3: The adhesion index of the said surface layer in the stretch-melting adhesion test method is 3 or more.

<3> The laminated film according to <1> or <2>, wherein the following condition 4 is satisfied.

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

<4> The laminated film according to any one of <1> to <3>, wherein the following conditions 5 to 7 are satisfied.

Condition 5: The storage elastic modulus at 25 degreeC of the said surface layer in a dynamic viscoelasticity method is 10 MPa or more and 1,000 MPa or less.

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

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

<5> The laminated film according to any one of <1> to <4>, wherein the following condition 8 is satisfied.

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

<6> The laminated film according to any one of <1> to <5>, wherein 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.

<7> The laminated film according to any one of <1> to <6>, wherein the following condition 10 is satisfied.

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

(5) fluorine compound segment

<8> The laminated film according to any one of <1> to <7>, wherein the following condition 11 is satisfied.

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

(6) polycarbonate segment

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the laminated|multilayer film which satisfy|fills moldability, self-healing property, adhesion durability, and antifouling property can be obtained.

1 is an example of logarithmic damping rate data obtained by a rigid pendulum test method.
2 is an example of storage elastic modulus data obtained by a dynamic viscoelasticity method.
3 is an example of loss modulus data obtained by the dynamic viscoelasticity method.
4 is an example of loss tangent data obtained by the dynamic viscoelasticity method.

Before describing the embodiment of the present invention, problems of the prior art, that is, coexistence of moldability, self-healing properties, adhesion durability, and antifouling properties, will be considered from the point of view of the present inventor.

First of all, the reason why the self-healing materials of the prior art described in Patent Documents 1 and 2 are incompatible with adhesion durability is that in the prior art, in order to make the coating film flexible, the self-healing property is improved by lowering the density of the crosslinked structure in the coating film. moldability is obtained. However, as a side effect, the amount of moisture in the air permeating into the coating film increased, and under long-term use conditions, adhesion durability was not sufficient, such as destruction of the coating film or peeling of the coating film from the substrate.

In addition, the techniques of Patent Documents 3 to 5 show excellent adhesion durability and dye transfer resistance in order to increase the crosslinking density of the material surface and prevent the penetration of moisture or dye in the air, but do not show moldability or self-healing properties. . Moreover, even if the material of patent document 3 or 4 is combined with the material of patent document 1 or 2, since self-healing property, a moldability, close_contact|adherence durability, and antifouling property become a trade-off relationship, it is incompatible. Moreover, in the technique of patent document 4, since the intensity|strength of a material is inferior, the abrasion resistance requested|required of a molding material is inadequate.

Therefore, the present inventors proceeded to examine the moldability and self-healing properties required for a molding material, and in examining the scratch resistance, viscoelastic properties, that is, storage modulus showing elastic properties, and loss modulus showing viscous properties, as mechanical properties of the surface layer. , focused on the loss tangent obtained by subtracting the loss modulus from the storage modulus. In addition, attention was paid to the logarithmic decay rate having the same meaning as the loss tangent.

When the surface layer receives a load from the outside, its mechanical response depends on the viscoelastic properties described above. In a material with low loss tangent, that is, a material with strong elastic properties, most of the load is stored as mechanical energy. In such a case, abrasion resistance will become inadequate, such as a scratch generate|occur|produced in a surface layer. On the other hand, in a material having a high loss tangent, that is, a material having a strong viscous property, the effect of missing a load as loss energy, that is, heat energy is large, and thus the mechanical energy to be stored is relatively small. Therefore, even if the load is large, the possibility that it falls below the storable range increases, and it becomes difficult to destroy a material. As a result, the occurrence of scratches on the surface layer and the like can be suppressed, and thus the scratch resistance is excellent.

In addition, since the effect of the loss tangent described above is higher by setting the storage modulus within a certain range, setting the storage modulus and loss tangent of the surface layer to a specific range improves the formability and self-healing properties of the surface layer, which is preferable.

Specifically, it is preferable that the logarithmic damping rate of the surface layer in the rigid pendulum test method be within a specific range, and/or that the storage elastic modulus and loss tangent of the surface layer in the dynamic viscoelasticity method be within a specific range.

In addition, the reason for paying attention to the temperature dependence of the viscoelastic behavior of the surface layer with respect to the self-healing property of the surface layer of the laminated film is that in a self-healing material having a storage elastic modulus at a high temperature higher than that at a certain temperature, storage of the surface layer by heating It is based on the discovery that self-healing property improves with an increase in elastic modulus.

As a result of the present inventors' analysis of the above phenomenon, it was found that when a scratch occurs in the surface layer, there is a correlation between the residual stress generated according to the displacement and the storage elastic modulus. That is, it was found that when the storage elastic modulus of the surface layer increased, the elastic force inside the surface layer became a force for releasing the residual stress accompanying the scratch, and consequently the scratch was repaired.

When the use of this property is assumed in actual use, the laminated film of the present invention is suitably used as a molding material for smartphones, etc., so that various electronic devices such as smartphones are used to dissipate heat generated inside from the housing surface. As a result, when the surface temperature rises, the self-healing material also interlocks and the temperature rises, and since scratches generated at room temperature are repaired, it is expected that the self-healing properties will be improved.

Specifically, it is preferable that the relative storage elastic modulus at 100°C of the surface layer in the rigid pendulum test method is higher than the relative storage elastic modulus at 25°C. Moreover, it is preferable that the storage elastic modulus in 100 degreeC of the surface layer in a dynamic viscoelasticity method is higher than the storage elastic modulus in 25 degreeC.

Moreover, the present inventors paid attention to the moisture in the air which penetrate|invaded the surface layer in analyzing the adhesion durability. In particular, it has been found that, under long-term use conditions, moisture that has penetrated reaches to the surface layer-supporting substrate interface and breaks the interface, causing the surface layer to peel from the supporting substrate. In particular, in the self-healing material, since the crosslinking density of the surface layer is lowered, it is considered that a large amount of moisture penetrates into the surface layer.

Although the study of a method for preventing the destruction of the surface layer-supporting substrate interface was advanced, adhesion durability was improved as a result of increasing the density of the crosslinked structure in the surface layer initially, but as described above, it was not compatible with formability and self-healing properties.

Then, as a result of examining the method of making moldability, self-healing property, and adhesion durability compatible, it discovered that introduction|transduction of the hydrophobic segment into resin contained in a surface layer is effective.

When the resin included in the surface layer includes a hydrophobic segment, moisture in the air penetrating into the surface layer decreases. In addition, paying attention to the penetrating moisture, the amount of moisture reaching the interface is further reduced because the minor segments are repeatedly contacted from the surface of the surface layer to the interface of the surface layer-supporting substrate. Therefore, it is possible to suppress the destruction of the surface layer-supporting substrate interface caused by the invading moisture, and as a result, it becomes possible to improve the adhesion durability.

Moreover, as a result of repeating verification about the said effect, it discovered that introduction of the hydrophobic segment derived from an alicyclic structure is effective especially. Since the alicyclic structure has a three-dimensional structure, its mobility is relatively lower than that of a segment derived from a chain structure. Therefore, even when the surface layer is deformed during molding or due to an external load, it is possible to suppress the occurrence of densification in the distribution state of the hydrophobic segments in the surface layer, so that it is possible to prevent a decrease in adhesion durability. Moreover, since this effect does not change the crosslinked structure density of a surface layer, moldability and self-healing property are hard to fall by an alicyclic structure.

Specifically, it is preferable that the resin contained in the surface layer contains a tricyclodecyl segment.

Moreover, the present inventors paid attention to the transfer process of dye in the analysis of dye transferability. In doing so, it was found that the process by which the dye penetrates, the process in which the dye settles, and each separation are important for the transferability of the dye to the surface layer.

First, with respect to the process in which the dye penetrates, since water is a medium in the penetration of the dye, it is possible to suppress the penetration of the dye by preventing the penetration of water into the surface layer. By suppressing the intrusion of the dye, it is possible to reduce the chance that the dye, which will be described later, occurs, and as a result, it is possible to improve the dye migration resistance. In this way, it is effective to introduce a hydrophobic segment, particularly a hydrophobic segment derived from an alicyclic structure, into the resin contained in the surface layer described above.

Specifically, with respect to the penetration of the dye, it is preferable that the resin contained in the surface layer contains a tricyclodecyl segment.

Subsequently, with respect to the process of fixing the dye, if the affinity between the resin and the dye contained in the surface layer is high, the probability of fixing the dye increases. Therefore, by lowering the affinity between the resin and the dye contained in the surface layer, it becomes possible to suppress the fixation of the dye, and as a result, the dye migration resistance can be improved. In this way, it is effective to introduce a segment having a low affinity for dye into the resin contained in the above-mentioned surface layer.

Specifically, it is preferable that the resin included in the surface layer includes a tricyclodecyl segment, a polycaprolactone segment, and a polycarbonate segment.

In addition, the present inventors paid attention to the load generated at the interface of the surface layer-supporting substrate, such as a load during molding or under long-term use conditions. It has been found that, during molding, a mechanical load, that is, stress or strain, occurs at the interface between the surface layer and the supporting substrate, and local adhesion failure occurs at the interface of the surface layer and the supporting substrate, which is the cause of lowering the moldability. did. Further, it has been found that, under long-term use conditions, the surface layer is peeled off from the supporting substrate because moisture in the air penetrates the surface layer and destroys the interface between the surface layer and the supporting substrate, which is the cause of lowering the adhesion durability. Then, as a result of examining a method for preventing the adhesion breakage of these surface layer-supporting substrate interfaces, it was found that selection of a supporting substrate having a surface having a surface having a certain affinity or more with a solvent is effective.

When the affinity between the surface of the supporting substrate and the solvent is high, since components of the surface layer permeate onto the supporting substrate when the surface layer is formed on the supporting substrate, the adhesion between the surface layer and the supporting substrate can be improved. Since this is effective for suppressing local adhesion breakage at the surface layer-supporting substrate interface and suppression of peeling of the surface layer from the substrate, moldability and adhesion durability can be improved. Specifically, it is preferable to make the swelling degree index of the supporting substrate into a specific range.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is demonstrated concretely.

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

Condition 1: The logarithmic damping factor at 25°C of the surface layer in the rigid pendulum test method is 0.1 or more.

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

(1) polycaprolactone segment

(2) urethane bond

(3) polysiloxane segments and/or polydimethylsiloxane segments

(4) tricyclodecyl segment

In addition, the rigid pendulum test method will be described later.

