JP2020116951A - Resin film and laminated body - Google Patents

Abstract

To provide a resin film that satisfies both elasticity and tack resistance.SOLUTION: There is provided a resin film having a restoration rate of 80% or more, and having an uneven structure on at least one surface thereof.SELECTED DRAWING: Figure 3

Description

The present invention relates to a resin film and a laminate that have both elasticity and tack resistance.

In recent years, display-equipped devices such as smartphones, tablets, personal computers and liquid crystal televisions, and various devices have become widespread, and a large number of films and sheet materials made of synthetic resin or the like are used as constituent members thereof. .. Under such circumstances, research and development of flexible devices/wearable devices have been actively conducted in recent years, and development of deformable devices and members has been promoted.

Due to this situation, it is considered that new technical fields that are difficult to apply with the materials used for conventional displays and devices will be newly created, and the need for new materials with high flexibility and elasticity will increase. Expected.

On the other hand, as an example of an existing material having flexibility and stretchability, Patent Document 1 discloses “a layer made of a first polyethylene, a thermoplastic polyurethane layer laminated on the layer made of the first polyethylene, and the thermoplastic resin layer”. A layered body having at least a layer made of a second polyethylene laminated on a plastic polyurethane layer, wherein the heat of crystallization of the first polyethylene is larger than the heat of crystallization of the second polyethylene. And a laminate having a thermoplastic polyurethane layer."

Non-Patent Document 1 mentions a so-called “silicone material”, and a sheet material using silicone rubber is proposed as an example of the silicone material.

In addition, in Patent Document 2, "styrene-butadiene-styrene copolymer (SBS-A) containing a styrene component in an amount of 65 to 95 mass% and styrene-butadiene-styrene copolymer containing a styrene component in an amount of 5 to 40 mass%". The SBS resin composition obtained by mixing the combined (SBS-B) at a composition ratio of (SBS-A)/(SBS-B)=75/25 to 95/5, and 100 parts by mass of the SBS resin composition. An elastic film containing a filler (C) blended in a proportion of 20 to 45 parts by mass and having a specific gravity of 1.10 to 1.32."

Further, in Patent Document 3, "a mixture of a urethane resin, an organic solvent, water and a fluorosurfactant is a film of any one of a polyethylene terephthalate film, a polypropylene film or a methylpentene polymer film, and an adhesive is provided on one side. A urethane foam sheet having a foam obtained by coating and heating on a base material having the base material, wherein the organic solvent is a mixed solution of toluene and methyl ethyl ketone, and the foam has a continuous ventilation structure. A urethane foam sheet characterized by being composed of fine cells."

Further, if it is simply a material having high flexibility, the adhesive material described in Non-Patent Document 2 can be mentioned, although it cannot be said to be a material having elasticity.

In addition, as a flexible material having a specific shape on the surface, Patent Document 4 discloses that “the surface is structured and includes a resin cured layer made of a curable resin composition containing an organic compound and metal oxide nanoparticles, and is structured. The surface was pressed from above with a plane indenter at a pressing speed of 0.2031 mN/sec until the maximum compression force became 1 gf or 2 gf, and when the maximum compression force was reached, the sample was stopped for 5 seconds for compression. After that, when the compressive force is released, the optical sheet has an elastic recovery rate of 80% or more, which is represented by the following mathematical formula 1."

JP, 2013-91223, A JP, 2008-88293, A JP, 2014-231170, A Japanese Patent Publication No. 2015-514229

Silicone Handbook Nikkan Kogyo Shimbun Inc. 1990 Adhesives to learn from the beginning-Why stick? Why is it peeling? − Maruzen Publishing Co., Ltd.

However, as a result of confirming the material proposed in Patent Document 1, the inventors have confirmed that the material has a certain stretchability, but the heat resistance at high temperature is insufficient, so that the material is applied as a member of a display or a device. Therefore, it was unsuitable for post-processing that required heating.

In addition, the silicone rubber material proposed in Non-Patent Document 1 obtained a certain degree of stretchability and tack resistance, but was poor in adhesiveness to different materials and was not suitable for post-processing. Also, the elasticity was not sufficient.

Next, regarding the material proposed in Patent Document 2, although it was possible to confirm a certain degree of flexibility, it was found that stretchability and transparency were insufficient.

Further, regarding the material proposed in Patent Document 3, although a certain degree of flexibility and stretchability could be confirmed, the transparency was insufficient. Further, it was found that the presence of the foamed portion was also unsuitable for the post-processing step involving application.

In addition, the material proposed in Non-Patent Document 2 was confirmed to have a certain flexibility, but was not a material exhibiting elasticity. In addition, since it is an adhesive material, it is not suitable for post-processing, and it does not show tack resistance.

Further, regarding the material proposed in Patent Document 4, a certain degree of flexibility could be confirmed. However, the flexible resin film is used integrally with the supporting substrate, and the flexible resin film cannot be used alone, nor is it flexible.

Therefore, an object of the present invention is to provide a resin film having elasticity and excellent tack resistance, reworkability, and post-processability.

In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, completed the following invention. That is, the present invention is as follows.
<1>
A resin film having a restoration rate of 80% or more and having an uneven structure on at least one surface.
<2>
A laminate having a resin film on one surface of a release film,
The release film has an uneven structure on at least one surface,
The resin film has a restoration rate of 80% or more and has an uneven structure on at least one surface,
The protrusions of the relief structure of the release film enter the recesses of the relief structure of the resin film, and the projections of the relief structure of the resin film enter the recesses of the relief structure of the release film. The surface having the uneven structure of the mold film and the surface having the uneven structure of the resin film are in contact with each other,
A peeling force between the release film and the resin film is 1,000 mN/50 mm or less, a laminate.

According to the present invention, it is possible to obtain a resin film and a laminate which are flexible and have good post-processability and tack resistance.

It is sectional drawing which shows an example of the laminated body, resin film, and release film in this invention. It is sectional drawing which shows an example of the laminated body, resin film, and release film in this invention. It is sectional drawing which shows an example of the laminated body, resin film, and release film in this invention. It is sectional drawing which shows an example of the resin film in this invention. It is an overhead view showing an example of the resin film in the present invention, and is an example in the case where the surface uneven structure is a stripe shape. It is an example of a method for forming a concavo-convex structure on a release film in the present invention. It is a perspective view which shows an example of the metal mold|die for forming the uneven structure in this invention. It is sectional drawing which shows an example of the metal mold|die for forming the uneven structure in this invention. It is sectional drawing which shows an example of the formation method of the resin film in this invention. It is sectional drawing which shows an example of the formation method of the resin film in this invention. It is sectional drawing which shows an example of the formation method of the resin film in this invention.

Before describing the embodiments of the present invention, the problems of the prior art, that is, compatibility between elasticity and tack prevention and reworkability will be considered from the viewpoint of the present inventor.

[Comparison of the Present Invention and Prior Art]
In the prior art, there are materials that exhibit elasticity, but since they have elasticity, they lack tack resistance and reworkability. Therefore, even if the material is suitable from the viewpoint of elasticity, the film material is often used after being subjected to various post-processing in applications such as displays, devices and sensors. It could not be processed and was difficult to apply in practice. Also, in applications such as wearable sensors and sanitary materials where such stretchable materials come into direct contact with human skin, the stretchability creates tackiness, causing discomfort when touching human skin, and In some cases, it may not be possible to peel well when correcting the attachment position, and the reworkability may be insufficient.

Therefore, the present inventors have examined a method of imparting the above-described tack prevention property and reworkability to the material exhibiting such stretchability while making the most of its characteristics. As a result, they have found that it is effective to impart a concavo-convex structure to the surface of a stretchable material. When the uneven structure is provided on the surface, the contact area can be reduced when the resin film is attached to human skin or the like. Therefore, since it has the effect of preventing tacking, discomfort can be suppressed. Further, since it is easy to peel off after being attached once, reworkability can be improved. When processing for use as a display device, sensor, etc., when attaching to human skin, it is possible to easily correct the positioning, so not only for proper use but also for reducing material loss However, it is preferable.

Specifically, it is preferable that at least one surface of the resin film has an uneven structure.

Further, the inventors of the present invention have studied the above concavo-convex structure, and found that the concavo-convex structure having a specific shape can provide air release properties at the time of attachment. When the resin film having the concavo-convex structure is attached, the convex part of the concavo-convex structure becomes the part that actually contacts, and the concave part floats without contact. Therefore, by forming the concavo-convex structure in the shape of a stripe, the concave portion becomes a continuous and floating portion, which serves as a passage for an air reservoir that is likely to occur during attachment. As a result, it becomes possible to improve the air release property when the resin film is attached.

Further, when the present inventors focused their attention on the height of the concavo-convex structure, it was found that the maximum height is preferably within a certain range. As described above, when the resin film has an uneven structure, tackiness and reworkability can be imparted. However, it was found that when the height of the concavo-convex structure is too low, the above effect becomes insufficient, and a certain height or more is required. On the other hand, if the height of the concavo-convex structure is too high, the concavo-convex structure may be deformed when the resin film is stuck or otherwise. In such a case, even if an attempt is made to reduce the contact area at the time of sticking due to the uneven structure, the uneven structure may be deformed and unintended increase in the contact area may result in insufficient tack prevention and reworkability. It was Moreover, since the uneven structure is deformed, the rigidity of the resin film may be insufficient. Therefore, it has been found that it is effective to set the height of the uneven structure to a certain level or less.

Specifically, it is preferable that the uneven structure of the resin film has a stripe shape and that the maximum height of the uneven structure is 5 μm or more and 100 μm or less.

In addition, the present inventors have conducted a study on a method of imparting an uneven structure to the surface of the resin film. Examples of the method of imparting the surface shape to the resin film include a method of applying a heated mold to the resin film. However, in the case of a resin film having a high restoration rate as in the present invention, its shape is restored even when a mold is applied, and it is not possible to give an uneven structure well. Further, the material of such a resin film does not necessarily have thermoplasticity, and it is considered that it is difficult to give a shape by utilizing heating.

As a result of studying other means, a method of applying a roll of a specific shape to the resin before curing to form a surface structure, or giving a specific shape to a release film serving as a supporting base material in advance and releasing it It has been found that the method of applying a resin film to the film is effective. In particular, it has been found that the latter method can protect the uneven structure formed on the surface of the resin film until the resin film is peeled from the release film for use.

Specifically, a step of applying a coating composition containing a component constituting a resin film to the surface of the release film having an uneven structure on at least one surface, the surface having the uneven structure, and curing the component. The manufacturing method of the laminated body characterized by having the process of performing.

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

[Resin film]
In order to satisfy the above-mentioned problems, that is, stretchability, tack resistance, reworkability, and post-processability, the resin film of the present invention has a restoration rate of 80% or more and has an uneven structure on at least one surface. It is preferable that it is a resin film.

The method of measuring the restoration rate will be described later.

From the viewpoint of stretchability, the restoration rate of the resin film is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.

With respect to the restoration rate of the resin film, it is preferable that the restoration rate is 80% or more because even if the resin film is deformed under a load, the effect of returning to the original shape becomes large when the load is removed. The higher the restoration rate, the greater the above effect, but the upper limit of the restoration rate is 100%.

The resin film of the present invention preferably has a concavo-convex structure on at least one surface of the resin film from the viewpoint of tackiness and reworkability. When the surface of the resin film has a concavo-convex structure, due to the above-mentioned effects, tackiness and reworkability can be imparted to the elastic material without impairing the characteristics thereof. The concavo-convex structure formed on at least one surface of the resin film is not particularly limited from the viewpoint of tack resistance, reworkability, and post-processability, and may be a random shape or a regular shape. From the viewpoint of air bleeding property, it is more preferable that the concave portions of the concavo-convex structure portion of the resin film are not independent, but some or all are connected in the in-plane direction. As an example of the concavo-convex structure in which some or all of the concave portions of the concavo-convex structure are connected, a stripe shape, a cross shape, a lattice shape and the like can be exemplified. As will be described later, it is particularly preferable that the uneven structure of the resin film has a stripe shape.

Further, from the viewpoint of flexibility, the resin film preferably satisfies the following condition 1.

Condition 1: The 5% strain stress of the resin film is 10 MPa or less.

The method for measuring the 5% strain stress will be described later.

From the viewpoint of flexibility, in the resin film of the present invention, the 5% strain stress of the resin film is preferably 10 MPa or less, more preferably 5 MPa or less.

Regarding the 5% strain stress of the resin film, when the 5% strain stress is 10 MPa or less, the resin film exhibits favorable stretchability. The lower limit of the 5% strain stress is not particularly limited, and the lower the value, the more the stretchability improves. However, if it is extremely low, the rigidity of the resin film may be insufficient, so the lower limit is considered to be about 0.01 MPa. On the other hand, when the 5% strain stress exceeds 10 MPa, the stretchability of the resin film may be insufficient.

In order to set the 5% strain stress of the resin film to 10 MPa or less, for example, it is possible to use the materials described below.

Furthermore, from the viewpoint of transparency, it is preferable that the resin film satisfy the following condition 2.

Condition 2: The resin film has a total light transmittance of 80% or more.

The method for measuring the total light transmittance will be described later.

From the viewpoint of transparency, in the resin film of the present invention, the total light transmittance of the resin film is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.

With respect to the total light transmittance of the resin film, when the total light transmittance is 80% or more, the resin film exhibits good transparency. The higher the total light transmittance, the higher the transparency, but the upper limit of the total light transmittance is 100%. On the other hand, if the total light transmittance is less than 80%, it may be unsuitable for applications requiring transparency.

In order to make the total light transmittance of the resin film 80% or more, for example, it is possible to use the materials described later.

Further, from the viewpoint of air bleeding property, it is preferable that the resin film satisfies the following condition 3.

Condition 3: The uneven structure of the resin film has a stripe shape.

When the concavo-convex structure of the resin film has a stripe shape, tackiness, air bleeding, and reworkability can be improved due to the effects described above.

Here, the concavo-convex structure of the resin film has a stripe shape, and it is sufficient if even a part of the concavo-convex structure has a stripe shape, but the larger the ratio of the stripe shape is, the more preferable. Is a stripe shape.

Furthermore, from the viewpoint of tackiness, it is preferable that the resin film satisfy the following condition 4.

Condition 4: The maximum height of the uneven structure of the resin film is 5 μm or more and 100 μm or less.

The method for measuring the maximum height will be described later.

From the viewpoint of tackiness prevention, in the resin film of the present invention, the maximum height of the uneven structure is preferably 5 μm or more and 100 μm or less, more preferably 5 μm or more and 100 μm or less, and particularly preferably 5 μm or more and 100 μm or less. is there.

Regarding the maximum height of the uneven structure of the resin film, when the maximum height is within a certain range, both elasticity and tackiness can be achieved. On the other hand, when the maximum height exceeds 100 μm, the rigidity of the resin film may be insufficient. Further, if the maximum height is less than 5 μm, tackiness may be insufficient.

The maximum height of the uneven structure of the resin film refers to the difference between the lowest position of the concave portion and the highest position of the convex portion of the resin film. The concavo-convex structure can be formed, for example, by the method described below, and a plurality of concavo-convex structures having different heights can be formed. In that case, the difference between the lowest position of each concave part and the highest position of the convex part is Refers to the average. A specific measuring method will be described in the section of Examples.

[Laminate]
Further, the laminate of the present invention is a laminate having a resin film on one surface of the release film, the release film has an uneven structure on at least one surface, the resin film is restored. The release rate is 80% or more and has a concavo-convex structure on at least one surface, and the convex part of the concavo-convex structure of the release film enters the concave part of the concavo-convex structure of the resin film, As the convex portion enters the concave portion of the concave-convex structure of the release film, the surface having the concave-convex structure of the release film is in contact with the surface having the concave-convex structure of the resin film, and the release film and the The peeling force between the resin films is preferably 1,000 mN/50 mm or less.

The concavo-convex structure and the recovery rate of the resin film in the laminate are as described in the above section [resin film]. That is, the resin film in the laminate also has a restoration rate of 80% or more and has a concavo-convex structure on at least one surface, and the resin film in the laminate also has the above-mentioned conditions 1, 2 and conditions. It is preferable that Condition 3 and Condition 4 are satisfied.

The release film in the laminate of the present invention has an uneven structure on at least one surface. Regarding the uneven structure of the release film, when the release film has a specific uneven structure, an uneven structure corresponding to the uneven structure of the release film can be formed on the surface of the resin film by, for example, the manufacturing method described later. ..

The peel strength between the release film and the resin film of the laminate of the present invention is 1,000 mN/50 mm or less, preferably 700 mN/50 mm or less, and particularly preferably 500 mN/50 mm or less.

Regarding the peeling force between the release film and the resin film, when the peeling force is in the range of 1,000 mN/50 mm or less, the resin film is easily peeled from the release film, which is preferable. On the other hand, when the peeling force exceeds 1,000 mN/50 mm, the resin film may not be peeled from the release film and may not be used as the resin film.

The peeling force between the resin film and the release film can be set to 1,000 mN/50 mm or less by using, for example, the materials described below.

Furthermore, in the laminate of the present invention, the convex portion of the uneven structure of the release film enters the concave portion of the uneven structure of the resin film, and the convex portion of the uneven structure of the resin film enters the concave portion of the uneven structure of the release film. In addition, it is important that the surface of the release film having the uneven structure and the surface of the resin film having the uneven structure are in contact with each other. By arranging the release film and the resin film in the laminate in this manner, the uneven structure of the resin film can be protected from an external load until the resin film is peeled from the release film. Further, the concavo-convex structure of the resin film can be exposed at an arbitrary timing, and the effect due to the concavo-convex structure described above can be exhibited when necessary.

Furthermore, it is preferable that the laminated body satisfies the following condition 1.

Condition 1: The 5% strain stress of the resin film is 10 MPa or less.

The 5% strain stress of the resin film is as described above.

Furthermore, it is preferable that the laminated body satisfies the following condition 2.

Condition 2: The resin film has a total light transmittance of 80% or more.

The method for measuring the total light transmittance will be described later.

The total light transmittance of the resin film is as described above.

Furthermore, it is preferable that the laminate satisfy the following conditions 3 and 5.