Here, the resin refers to a material containing a high molecular compound.

From the viewpoint of formability and self-healing properties, in the laminated film of the present invention, in the rigid pendulum test method, the surface layer preferably has a logarithmic damping factor at 25°C of 0.1 or more, more preferably 0.2 or more, and particularly preferably 0.4 or more. am. The logarithmic damping ratio shows the responsiveness when subjected to a mechanical load, and by setting the logarithmic damping ratio to a specific value, moldability and self-healing properties can be improved.

When the logarithmic damping ratio is large, the effect of missing the above-mentioned external load as thermal energy increases, so that the formability and self-healing properties are improved, which is preferable. The larger the logarithmic decay rate, the greater this effect, but there is a limit because the self-healing material has a cross-linked network, and the upper limit is considered to be about 1.0. On the other hand, when the logarithmic decay rate is smaller than 0.1, the surface layer is destroyed by an external load, and the formability and self-healing properties may be deteriorated.

In order to make the logarithmic damping factor at 25 degreeC of the said surface layer in the rigid pendulum test method 0.1 or more, it becomes possible by making the resin contained in the said surface layer satisfy|fill the above-mentioned condition 2 .

The (1) polycaprolactone segment refers to the segment represented by Formula 1, (2) the urethane bond refers to the bond represented by Formula 2, (3) the polysiloxane segment refers to the segment represented by Formula 3, and polydimethyl The siloxane segment refers to the segment represented by the formula (4), and the tricyclodecyl segment refers to the segment represented by the general formula (5). These details will be described later.

[n is an integer from 1 to 35]

[R ₁ , R ₂ is any one of OH or an alkyl group having 1 to 8 carbon atoms, each having at least one or more in the formula, 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) polycaprolactone segments, the self-healing properties of the obtained surface layer can be improved, and it is preferable.

When the resin contained in the surface layer has (2) a urethane bond, it is preferable because the toughness of the obtained surface layer can be improved and the self-healing properties can be improved.

When the resin contained in the surface layer has (3) a polysiloxane segment and/or a polydimethylsiloxane segment, the heat resistance and weather resistance of the obtained surface layer can be improved, and the scratch resistance due to the lubricity of the surface layer can be improved, which is preferable.

When the resin contained in the surface layer contains the (4) tricyclodecyl segment, the moldability of the obtained surface layer, adhesion durability, dye transfer resistance, and toughness of the coating film can be improved, which is preferable.

Moreover, the said laminated|multilayer film WHEREIN: It is preferable to satisfy|fill the following condition 3 from a viewpoint of close_contact|adherence durability.

Condition 3: The adhesion index of the said surface layer in the stretch-melting adhesion test method is 3 or more.

In addition, the draw-drain adhesion test method will be described later.

From the viewpoint of adhesion durability, in the stretch-rendering adhesion test method, it is preferable that the adhesion index of the surface layer is 3 or more, but 4 or more is more preferable, and 5 is particularly preferable. The adhesion index indicates the adhesion between the surface layer and the support layer, and the height of the adhesion index indicates the height of adhesion and adhesion durability.

When the adhesion index is high, especially under long-term use conditions, peeling of the surface layer from the supporting substrate can be suppressed, and adhesion durability is improved, which is preferable. On the other hand, when an adhesion index becomes smaller than 3, especially on long-term use conditions, a surface layer may peel from a support base material, and adhesion durability may fall.

In the stretch-melt adhesion test method, in order to set the adhesion index of the surface layer to 3 or more, it becomes possible by making the resin contained in the surface layer satisfy the above-mentioned condition 2 .

Moreover, in the said laminated|multilayer film, it is preferable to satisfy the following condition 4 from a viewpoint of self-healing property and a moldability.

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

In addition, the rigid pendulum test method will be described later.

From the viewpoint of self-healing properties and formability, it is preferable that the relative storage elastic modulus at 100°C of the surface layer in the rigid pendulum test method is higher than the relative storage elastic modulus at 25°C. The relative storage modulus indicates to what extent a material can recover when a load is applied, and an increase in the relative storage modulus indicates improved self-healing properties.

When the relative storage elastic modulus at 100° C. of the surface layer is higher than the relative storage elastic modulus at 25° C., the self-healing property is improved by the above-described effect.

In order to make the relative storage elastic modulus at 100 degreeC of the said surface layer higher than the relative storage elastic modulus at 25 degreeC, it becomes possible by the resin contained in the surface layer satisfying condition 2.

Moreover, in the said laminated|multilayer film from a viewpoint of self-healing property and a moldability, it is preferable to satisfy|fill the following conditions 5 - condition 7.

Condition 5: The storage elastic modulus at 25 degreeC of the said surface layer in a dynamic viscoelasticity method is 10 MPa or more and 1,000 MPa or less.

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

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

In addition, the dynamic viscoelasticity method is mentioned later.

From the viewpoint of self-healing properties and moldability, in the dynamic viscoelastic method, the storage modulus at 25°C of the surface layer is preferably 10 MPa or more and 1,000 MPa or less, more preferably 10 MPa or more and 800 MPa or less, 150 MPa or more and 500 MPa The following are particularly preferred. The storage modulus shows the elastic responsiveness when subjected to a mechanical load, and by setting the storage modulus to a specific value, moldability and self-healing properties can be improved.

When the storage elastic modulus is small to a certain extent, the effect of the loss tangent described above is enhanced, and the effect of missing an external load as thermal energy is enhanced. This effect is so large that the storage elastic modulus is small, but when it becomes too small, since the toughness of a surface layer will fall, a lower limit is considered about 10 MPa. On the other hand, when the storage elastic modulus becomes larger than 1,000 MPa, the surface layer is destroyed by an external load, and moldability and self-healing properties may be deteriorated.

In order to make the storage elastic modulus at 25 degreeC of the said surface layer in a dynamic viscoelasticity method into 10 MPa or more and 1,000 MPa or less, it becomes possible by making resin contained in the said surface layer satisfy|fill the above-mentioned condition 2.

From the viewpoint of self-healing properties, it is preferable that the storage elastic modulus at 100°C of the surface layer in the dynamic viscoelastic method is higher than the storage elastic modulus at 25°C. The storage modulus indicates to what extent a material can recover when a load is applied, and an increase in the storage modulus indicates improved self-healing properties.

When the storage elastic modulus at 100° C. of the surface layer is higher than the storage elastic modulus at 25° C., the self-healing property is improved by the above-described effect. In order to make the storage elastic modulus at 100 degreeC of the said surface layer higher than the storage elastic modulus at 25 degreeC, it becomes possible by making the resin contained in the said surface layer satisfy|fill the above-mentioned condition 2.

From the viewpoint of moldability and self-healing properties, in the dynamic viscoelasticity method, the loss tangent of the surface layer at 25° C. of the laminated film of the present invention is preferably 0.15 or more, more preferably 0.20 or more, and particularly preferably 0.30 or more. The loss tangent represents the responsiveness when subjected to a mechanical load, and by setting the loss tangent to a specific value, the formability and self-healing properties can be improved.

When the loss tangent is large, the effect of missing the above-described external load as thermal energy increases, and thus the formability and self-healing properties are improved, which is preferable. The larger the loss tangent, the greater this effect, but the self-healing material has a limit because it has a cross-linked network, and the upper limit is considered to be about 1.00. On the other hand, when the loss tangent becomes smaller than 0.15, the surface layer is destroyed by an external load, and the formability and self-healing property may be deteriorated.

In order to make the loss tangent at 25 degreeC of the said surface layer in a dynamic viscoelastic method into 0.15 or more, it becomes possible by the resin contained in the said surface layer satisfying|fulfilling the above-mentioned condition 2.

Moreover, in the said laminated|multilayer film from a moldability viewpoint, it is preferable to satisfy|fill the following condition 8.

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

In addition, the tensile force test method will be described later.

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

When the crack elongation at 25°C is large, the formability is improved because the laminated film can follow the shape of the article to be molded. The higher the crack elongation at 23°C, the more preferable. On the other hand, when the crack elongation at 25°C is less than 20%, cracks are generated in the surface layer during molding, resulting in poor molding, and thus the moldability may be lowered.

In order to make the crack elongation at 25 degreeC 20% or more, it becomes possible if the resin contained in the said surface layer satisfy|fills the above-mentioned condition 2.

Moreover, in the said laminated|multilayer film from a moldability and a viewpoint of close_contact|adherence durability, it is preferable to satisfy|fill the following condition 9.

Condition 9: The swelling index of the supporting substrate is 0.01 or more.

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

0.01 or more is preferable, as for the swelling degree index of the said support base material, 0.05 or more are more preferable, and 0.10 or more are still more preferable. The swelling index indicates affinity with the solvent and the coating composition, and the size of the swelling index indicates the height of adhesion between the supporting substrate and the surface layer, that is, the height of moldability and adhesion durability.

Since the adhesiveness of a surface layer and a support base material will improve when the swelling degree index of a support base material is large, a moldability and adhesion durability will improve. It is preferable that the swelling degree index is larger, but if it is too large, the supporting base material is destroyed at the time of forming the surface layer, so the upper limit is considered to be about 10. On the other hand, when the swelling degree index is less than 0.01, the interface between the surface layer and the supporting substrate is destroyed during deformation during molding or deterioration with time due to long-term use, thereby reducing moldability and adhesion durability.

In order to make the swelling degree index of a support base material 0.01 or more, it becomes possible by selecting a support base material which has specific surface properties.

Moreover, in the said laminated|multilayer film from an antifouling|stain-resistant viewpoint, it is preferable to satisfy|fill the following condition 10.

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

(5) fluorine compound segment

Here, the resin refers to a material containing a high molecular compound, and the range includes a range from a polymer to an oligomer.

The fluorine compound segment described in (5) above refers to a segment comprising at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group, More preferably, the fluorine compound segment is a fluoropolyether segment. The said fluoropolyether segment is a segment which consists of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoro alkanediyl group, etc., and has a structure represented by Formula (6) and Formula (7).

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

Although the detail of the said fluoropolyether segment is mentioned later, when resin which comprises a surface layer contains them, the molecule|numerator which shows a low surface energy can be made to exist in a high density on the outermost surface.

The chain length of this fluoropolyether segment has a preferable range, 4 or more and 12 or less are preferable, as for carbon number, 4 or more and 10 or less are more preferable, 6 or more and 8 or less are especially preferable. If the number of carbon atoms is 3 or less, the oil repellency may decrease because the surface energy does not sufficiently decrease, and if the number of carbon atoms is 13 or more, the quality of the surface layer may decrease because the solubility in the solvent decreases.