Condition 3: The uneven structure of the resin film has a stripe shape.

Condition 5: The uneven structure of the release film has a stripe shape.

The concavo-convex structure of the resin film is as described above.

Regarding the uneven structure of the release film, when the release film has a specific uneven structure, an uneven structure corresponding to the uneven structure of the release film can be formed on the surface of the resin film by, for example, a manufacturing method described later. Therefore, by making the relief structure of the release film have a stripe shape, the relief structure formed on the resin film can have a stripe shape.

Furthermore, it is preferable that the laminate satisfy the following conditions 4 and 6.

Condition 4: The maximum height of the uneven structure of the resin film is 5 μm or more and 100 μm or less.

Condition 6: The maximum height of the uneven structure of the release film is 5 μm or more and 100 μm or less.

The maximum height of the uneven structure of the resin film is as described above. Regarding the maximum height of the uneven structure of the release film, as described above, the uneven structure corresponding to the uneven structure of the release film can be formed on the resin film.

[Method for producing resin film]
The method for producing the resin film of the present invention is not particularly limited, but the method for producing the resin film of the present invention is preferably as follows.

A method for producing a resin film having a restoration rate of 80% or more and having a concavo-convex structure on at least one surface thereof, comprising the step of peeling a release film from the laminate of the present invention. Method.

As a method for producing the resin film of the present invention, by adopting a method having a step of peeling the release film from the laminate of the present invention, until the resin film is peeled from the release film, the uneven structure of the resin film Can be protected from external loads. Further, the concavo-convex structure of the resin film can be exposed at an arbitrary timing, and the effect due to the concavo-convex structure described above can be exhibited when necessary.

[Method for producing laminated body]
The method for producing a laminate of the present invention is not particularly limited, but the method for producing a laminate of the present invention is a release film having an uneven structure on at least one surface, a resin film on the surface having the uneven structure. It is preferable to have a step of applying a coating composition containing the components constituting the above and a step of curing the above components.

According to the method for producing a laminate of the present invention, as described above, the desired uneven structure can be formed even on a resin that does not exhibit thermoplasticity such as the resin film of the present invention.

The details of the step of applying the coating composition containing the component forming the resin film to the surface of the release film having the concave-convex structure and the step of curing the component subsequent to this step will be described later.

[Release film]
In the release film used in the present invention, a base film composed of a resin having a releasability may be used as the release film, or a release layer may be formed on the surface of the base film. You may use the base film which gave the mold release property as a mold release film. As a material for forming the release layer, a commercially available resin having general releasability or a general release coating can be used.

The resin constituting the base film used in the release film of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, and may be a copolymer or a blend of two or more kinds. Good. It is preferable that the resin constituting the supporting base material has good moldability, and from this point, a thermoplastic resin is more preferable.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polystyrene and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyimide resins, polyester resins, polycarbonate resins, Fluorine such as polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene-6-fluoropropylene copolymer, vinylidene fluoride resin, etc. Resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins and the like can be used. Examples of thermosetting resins that can be used include phenol resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, polyurethane resins, polyimide resins, and silicone resins. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is more preferably a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, or a methacrylic resin, from the viewpoint of moldability for forming an uneven structure on the surface. In particular, a polyolefin resin is particularly preferable as the resin itself having a releasing property.

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

The polyolefin resin in the present invention refers to a polymer having a repeating unit derived from an olefin-based monomer. The polyolefin resin may be a polymer composed only of repeating units derived from an olefinic monomer, or together with a repeating unit derived from an olefinic monomer, a repeating unit derived from a monomer other than an olefinic monomer. It may be a copolymer having

The olefin-based monomer may have only one double bond in the molecule, or may have a plurality of double bonds in the molecule such as diene, triene and tetraene. Specific examples of the olefin-based monomer include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, butadiene, pentadiene and isoprene. These olefinic monomers can be used alone or in combination of two or more.

Further, the olefin-based monomer may be a cyclic olefin monomer. Specific examples of the cyclic olefin monomer include cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclopentadiene, and monocyclic olefins such as 1,3-cyclohexadiene, bicyclo[2,2,1]hept-2-ene, and 5-methyl. -Bicyclo[2,2,1]hept-2-ene, 5,5-dimethyl-bicyclo[2,2,1]hept-2-ene, 5-ethyl-bicyclo[2,2,1]hept-2 -Ene, 5-butyl-bicyclo[2,2,1]hept-2-ene, 5-ethylidene-bicyclo[2,2,1]hept-2-ene, 5-hexyl-bicyclo[2,2,1] ] Hept-2-ene, 5-octyl-bicyclo[2,2,1]hept-2-ene, 5-octadecyl-bicyclo[2,2,1]hept-2-ene, 5-methylidene-bicyclo[2 ,2,1]hept-2-ene, 5-vinyl-bicyclo[2,2,1]hept-2-ene, 5-propenyl-bicyclo[2,2,1]hept-2-ene Olefin, tricyclo[4,3,0,12.5]deca-3,7-diene, tricyclo[4,3,0,12.5]deca-3-ene, tricyclo[4,3,0,12. 5] Undeca-3,7-diene, tricyclo[4,3,0,12.5]undeca-3,8-diene, tricyclo[4,3,0,12.5]undec-3-ene, 5- Cyclopentyl-bicyclo[2,2,1]hept-2-ene, 5-cyclohexyl-bicyclo[2,2,1]hept-2-ene, 5-cyclohexenylbicyclo[2,2,1]hept-2- Tricyclic olefins such as ene, 5-phenyl-bicyclo[2,2,1]hept-2-ene, tetracyclo[4,4,0,12.5,17.10]dodec-3-ene, 8-methyl Tetracyclo[4,4,0,12.5,17.10]dodec-3-ene, 8-ethyltetracyclo[4,4,0,12.5,17.10]dodec-3-ene,8 -Methylidene tetracyclo[4,4,0,12.5,17.10]dodeca-3-ene, 8-ethylidene tetracyclo[4,4,0,12.5,17.10]dodeca-3- Ene, 8-vinyltetracyclo[4,4,0,12.5,17.10]dodeca-3-ene, 8-propenyl-tetracyclo[4,4,0,12.5,17.10]dodeca- Tetracyclic olefins such as 3-ene, and 8-cyclopentyl-tetracyclo[4,4,0,12.5 , 17.10] Dodeca-3-ene, 8-cyclohexyl-tetracyclo[4,4,0,12.5,17.10]dodec-3-ene, 8-cyclohexenyl-tetracyclo[4,4,0, 12.5,17.10]dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4,4,0,12.5,17.10]dodec-3-ene, tetracyclo[7,4,13. 6,01.9,02.7]tetradeca-4,9,11,13-tetraene, tetracyclo[8,4,14.7,01.10,03.8]pentadeca-5,10,12,14- Tetraene, pentacyclo[6,6,13.6,02.7,09.14]-4-hexadecene, pentacyclo[6,5,1,13.6,02.7,09.13]-4-pentadecene, Pentacyclo[7,4,0,02.7,13.6,110.13]-4-pentadecene, heptacyclo[8,7,0,12.9,14.7,111.17,03.8,012 .16]-5-eicosene, heptacyclo[8,7,0,12.9,03.8,14.7,012.17,113.16]-14-eicosene, cyclopentadiene, and other polymers. A cyclic olefin etc. are mentioned. These cyclic olefin monomers may be used alone or in combination of two or more.

Examples of the monomer other than the olefin-based monomer include vinyl acetate, (meth)acrylic acid ester, and styrene.

Specific examples of the polyolefin resin include ultra low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP ), ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, etc. Is mentioned. Further, the base film, various additives, for example, antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A doping agent or the like for adjusting the refractive index may be added. The supporting substrate may have either a single-layer structure or a laminated structure.

The surface of the base film may be subjected to various surface treatments before the resin film is formed. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferable, and glow discharge treatment and ultraviolet treatment are more preferable.

In addition to the resin film of the present invention, a functional layer such as an easy-adhesion layer, an antistatic layer, an undercoat layer, an ultraviolet absorbing layer, and a release layer can be previously provided on the surface of the base film. In the laminate of the present invention, it is particularly preferable to provide a release layer in order to reduce the peeling force between the base material film and the resin film.

As an example of the film made of the polyester resin provided with the release layer, "Therapyle" (registered trademark) manufactured by Toray Film Co., Ltd., "Unipeal" (registered trademark) manufactured by Unitika Ltd., Panac stock "Panapeel" (registered trademark) manufactured by the company, "Toyobo ester" (registered trademark) manufactured by Toyobo Co., Ltd., "Purex" (registered trademark) manufactured by Teijin Co., Ltd., and the like can be used. can do.

[Applying surface shape to release film (providing concavo-convex structure)]
The method for producing the release film having an uneven structure on the surface is not particularly limited, but 1. 1. A method of providing a release layer on a base film having an uneven structure on its surface, 2. A method of providing a release layer having a concavo-convex structure on a flat base film. A method of imparting an uneven structure to the base film having releasability is preferable. Furthermore, from the viewpoint of air release property, the above method 3. Is more preferable. 1 to 3 are sectional views showing a laminate using the release film produced by the above methods 1 to 3 and a method for producing a resin film from the laminate. Hereinafter, method 3. The method for imparting an uneven structure to the release film having the releasing property will be described in detail. FIG. 6 shows an embodiment relating to a method for forming an uneven structure using a mold on the surface of the release film of the present invention. It is the flowchart which showed an example. FIG. 7 is a perspective view showing an example of a mold to be applied.
First, a release film is prepared as shown in FIG. The glass transition temperature of the release film is Tgr.

The release film prepared here may be a base film having releasability by itself, or a release film provided on the surface of the base film. In addition, a surface uneven structure may be formed on a base material film having no releasability by a method described below, and then a release layer may be provided later. Here, these are collectively described as a release film.

The release film for forming the uneven structure on the surface may be a roll-to-roll continuous film or a sheet.

The glass transition temperature is a method according to the method described in JIS K 7244 (2007), the sample dynamic amplitude speed (driving frequency) is 1 Hz, the tension mode, the chuck distance is 5 mm, and the temperature rising rate is 2° C./minute. It is the temperature at which tan δ reaches a maximum when the temperature dependence (temperature dispersion) at is measured.

In the present invention, it is preferable to heat the mold 26 having the protrusion structure 27 on its surface. The heating is preferably performed so that the mold has a temperature range of the glass transition temperature of the release film or higher. The heating may be performed while the mold and the release film are in contact with each other. By bringing them into contact with each other, the flatness of the release film can be maintained in a good state.

Although the upper limit of the heating temperature of the mold is not limited, it is preferably not higher than the thermal decomposition point of the release film.

Next, as shown in FIG. 6B, it is preferable to press and press the mold 26 against the release film such that the heated protrusion structure surface 27 comes into contact with the mold release film. When the protrusion structure 27 has an appropriate height by being pressed, the protrusion structure 27 pierces the release film. Then, the mold 26 and the release film are in contact with each other without a gap.

The necessary pressure and pressing time at this time depend on the material of the film, the transfer shape, especially the aspect ratio of the unevenness, and the preferable range of the pressing pressure is generally 1 MPa or more, and the preferable range of the molding time is 0. It is 01 seconds or more.

Alternatively, the mold 26 may be pressed against the release film by position control. That is, the mold 26 may be moved to a preset position and pressed against the release film. The preset position is a position at which the protrusion structure 27 of the mold can come into contact with the surface of the release film or the base material film on which the uneven structure is to be formed without a gap.

It should be noted that the pressure may be released while the position of the mold is maintained after the pressure is raised to maintain the contact state between the mold 26 and the release film.

Next, as shown in FIG. 6(b), it is preferable to cool the mold while maintaining the pressed state or the contacted state. It is preferable that the temperature is not higher than the glass transition temperature of the release film. By cooling to below the glass transition temperature, resin deformation after peeling the mold 26 from the release film can be suppressed, and a groove shape with high accuracy can be formed, which is preferable.

Next, as shown in FIG. 6C, the release film is peeled from the mold 26. In the peeling, it is preferable to move the mold and the release film in a direction perpendicular to the surface of the release film so as to separate them. When the release film is a continuous film, it is preferable to continuously apply tension in the direction perpendicular to the surface of the release film so that the linear peeling position moves continuously for peeling. .. As a result, the recess 29 is formed in the release film.

In the above manufacturing method, when the protrusion structure 27 is pushed in, viscoelastic deformation is caused in the release film, and the protrusion structure 27 can smoothly enter the inside of the release film. A concave portion 29 having a shape corresponding to is formed and suitable molding is performed.

In order to cause such viscoelastic deformation of the release film, it is preferable that the temperature T for heating the mold 26 having the protrusion structure 27 on its surface is equal to or higher than the glass transition temperature of the release film. Further, the heating temperature T of the mold 26 is preferably 5° C. to 60° C. higher than the glass transition temperature of the release film. If the difference between the glass transition temperature of the release film and the heating temperature T of the mold 26 is less than 5° C., a large force is required to deform the release film, and the formation of the release film uneven structure is insufficient. May be. On the contrary, when the difference between the glass transition temperature of the release film and the heating temperature T of the mold 26 is larger than 60° C., the rear surface of the mold 26 is deformed while the surface of the release film is deformed. It may start and it may be difficult to flatten the back surface of the release film.

Further, the storage elastic modulus of the resin contained in the release film at the temperature T of the mold 26 during molding is in the range of 0.005 GPa or more and 0.5 GPa or less, and more preferably 0.01 GPa or more and 0.1 GPa or less. The shape accuracy of the recess 29 of the release film can be further improved. If it is less than 0.005 GPa, the shape of the release film concave portion 29 may be easily deformed. On the other hand, when it is larger than 0.5 GPa, the release film is less likely to be deformed, the protrusion structure 27 of the mold 26 is not inserted into the release film, and it may be difficult to form the groove shape with a predetermined shape accuracy. ..

The depth and width of the recessed portion 29 formed in the release film can be arbitrarily selected according to the application, but both the width and the depth are preferably 1 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or more. It is as follows. If the groove width and the depth are less than 1 μm, it may be difficult in terms of accuracy, and if the groove width and the depth are more than 100 μm, a large pressing force is required to form the groove, and the apparatus may become large. When the thickness is larger than 100 μm, mechanical processing such as cutting the release film directly is often suitable, and the processing suitability may be difficult in some cases.

Next, the mold shape will be described with reference to FIGS. 7 and 8. 7A and 7B are perspective views showing an example of a mold applied to the present invention, and FIGS. 8A and 8B are sectional views showing an example of a mold applied to the present invention.

As shown in FIG. 7, it is preferable that the protrusion structure 27 is arranged at a predetermined position on the outer surface of the mold 26. The protrusion structure refers to a convex structure provided on the mold, and the protrusion structure may have only the same shape or may have a plurality of different shapes. The shape may be such that the width and height of the convex portion change midway.

It is preferable that the arrangement and density of the protrusion structures 27 be the same as the arrangement and density of the groove shapes required as product specifications. Generally, the pitch is 100 nm or more and 1 mm or less. The pitch means the repeating interval of the protrusion structure 21.

The protrusion structure 227 may be a wall-shaped structure as shown in FIG. 7A, or may be a cross-shaped structure as shown in FIG. 7B. It is preferred that the direction is periodically repeated.

The height and sectional shape of the protrusion structure 21 are determined by the required groove shape and film thickness. The protrusion structure may have a rectangular shape with a flat tip as shown in FIG. 8A, or may have a sharp tip as shown in FIG. 8B.

The material of the mold is preferably a metal having high strength and high thermal conductivity, and for example, nickel, steel, stainless steel, copper or the like is preferable. Moreover, you may use what plated the outer surface in order to improve workability.

The method of creating each mold having a protrusion structure on the surface is to perform cutting, laser processing or electron beam processing directly on the metal surface, or to directly apply plating, laser processing or electron beam processing to the plating film formed on the metal surface. And a method of subjecting these to electroforming. In addition, a method of applying a resist on a substrate, forming a resist with a predetermined patterning by a photolithography method, then etching the substrate to form recesses, and obtaining the inverted pattern by electroforming after removing the resist And so on. A concave pattern can be obtained by applying anisotropic etching. As the substrate, a glass plate, a silicon substrate, or the like can be applied instead of the metal plate.

[Resin film, laminate]
The resin film and the laminate of the present invention may have either a planar state or a three-dimensional shape after being molded as long as they have the resin film having the above-mentioned physical properties. The number of layers of the resin film is not particularly limited, and the resin film may be formed of one layer, or may be formed of two or more layers.

The thickness of the resin film is not particularly limited, but the lower limit thereof is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 10 μm or more. The upper limit thereof is preferably 500 μm or less, more preferably 300 μm or less, particularly preferably 200 μm or less. The thickness of the resin film can be selected according to the other functions described above.

The resin film, in addition to stretchability and tack as the subject of the present invention, gloss, fingerprint resistance, moldability, designability, scratch resistance, antifouling property, solvent resistance, antireflection, antistatic, conductive It may have other functions such as heat resistance, heat ray reflection, near infrared absorption, electromagnetic wave shielding, and easy adhesion.

Further, one or more layers may be further formed on the resin film, for example, a functional layer having the above-mentioned function, an adhesive layer, an electronic circuit layer, a printed layer, an optical adjustment layer, or another functional layer. May be provided.

[Coating composition]
Although the method for producing the laminate of the present invention is not particularly limited, the laminate of the present invention is applied to the surface of the release film having the concavo-convex structure on the side thereof with a coating composition containing a component constituting a resin film. It can be obtained through a step, a step of drying if necessary, and a step of curing the above components. Here, the "coating composition" is a liquid composed of a solvent and a solute, and a material capable of forming a resin film by coating on the release film and volatilizing, removing and curing the solvent in the drying step. Point to.

Here, the “type” of the coating composition refers to a liquid in which the types of solutes constituting the coating composition are partially different. This solute is a resin or a material capable of forming them in the coating process (hereinafter referred to as a precursor), particles, and a polymerization initiator, a curing agent, a catalyst, a leveling agent, an ultraviolet absorber, an antioxidant, etc. It consists of various additives.