When the resin contained in the surface layer contains (5) a fluorine compound segment, the adhesion durability and dye transfer resistance of the obtained surface layer can be improved, so it is preferable.

Moreover, in the said laminated|multilayer film from a viewpoint of self-healing property and a moldability, it is preferable to satisfy|fill the following condition 11.

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

(6) polycarbonate segment

Here, the resin refers to a material containing a high molecular compound, and the range includes a range from a polymer to an oligomer.

The (6) polycarbonate segment refers to a segment represented by the general formula (8). These details will be described later.

[n is an integer from 2 to 16. R ₃ represents an alkylene group having 1 to 8 carbon atoms or a cycloalkylene group]

When the resin contained in the surface layer has (6) polycarbonate segments, the self-healing properties and moldability of the obtained surface layer can be improved, so it is preferable.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

[Lamination film and surface layer]

The laminated film of the present invention may have a surface layer exhibiting specific characteristics and may have a flat shape (film, sheet, plate). Here, the surface layer exhibiting specific characteristics means a surface layer that satisfies the conditions 1 and 2 described above.

The surface layer has, in addition to the moldability, self-healing properties, adhesion durability, and antifouling properties of the present invention, luster, anti-fingerprint properties, design properties, anti-reflection, anti-static, conductivity, heat ray reflection, near-infrared absorption, electromagnetic wave shielding, easy adhesion It may have other functions such as

Although the thickness of the said surface layer is not specifically limited, 5 micrometers or more and 200 micrometers or less are preferable, 10 micrometers or more and 100 micrometers or less are more preferable, The thickness can be selected according to functions other than those mentioned above.

[support mention]

Any of a thermoplastic resin and a thermosetting resin may be sufficient as resin which comprises the support base material used for the laminated|multilayer film of this invention, a homo resin may be sufficient, copolymerization, or a blend of 2 or more types may be sufficient as it. More preferably, since resin which comprises a support base material has favorable moldability, a thermoplastic resin is preferable.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene/polypropylene/polystyrene/polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6/nylon 66, aramid resins, polyester resins, polycarbonate resins, and polyarylate resins. , polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, ethylene trifluoride resin, ethylene trifluorochloride resin, tetrafluoroethylene-6 fluoropropylene copolymer, vinylidene fluoride resin, fluororesin, acrylic resin, meta A krill resin, a polyacetal resin, a polyglycolic acid resin, a polylactic acid resin, etc. can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. It is more preferable that a thermoplastic resin is a polyester resin, polycarbonate resin, an acrylic resin, or a methacryl resin especially from a viewpoint of strength, heat resistance, and transparency.

The polyester resin in the present invention is a generic term for polymers having an ester bond as the main bond chain of the main chain, and is obtained by polycondensation of an acid component and its ester and a diol component. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate. Moreover, what copolymerized these with other dicarboxylic acid, its ester, and a diol component as an acid component or a diol component may be sufficient. Among these, points, such as transparency, dimensional stability, and heat resistance, polyethylene terephthalate and polyethylene-2,6-naphthalate are especially preferable.

In addition, various additives such as antioxidants, antistatic agents, nucleating agents, inorganic particles, organic particles, viscosity reducing agents, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, dope agents for adjusting refractive index, etc. are added to the supporting substrate. good to be The supporting base material may have either a single layer configuration or a laminate configuration.

It is also possible to give various surface treatment to the surface of a support base material before forming the said surface layer. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, 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, as for the support base material used for the laminated|multilayer film of this invention, as mentioned above, it is preferable to use a support base material (hereinafter, support base material A) having a swelling degree index of 0.01 or more. Since the adhesiveness of a surface layer and a support base material improves as mentioned above when the support base material A is used, since moldability and adhesion durability improve as a result, it is preferable.

As the supporting substrate A used in the present invention, products such as "COSMOSHINE" (registered trademark) A4300, A4100 (TOYOBO CO., LTD.), "Panlight" (registered trademark) PC-2151 (TEIJIN LIMITED.) etc. are suitably exemplified can do.

[Paint composition]

Although the manufacturing method of the laminated|multilayer film of this invention is not specifically limited, The laminated|multilayer film of this invention can be obtained through the process of apply|coating a coating composition to at least one of the above-mentioned support base materials, and a process of drying or curing if necessary. . This coating composition comprises the above-mentioned (1) polycaprolactone segment, (2) urethane bond, (3) polysiloxane segment and/or polydimethylsiloxane segment, (4) tricyclodecyl segment, or a resin containing them in the application process. It is preferable to include a formable material (hereinafter referred to as a precursor), and the resin contained in the surface layer can have these segments and bonds by using the coating composition in a manufacturing method described later.

Moreover, it is more preferable that the said coating composition contains the resin or precursor containing (5) a fluorine compound segment. In addition, (5) a resin or precursor containing a fluorine compound segment may be included, (6) a resin or precursor containing a polycarbonate segment may be included, (5) a resin or precursor containing a fluorine compound segment, and (6) poly You may contain both resin or precursor containing a carbonate segment.

Moreover, you may contain the solvent and other components mentioned later in the coating composition.

[Polycaprolactone Segment]

The laminated|multilayer film of this invention WHEREIN: It is preferable that resin contained in a surface layer contains (1) polycaprolactone segment. Here, the polycaprolactone segment refers to the segment represented by the above-described formula (1). When the resin contained in the surface layer contains (1) polycaprolactone segments, it is preferable because the self-healing properties and moldability of the surface layer can be improved.

When the coating composition used for forming the surface layer contains the resin or precursor containing the polycaprolactone segment, it becomes possible for the resin contained in the surface layer to have the polycaprolactone segment.

It is preferable that the resin containing the polycaprolactone segment has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin comprising the polycaprolactone segment.

As resin containing a polycaprolactone segment, especially polycaprolactone which has a 2-3 functional hydroxyl group is preferable. Polycaprolactone having a 2- to trifunctional hydroxyl group, specifically, polycaprolactonediol represented by Formula 9, polycaprolactone triol represented by Formula 10, or polycaprolactone-modified hydroxyethyl (Meta) represented by Formula 11 ) acrylates. Here, the polycaprolactonediol represented by the formula (9) and the polycaprolactone triol represented by the formula (10) are generally referred to as polycaprolactone polyols.

The polycaprolactonediol represented by the formula (9) is shown below.

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 .

In addition, the polycaprolactone triol represented by Formula (10) is shown below.

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 .

In addition, polycaprolactone modified|denatured hydroxyethyl (meth)acrylate is shown below.

Here, n is an integer of 1 to 25, and R ₆ is either H or CH ₃ . In addition, when R ₆ is either H or CH ₃ , these are called active energy ray polymerizable caprolactones. In addition, (meth)acrylate shows a methacrylate or an acrylate.

Here, active energy ray polymerizability is a property in which crosslinking advances by active energy rays, such as an ultraviolet-ray (UV ray) and an electron beam (EB ray), and a compound which has functional groups, such as a (meth)acrylate group, corresponds. Examples of other active energy ray-polymerizable caprolactone include polycaprolactone-modified hydroxypropyl (meth)acrylate and polycaprolactone-modified hydroxybutyl (meth)acrylate.

In the present invention, the resin containing the polycaprolactone segment may contain (or copolymerize) other segments or monomers other than the polycaprolactone segment. For example, the compound containing the tricyclodecyl segment mentioned later, a polydimethylsiloxane segment, a polysiloxane segment, a polycarbonate segment, and an isocyanate compound may be contained (or copolymerized).

Moreover, in this invention, it is preferable that the weight average molecular weights of the polycaprolactone segment in resin containing a polycaprolactone segment are 500-2,500, More preferable weight average molecular weights are 1,000-1,500. When the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, the self-healing effect is more expressed and scratch resistance is further improved, which is preferable.

Whether the polycaprolactone segment is copolymerized or separately added, if the content of the polycaprolactone segment is 5 to 50 mass% in the total solid content of 100% by mass of the coating composition used to form the surface layer, self-healing properties and design It is preferable from the point of property and moldability.

[Urethane bond]

The laminated|multilayer film of this invention WHEREIN: It is preferable that resin contained in a surface layer contains (2) a urethane bond. Here, the urethane bond refers to a segment represented by the above-described 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 the self-healing property can be improved, which is preferable.

When the coating composition used for forming the surface layer contains a commercially available urethane-modified resin, it becomes possible for the resin contained in the surface layer to have a urethane bond. In addition, when the surface layer is formed, a urethane bond can be generated in the coating step by applying a coating composition containing a compound containing an isocyanate group and a compound containing a hydroxyl group as precursors, so that the surface layer can contain a urethane bond.

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

In addition, the resin containing the above-mentioned polycaprolactone segment, the resin containing the tricyclodecyl segment, the resin containing the polycarbonate segment, the resin containing the polysiloxane segment mentioned later, the resin containing the polydimethylsiloxane segment, etc. are hydroxyl groups It is also possible to form a urethane bond between these resins and a compound containing an isocyanate group as a precursor by heat or the like. When a surface layer is formed using a compound containing an isocyanate group and a resin containing a polysiloxane segment having a hydroxyl group or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the toughness and elastic recovery properties (self-healing properties) of the surface layer and the surface Since sliding property can be improved, it is preferable.

In this invention, the compound containing an isocyanate group refers to resin containing an isocyanate group, and the monomer and oligomer containing an isocyanate group. The compound containing an isocyanate group is, for example, methylenebis-4-cyclohexyl isocyanate, a trimethylol propane adduct body of tolylene diisocyanate, a trimethylol propane adduct body of hexamethylene diisocyanate, and trimethylol propane of isophorone diisocyanate. Polyisocyanates, such as the isocyanurate body of an adduct body, the isocyanurate body of tolylene diisocyanate, the isocyanurate body of hexamethylene diisocyanate, and the biuret body of hexamethylene isocyanate, and the block body of the said isocyanate, etc. are mentioned.

Among the compounds containing these isocyanate groups, aliphatic isocyanates have high self-healing properties and are preferable compared to alicyclic or aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Moreover, as for the compound containing an isocyanate group, the isocyanate which has an isocyanurate ring is especially preferable from a heat resistant point, and the isocyanurate body of hexamethylene diisocyanate is the most preferable. The isocyanate having an isocyanurate ring forms a surface layer having both self-healing properties and heat resistance properties.