Further, in the resin film and the laminate of the present invention, it is preferable to form a resin film by applying the following coating composition onto a release film.

The coating composition is a liquid containing components suitable for constituting the resin film of the present invention, and preferably contains a resin or precursor containing the following segments (1) to (2) as a solute. It may also contain a resin or precursor containing the segment (3).
(1) A segment containing at least one selected from the group consisting of polycaprolactone segment, polycarbonate segment and polyalkylene glycol segment (2) Urethane bond (3) Fluorine compound segment, polysiloxane segment and polydimethylsiloxane segment A segment containing at least one selected.

Each segment included in the component that constitutes this resin film can be confirmed by TOF-SIMS, FT-IR, or the like.

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

The details of the (1) polycaprolactone segment, polycarbonate segment, and polyalkylene glycol segment will be described later, but the components constituting the resin film have these segments, thereby improving stretchability and flexibility of the resin film. be able to. From the viewpoint of durability of the resin film, it is particularly preferable that the component forming the resin film has a polyalkylene glycol segment.

Although the details of the urethane bond will be described later, the resin constituting the layer A on the surface of the resin film has this bond, whereby the toughness and stretchability of the entire resin film can be improved.

The details of the fluorine compound segment, the polysiloxane segment, and the polydimethylsiloxane segment will be described later, but the components constituting the resin film may include these so that molecules exhibiting low surface energy can be present at a high density on the outermost surface. It is possible to improve the solvent resistance of the resin film.

In addition, urethane acrylate is mentioned as an example of a resin preferable as a solute of the coating composition. Various general-purpose products of urethane acrylate are available, and materials having various physical properties can be synthesized according to the purpose.

In the present invention, a method of lowering the glass transition temperature of the resin film is mentioned as one of the more preferable forms, and the kind of urethane acrylate can be selected as one of the means. Similarly, as one of the more preferable modes, it is possible to use a component obtained by curing a urethane acrylate having a constant number average molecular weight in a resin film. One of the means is to select the type of urethane acrylate. be able to.

Examples of commercially available urethane acrylates include urethane acrylates manufactured by Asia Kogyo Co., Ltd., urethane acrylates manufactured by Kyoeisha Chemical Co., Ltd., urethane acrylates manufactured by Shin Nakamura Chemical Co., Ltd., urethane acrylates manufactured by Taisei Fine Chemical Co., Ltd. "New Frontier" (registered trademark) manufactured by Ichikohyo Pharmaceutical Co., Ltd., "EBECRYL" (registered trademark) manufactured by Daicel Ornex Co., Ltd., "Shikou" (registered trademark) manufactured by Nippon Gosei Co., Ltd., and urethane acrylate manufactured by DIC Corporation. Etc., and these products can be used.

Further, the coating composition for resin film preferably contains the resin or precursor containing the polyether segment of (4). Including a resin or a precursor containing the segments (1) to (3), these may be all present in one type of polymer or oligomer, or may be a mixture of another polymer or oligomer containing each of them. May be.

In the resin film of the present invention, mechanical properties such as flexibility and stretchability of the resin film are important. Therefore, a method capable of controlling the structure of the polymer forming the resin film is preferable. Further, the laminate of the present invention is required to have a high level of appearance quality and smoothness of thickness with respect to the resin film. Therefore, in the method for producing a laminate described below, the viscosity of the resin film-forming coating composition Has a preferred range. Furthermore, since the laminate of the present invention is processed in a later step, it is preferable that it has durability against solvents and the like as much as possible.

Therefore, the coating composition for a resin film is an oligomer obtained by polymerizing a precursor containing a polyether segment of the chemical formula 3, a (meth)acrylic segment of the chemical formula 1 and a urethane segment of the chemical formula 2 in a situation where the molecular weight can be controlled, and then To this, various additives are added to prepare a coating composition for forming a resin film, and in the method for producing a laminate described below, the composition is applied onto a supporting substrate and crosslinked to form a resin film. Is preferred.

Specifically, a compound containing a polyether polyol and an isocyanate group and a hydroxyalkyl (meth)acrylate, or an acrylic modified polyether polyol and a compound containing an isocyanate group are preliminarily polymerized to prepare a urethane acrylate oligomer. It is preferable to add a suitable additive to the above to obtain a coating composition for forming a resin film.

Examples of the polyether polyol include polyalkylene glycol and various derivatives thereof such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol.

Examples of hydroxyalkyl (meth)acrylates include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and the like.

[Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]
First, the polycaprolactone segment refers to the segment represented by Chemical Formula 4. Polycaprolactone also includes those having 1 (monomer), 2 (dimer), 3 (trimer) repeating units of caprolactone and oligomers having up to 35 repeating units of caprolactone.

Here, n is an integer of 1 to 35.

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

As the resin containing the polycaprolactone segment, polycaprolactone having a bifunctional or trifunctional hydroxyl group is particularly preferable. Specifically, polycaprolactone diol represented by Chemical Formula 5,

Here, m+n is an integer of 4 to 35, m and n are integers of 1 to 34, respectively, and R is C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ or C(CH ₃ ) ₃ (CH ₂ ) _2.
Or polycaprolactone triol represented by the chemical formula 6,

Here, l+m+n is an integer of 3 to 30, l, m, and n are integers of 1 to 28, respectively, and R is CH ₂ CHCH ₂ , CH ₃ C(CH ₂ ) ₃ or CH ₃ CH ₂ C(CH ₂ ). _Three
Such as polycaprolactone polyol and polycaprolactone-modified hydroxyethyl (meth)acrylate represented by the chemical formula 7

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

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

In the present invention, the weight average molecular weight of the polycaprolactone segment in the resin containing the polycaprolactone segment is preferably 500 to 2,500, and more preferably 1,000 to 1,500. .. When the weight average molecular weight of the polycaprolactone segment is 500 to 2,500, stretchability and flexibility are further improved, which is preferable.

Next, the polyalkylene glycol segment refers to a segment represented by the chemical formula 8. Polyalkylene glycols include those having repeating units of alkylene glycol such as 2 (dimer) and 3 (trimer), and oligomers having repeating units of alkylene glycol up to 11.

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

The resin containing the polyalkylene glycol segment preferably has at least one or more hydroxyl groups. The hydroxyl group is preferably at the terminal of the resin containing the polyalkylene glycol segment.

The resin containing the polyalkylene glycol segment is preferably polyalkylene glycol (meth)acrylate having an acrylate group at the end in order to impart elasticity. The number of acrylate functional groups (or methacrylate functional groups) of polyalkylene glycol (meth)acrylate is not limited, but monofunctional is most preferable from the viewpoint of stretchability and flexibility of the cured product.

Examples of the polyalkylene glycol (meth)acrylate contained in the coating composition used for forming the resin film include polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, and polybutylene glycol (meth)acrylate. .. The structures are represented by the following chemical formulas 9, 10, and 11, respectively.

Polyethylene glycol (meth)acrylate:

Polypropylene glycol (meth)acrylate:

Polybutylene glycol (meth)acrylate:

In Chemical Formula 11, Chemical Formula 12, and Chemical Formula 13, R is hydrogen (H) or a methyl group (—CH ₃ ), and m is an integer of 2 to 11.

In the present invention, preferably, a component constituting a resin film by reacting a compound containing an isocyanate group described below with a hydroxyl group of (poly)alkylene glycol (meth)acrylate and using it as a urethane (meth)acrylate in a resin film. However, it is preferable that (2) urethane bond and (3) (poly)alkylene glycol segment can be contained, and as a result, the toughness of the resin film can be improved and the elasticity and flexibility can be improved.

Examples of hydroxyalkyl (meth)acrylates that are simultaneously added during the urethane reaction of a compound containing an isocyanate group and polyalkylene glycol (meth)acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl. (Meth)acrylate and the like are exemplified.

Next, the polycarbonate segment refers to a segment represented by the chemical formula 12. Polycarbonates also include those having 2 (dimers), 3 (trimers) carbonate repeating units, and oligomers having up to 16 carbonate repeating units.

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

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

As the resin containing a polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferable. Specifically, it is represented by Chemical Formula 13.
Polycarbonate diol:

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

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

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

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

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

In the present invention, preferably, the component constituting the resin film is the above-mentioned (2) by reacting a compound containing an isocyanate group described later with a hydroxyl group of polycarbonate diol and using it as a urethane (meth)acrylate in the resin film. It can have a urethane bond and (1) a polycarbonate diol segment, and as a result, the toughness of the resin film can be improved and at the same time the stretchability and flexibility can be improved.

[Compound containing urethane bond and isocyanate group]
In the present invention, the “urethane bond” refers to the bond represented by the above chemical formula 2.

When the component forming the resin film has this bond, the toughness and stretchability of the entire resin film can be improved.

By including a commercially available urethane-modified resin in the coating composition, it becomes possible for the components constituting the resin film to have a urethane bond. Further, when a resin film is formed, a coating composition containing a compound having an isocyanate group and a compound having a hydroxyl group as a precursor is applied, dried, and cured to generate a urethane bond, thereby forming a resin film. A urethane bond can also be included.