[polysiloxane segment and/or polydimethylsiloxane segment]

The laminated|multilayer film of this invention WHEREIN: It is preferable that resin contained in a surface layer contains (3) a polysiloxane segment and/or a polydimethylsiloxane segment. Here, the polysiloxane segment refers to the segment represented by the above-described formula (3), and the polydimethylsiloxane segment refers to the segment represented by the above-described formula (4). When the resin contained in the surface layer contains (3) a polysiloxane segment and/or a polydimethylsiloxane segment, the polydimethylsiloxane segment coordinates to the most surface side of the surface layer, so that the lubricity of the surface layer is improved, so there is an effect of missing a load, and It is preferable because the self-healing properties of the surface layer can be improved in order to suppress the occurrence of non-repairable abrasions.

Since the coating composition used for forming the surface layer contains a resin or precursor containing a polysiloxane segment and/or a polydimethylsiloxane segment, it becomes possible for the resin contained in the surface layer to have a polysiloxane segment and/or a polydimethylsiloxane segment.

In addition, it is preferred that the resin or precursor comprising the polysiloxane segment and/or the polydimethylsiloxane segment contains a reactive moiety. This reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such a reactive moiety include a silanol group in which an alkoxysilyl group and an alkoxysilyl group are hydrolyzed from the viewpoint of reactivity, a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, and the like. Among them, a vinyl group, an allyl group, an alkoxysilyl group, a silyl ether group or a silanol group, an epoxy group, an acryloyl group, and a methacryloyl group are preferable from the viewpoint of reactivity and handling properties.

Hereinafter, the details of the polysiloxane segment and the polydimethylsiloxane segment will be described in order.

[Polysiloxane Segment]

In the present invention, the polysiloxane segment refers to the segment represented by the above formula (3).

In the present invention, a partial hydrolyzate of a silane compound containing a hydrolysable silyl group, an organosilicasol, or a composition obtained by adding a hydrolyzable silane compound having a radical polymer to the organosilicasol can be used as the compound having a polysiloxane segment.

The compound having a polysiloxane segment is tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane , γ-methacryloxypropylalkyldialkoxysilane complete or partial hydrolyzate of a silane compound having a hydrolyzable silyl group, or an organosilicasol dispersed in an organic solvent, the hydrolyzable silyl group on the surface of the organosilicasol What added a decomposed silane compound, etc. can be illustrated.

In addition, in this invention, resin containing a polysiloxane segment may contain (copolymerization) another segment other than a polysiloxane segment. For example, the monomer component which has a polycaprolactone segment, a tricyclodecyl segment, a polycarbonate segment, and a polydimethylsiloxane segment may contain (copolymerization).

In this invention, it is preferable that the monomer etc. which have a hydroxyl group which reacts with an isocyanate group are copolymerized as resin containing a polysiloxane segment. When a monomer or the like having a hydroxyl group reacting with an isocyanate group is copolymerized with the resin containing the polysiloxane segment, the toughness of the surface layer is improved.

When the resin containing the polysiloxane segment is a copolymer having a hydroxyl group, the polysiloxane segment is efficiently formed by forming a surface layer using a coating composition comprising a resin (copolymer) containing a polysiloxane segment having a hydroxyl group and a compound containing an isocyanate group. and a surface layer having a urethane bond.

[Polydimethylsiloxane Segment]

In the present invention, the polydimethylsiloxane segment refers to a segment represented by the above formula (4).

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

When the compound having a polydimethylsiloxane segment is a copolymer with a vinyl monomer, any of a block copolymer, a graft copolymer, and a random copolymer may be used. When the compound having a polydimethylsiloxane segment is a copolymer with a vinyl monomer, it is referred to as a polydimethylsiloxane-based copolymer.

In synthesizing a polydimethylsiloxane-based block copolymer as a compound having a polydimethylsiloxane segment (polydimethylsiloxane-based copolymer), it can be produced by a living polymerization method, a polymer initiator method, a polymer chain transfer method, etc., but considering the productivity It is preferable to use a polymer initiator method or a polymer chain transfer method.

When using the polymer initiator method, the compound having a polydimethylsiloxane segment (polydimethylsiloxane-based copolymer) is a polymer azo radical polymerization initiator represented by Formula 12

[m is an integer from 10 to 300, n is an integer from 1 to 50]

It can be obtained by copolymerizing with other vinyl monomers using

In addition, a two-step polymerization of copolymerizing a peroxy monomer and polydimethylsiloxane having an unsaturated group at a low temperature to synthesize a prepolymer in which a peroxide group is introduced into a side chain, and copolymerizing the prepolymer with a vinyl monomer may be carried out.

When the polymer chain transfer method is used, the compound having a polydimethylsiloxane segment (polydimethylsiloxane-based copolymer) is, for example, a silicone oil represented by the formula (13).

[m is an integer from 10 to 300]

It can be obtained by adding HS-CH ₂ COOH or HS-CH ₂ CH ₂ COOH to a compound having an SH group, and then copolymerizing the silicone compound with a vinyl monomer using the chain transfer of the SH group.

For synthesizing a polydimethylsiloxane-based graft copolymer as a compound having a polydimethylsiloxane segment (polydimethylsiloxane-based copolymer), for example, a compound represented by the general formula (14)

[m is an integer from 10 to 300]

That is, it can obtain easily by copolymerizing the methacrylic ester of polydimethylsiloxane, etc. with a vinyl monomer.

Examples of the vinyl monomer used for the copolymer with the compound having a polydimethylsiloxane segment include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetra Hydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl Vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, glycidyl acryl Late, glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, diacetitoacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate a rate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, allyl alcohol, etc. are mentioned.

In addition, polydimethylsiloxane-based copolymers include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, isopropyl alcohol, and the like. It is preferable to be prepared by solution polymerization in an alcohol-based solvent or the like alone or in a mixed solvent. Moreover, it is preferable to use together polymerization initiators, such as benzoyl peroxide and azobisisobutylnitrile, as needed. It is preferable to perform polymerization reaction at 50-150 degreeC for 3-12 hours.

The amount of the polydimethylsiloxane segment in the polydimethylsiloxane-based copolymer in the present invention is preferably 1 to 30% by mass based on 100% by mass of all the components of the polydimethylsiloxane-based copolymer from the viewpoint of lubricity and stain resistance of the surface layer. . Moreover, it is preferable that the weight average molecular weight of a polydimethylsiloxane segment sets it as 1,000-30,000.

Even if the polydimethylsiloxane segment is copolymerized or added separately, if the dimethylsiloxane segment is 1 to 20 mass% in 100 mass% of the total component of the coating composition used to form the surface layer, self-healing properties, stain resistance, weather resistance, It is preferable from a heat resistant point. A solvent not involved in the reaction is not included in 100% by mass of all components of the coating composition. Monomer components involved in the reaction are included.

In the present invention, when a resin containing a polydimethylsiloxane segment is used as the coating composition used to form the surface layer, other segments other than the polydimethylsiloxane segment may be contained (copolymerized). For example, a polycaprolactone segment, a tricyclodecyl segment, a polycarbonate segment, or a polysiloxane segment may be contained (copolymerized).

The coating composition used to form the surface layer includes a copolymer of a polycaprolactone segment and a polydimethylsiloxane segment, a copolymer of a polycaprolactone segment and a polysiloxane segment, a copolymer of a polycaprolactone segment, a polydimethylsiloxane segment, and a polysiloxane segment, etc. It is possible to use It becomes possible for the surface layer obtained using such a coating composition to have a polycaprolactone segment, a polydimethylsiloxane segment, and/or a polysiloxane segment.

The reaction of the polydimethylsiloxane copolymer, polycaprolactone and polysiloxane in the coating composition used to form a surface layer having a polycaprolactone segment, a polysiloxane segment and a polydimethylsiloxane segment is appropriately carried out when synthesizing the polydimethylsiloxane copolymer. It can copolymerize by adding a caprolactone segment and a polysiloxane segment.

[Tricyclodecyl segment]

The laminated|multilayer film of this invention WHEREIN: It is preferable that resin contained in a surface layer contains the (4) tricyclodecyl segment. Here, the tricyclodecyl segment refers to a segment represented by the above-described formula (5). When the resin contained in the surface layer contains the (4) tricyclodecyl segment, the antifouling property and adhesion durability of the surface layer can be improved, and it is preferable.

When the coating composition used for forming the surface layer contains the resin or precursor containing the tricyclodecyl segment, it becomes possible for the resin contained in the surface layer to have the tricyclodecyl segment.

Although the structure of the tricyclodecyl segment is the same as described with the above-mentioned formula (5), a resin or precursor containing the tricyclodecyl segment preferred for the above-described coating composition is a compound represented by the formula (15).

R ₇ represents an alkanediyl group, an alkanetriyl group, an oxyalkanediyl group, an oxyalkanetoluyl group and any one of an ester structure, a urethane structure, an ether structure, and a triazine structure derived therefrom, and D ₁ represents a reactive site.

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

More preferably, R ₇ is any one of an alkanediyl group, a urethane structure, or an ester structure, and D ₁ is an acryloyl (methacryloyl) group or a hydroxyl group.

Commercially available (meth)acrylate having an acryloyl (methacryloyl) group, that is, a tricyclodecyl segment, _{in which D 1} in the above formula (15) as a resin or precursor containing a tricyclodecyl segment preferred for the above-mentioned coating composition Examples of the material used include IRR214-K (DAICEL-ALLNEX LTD.), SR833S (SARTOMER Inc.), FA-513AS, FA-513M (Hitachi Chemical Co., Ltd.), A-DCP, DCP (Shin Nakamura Chemical Co.) ., Ltd.) and LIGHT ACRYLATE DCP-A (kyoeisha Chemical Co., Ltd.).

[Fluorine compound segment]

The laminated|multilayer film of this invention WHEREIN: It is preferable that resin contained in a surface layer contains the (5) fluorine compound segment. When the resin contained in the surface layer contains (5) the fluorine compound segment, the antifouling properties and anti-fingerprint properties of the surface layer can be improved, which is preferable.

When the coating composition used in order to form a surface layer contains resin or precursor containing a fluorine compound segment, resin contained in a surface layer becomes possible to have a fluorine compound segment.

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

Here, a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group refer to a part of hydrogen that an alkyl group, an oxyalkyl group, an alkenyl group, an alkanediyl group, or an oxyalkanediyl group has. Or all of them are substituents substituted with fluorine, all of which are substituents mainly composed of fluorine atoms and carbon atoms, and may have branches in the structure, and may form a dimer, trimer, oligomer, or polymer structure in which a plurality of structures having these moieties are linked. .

Further, as the fluorine compound segment, a fluoropolyether segment is preferable, which is a moiety composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc. More preferably, the general formulas (6) and (7) The fluoropolyether segment represented by is as already described.

In order that the resin contained in this surface layer contains a fluorine compound segment, it is preferable that the above-mentioned coating composition contains the following fluorine compounds. This fluorine compound is a compound represented by the 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, or a triazine structure, and D ¹ represents a reactive site.

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

An example of a fluorine compound is the compound shown below. 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3- Trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanatesilane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluoro Octylethyltriisopropoxysilane, 2-perfluorooctylethyltrichlorosilane, 2-perfluorooctylisocyanatesilane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3 -Pentafluoropropylacrylate, 2-perfluorobutylethylacrylate, 3-perfluorobutyl-2-hydroxypropylacrylate, 2-perfluorohexylethylacrylate, 3-perfluorohexyl- 2-Hydroxypropylacrylate, 2-perfluorooctylethylacrylate, 3-perfluorooctyl-2-hydroxypropylacrylate, 2-perfluorodecylethylacrylate, 2-perfluoro-3 -Methylbutylethylacrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropylacrylate, 2-perfluoro-5-methylhexylethylacrylate, 3-perfluoro-5-methyl Hexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate , hexadecafluorononyl acrylate, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- Perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate Rate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2- Perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3- Perfluoro-6-methyloctylmethacrylate, tetrafluoro Propyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate acrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol, and the like.

Further, the fluorine compound may have a plurality of fluoropolyether moieties per molecule.

Commercially available examples of the fluorine compound include RS-75 (DIC Corporation), Optool DAC-HP (DAIKIN INDUSTRIES, ltd.), C10GACRY, C8HGOL (YUSHI-SEIHIN CO., LTD.), and the like, and their products. is available.

[Polycarbonate Segment]

The laminated|multilayer film of this invention WHEREIN: It is preferable that resin contained in a surface layer contains (6) polycarbonate segment. Here, the polycarbonate segment refers to a segment represented by the above-described formula (8). When the resin contained in the surface layer contains the (6) polycarbonate segment, the toughness and self-healing properties of the surface layer can be improved, which is preferable.

When the coating composition used in order to form a surface layer contains resin or precursor containing a polycarbonate segment, it becomes possible that resin contained in a surface layer has a polycarbonate segment.

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

As resin containing a polycarbonate segment, especially the polycarbonate diol which has a bifunctional hydroxyl group is preferable. Specifically, it is a polycarbonate diol represented by general formula (17).

[R ₉ is any one of an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 or more]

Polycarbonate diol may have any number of repetitions of carbonate units, but if the number of repetitions of carbonate units is too large, the strength of the cured product of urethane (meth)acrylate is lowered. Therefore, the number of repetitions n is preferably 10 or less. Further, the polycarbonate diol may be a mixture of two or more types of polycarbonate diols from which the repeating number of carbonate units differs.

It is preferable that the number average molecular weights are 500-10,000, and, as for polycarbonate diol, it is more preferable that it is 1,000-5,000. When the number average molecular weight is less than 500, suitable flexibility may be difficult to be obtained, and if the number average molecular weight exceeds 10,000, heat resistance and solvent resistance may decrease, so the above-mentioned level is suitable.

In addition, as the polycarbonate diol used in the present invention, UH-CARB, UD-CARB, UC-CARB (Ube Industries, Ltd.), PLACCEL CD-PL, PLACCEL CD-H (Daicel Corporation), kuraray polyol C series (KURARAY) CO., LTD.), Duranol series (Asahi Kasei Corporation), etc. can be exemplified suitably. These polycarbonate diols can also be used individually or in combination of 2 or more types.

In the present invention, the resin or precursor containing the polycarbonate segment may contain (or copolymerize) other segments or monomers other than the polycarbonate segment. For example, the compound containing the above-mentioned polycaprolactone segment, tricyclodecyl segment, polydimethylsiloxane segment, polysiloxane segment, and an isocyanate compound may be contained (or copolymerized).

In the present invention, preferably, the surface layer has (6) polycarbonate segments and (2) urethane bonds by reacting the above-described compound containing an isocyanate group with the hydroxyl group of polycarbonate diol and using it in a coating composition as a urethane (meth)acrylate. As a result, the toughness of the surface layer can be improved, and the self-healing property can be improved, which is preferable.

[menstruum]

The coating composition may contain a solvent. As the number of types of solvent, 1 or more and 20 or less are preferable, More preferably, they are 1 or more and 10 or less, More preferably, they are 1 or more and 6 or less, Especially preferably, they are 1 or more and 4 or less.

Here, "solvent" refers to a substance that is liquid at room temperature and pressure capable of evaporating substantially the entire amount in the drying step after application.

Here, the type of solvent is determined by the molecular structure constituting the solvent. That is, they have the same elemental composition and have different bonding relationships even if the types and numbers of functional groups are the same (structural isomers). Silver is treated as a different solvent. For example, 2-propanol and n-propanol are treated as different solvents.

Moreover, when a solvent is included, it is preferable that it is a solvent which shows the following characteristics.

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

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

When the relative evaporation rate of the solvent is greater than 0.4, the time required for orientation to the outermost surface of the polysiloxane segment and/or the polydimethylsiloxane segment and the fluorine compound segment in the surface layer becomes shorter. And the fall of antifouling property may generate|occur|produce. The lower limit of the relative evaporation rate of the solvent B is not problematic as long as it is a solvent that can be evaporated and removed from the coating film in the drying step, and may be 0.005 or more in the general application step.

As solvent B, isobutyl ketone (relative evaporation rate: 0.2), isophorone (relative evaporation rate: 0.026), distyrene 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), cyclohexanone (relative evaporation rate: 0.32);

[Other components in the coating composition]

In addition, it is preferable that the said coating composition contains a polymerization initiator, a hardening|curing agent, and a catalyst. A polymerization initiator and a catalyst are used to promote curing of the surface layer. The polymerization initiator is preferably one capable of initiating or accelerating polymerization, condensation or crosslinking reaction of components contained in the coating composition by anionic, cationic, radical polymerization reaction or the like.

A polymerization initiator, a hardening|curing agent, and a catalyst can use various things. In addition, a polymerization initiator, a hardening|curing agent, and a catalyst may be used independently, respectively, and a some polymerization initiator, a hardening|curing agent, and a catalyst may be used simultaneously. Moreover, you may use together an acidic catalyst and a thermal-polymerization initiator. Examples of the acid catalyst include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include an alkylphenone-based compound, a sulfur-containing compound, an acylphosphine oxide-based compound, and an amine-based compound. Moreover, dibutyltin dilaurate, dibutyltin diethylhexoate, etc. are mentioned as an example of the crosslinking catalyst which accelerates|stimulates the formation reaction of a urethane bond.

In addition, the coating composition may contain other crosslinking agents such as melamine crosslinking agents such as alkoxymethylolmelamine, acid anhydride crosslinking agents such as 3-methyl-hexahydrophthalic anhydride, and amine crosslinking agents such as diethylaminopropylamine. .

As a photoinitiator, an alkylphenone type compound is preferable from a sclerosing|hardenable point. 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-dimethylamino-1-(4-morpholinophenyl)-1-butane, 2-(dimethylamino)-2-[(4 -Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 1-cyclohysyl-phenylketone, 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)oxybisethylene and high molecular weight of these materials things and the like.

Moreover, as long as it is a range which does not impair the effect of this invention, you may add a leveling agent, a ultraviolet absorber, a lubricant, an antistatic agent, etc. to the coating composition used in order to form a surface layer. Thereby, the surface layer can contain a leveling agent, a ultraviolet absorber, a lubricant, an antistatic agent, etc. As an example of a leveling agent, the leveling agent of an acrylic copolymer or a silicone type, and a fluorine type is mentioned. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalic acid anilide-based, triazine-based and hindered amine-based ultraviolet absorbers. Examples of the antistatic agent include metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt and calcium salt.

[Method for producing laminated film]

The surface layer formed on the surface of the laminated film of the present invention is preferably formed by applying-drying-curing the above-described coating composition onto the above-mentioned supporting substrate. Hereinafter, the application process is described as a coating process, a drying process is described as a drying process, and a curing process is described as a curing process.

In the application step, the method for applying the coating composition is not particularly limited, but the coating composition is coated by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, or a die coating method (US Patent No. 2681294 specification). It is preferable to form a surface layer by apply|coating to a support base material. Further, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.

Following the application step, the liquid film applied on the support substrate by the drying step is dried. From a viewpoint of completely removing a solvent from the laminated|multilayer film obtained, it is preferable to be accompanied by heating of a liquid film in a drying process.

Examples of the drying method in the drying step include electrothermal drying (adherence to a high-heat object), convection heat transfer (hot air), radiant heat (infrared), and others (microwave, induction heating). Among these, in the manufacturing method of this invention, the method using convective heat transfer or radiation heat transfer is preferable from the need to make a drying rate uniform also precisely in the width direction.

The drying process in the drying process is generally divided into (A) constant rate drying period and (B) decreasing rate drying period. is constant in this section, and the drying rate is governed by the partial pressure of the solvent to be evaporated in the atmosphere, the wind speed, and the temperature. In the latter case, since the diffusion of the solvent in the liquid film is rate-limited, the drying rate does not show a constant value in this section and continues to decrease, and is governed by the diffusion coefficient of the solvent in the liquid film, and the film temperature rises. Here, the drying rate indicates the amount of solvent evaporation per unit time and unit area, and has a dimension of ^{g·m -2} ·s ^-1.

The drying rate has a preferable range, and is preferably 0.1 g·m ^-2 ·s ^-1 or more and 10 g·m ^-2 ·s ^-1 or less, and 0.1 g·m ^-2 ·s ^-1 or more 5 g·m ⁻ It is more preferable that it is ² *s ^{-1 or less.} By setting the drying rate in the constant-rate drying section into this range, it is possible to prevent variations due to the non-uniformity of the drying rate. If a drying rate in the range of 0.1 g·m ^-2 ·s ^-1 or more and 10 g·m ^-2 ·s ^-1 or less is obtained, it will not be limited to a specific wind speed and temperature in particular.