In the present invention, it is preferable to introduce a urethane bond into the component forming the resin film by reacting an isocyanate group and a hydroxyl group to generate a urethane bond. By reacting an isocyanate group and a hydroxyl group to generate a urethane bond, it is possible to improve the toughness of the resin film and also the elasticity.

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

When a resin film is formed using a compound containing an isocyanate group and a resin containing a polysiloxane segment having a hydroxyl group described below, or a component containing a polydimethylsiloxane segment having a hydroxyl group, the toughness and stretchability of the resin film are improved. In addition, it is possible to improve the surface slipperiness, and it is more preferable from the viewpoint of solvent resistance.

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

Among these isocyanate group-containing compounds, aliphatic isocyanates are preferable because they have higher elasticity and flexibility than alicyclic or aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. Further, as the compound containing an isocyanate group, an isocyanate having an isocyanurate ring is particularly preferable in terms of heat resistance, and an isocyanurate body of hexamethylene diisocyanate is most preferable. Isocyanate having an isocyanurate ring forms a resin film having both elasticity and heat resistance.

[Polysiloxane segment, polydimethylsiloxane segment]
In the laminate of the present invention, the component forming the resin film may have a segment containing at least one selected from the group consisting of polysiloxane segments and polydimethylsiloxane segments.

Furthermore, a coating composition containing a resin or a precursor containing a segment containing at least one selected from the group consisting of polysiloxane segments and polydimethylsiloxane segments is used as one of the coating compositions forming a resin film. Thus, the component forming the resin film can have these.

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

The polysiloxane segment will be described. In the present invention, the polysiloxane segment refers to a segment represented by the chemical formula 14 described later.

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

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

Although details of the polysiloxane segment and the polydimethylsiloxane segment will be described later, the components constituting the resin film have these segments to improve heat resistance and weather resistance, and to improve lubricity of the resin film. Can be improved. From the viewpoint of lubricity, it is more preferable to include a polydimethylsiloxane segment represented by Chemical Formula 20 described later.

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

The resin containing the polysiloxane segment is tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxy. A complete or partial hydrolyzate of a silane compound having a hydrolyzable silyl group such as alkoxysilane or γ-methacryloxypropylalkyldialkoxysilane, or an organosilica sol dispersed in an organic solvent, or a hydrolyzable silyl group on the surface of the organosilica sol. And the like, to which the hydrolyzed silane compound is added.

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

When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, a resin is used by using a coating composition containing a resin (copolymer) containing a polysiloxane segment having a hydroxyl group and a compound containing an isocyanate group. By forming a film, a resin film having a polysiloxane segment and a urethane bond can be efficiently formed.

Next, the polydimethylsiloxane segment will be described. In the present invention, the polydimethylsiloxane segment refers to the segment represented by the chemical formula 15. The polydimethylsiloxane includes both low molecular weight dimethylsiloxane repeating units of 10 to 100 (so-called oligomers) and high molecular weight dimethylsiloxane repeating units exceeding 100 (so-called polymers).

m is an integer of 10 to 300.

When the component forming the resin film has a polydimethylsiloxane segment, the polydimethylsiloxane segment is coordinated on the surface of the resin film. By coordinating the polydimethylsiloxane segment on the surface of the resin film, the lubricity of the surface of the resin film is improved and the frictional resistance can be reduced. It is also preferable from the viewpoint of solvent resistance.

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

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

When the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, a coating composition containing a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group is used. By forming a resin film by using the resin film, a resin film having a polydimethylsiloxane segment and a urethane bond can be efficiently formed.

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

When the polymer initiator method is used, the polymer azo radical polymerization initiator represented by Chemical Formula 16 can be used for copolymerization with other vinyl monomers. Also, a two-step polymerization in which a peroxy monomer and a polydimethylsiloxane having an unsaturated group are copolymerized at a low temperature to synthesize a prepolymer in which a peroxide group is introduced into a side chain, and the prepolymer is copolymerized with a vinyl monomer. You can also do

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

When the polymer chain transfer method is used, for example, after adding HS—CH ₂ COOH, HS—CH ₂ CH ₂ COOH, or the like to the silicone oil represented by the chemical formula 17 to form a compound having an SH group, a A block copolymer can be synthesized by copolymerizing the silicone compound and a vinyl monomer by utilizing chain transfer.

m is an integer of 10 to 300.

In order to synthesize a polydimethylsiloxane-based graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound represented by Chemical Formula 18, that is, a methacrylic ester of polydimethylsiloxane with a vinyl monomer. it can.

m is an integer of 10 to 300.

Examples of the vinyl monomer used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, 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 acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylol acrylamide, N, N-dimethylacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, diacetyltone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , Allyl alcohol and the like.

Polydimethylsiloxane 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 and isopropyl alcohol. It is preferable that the alcohol-based solvent is used alone or in a mixed solvent by a solution polymerization method.

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

The amount of the polydimethylsiloxane segment in the polydimethylsiloxane-based copolymer in the present invention is 1 to 100% by mass of all components of the polydimethylsiloxane-based copolymer in terms of lubricity and solvent resistance of the resin film. It is preferably 30% by mass. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1,000 to 30,000.

In the present invention, when a resin containing a polydimethylsiloxane segment is used as the coating composition used for forming the resin film, other segments are contained (copolymerized) in addition to the polydimethylsiloxane segment. May be. For example, a polycaprolactone segment or a polysiloxane segment may be contained (copolymerized).

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

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

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

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

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

Furthermore, when a solvent is included, it is preferably a solvent having the following characteristics.

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

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

When the relative evaporation rate of the solvent is larger than 0.4, the time required for the above-mentioned polysiloxane segment and/or polydimethylsiloxane segment and the fluorine compound segment to be oriented to the outermost surface in the resin film becomes shorter. Therefore, the solvent resistance of the resin film in the obtained laminate may decrease. Further, the lower limit of the relative evaporation rate of the solvent is not a problem as long as it is a solvent that can be evaporated and removed from the coating film in the drying step, and may be 0.005 or more in a general coating step.

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

[Other components in coating composition]
Further, the coating composition preferably contains a polymerization initiator, a curing agent, and a catalyst. The polymerization initiator and the catalyst are used to accelerate the curing of the resin film. As the polymerization initiator, those which can initiate or accelerate the polymerization, condensation or crosslinking reaction of the components contained in the coating composition by anion, cation, radical polymerization reaction and the like are preferable.

Various kinds of polymerization initiators, curing agents and catalysts can be used. Further, the polymerization initiator, the curing agent and the catalyst may be used alone or a plurality of polymerization initiators, the curing agent and the catalyst may be used at the same time. Further, an acidic catalyst or a thermal polymerization initiator may be used together. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of thermal polymerization initiators include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds and the like. Examples of the crosslinking catalyst that accelerates the urethane bond forming reaction include dibutyltin dilaurate and dibutyltin diethylhexoate.

In addition, the coating composition may include other crosslinking agents such as melamine crosslinking agents such as alkoxymethylolmelamine, acid anhydride crosslinking agents such as 3-methyl-hexahydrophthalic anhydride, amine crosslinking agents such as diethylaminopropylamine. It is also possible to include.

As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone type compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-phenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-(4-phenyl)-1-butane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl) ) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1-[4-(2-ethoxy) )-Phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, and those obtained by polymerizing these materials. ..

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

[Method for producing resin film and laminate]
The method for producing the laminate of the present invention is not particularly limited, but a release film having an uneven structure on at least one surface thereof, on the surface having the uneven structure, a coating composition containing a component constituting a resin film is provided. It is preferably manufactured by a manufacturing method including a step of applying and a step of curing the components. Further, the method for producing the resin film of the present invention is not particularly limited, but as a method for producing a resin film having a restoration rate of 80% or more and having a concavo-convex structure on at least one surface, it is separated from the laminate of the present invention. It is preferably manufactured by a manufacturing method including a step of peeling the shaped film. Hereinafter, the step of applying each coating composition will be referred to as a coating step, the step of drying as a drying step, and the step of curing as a curing step. As the coating composition, two or more types of coating compositions may be sequentially or simultaneously applied to form a resin film having two or more layers.

Here, “sequentially coating” means that one type of coating composition is coated on a release film, dried and cured, and then another coating composition is coated and dried. It means that a resin film composed of two or more layers is formed by curing. By appropriately selecting the type of coating composition to be used, it is possible to control the flexibility and stretchability of the resin film on the resin film side-release film side and the gradient, and the flexibility and stretchability of the resin film. You can Furthermore, by appropriately selecting the type, composition, drying conditions and curing conditions of the coating composition, it is possible to control the form of distribution of flexibility and stretchability in the resin film stepwise or continuously.

Further, "simultaneously coating" means that two or more kinds of coating compositions are simultaneously coated on the release film, and then dried and cured in the coating step.

The method of applying the coating composition in the coating step is not particularly limited, but the coating composition may be subjected to a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Pat. No. 2,681,294). It is preferable to apply to the supporting substrate by Further, of these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.

When two or more kinds of coating compositions are simultaneously coated, the method such as a multilayer slide die coating, a multilayer slot die coating, and a wet-on-wet coating can be used, although not particularly limited thereto.