In the manufacturing method of the laminated|multilayer film of this invention, the orientation of a polysiloxane segment and/or a polydimethylsiloxane segment, and a fluorine compound segment is performed with evaporation of a residual solvent in a reduced rate drying period. In this process, since time is required for orientation, a preferable range exists for the film surface temperature rise rate in the reduced rate drying period, and it is preferable that it is 5 degrees C/sec or less, and it is more preferable that it is 1 degrees C/sec or less.

Moreover, you may perform the additional hardening operation (hardening process) by irradiating a heat|fever or an energy-beam.

Moreover, when hardening|curing with an active energy ray, it is preferable that it is an EB ray and/or a UV ray from a versatility point. In the case of curing by ultraviolet rays, the oxygen concentration is preferably as low as possible from the viewpoint of preventing oxygen inhibition, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable. When the oxygen concentration is high, hardening of the outermost surface is inhibited, hardening of the surface becomes insufficient, and self-healing property and adhesion durability may become insufficient. Moreover, as a kind of the ultraviolet lamp used when irradiating an ultraviolet-ray, a discharge lamp system, a flash system, a laser system, an electrodeless lamp system, etc. are mentioned, for example. When UV curing is performed using a high-pressure mercury lamp, which is a discharge lamp, the illuminance of UV light 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 It is preferable to irradiate, and it is preferable to perform ultraviolet irradiation under the condition that the accumulated light amount of ultraviolet rays is 100 to 3,000 mJ/cm 2 , preferably 200 to 2,000 mJ/cm 2 , more preferably 300 to 1,500 mJ/cm 2 . Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and it changes depending on the lamp output, the luminous spectral efficiency, the diameter of the luminous valve, the design of the reflector, and the distance of the light source to the irradiated object. However, the illuminance does not change with the conveying speed. In addition, the amount of ultraviolet-integrated light is the irradiation energy received per unit area, and is the total amount of photons which reach the surface. The accumulated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

[Application example]

The laminated film of the present invention takes advantage of the advantages of moldability, self-healing properties, adhesion durability, and antifouling properties, and is particularly high in abrasion resistance in use to be molded into various molded articles by molding, so that scratches are difficult to stand out. It can be used as appropriate for the intended use.

For example, plastic molded products such as eyeglasses/sunglasses, makeup boxes, and food containers, home appliances such as smartphone housings, touch panels, keyboards, remote controls for TV/air conditioners, buildings, dashboards, car navigation/touch panels, rooms It can be suitably used for vehicle interiors such as mirrors, and for each surface of various printed materials.

Example

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

[Urethane (meth)acrylate A]

[Synthesis of urethane (meth)acrylate A1]

Toluene 50 parts by mass, isocyanurate-modified type of hexamethylene diisocyanate ("TAKENATE" (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.) 50 parts by mass, polycaprolactone-modified hydroxyethyl acrylate (Daicel Corporation) 76 parts by mass of "Placcel" (registered trademark) FA5), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and maintained at 70°C for 5 hours. Then, 79 mass parts of toluene was added, and the toluene solution of the urethane (meth)acrylate A1 of 50 mass % of solid content concentration was obtained.

[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., 13.5 mass % of NCO content), 67 parts by mass of polycaprolactone-modified hydroxyethyl acrylate ("Placcel" (registered trademark) FA5 manufactured by Daicel Corporation) ) 76 parts by mass, 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and maintained at 70°C for 5 hours. Then, 79 mass parts of toluene was added, and the toluene solution of the urethane (meth)acrylate A2 of 50 mass % of solid content concentration was obtained.

[Synthesis of urethane (meth)acrylate A3]

50 parts by mass of toluene, burette-modified type of hexamethylene diisocyanate ("DURANATE" (registered trademark) 24A-90CX manufactured by Asahi Kasei Corporation, non-volatile content: 90 mass %, isocyanate content: 21.2 mass %) 50 mass parts, polycaprolactone 92 parts by mass of modified hydroxyethyl acrylate ("Placcel" (registered trademark) FA2D manufactured by Daicel Corporation), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were mixed, and the mixture was held at 70°C for 5 hours. . Then, 82 mass parts of toluene was added, and the toluene solution of the urethane (meth)acrylate A3 of 50 mass % of solid content concentration was obtained.

[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 Hakko Kirin Co., Ltd.) and polycarbonate diol (“Placcel” (registered trademark) CD-210HL manufactured by Daicel Corporation) 119 mass parts were mixed, and it heated up to 40 degreeC and hold|maintained 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.), hydro After adding 0.02 mass part of quinone monomethyl ether and hold|maintaining at 70 degreeC for 30 minutes, 0.02 mass part of dibutyltin laurate was added and it hold|maintained at 80 degreeC for 6 hours. And finally, 97 mass parts of toluene was added, and the toluene solution of the urethane (meth)acrylate B1 of 50 mass % of solid content concentration was obtained.

[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 Hakko Kirin Co., Ltd.) and polycarbonate diol (“Placcel” (registered trademark) CD-220 manufactured by Daicel Corporation) 150 mass parts was mixed, it heated up to 40 degreeC, and hold|maintained 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.), hydro After adding 0.02 mass part of quinone monomethyl ether and hold|maintaining at 70 degreeC for 30 minutes, 0.02 mass part of dibutyltin laurate was added and it hold|maintained at 80 degreeC for 6 hours. And finally, 97 mass parts of toluene was added, and the toluene solution of the urethane (meth)acrylate B2 of 50 mass % of solid content concentration was obtained.

[Urethane (meth)acrylate C]

[Synthesis of urethane (meth)acrylate C1]

Isocyanurate modified product of hexamethylene diisocyanate ("TAKENATE" (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc., isocyanate group content: 20.9 mass %) 50 parts by mass, polyethylene glycol monoacrylate (manufactured by NOF CORPORATION) 53 parts by mass of "BLEMMER" (registered trademark) AE-150, hydroxyl value: 264 (mgKOH/g)), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were prepared. And it reacted by holding|maintaining at 70 degreeC for 5 hours. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) were added to the reaction solution to obtain urethane (meth)acrylate C1 having a solid content concentration of 50% by mass.

[Siloxane compound]

[Siloxane Compound 1]

As the siloxane compound 1, the silicone diacrylate compound (EBECRYL350 Daicel-Cytec Company, Ltd. solid content concentration 100 mass %) was used.

[Siloxane Compound 2]

As the siloxane compound 2, the silicone hexaacrylate compound (EBECRYL1360 Daicel-Cytec Company, Ltd. solid content concentration 100 mass %) was used.

[Synthesis of polysiloxane (a)]

106 parts by mass of ethanol, 320 parts by mass of tetraethoxysilane, 21 parts by mass of deionized water, and 1 part by mass of 1 mass % hydrochloric acid were injected into a 500 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, and 85 ° C. After holding for 2 hours, ethanol was recovered while the temperature was raised and maintained at 180° C. for 3 hours. Thereafter, it cooled to obtain a viscous polysiloxane (a).

[Polydimethylsiloxane-based block copolymer (a)]

50 parts by mass of toluene, 50 parts by mass of methyl isobutyl ketone, and 20 parts by mass of a polydimethylsiloxane-based polymer polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., VPS-0501) using the same apparatus as for the synthesis of polysiloxane (a). , 30 parts by mass of methyl methacrylate, 26 parts by mass of butyl methacrylate, 23 parts by mass of 2-hydroxyethyl methacrylate, 1 part by mass of methacrylic acid, and 0.5 parts by mass of 1-thioglycerin are injected, and 8 parts by mass at 80°C It was made to time-react, and the polydimethylsiloxane type block copolymer (a) was obtained. The ratio of the block copolymer (a) in the obtained solution was 50 mass % in 100 mass % of solutions.

[Polydimethylsiloxane-based graft copolymer (b)]

Using the apparatus used for the synthesis|combination of polysiloxane (a), 50 mass parts of toluene and 50 mass parts of isobutyl acetate were inject|poured, and it heated up to 110 degreeC. Separately, 20 parts by mass of methyl methacrylate, 20 parts by mass of butyl methacrylate, 32 parts by mass of caprolactone methacrylic ester (“Placcel” (registered trademark) FM-5 manufactured by Daicel Corporation), 23 parts by mass of 2-hydroxyethyl methacrylate 10 parts by mass of polysiloxane (a), 20 parts by mass of single-terminal methacrylic-modified polydimethylsiloxane (manufactured by TOAGOSEI CO., LTD., X-22-174DX) and 1 part by mass of methacrylic acid, 1,1-azo 2 parts by mass of biscyclohexane-1-carbonitrile was mixed. This mixed monomer was dripped at the liquid mixture of the said toluene and butyl acetate over 2 hours. Then, it was made to react at 110 degreeC for 8 hours, and the polydimethylsiloxane-type graft copolymer (b) which has a hydroxyl group with a solid content concentration of 50 mass % was obtained. The proportion of the graft copolymer (b) in the obtained solution was 50% by mass in 100% by mass of the solution.

[Tricyclodecyl compound]

[Tricyclodecyl Compound 1]

As tricyclodecyl compound 1, the acrylate compound (IRR214-K DAICEL-ALLNEX LTD. solid content concentration 100 mass %) containing a tricyclodecyl segment was used.

[Tricyclodecyl compound 2]

As the tricyclodecyl compound 2, the acrylate compound (FA-513AS Hitachi Chemical Co., Ltd. product solid content concentration 100 mass %) containing a tricyclodecyl segment was used.

[Tricyclodecyl compound 3]

As tricyclodecyl compound 3, the acrylate compound (SR833S SARTOMER Inc. product solid content concentration of 100 mass %) containing a tricyclodecyl segment was used.

[Fluorine compound]

[Fluorine compound 1]

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

[Fluorine compound 2]

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

[Radical Photopolymerization Initiator]

[Radical Photopolymerization Initiator 1]

As the radical photopolymerization initiator 1, "IRGACURE" (trademark) 184 (made by BASF Japan Co., Ltd. solid content concentration of 100 mass %) was used.

[Combination of paint composition A]

[Paint composition A1]

The following materials were mixed and diluted using methyl ethyl ketone to obtain a coating composition A1 having a solid content concentration of 30% by mass.

-95 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %) 95 mass %

· 2.5 parts by mass of tricyclodecyl compound 1

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A2]

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

- 90 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A3]

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

-85 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

7.5 parts by mass of tricyclodecyl compound 1

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A4]

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

-80 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

- 10 parts by mass of tricyclodecyl compound 1

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A5]

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

- 90 mass parts of urethane (meth)acrylate A1 solution (50 mass % of solid content concentration).

· 5 parts by mass of tricyclodecyl compound 2

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A6]

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

- 90 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 3 5 parts by mass

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A7]

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

- 90 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

· 3 parts by mass of siloxane compound 2

· Fluorine compound 1 solution (solid content concentration: 40 mass%) 3.8 parts by mass

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A8]

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

- 90 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

- 7.5 mass parts of fluorine compound 2 solution (solid content concentration 20 mass %)

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A9]

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

- 90 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A10]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition A10 with a solid content concentration of 30 mass % was obtained.

- 90 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

· Fluorine compound 1 solution (solid content concentration: 40 mass%) 6.3 parts by mass

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A11]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition A11 with a solid content concentration of 30 mass % was obtained.

- 90 mass parts of urethane (meth)acrylate A2 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

· Fluorine compound 1 solution (solid content concentration: 40 mass%) 3.8 parts by mass

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A12]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition A12 with a solid content concentration of 30 mass % was obtained.

-90 mass parts of urethane (meth)acrylate A3 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A13]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition A13 with a solid content concentration of 30 mass % was obtained.

-45 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

-45 mass parts of urethane (meth)acrylate B1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

· Fluorine compound 1 solution (solid content concentration: 40 mass%) 3.8 parts by mass

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A14]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition A14 with a solid content concentration of 30 mass % was obtained.

-45 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

-45 mass parts of urethane (meth)acrylate B2 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

- Fluorine compound 1 solution (solid content concentration: 40 mass %) 3.8 mass parts

・1.5 parts by mass of radical photopolymerization initiator 1

- 10 parts by mass of ethylene glycol monobutyl ether.

[Combination of paint composition B]

[Paint composition B1]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition B1 of 40 mass % of solid content concentration was obtained.

・15 parts by mass of polycaprolactone triol

("Placcel" (registered trademark) 308 Daicel Corporation)

· 15 parts by mass of hexamethylene diisocyanate

("TAKENATE" (registered trademark) D-170 manufactured by Mitsui Chemicals, Inc.)

-75 mass parts of polydimethylsiloxane-type block copolymer (a) solution

(50% by mass of solid content concentration)

- 10 parts by mass of polysiloxane (a).

[Paint composition B2]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition B2 of 40 mass % of solid content concentration was obtained.

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

(50% by mass of solid content concentration)

12 parts by mass of hexamethylene diisocyanate

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

[Combination of paint composition C]

[Paint composition C1]

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

- 100 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Paint composition C2]

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

- 100 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

·Siloxane compound 1 3 parts by mass

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Paint composition C3]

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

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

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Paint composition C4]

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

- 50 mass parts of urethane (meth)acrylate A1 solution (solid content concentration 50 mass %)

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

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Paint composition C5]

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

- 90 mass parts of urethane (meth)acrylate C1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

·Siloxane compound 1 3 parts by mass

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Combination of paint composition D]

[Paint composition D1]

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

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

· 1 part by mass of siloxane compound 1

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Paint composition D2]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition D2 with a solid content concentration of 40 mass % was obtained.

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

· 1 part by mass of siloxane compound 1

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Paint composition D3]

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

- 90 mass parts of urethane (meth)acrylate B1 solution (solid content concentration 50 mass %)

· Tricyclodecyl compound 1 5 parts by mass

· 1 part by mass of siloxane compound 1

- 1.5 mass parts of radical photopolymerization initiator 1 .

[Paint composition D4]

The following materials were mixed, diluted using methyl ethyl ketone, and the coating composition D4 with a solid content concentration of 30 mass % was obtained.

- 90 mass parts of urethane (meth)acrylate B1 solution (solid content concentration 50 mass %)

· 5 parts by mass of tricyclodecyl compound 2

· 1 part by mass of siloxane compound 1

- 1.5 mass parts of radical photopolymerization initiator 1 .

[support mention]

[Support material A1]

As the supporting substrate A1, “COSMOSHINE” (registered trademark) A4300 (thickness 125 µm, manufactured by TOYOBO CO., LTD.) was used.

[Support Equipment A2]

As the supporting substrate A2, “Panlite” (registered trademark) PC-2151 (thickness 125 µm, manufactured by TEIJIN LIMITED) was used.

[Support Base B1]

"Lumirror" (trademark) U48 (125 micrometers in thickness, Toray Industries, Inc. make) was used as the support base material 1.

[Evaluation of supporting equipment]

Table 1 shows the result obtained by performing the performance evaluation shown next about a support base material. Except where otherwise specified, the measurement was performed three times by changing the location for each sample, and the average value was used.

[Swelling index of the supporting substrate]

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

Swelling index: h=|h ₂ -h ₁ |

In addition, the haze measurement was carried out in accordance with JIS K 7136 (2000), using a haze meter manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD., placed in the apparatus so as to transmit light from the side to which the methyl ethyl ketone of the supporting substrate was applied.

The evaluation result of the support base material obtained in Table 1 was put together.

[Method for producing laminated film]

[Production of laminated film 1]

The coating composition A (A1 to A14), the coating composition C (C1 to C5), and the coating composition D (D1 to D4) on the supporting substrate were dried using a continuous coating device by a slot die coater, and the thickness of the surface layer after drying was specified. It applied by adjusting the discharge flow rate from the slot so that it might become a film thickness. The conditions of the drying wind which hit the liquid film between application|coating, drying, and hardening are as follows.

[Drying process]

Blowing temperature and humidity: Temperature: 80℃, Relative humidity: 1% or less

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

Wind direction: coated surface side: parallel to the described surface, semi-coated surface side: perpendicular to the described surface

Duration of residence: 2 minutes

[curing process]

Irradiation power: 400W/cm2

Integrated light intensity: 120mJ/cm2

Oxygen concentration: 0.1% by volume.

[Production of laminated film 2]

The coating composition B (B1 to B2) was applied on the supporting substrate by adjusting the discharge flow rate from the slot so that the thickness of the surface layer after drying became the specified film thickness using a continuous coating device with a slot die coater. The conditions of the drying wind suitable for the liquid film between application|coating, drying, and hardening are as follows.

[Drying process]

Blowing temperature and humidity: Temperature: 80℃, Relative humidity: 1% or less

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

Wind direction: coated surface side: parallel to the described surface, semi-coated surface side: perpendicular to the described surface

Residence time: 1 minute

[curing process]

Blowing temperature and humidity: Temperature: 160℃, Relative humidity: 1% or less

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

Wind direction: coated surface side: perpendicular to the described surface, semi-coated surface side: perpendicular to the indicated surface

Duration of residence: 2 minutes

In addition, for the said wind speed and temperature and humidity, the measured value by the hot wire type anemometer (KANOMAX JAPAN INC. ANEMOMASTER wind speed/volume meter MODEL 6034) was used.

By the above method, the laminated|multilayer film of Examples 1-16 and Comparative Examples 1-11 were created. The preparation method of the said laminated|multilayer film corresponding to each Example and a comparative example, and the film thickness of each each layer were described in Table 2 and Table 3 mentioned later.

[Evaluation of laminated film]

About the produced laminated|multilayer film, the performance evaluation shown next was performed, and the result obtained is shown in Table 2 and Table 3. In each Example and Comparative Example, the measurement was carried out three times by changing the location for one sample, and the average value was used, unless otherwise specified.

[Logarithmic damping factor of the surface layer, relative storage modulus (rigid pendulum test method)]

Based on the free damping vibration method of the rigid pendulum (this is referred to as the rigid pendulum test method), the logarithmic damping rate and the relative storage elastic modulus of the surface layer were measured using a rigid pendulum type physical property tester RPT-3000 manufactured by A&D Company, Limited. The temperature of the tester was previously adjusted to 15°C, and after setting the sample and the pendulum, the measurement was performed while the temperature was raised to 150°C at a rate of 10°C/min. The measurement was performed 5 times at a time, and the average value was evaluated. In addition, the following pendulums were used.

Edge used: Round bar cylinder edge (RBP-040 manufactured by A&D Company, Limited) Knife-shaped edge (RBE-160 manufactured by A&D Company, Limited)

Pendulum mass/inertia efficiency: 15 g/640 g cm (FRB-100 manufactured by A&D Company, Limited)

In addition, and the relative storage elastic modulus at a measuring temperature 25 ℃ as G _{r '25,} the external storage elastic modulus at a measuring temperature ₁₀₀ ℃ G _r' 100. The magnitude of each value was compared, and the case where G _r ' ₂₅ <G _r ' ₁₀₀ was established was designated as Y, and the case where it did not hold was designated as N.

[Adhesive index of the surface layer (stretching - boiling adhesion test method)]

About evaluation of the adhesion index of a surface layer, as shown below, it is performed by three steps of an extending|stretching process, a boiling process, and an adhesion test. In addition, let this series of flow be a draw-boil adhesion test method.

[Stretching treatment]

The laminated film was cut out to a width of 20 mm and a length of 200 mm, gripped with a chuck so as to be stretched in the long side direction, and stretched at a tensile rate of 100 mm/min with an Instron type tensile testing machine (Instron Corporation ultra-precision material testing machine MODEL 5848). The measurement atmosphere at this time is 23 degreeC. The stretching treatment was performed until the amount of deformation was 20%, and a test piece was collected.

In addition, the deformation amount x (%) was computed with the following formula|equation with the distance between initial tension chucks being 50 mm and the distance between tension chucks being a (mm).

Deformation amount: x=((a-50)/50)×100.

[merciful treatment]

Next, the test piece was immersed in boiling hot water (100 degreeC) which consists of pure water with respect to the test piece which performed the extending|stretching process for 6 hours. After that, the test piece was taken out and dried.

[Adhesion test]

Moreover, 100 crosscuts of 1 mm<2> were put into the surface layer of the test piece after a boiling process. The operation was performed according to the procedure of clause 7 of JIS K5600-5-6 (1999) except for the following parts.

Test conditions and number of tests: Test conditions were made into 23 degreeC and 65% of relative humidity. In addition, the number of tests was set to 1.

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

Number of cuts: The number of cuts was set to 11.

Interval of cutting: The interval of cutting was set to 1 mm.

Cutting and removal of laminated film by manual procedure: Brushing with a brush was not performed. In addition, 7. 2. 6 of JIS K5600-5-6 (1999) is specified in the second paragraph (“The center of the tape is placed on the grid in a direction parallel to one set of corner cuts as shown in FIG. , flatten the tape with your finger at the location caught in the grid and at least 20 mm in length”), and other regulations do not apply mutatis mutandis. In addition, as a tape, cellophane tape ("CELLOTAPE" (trademark) CT405AP manufactured by Nichiban Co., Ltd.) was used.

In addition, the tape was applied by applying a hand roller (HP515 manufactured by Audio-Technica Corporation) to make three reciprocations with a load of 19.6 N/m and a roller moving speed of 5 cm/sec and press. Next, the tape was peeled off at a speed of 10 cm/sec per second in a direction 90° with respect to the surface direction of the surface layer, and five-level evaluation was performed based on the number of remaining grids formed on the surface layer.

Adhesion index 5: The remaining number of surface layers was 100.

Adhesion index 4: The number of remaining surface layers is not less than 90 and less than 100.

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

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

Adhesion index 1: The number of remaining surface layers is less than 50.

[Dye transfer resistance]

The gin (containing dye) moistened with water of 6 cm × 6 cm was adhered to the surface layer of the laminated film cut out to a size of 9 cm × 6 cm, and sandwiched with a glass plate of 6 cm × 6 cm. Wrapped with a polyethylene film so that moisture does not evaporate, a weight of 3 kg was placed on a glass plate, and it was placed in an oven at 70° C. and left to stand. After 24 hours, take it out and place the laminated film on a white paper equivalent to the white part of the gray scale for contamination to be described later, and the degree of contamination of the surface of the surface layer is in the gray scale for contamination (JIS L0805 (2005)), a grade of 1 to 5 (Level 1 means that the pollution is gray scale No. 1 or more for pollution (contaminants remain thick), Level 2 means that the pollution is gray scale No. 2 for pollution (a lot of pollution remains), and level 3 is Contaminant is about gray scale No. 3 for pollution (a little contaminant remains), level 4 means that the contaminant is gray scale No. 4 for pollution (almost no contaminants remain), level 5 means that the contaminant is gray scale 5 for pollution It was judged to be a good degree (no contaminants remain). In addition, according to the notation of JIS L0805 (2005), in the case of between each class, for example, between class 1 and class 2, it is expressed as "1-2".

[Crack elongation of the surface layer]

The laminated film was cut out to a length of 10 mm width x 200 mm, gripped with a chuck in the longitudinal direction, pulled by an Instron type tensile tester (Ultra-precision material testing machine MODEL 5848 manufactured by Instron Corporation), and stretched at a speed of 100 mm/min. The measurement temperature was performed at 23 degreeC. At the time of extending|stretching, the sample in extending|stretching was observed, and when a crack (crack) generate|occur|produced visually, it stopped (deformation amount at the time of stopping was adjusted so that it might become an integer of 5). For the samples to be measured from the following, samples in which the amount of deformation is lowered by 5% from the amount of deformation at rest were sequentially taken, and finally, the deformation amount at which cracks did not enter with the naked eye was carried out.

In addition, the deformation amount x (%) was computed with the following formula|equation with the distance between initial tension chucks being 50 mm and the distance between tension chucks being a (mm).

Deformation amount: x=((a-50)/50)×100.

The thin film section of the crack portion of the sample is cut out, and the thickness of the surface layer to be observed is on the observation screen of a transmission electron microscope, the surface layer is observed at a magnification of 30 mm or more, and cracks of 50% or more of the average thickness of the surface layer are found The case where it occurred was defined as having cracks (with fracture of the surface layer), and the value of the deformation amount of the sample having the lowest deformation amount among the samples with cracks was taken as the crack elongation. And the same measurement was performed 3 times in total, and the average value of those crack elongation was made into the crack elongation of the surface layer.

[Peeling of the surface layer]

As a pretreatment of the dynamic viscoelasticity method, only the surface layer was peeled off from the laminated film by the following method to obtain a test sample.

First, the laminated|multilayer film was immersed in ethanol, and it was left to stand for 10 minutes on 25 degreeC conditions. Then, the surface layer of the laminated|multilayer film was peeled from the support base material, and the sample was collect|collected.

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

Based on the tensile vibration-non-resonance method of JIS K7244 (1998) (this is referred to as the dynamic viscoelasticity method), the storage elastic modulus and the loss elastic modulus of the surface layer were determined using a dynamic viscoelasticity measuring device "DMS 6100" manufactured by Seiko Instruments Inc.

Measuring Mode: Tensile

Distance between chucks: 20mm

Width of test piece: 10 mm

Frequency: 1Hz

Strain amplitude: 10 μm

Force amplitude initial value: 400mN

Measuring temperature: from -150℃ to 250℃

Temperature increase rate: 5°C/min

Further, the storage elastic modulus at a measuring temperature was 25 ℃ 'the storage modulus at _25, measured temperature 100 ℃ G' G to _100. The magnitude of each value was compared, and the case where G' ₂₅ <G' ₁₀₀ was established was set to Y, and the case where it did not hold was set to N.

_{In addition, tan δ 25} representing a loss tangent at a measurement temperature of 25°C was obtained by the following equation, with the loss elastic modulus at a measurement temperature of 25°C being G″ _25.

tanδ ₂₅ =G" ₂₅ /G' ₂₅ .

[Self-healing properties of the surface layer]

After standing at a temperature of 20℃ for 12 hours, in the same environment, apply the following load to the surface of the surface layer to a brass brush (manufactured by TRUSCO NAKAYAMA CORPORATION) and scrape horizontally 5 times. According to it, it judged visually, and 4 or more points|pieces were made into the pass.

10 points: No scratch left under a load of 9.8N (weight of 1kg)

7 points: Scratch remains at a load of 9.8N (weight of 1kg), but no scratch remains at 6.9N (weight of 700g)

4 points: Scratch remains at a load of 6.9N (weight of 700g), but no scratch remains at 4.9N (weight of 500g)

1 point|piece: A scratch remains under the load of 4.9N (500g).

[Formability of surface layer]

The moldability of the surface layer was judged according to the following criteria about the crack elongation of the said surface layer.

10 points|pieces: The crack elongation of the surface layer is 40 % or more.

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

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

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

[Adhesive durability of the surface layer]

The adhesion durability of the surface layer was judged according to the following criteria with respect to the adhesion index of the said surface layer.

10 points: The adhesion index of the surface layer was 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.

[Anti-fouling property of the surface layer]

The antifouling property of the surface layer was judged according to the following criteria about the dye migration resistance of the said surface layer.

10 points|pieces: The dye transfer resistance of the surface layer is 5th grade.

7 points|pieces: The dye transfer resistance of the surface layer is grade 4 or more and less than grade 5.

4 points|pieces: The dye transfer resistance of the surface layer is grade 3 or more and less than grade 4.

1 point|piece: The dye transfer resistance of the surface layer is less than 3rd grade.

The evaluation result of the laminated|multilayer film finally obtained in Table 3 was put together.

The laminated film of the present invention takes advantage of the advantages of moldability, self-healing properties, antifouling properties and adhesion durability, plastic molded articles such as glasses/sunglasses, makeup boxes, food containers, and the like, smartphone housings, touch panels, keyboards, TV remotes and air conditioners. It can be used suitably for home appliances such as controls, buildings, dashboards, car navigation/touch panels, vehicle interiors such as rearview mirrors, and the surface of various printed materials.

1: Temperature (℃) 2: Logarithmic decay rate
3: Temperature dependence graph of logarithmic decay rate 4: Temperature (℃)
5: storage modulus (MPa)
6: Temperature dependence graph of storage modulus 7: Temperature (℃)
8: loss modulus (MPa)
9: Temperature dependence graph of loss modulus 10: Temperature (℃)
11: Loss tangent
12: Temperature dependence graph of loss tangent

Claims (8)

A laminated film having a surface layer on at least one of a supporting substrate, comprising:
The following conditions 1 and 2 are satisfy|filled, The laminated|multilayer film characterized by the above-mentioned.
Condition 1: The logarithmic damping factor at 25°C of the surface layer in the rigid pendulum test method is 0.1 or more.
Condition 2: The resin contained in the surface layer contains the following (1) to (4).
(1) polycaprolactone segment
(2) urethane bond
(3) at least one of a polysiloxane segment and a polydimethylsiloxane segment
(4) tricyclodecyl segment The method of claim 1,
Said laminated|multilayer film WHEREIN: The following condition 3 is satisfy|filled, The laminated|multilayer film characterized by the above-mentioned.
Condition 3: The adhesion index of the said surface layer in the stretch-melting adhesion test method is 3 or more. 3. The method according to claim 1 or 2,
Said laminated|multilayer film WHEREIN: The following condition 4 is satisfy|filled, The laminated|multilayer film characterized by the above-mentioned.
Condition 4: The relative storage modulus at 100°C of the surface layer in the rigid pendulum test method is higher than the relative storage modulus at 25°C. 3. The method according to claim 1 or 2,
Said laminated|multilayer film WHEREIN: The following conditions 5 - condition 7 are satisfy|filled, The laminated|multilayer film characterized by the above-mentioned.
Condition 5: The storage elastic modulus at 25 degreeC of the said surface layer in a dynamic viscoelasticity method is 10 MPa or more and 1,000 MPa or less.
Condition 6: The storage modulus at 100°C of the surface layer in the dynamic viscoelastic method is higher than the storage modulus at 25°C.
Condition 7: The loss tangent at 25°C of the surface layer in the dynamic viscoelasticity method is 0.15 or more. 3. The method according to claim 1 or 2,
In the laminated film, the following condition 8 is satisfied.
Condition 8: The crack elongation at 23°C of the surface layer in the tensile force test method is 20% or more. 3. The method according to claim 1 or 2,
Said laminated|multilayer film WHEREIN: The supporting base material which forms a surface layer satisfy|fills the following condition 9, The laminated|multilayer film characterized by the above-mentioned.
Condition 9: The swelling index of the supporting substrate is 0.01 or more. 3. The method according to claim 1 or 2,
Said laminated|multilayer film WHEREIN: The following condition 10 is satisfy|filled, The laminated|multilayer film characterized by the above-mentioned.
Condition 10: The resin contained in the surface layer includes the following (5).
(5) fluorine compound segment 3. The method according to claim 1 or 2,
Said laminated|multilayer film WHEREIN: The following condition 11 is satisfy|filled, The laminated|multilayer film characterized by the above-mentioned.
Condition 11: The resin contained in the surface layer includes the following (6).
(6) polycarbonate segment

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