An example of the multilayer slide die coat is shown in FIG. In the multi-layer slide die coating, liquid films composed of two or more kinds of coating compositions are sequentially laminated using the multi-layer slide die 31, and then applied on a supporting base material or a release film.

An example of the multilayer slot die coat is shown in FIG. In the multi-layer slot die coating, a liquid film composed of two or more kinds of coating compositions is laminated on a supporting base material or a release film at the same time as coating using a multi-layer slot die 32.

An example of a wet-on-wet coat is shown in FIG. In the wet-on-wet coating, after forming a one-layer liquid film made of the coating composition discharged from the single-layer slot die 33 on the supporting substrate, the liquid film is undried and Liquid films made of another coating composition discharged from the single-layer slot die 8 are laminated.

Subsequent to the coating step, the liquid film coated on the release film is dried in the drying step. From the viewpoint of completely removing the solvent from the obtained laminate, the drying step preferably involves heating the liquid film.

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

The temperature is preferably 15° C. to 129° C., more preferably 50° C. to 129° C., and more preferably 50° C., in order to obtain the above drying rate, as long as a preferable drying rate is obtained. It is particularly preferable that the temperature is from to 99°C.

Following the drying step, it is preferable to perform a further curing operation (curing step) by irradiating with heat or an active energy ray.

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

[Application example]
INDUSTRIAL APPLICABILITY The resin film of the present invention takes advantage of optical characteristics, flexibility, stretchability, tackiness, transportability, air release properties, reworkability (repeated bonding/peeling), followability, and anti-slip properties. It can be preferably used for applications in which these characteristics are required.

Examples include plastic molded products such as glasses/sunglasses, cosmetic boxes, food containers, water tanks, showcases for exhibition, smartphone cases, touch panels, color filters, flat panel displays, flexible displays, flexible devices, wearables. Devices, sensors, circuit materials, electrical and electronic applications, keyboards, home electric appliances such as remote controls for TVs and air conditioners, mirrors, window glasses, buildings, dashboards, car navigation touch panels, vehicle parts such as room mirrors and windows, and various other products. , Printed films for medical use, films for sanitary materials, medical films, agricultural films, films for building materials, etc., can be suitably used for surface materials, internal materials, constituent materials and materials for manufacturing processes.

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

[Urethane (meth)acrylate]
[Synthesis of urethane (meth)acrylate 1]
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Hakko Kirin Co., Ltd.) and 119 parts by mass of polycarbonate diol ("Plaxel" (registered trademark) CD-210HL manufactured by Daicel Chemical Industries, Ltd.) The parts were mixed, the temperature was raised to 40° C., and the temperature was 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.), and 0.02 parts by mass of hydroquinone monomethyl ether were added. After maintaining at 70°C for 30 minutes, 0.02 parts by mass of dibutyltin laurate was added and the mixture was maintained at 80°C for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane (meth)acrylate 1 having a solid content concentration of 50% by mass. The number average molecular weight of urethane (meth)acrylate 1 was 5,800.

[Urethane (meth)acrylate 2]
As the urethane (meth)acrylate 2, SUA-017 (manufactured by Asia Kogyo Co., Ltd., solid content concentration 100% by mass) having a number average molecular weight of 4,600 was used.

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

[Base film]
[Base film 1]
As the base film 1, "Trephan" (registered trademark) NO 3429K (thickness 100 μm, manufactured by Toray Film Co., Ltd.) was used.

[Base film 2]
As the base film 2, "Lumirror" (registered trademark) X42 (thickness: 50 μm, manufactured by Toray Industries, Inc.) having a matte surface was used.

[Base film 3]
As the substrate film 3, "Lumirror" (registered trademark) S10 (thickness: 50 μm, manufactured by Toray Industries, Inc.) having a smooth surface was used.

[Release film preparation method [Release film 1]
The mold 1 was previously heated to 160° C., the base film 1 and the uneven surface of the mold 1 were brought into contact with each other, pressed at 5 MPa, and held in that state for 60 seconds. Then, after cooling to 50° C., the press was released and the release film 1 was taken out from the mold. The method of forming the mold 1 is as follows.

A stripe-shaped mold in which wall-shaped structures having a width of 40 μm and a height of 60 μm were periodically arranged at a pitch of 60 μm was used as the mold 1. The area where the protrusion structure is processed is an area of 50 mm×50 mm. The mold was formed by cutting a Starbucks material having a thickness of 10 mm, which was plated with 200 μm of nickel phosphorus.

[Release film 2]
The mold 2 was heated to 160° C. in advance, the release base film 1 and the uneven surface of the mold 2 were brought into contact with each other, pressed at 5 MPa, and held in that state for 60 seconds. Then, after cooling to 50° C., the press was released and the release film 2 was taken out from the mold. The method of forming the mold 2 is as follows.

A stripe-shaped mold in which wall-shaped structures having a width of 12 μm and a height of 8 μm were periodically arranged at a pitch of 17 μm was used as the mold 1. The area where the protrusion structure is processed is an area of 50 mm×50 mm. The mold was formed by cutting a Starbucks material having a thickness of 10 mm, which was plated with 200 μm of nickel phosphorus.

[Release film 3]
The following materials were mixed and diluted with a methyl ethyl ketone/isopropyl alcohol mixed solvent (mass mixing ratio 50/50) to prepare a release layer coating composition A having a solid content concentration of 5 mass %.
-Acrylic modified alkyd resin (Haliftar KV-905, Harima Chemicals Co., Ltd., solid content concentration 53 mass%): 100 parts by mass, isobutyl alcohol-modified melamine resin (Melan 2650L, Hitachi Chemical Co., Ltd. solid content concentration 60 mass%): 20 masses Parts-paratoluenesulfonic acid: 5 parts by mass-side chain type modified reaction type silicone oil (KF-6123 Shin-Etsu Chemical Co., Ltd. 100% by mass of active ingredient): 5 parts by mass Release to the base film 2 having a matte surface The coating composition A for layers is coated with a coating device having a small-diameter gravure coater so that the thickness of the release layer is about 200 nm, the number of lines of the gravure roll, the peripheral speed of the gravure roll, and the coating composition for the release layer. The solid content concentration of the product was adjusted and applied, and the product was dried and crosslinked by maintaining the hot air temperature at 140° C. for 30 seconds to form a release layer.

[Release film 4]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mass mixing ratio 50/50) to prepare a coating composition B for mat release layer having a solid content concentration of 5% by mass.
-Acrylic modified alkyd resin (Haliftar KV-905, Harima Chemicals Co., Ltd., solid content concentration 53 mass%): 100 parts by mass, isobutyl alcohol-modified melamine resin (Melan 2650L, Hitachi Chemical Co., Ltd. solid content concentration 60 mass%): 20 masses Parts/paratoluenesulfonic acid: 5 parts by mass/side chain type modified reaction type silicone oil (KF-6123 Shin-Etsu Chemical Co., Ltd. 100% by mass of active ingredient): 5 parts by mass/melamine resin/silica composite particles (Optobeads 3500M Nissan Chemical Co., Ltd.: 14 parts by mass, using a coating device having a release layer coating composition B on the base film 3 and a small diameter gravure coater so that the release layer has a thickness of about 200 nm. Number, the peripheral speed of the gravure roll, and the solid content concentration of the coating composition for the release layer are adjusted and applied, and drying and crosslinking are performed by maintaining the hot air temperature at 140° C. for 30 seconds to form the release layer. Formed.

[Release film 5]
The base film 1 was used as it was as a release film without forming an uneven structure.

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

-Urethane (meth)acrylate 1 solution: 100 parts by mass-Radical radical polymerization initiator 1: 1.5 parts by mass.

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

-Urethane (meth)acrylate 2 solution: 50 parts by mass-Radical radical polymerization initiator 1: 1.5 parts by mass.

[How to make resin film]
[Production of resin film]
The coating composition was applied onto the release film by using a continuous coating device using a slot die coater and adjusting the discharge flow rate from the slot so that the thickness of the dried resin film would be a specified film thickness. The coating composition combinations used are as shown in Table 1.

The conditions of the dry air which hits the liquid film from the application to the drying and curing are as follows.

Then, the resin film was peeled from the release film.

[Drying process]
Blower temperature/humidity: Temperature: 80°C, relative humidity: 1% or less Air velocity: Coating surface side: 5 m/sec, non-coating surface side: 5 m/sec Wind direction: Coating surface side: parallel to the surface of the substrate, anti-coating Surface side: perpendicular to the surface of the substrate Residence time: 2 minutes [Curing step]
Irradiation output: 400 W/cm ²
Integrated light intensity: 120 mJ/cm ²
Oxygen concentration: 0.1% by volume.

[Evaluation of resin film, release film, laminate]
The following performance evaluation was performed on the laminate, the resin film, and the release film, and the obtained results are shown in Tables 2 and 3. Unless otherwise specified, in each of the examples and comparative examples, one sample was measured at three different locations, and the average value was used.

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

[Restore rate]
The resin film was cut into a rectangle having a width of 10 mm and a length of 150 mm to obtain a test piece. The direction of 150 mm length was aligned with the longitudinal direction of the laminate. Using a tensile tester (RTG-1210 manufactured by A&D), the initial tensile chuck distance was set to 50 mm, the tensile speed was set to 50 mm/min, and the tensile test was performed at a measurement temperature of 23°C. At that time, after stretching the sample to a strain amount of 10 mm (=20%), the tensile load on the sample was released.

The elastic recovery rate z% was calculated from the following formula by measuring the distance marked as the initial test length before the measurement and setting it as Lmm.
Recovery rate: z=(1-(L-50)/20)×100 (%).

[5% strain stress]
In the evaluation of the resin film, the laminate was cut into a rectangle having a width of 10 mm and a length of 150 mm, and the resin film was peeled from the release film to obtain a test piece. The direction of 150 mm length was aligned with the longitudinal direction of the laminate. Using a tensile tester (RTG-1210 manufactured by A&D), the initial tensile chuck distance was set to 50 mm, the tensile speed was set to 300 mm/min, and the tensile test was performed at a measurement temperature of 23°C. When evaluating the resin film having no release film, the measurement was performed as described above except that the resin film was cut into the size described above.

The load b (N) applied to the sample when the chuck distance was a (mm) was read, and the strain amount x (%) and the stress y (N/mm 2) were calculated from the following formulas. However, the sample thickness before the test is k (mm).
Strain amount: x=((a-50)/50)×100
Stress: y=b/(k×10).

Of the data obtained above, the stress at a strain amount of 5% was defined as 5% strain stress.

[Total light transmittance]
The resin film was cut into a 100 mm width×100 mm length to obtain a test piece. The haze measurement was performed using a haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K 7361-1 (1997). In addition, when evaluating the resin film in a laminated body, it measured as mentioned above except peeling a resin film from a laminated body.

[Maximum height]
On the surface of the resin film having the surface uneven structure, the maximum height of the surface uneven structure was measured with a laser microscope (VK-9700 manufactured by Keyence Corporation). The observation was performed with a 50× objective lens, and both the concave portion and the convex portion of the surface uneven structure were included in the observation visual field. The maximum height is defined as the difference between the position where the concave portion of the surface uneven structure has the smallest height and the position where the coated particles of the surface uneven structure have the largest height. The maximum height of the uneven structure of the release film was measured in the same manner.

[Peeling force]
In the laminate, the resin film and the release film were slightly peeled off from the ends in advance, and a gripping margin for measurement with a tensile tester was formed. Then, in a 23° C. 65% RH environment, a resistance value (N) was measured when peeling 180 degrees at a speed of 300 (mm/min) using a tensile tester. The resistance value (N) was divided by the width (mm) of the release film and the resin film and then multiplied by 50 to convert it into a peeling force (mN/50 mm) corresponding to each width of 50 mm.

[Evaluation of stretchability 1]
In the laminated body, after peeling the resin film from the release film, the resin film was pulled by hand and judged according to the following criteria. In addition, the resin film was evaluated in the same manner as the resin film, and the judgment was made according to the following criteria, and 4 points or more were regarded as passing.
10 points: It can be deformed with a very light force.
7 points: It can be deformed with a light force.
4 points: It can be transformed by applying a slightly stronger force.
1 point: Others (strong force is required to deform, etc.).

[Evaluation of stretchability 2]
In the laminate, after peeling the resin film from the release film, a light force was applied to the resin film by hand to give tensile deformation, and the judgment was made according to the following criteria. In addition, the resin film was evaluated in the same manner as the resin film, and the judgment was made according to the following criteria, and 4 points or more were regarded as passing.
10 points: After the deformation, the load is removed and the original shape is restored.
7 points: Most of the original shape is restored after deformation without load.
4 points: Restores the original shape a little after removing the load after deformation.
1 point: Other (no restoration, etc.).

[Evaluation of tack prevention and reworkability]
The resin film was placed on a glass plate, and a load was applied in the vertical direction of the resin film to press it. Then, the resin film was pulled in the plane direction, and the behavior at that time was judged according to the following criteria, and 4 points or more were judged to be acceptable. Regarding the resin film having the uneven structure on the surface, the surface pressed against the glass plate was the surface having the uneven structure.
10 points: Peeling is possible with almost no resistance, and the position can be corrected.
7 points: Peeling can be performed with a slight force, and the position can be corrected.
4 points: Peeling can be done with a little strong force, and the position can be corrected.
1 point: Others (can be peeled, but required force is large, cannot be peeled, etc.).

[Evaluation of air release properties]
The resin film was lightly pressed against the glass plate, the behavior of the air pool generated between the glass plate and the resin film at that time was observed, and judgment was made according to the following criteria, and 4 points or more were passed. Regarding the resin film having the uneven structure on the surface, the surface pressed against the glass plate was the surface having the uneven structure.
10 points: Air quickly escapes.
7 points: It takes some time, but the air escapes.
4 points: A little air remains.
1 point: Others (a lot of air remains, air does not escape at all).

[Evaluation of peelability]
In the laminate, the support base material and the resin layer are slightly peeled from the end in advance, and the support base material and the resin layer are manually peeled in the 180 degree direction by grasping the peeled portion, and the judgment is made according to the following criteria. went.
10 points: At the time of peeling, it is possible to peel without feeling a catch.
7 points: A slight catch is felt during peeling.
4 points: When peeling, a strong catch is felt.
1 point: Others (cannot be peeled off, etc.).

Tables 2 to 3 summarize the evaluation results of the finally obtained laminates.

1, 9, 18, 23 Laminates 2, 5, 10, 14, 19, 21 Resin film 3, 6, 11, 15 Release layer 4, 7, 12, 16 Base film 5, 8, 13, 17, 20, 22 Release film 6 Release film 7 Resin film 8 Release film 24 Convex portion of resin film 25 Recessed portion of resin film 26 Mold 27 Mold structure 28 Release film 29 Recessed portion 31 Multilayer slide die 32 Multilayer slide die 33 Single layer slot die

The resin film and laminate of the present invention are excellent in optical properties, flexibility, elasticity, tackiness, transportability, air release properties, reworkability (repeated bonding/peeling), followability, and slip resistance. By utilizing the advantages, it can be suitably used for applications in which these characteristics are required.

Examples include plastic molded products such as glasses/sunglasses, cosmetic boxes, food containers, water tanks, showcases for exhibition, smartphone cases, touch panels, color filters, flat panel displays, flexible displays, flexible devices, wearables. Devices, sensors, circuit materials, electrical and electronic applications, keyboards, home electric appliances such as remote controls for TVs and air conditioners, mirrors, window glasses, buildings, dashboards, car navigation touch panels, vehicle parts such as room mirrors and windows, and various other products. , Printed films for medical use, films for sanitary materials, medical films, agricultural films, films for building materials, etc., can be suitably used for surface materials, internal materials, constituent materials and materials for manufacturing processes.

Claims (12)

A resin film having a restoration rate of 80% or more and having an uneven structure on at least one surface. The resin film according to claim 1, wherein the following condition 1 is satisfied.
Condition 1: The 5% strain stress of the resin film is 10 MPa or less. The resin film according to claim 1 or 2, which satisfies the following condition 2.
Condition 2: The resin film has a total light transmittance of 80% or more. The resin film according to any one of claims 1 to 3, which satisfies the following condition 3.
Condition 3: The uneven structure of the resin film has a stripe shape. The following condition 4 is satisfy|filled, The resin film in any one of Claim 1 to 4 characterized by the above-mentioned.
Condition 4: The maximum height of the uneven structure of the resin film is 5 μm or more and 100 μm or less. A laminate having a resin film on one surface of a release film,
The release film has an uneven structure on at least one surface,
The resin film has a restoration rate of 80% or more and has an uneven structure on at least one surface,
The protrusions of the relief structure of the release film enter the recesses of the relief structure of the resin film, and the projections of the relief structure of the resin film enter the recesses of the relief structure of the release film. The surface having the uneven structure of the mold film and the surface having the uneven structure of the resin film are in contact with each other,
A peeling force between the release film and the resin film is 1,000 mN/50 mm or less, a laminate. The laminate according to claim 6, which satisfies the following condition 1.
Condition 1: The 5% strain stress of the resin film is 10 MPa or less. The laminated body according to claim 6 or 7, which satisfies the following condition 2.
Condition 2: The resin film has a total light transmittance of 80% or more. The laminated body according to any one of claims 6 to 8, which satisfies the following conditions 3 and 5.
Condition 3: The uneven structure of the resin film has a stripe shape.
Condition 5: The uneven structure of the release film has a stripe shape. The laminate according to any one of claims 6 to 9, which satisfies the following conditions 4 and 6.
Condition 4: The maximum height of the uneven structure of the resin film is 5 μm or more and 100 μm or less.
Condition 6: The maximum height of the uneven structure of the release film is 5 μm or more and 100 μm or less. A method for producing a resin film, which has a restoration rate of 80% or more and has an uneven structure on at least one surface,
A method for producing a resin film, comprising a step of peeling a release film from the laminate according to any one of claims 6 to 10. It is a manufacturing method of the laminated body in any one of Claims 6-10, Comprising:
On the surface of the release film having an uneven structure on at least one surface, on the surface having the uneven structure, a step of applying a coating composition containing a component forming a resin film, and a step of curing the component A method for producing a laminated body, comprising: