JP2022113785A - laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in conveyance property while being flexible.

SOLUTION: A laminate has a resin layer on at least one surface of a support base material, and satisfies all of the following condition 1 to condition 5: condition 1 of 5% strain stress S_F of the resin layer of 10 MPa or less; condition 2 of 5% strain stress S_L of the laminate of 20 MPa or more; condition 3 of peel force R_b between the support base material and the resin layer of 1,000 mN/50 mm or less; condition 4 of thermal shrinkage in a longitudinal direction at 150°C of the laminate of 2.0% or less; and condition 5 of a haze of the laminate of 15% or less.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

TECHNICAL FIELD The present invention relates to a laminate that achieves both flexibility and transportability.

In recent years, devices equipped with displays, such as smartphones, tablets, personal computers, and liquid crystal televisions, and various other devices have become widespread. . Under these circumstances, research and development of flexible devices and wearable devices have been actively carried out in recent years, and the development of deformable devices and members is progressing.

Due to this situation, it is thought that new technical areas will be created that are difficult to apply with materials that have been used in conventional displays and devices, so the need for new materials with high flexibility and elasticity will increase. expected to be

On the other hand, as an example of an existing material having flexibility and stretchability, Patent Document 1 describes "a layer made of a first polyethylene, a thermoplastic polyurethane layer laminated on the layer made of the first polyethylene, and the heat and a layer made of a second polyethylene laminated on the plastic polyurethane layer, wherein the amount of heat of crystallization of the first polyethylene is larger than the amount of heat of crystallization of the second polyethylene. Laminate having a thermoplastic polyurethane layer of .

Non-Patent Document 1 mentions a so-called "silicone material", and proposes a sheet material using silicone rubber as an example of the silicone material.

In addition, Patent Document 2 describes "a styrene-butadiene-styrene copolymer (SBS-A) containing 65 to 95% by mass of a styrene component and a styrene-butadiene-styrene copolymer containing 5 to 40% by mass of a styrene component. an SBS resin composition in which coalescence (SBS-B) is mixed at a composition ratio of (SBS-A)/(SBS-B) = 75/25 to 95/5; 20 to 45 parts by mass of a filler (C), and having a specific gravity of 1.10 to 1.32".

In addition, Patent Document 3 describes "A mixture of urethane resin, organic solvent, water and fluorine-based surfactant is a film of any one of polyethylene terephthalate film, polypropylene film or methylpentene polymer film, and an adhesive is applied on one side. A foamed urethane sheet having a foam on the substrate obtained by coating and heating the substrate, wherein the organic solvent is a mixed solution of toluene and methyl ethyl ketone, and the foam has a continuous ventilation structure A foamed urethane sheet characterized by being composed of fine cells." has been proposed.

JP 2013-91223 A JP 2008-88293 A JP 2014-231170 A

Silicone Handbook Nikkan Kogyo Shimbun 1990

However, when the present inventors confirmed the material proposed in Patent Document 1, although it was confirmed that it had a certain degree of flexibility and stretchability, it lacked heat resistance at high temperatures. It was not suitable for post-processing that involves heating, which is necessary for application as a

The silicone rubber material proposed in Non-Patent Document 1 has flexibility and stretchability, but is poor in adhesion to different materials and is unsuitable for post-processing.

Next, although the material proposed in Patent Document 2 was confirmed to have a certain degree of flexibility, it was found to be insufficient in stretchability and transparency.

Furthermore, although the material proposed in Patent Document 3 was confirmed to have a certain level of flexibility and stretchability, its transparency was insufficient. It was also found that the presence of foamed portions is unsuitable for a post-processing step involving coating.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a laminate that is excellent in transportability while having flexibility and stretchability.

In order to solve the above problems, the present inventors completed the following invention as a result of earnest research. That is, the present invention is as follows.
<1>
A laminate having a resin layer on at least one surface of a supporting substrate, wherein the laminate satisfies all of the following conditions 1 to 5.
Condition 1: 5% strain stress SF of the resin layer is 10 _MPa or less.
Condition 2: The 5% strain stress _SL of the laminate is 20 MPa or more.
Condition 3: The peel force _Rb between the supporting substrate and the resin layer is 1,000 mN/50 mm or less.
Condition 4: The longitudinal heat shrinkage of the laminate at 150°C is 2.0% or less.
Condition 5: The laminate has a haze of 15% or less.
<2>
The laminate according to <1>, which satisfies condition 6 below.
Condition 6: The elastic recovery rate of the resin layer is 70% or more in a tensile test method with a deformation amount of 20%.
<3>
The laminate according to <1> or <2>, which satisfies the following conditions 7 and 8.
Condition 7: Stress retention rate, which is the ratio of the stress F1 when the resin layer is stretched to a strain of 100% and the stress F2 after being held in that state for _{1 hour} in the stress relaxation test method at a deformation of 100%. F ₂ /F ₁ ×100 is 70% or more.
Condition 8: In the hysteresis test method with a deformation amount of 100%, the resin layer is stretched to a strain amount of 100%, held for 10 seconds, and then released. , is less than 1.0 MPa.
<4>
4. The laminate according to any one of claims 1 to 3, which satisfies condition 9 below.
Condition 9: The absolute value of the dimensional change rate of the resin layer at 150°C is 10% or less with respect to the dimension of the resin layer at 30°C.
<5>
The laminate according to any one of <1> to <4>, which satisfies Condition 10 below.
Condition 10: The glass transition temperature of the resin layer is 0° C. or lower in the dynamic viscoelasticity method.
<6>
The laminate according to any one of <1> to <5>, which satisfies the following conditions 11 and 12.
Condition 11: The resin layer is a resin composition obtained by curing urethane acrylate having a number average molecular weight of 3,000 or more.
Condition 12: A release layer is provided on at least one surface of the supporting substrate, and the supporting substrate and the resin layer are in contact with each other via the release layer.
<7>
A laminate according to any one of <1> to <6>, wherein a resin layer is formed on at least one surface of a supporting substrate, wherein the laminate satisfies the following condition 13: body manufacturing method.
Condition 13: A resin layer is formed by applying the coating composition onto the supporting substrate.

According to the present invention, it is possible to obtain a laminate that is flexible and has good transportability.

It is an example of a laminate in the present invention. It is sectional drawing which shows an example of the formation method of the resin layer in this invention. It is sectional drawing which shows an example of the formation method of the resin layer in this invention. It is sectional drawing which shows an example of the formation method of the resin layer in this invention. It is a figure which shows an example of the hysteresis area of the resin layer in this invention.

Before describing embodiments of the present invention, the problem of the prior art, ie, compatibility between flexibility and transportability, will be considered from the viewpoint of the present inventor.

[Comparison between the present invention and conventional technology]
In the prior art, materials exhibiting flexibility and stretchability exist, but due to their flexibility and stretchability, transportability, heat resistance, optical properties, and the like are insufficient. Therefore, although it can be used for specific purposes, film materials are often used after undergoing various post-processing in applications such as displays, devices, and sensors. However, it was difficult to apply.

In a continuous process such as Roll-to-Roll, the material is conveyed under tension, which causes deformation in flexible materials. There is something to do. Specifically, the material may be stretched or wrinkled, which may hinder the printing process, bonding process, or coating process performed as post-processing steps. Materials exhibiting flexibility are characterized by high mobility of the molecular structure of the material near room temperature, but this makes it difficult to maintain the shape at high temperatures, resulting in insufficient heat resistance. . In addition, if the optical properties (especially transparency) are insufficient, when inspecting products that have undergone post-processing, the inspection performance when using visual inspection or optical sensors is insufficient, making it difficult to distinguish between good products and defective products. There is also a problem.

Therefore, the inventors of the present invention have paid attention to the layer structure of the laminate in order to study compatibility between flexibility and transportability.

In applications such as display members and device members, transportability is required in the manufacturing process of the members, but it is considered that flexibility and stretchability are required during use. Therefore, the inventors conceived a method of imparting transportability as a laminate by combining a flexible resin layer and a support base material having transportability. At this time, by controlling the peeling force between the supporting base material and the resin layer to a certain level or less, the supporting base material can be peeled off at an arbitrary timing in accordance with the manufacturing process and usage conditions of the member. With this structure, a flexible material with excellent post-processing properties can be secured by securing transportability as a laminate structure when performing printing, bonding, or coating processing, and by peeling off the supporting base material at the timing of use. has become possible to provide In addition, by ensuring the dimensional stability of the laminate at high temperatures, it is possible to obtain a high-quality product even in post-processing involving heating. Furthermore, by increasing the transparency of the laminate, the inspectability after post-processing is improved, so that the productivity of the product can be improved.

Specifically, the 5% strain stress _{SF of the resin layer is 10 MPa or less, the 5% strain stress S L of} the laminate is 20 MPa or more, and the peel force _Rb between the supporting substrate and the resin layer is 1. ,000 mN/50 mm or less, the longitudinal heat shrinkage of the laminate at 150° C. is 2.0% or less, and the haze of the laminate is preferably 15% or less.

Furthermore, in the method for producing the laminate of the present invention, as a method other than the coating described above, for example, there is a production method by laminating a resin layer and a supporting substrate. However, in the case of lamination, for example, an adhesive layer is interposed between the resin layer and the supporting substrate, and when such a laminate is conveyed or heated, the adhesive migrates to the resin layer ( There is a so-called adhesive residue), so it may be unsuitable as a product. Also, when laminating without an adhesive, lamination is performed by applying heat or pressure. However, if the resin layer is flexible, unintended deformation or heat shrinkage may occur, resulting in wrinkles or deterioration in quality. It may be a cause or unsuitable as a product.

Therefore, as a result of intensive studies by the present inventors, as a method for solving the above-mentioned problems, the method for producing a laminate of the present invention comprises coating a coating composition on a supporting substrate to form a resin layer. It has been found that by doing so, transportability can be imparted while suppressing the load on the resin layer as much as possible. Moreover, in the manufacturing method described above, it is also possible to control the peeling force between the resin layer and the supporting substrate by selecting the type of the supporting substrate. It was also found that by obtaining the laminate of the present invention by coating, the smoothness on both the front and back surfaces of the resin layer can be enhanced.

Furthermore, the inventors of the present invention focused on the deformability of the materials constituting the laminate in conducting studies to improve the quality of the laminate. As described above, materials exhibiting flexibility and stretchability have insufficient transportability, and in addition, there is a problem in that the material is flexible and easily deformed. Specifically, fine irregularities, scratches, and unevenness occur in the flexible resin layer during the transportation process, which may lead to a decrease in the quality of the product when it is made into a product, or a decrease in the inspection performance after post-processing. be.

On the other hand, in order to improve the transportability of such a flexible material, conventionally, the transportability has been improved by hardening it within an allowable range as a product or thickening the film. was able to improve the transportability by paying attention to the layer structure of the laminate. Therefore, we investigated in detail what would happen when the resin layer was made more flexible, which was difficult with conventional designs. As a result, the inventors have found that the quality of the laminate can be improved by making the resin layer extremely flexible.

As a result of investigating this effect by the present inventors, as described above, unevenness, scratches, and unevenness are likely to occur in flexible materials, but in extremely flexible materials, the unevenness, scratches, and unevenness described above disappear in post-processing. I found it easier. This is because flexible materials are susceptible to deformation, so irregularities, scratches, and unevenness are likely to occur, but in extremely flexible materials, irregularities, scratches, and unevenness that occur once are smoothed out by heat and pressure in post-processing. It is thought that this is because the This effect can improve the quality of the laminate. In particular, it has been found that the deformability of the resin layer depends on the temperature, and that the above effect can be enhanced by lowering the glass transition temperature of the resin layer.

Specifically, it is preferable to set the glass transition temperature of the resin layer to 0° C. or lower in the dynamic viscoelasticity method.

Furthermore, the inventors of the present invention have conducted detailed studies on the laminate structure of the laminate, and as a result, have found that it is possible to improve the releasability and quality by making the support substrate and the resin layer have a specific configuration. . As one of the preferable lamination structures of the present invention, there is a structure in which a release layer is provided on the surface of the supporting base material in order to enhance the releasability between the resin layer and the supporting base material. On the other hand, since the resin layer is flexible, it is highly deformable, and if the resin layer is greatly deformed after laminating the supporting substrate and the resin layer, unintended detachment may partially occur during the transportation process. In particular, if the release layer provided on the surface of the support substrate has a very high releasability prescription and the curing shrinkage that occurs when the resin layer is cured is extremely large, part of the resin layer during curing In some cases, peeling may occur in the resin layer, and peeling may occur in a part of the resin layer when a further load is applied in a post-process, resulting in deterioration of the quality.

Therefore, as a result of examining a method for suppressing curing shrinkage of the resin layer, it was found that by setting the number average molecular weight of the resin composition used for the resin layer to a certain value or more, the above-mentioned partial peeling can be suppressed and the quality can be improved. I found This can also be applied when it is necessary to change the design of the release layer provided on the surface of the support substrate according to the application (especially when increasing the release property), and the release property of the resin layer and the quality of the laminate can be improved. can be increased.

Specifically, the resin layer is a resin composition obtained by curing urethane acrylate having a number average molecular weight of 3,000 or more, and a release layer is provided on at least one surface of the support substrate. It is preferable that the supporting substrate and the resin layer are in contact with each other via the release layer.

Furthermore, it was found that the conventional resin layer did not restore its original length after being strained for a long period of time, but became slack even when the strain was released. Therefore, the present inventors focused on the stress relaxation property of the resin layer in order to improve the resilience of the resin layer constituting the laminate after long-term deformation. Conventionally, it has been found that since the stress relaxation property is high, that is, the applied stress is reduced, the stress at the time of restoration is reduced, and the restoration property is reduced. Therefore, the present inventors have found that by setting the stress relaxation property of the resin layer to a specific range, high restorability can be obtained even if the resin layer continues to be strained for a long period of time.

Specifically, in the stress relaxation test method with a deformation amount of 100%, the stress that is the ratio of the stress F ₁ when the resin layer is stretched to a strain amount of 100% and the stress F ₂ after being held in that state for 1 hour The retention ratio F ₂ /F ₁ × 100 is 70% or more, and the resin layer is stretched to a strain amount of 100% in the hysteresis test method with a deformation amount of 100%, held for 10 seconds, and then released. Preferably, the hysteresis area enclosed by the stress-strain curve at release is less than 1.0 MPa.

Furthermore, the inventors of the present invention focused on the difference in deformation behavior between the resin layer and the supporting substrate during heating when examining the quality and post-processing suitability of the laminate. As described above, the laminate of the present invention is subjected to post-processing such as printing, bonding, and coating as an example of a method of use, and such post-processing may involve heating. many. Observation of the deformation behavior of the resin layer and the supporting substrate when this laminate is heated shows that when the deformation of the resin layer caused by heating is large relative to the deformation of the supporting substrate caused by heating, the thickness of the laminate It was found that internal stress is generated because the direction and magnitude of deformation are different depending on the position. This internal stress may deteriorate the surface properties or, in extreme cases, cause unintended separation between the resin layer and the supporting substrate, resulting in deterioration of quality and post-processing suitability.

Therefore, as a result of examining a method for suppressing such an unintended decrease due to internal stress, it was found that it is effective to suppress dimensional change during heating for a resin layer that is particularly susceptible to deformation. By suppressing the dimensional change during heating, even when the laminate is exposed to various post-processing processes, it is possible to suppress the generation of unnecessary internal stress in the laminate, improving the quality and post-processing suitability. can increase

Specifically, the absolute value of the dimensional change rate of the resin layer at 200° C. is preferably 10% or less when the dimension of the resin layer at 30° C. is used as a reference.

Furthermore, the present inventors also verified a thermoplastic urethane film (TPU) in examining the laminate. There are various commercially available thermoplastic urethane films, and they have shown certain characteristics in terms of transportability at room temperature. However, since the thermoplastic urethane film has thermoplasticity, it will deform when exposed to high temperatures above a certain level. In particular, when exposed to post-processing steps such as printing, bonding, and coating, the thermoplastic urethane film is greatly deformed, resulting in insufficient transportability. In addition, some thermoplastic urethane films have a supporting substrate. For example, a polyester film or the like is used as the supporting substrate. It was found that there was a difference in the quality and the post-processing aptitude was deteriorated.

In addition, the present inventors have studied the properties of a thermoplastic urethane film (TPU) in detail. As described above, in order to improve the resilience after long-term deformation of the resin layer that constitutes the laminate in the present invention, it is preferable to make the stress relaxation property of the resin layer constant as described above. However, it has been found that the thermoplastic urethane film is not suitable for the purpose of the present invention because it is difficult to make the stress relaxation property constant as described above.

A thermoplastic urethane film, as its name suggests, is a material having thermoplasticity, and having thermoplasticity means that plastic deformation is likely to occur. In other words, plastic deformation is a property derived from the macromolecular structure that constitutes the resin, and a characteristic of thermoplastic is that large plastic deformation occurs when heated. Plastic deformation can also occur in the environment. In particular, in a situation where strain is continuously applied from the outside for a long time, plastic deformation occurs even in a situation without heating. If plastic deformation occurs, it means that the resin layer does not return to its original shape after being deformed even if the stress is released, resulting in loss of restorability. Therefore, thermoplastic urethane film is considered to be an unsuitable material for applications that require high resilience in various environments.

[Mode of the present invention]
Embodiments of the present invention will be specifically described below.

In order to satisfy the above problems, that is, flexibility and transportability, the laminate of the present invention is a laminate having a resin layer on at least one surface of a supporting substrate, and satisfies the following conditions 1 to 5: All are preferred.

Condition 1: 5% strain stress SF of the resin layer is 10 _MPa or less.

Condition 2: The 5% strain stress _SL of the laminate is 20 MPa or more.

Condition 3: The peel force between the supporting substrate and the resin layer is 1,000 mN/50 mm or less.

Condition 4: The 150°C heat shrinkage in the longitudinal direction of the laminate is 2.0% or less.

Condition 5: The laminate has a haze of 15% or less.

Methods for measuring 5% strain stress, peel strength, 150° C. heat shrinkage, and haze will be described later. From the viewpoint of flexibility, the laminate of the present invention preferably has a 5% strain stress SF in the resin layer of 10 _MPa or less, more preferably 5 MPa or less, and particularly preferably 3 MPa or less. Setting _SF to a specific range allows greater flexibility.

When the 5% strain stress _SF of the resin layer is within a specific range, flexibility is improved, which is preferable. If the _SF is low, the flexibility is improved, but if it is excessively low, the rigidity may be insufficient, so the lower limit is considered to be about 0.01 MPa. On the other hand, if the SF is higher than 10 _MPa , the flexibility of the resin layer is lowered, which may make it unsuitable for the intended use.

In order to set the 5% strain stress SF of the resin layer to 10 _MPa or less, it is possible, for example, by selecting the material exemplified below for the resin contained in the resin layer.

From the viewpoint of transportability, the laminate of the present invention preferably has a 5% strain stress _SL of 20 MPa or more. By setting _SL within a specific range, the transportability of the laminate can be improved.

When the 5% strain stress _SL of the laminate is within a specific range, the transportability is improved, which is preferable. If the _SL is high, the rigidity is increased and the transportability is improved. On the other hand, when the SL is lower than 20 _MPa , the laminate may have insufficient rigidity and poor transportability, making it unsuitable for post-processing steps.

In order to make the 5% strain stress S _L of the laminate 20 MPa or more, it is possible, for example, by selecting a material exemplified later for the resin contained in the supporting base material.

From the viewpoint of operability, the laminate of the present invention preferably has a peel force _Rb between the support substrate and the resin layer of 1,000 mN/50 mm or less, more preferably 800 mN/50 mm or less. By setting the peel force to a specific value or less, the supporting substrate can be arbitrarily peeled off in the process of manufacturing or using the product manufactured using the laminate of the present invention.

When the peel strength _Rb is low, the supporting substrate can be arbitrarily peeled off in the product manufactured using the laminate of the present invention, which is preferable because the operability of the product is improved. The lower the peel force _Rb , the greater this effect. On the other hand, if the peel force _Rb is higher than 1,000 mN/50 mm, the product manufactured using the laminate of the present invention may have difficulty in peeling, or excessive load may be applied to the flexible resin layer during peeling. It may be unsuitable due to unintended deformation.

The release force _Rb of 1,000 mN/50 mm or less can be achieved, for example, by selecting a specific supporting substrate as described later.

From the viewpoint of transportability, the laminate of the present invention preferably has a longitudinal heat shrinkage rate of 2.0% or less at 150° C., more preferably 1.0% or less. By setting the longitudinal heat shrinkage ratio within a specific range, the transportability and post-processability of the laminate of the present invention can be enhanced.

By setting the longitudinal heat shrinkage rate at 150° C. to the above range, unintended deformation can be suppressed in the transporting process and the post-processing process involving heating, which is preferable because the transportability and post-processing properties are improved. . On the other hand, if the heat shrinkage in the longitudinal direction does not satisfy the above range, unevenness such as wrinkles and irregularities may occur in the film in a so-called post-processing step such as coating of the functional layer, and the film may be unsuitable as a product.

In order to make the longitudinal heat shrinkage rate within the above range, it is possible, for example, by selecting a specific supporting base material as described later.

From the viewpoint of optical properties, the laminate of the present invention preferably has a haze of 15% or less, more preferably 10% or less, and particularly preferably 7.0% or less. By setting the haze of the laminate to a specific range, it is possible to improve the optical quality of the product using the laminate of the present invention, and to improve the product inspectability in the manufacturing process.

In order to make the haze of the laminate within the above range, it is possible, for example, by selecting a specific resin to be described later for the resin layer or by selecting a specific supporting substrate as described later.

Furthermore, from the viewpoint of stretchability, the laminate preferably satisfies Condition 6 below.
Condition 6: The elastic recovery rate of the resin layer is 70% or more in a tensile test method with a deformation amount of 20%.

A method for measuring the elastic recovery rate will be described later.

From the viewpoint of stretchability, the resin layer in the laminate of the present invention preferably has an elastic recovery rate of 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The elastic recovery rate represents the resilience after strain is applied to the resin layer, and even if the flexible resin layer is unintentionally deformed, it can recover to its original shape.

When the elastic recovery rate is large, the resin layer can recover to its original shape even when a large load is applied to the resin layer due to the above-mentioned effect, and the operability is improved, which is preferable. The higher the elastic recovery rate, the better, and the upper limit is basically 100%. On the other hand, if the elastic recovery rate is less than 70%, unrecoverable deformation may occur when a load is applied to the resin layer, making it unsuitable as a product.

In order to achieve an elastic recovery rate of 70% or more in a tensile test method with a deformation amount of 20%, it is possible, for example, by selecting a material exemplified later for the resin contained in the resin layer.

Furthermore, from the viewpoint of resilience after long-term deformation, the laminate preferably satisfies Condition 7 and Condition 8 below.
Condition 7: Stress retention rate, which is the ratio of the stress F1 when the resin layer is stretched to a strain of 100% and the stress F2 after being held in that state for _{1 hour} in the stress relaxation test method at a deformation of 100%. F ₂ /F ₁ ×100 is 70% or more.
Condition 8: In the hysteresis test method with a deformation amount of 100%, the resin layer is stretched to a strain amount of 100%, held for 10 seconds, and then released. , is less than 1.0 MPa.

In the following description, the stress retention rate under condition 7 may be simply referred to as stress retention rate, and the hysteresis area under condition 8 may simply be referred to as hysteresis area.

Methods for measuring stress retention and hysteresis area will be described later.

From the viewpoint of stretchability, the resin layer in the laminate of the present invention preferably has a stress retention rate of 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The stress retention rate indicates the ratio of stress immediately after a constant strain is applied to the resin layer and after the constant strain is maintained for a long period of time. It is a parameter that serves as an indicator of whether it is possible to

When the stress retention rate is high, even when a large load is applied to the resin layer for a long period of time, the resin layer can quickly recover to its original shape due to the aforementioned effect, and the stretchability is improved, which is preferable. The higher the stress retention rate, the better, and the upper limit is basically 100%. On the other hand, if the stress retention rate is less than 70%, the resin layer may be unrecoverably deformed when a load is applied for a long period of time, making it unsuitable as a product.

A stress retention rate of 70% or more can be achieved by, for example, selecting the resin contained in the resin layer from the materials exemplified below.

Furthermore, from the viewpoint of stretchability, the resin layer in the laminate of the present invention preferably has a hysteresis area of less than 1.0 MPa, more preferably 0.5 MPa or less, and particularly preferably 0.3 MPa or less. is. The hysteresis area represents the difference in stress at each strain when a constant strain is applied to the resin layer and when the strain is released. It is an index parameter.

When the hysteresis area is small, even when a large load is applied to the resin layer, the resin layer can quickly recover to its original shape due to the above-mentioned effect, and the stretchability is improved, which is preferable. The smaller the hysteresis area, the better, and the lower limit is basically 0 MPa. On the other hand, if the hysteresis area is 1.0 MPa or more, deformation that cannot be immediately recovered occurs when a load is applied to the resin layer, which may make the product unsuitable.

A hysteresis area of less than 1.0 MPa can be achieved, for example, by selecting the resin contained in the resin layer from the materials exemplified below.

Furthermore, from the viewpoint of quality and suitability for post-processing, the resin layer preferably satisfies Condition 9 below.
Condition 9: The absolute value of the dimensional change rate of the resin layer at 200°C is 10% or less with respect to the dimension of the resin layer at 30°C.

Details of the dimensional change rate will be described later.

From the viewpoint of quality and post-processing suitability, the resin layer in the laminate of the present invention preferably has an absolute value of dimensional change rate of 10% or less, more preferably 8% or less, and particularly preferably 5%. It is below. By setting the absolute value of the dimensional change rate of the resin layer to a certain value or less, unintended deformation is unlikely to occur even when the laminate of the present invention is exposed to heat, and the quality and post-processing suitability can be improved, which is preferable.

When the absolute value of the dimensional change rate is below a certain value, the quality and suitability for post-processing can be improved as described above, which is preferable. This effect increases as the dimensional change rate of the dimensional change rate is smaller. On the other hand, if the absolute value of the dimensional change rate exceeds 10%, the aforementioned quality and suitability for post-processing may become insufficient.

In order to keep the absolute value of the dimensional change rate below a certain value, for example, materials exemplified below can be selected as the resin contained in the resin layer and its precursor.

Furthermore, from the viewpoint of quality, the laminate preferably satisfies Condition 10 below.
Condition 10: The glass transition temperature of the resin layer is 0° C. or lower in the dynamic viscoelasticity method.

Details of the dynamic viscoelasticity method will be described later.

From the viewpoint of quality, in the laminate of the present invention, the glass transition temperature of the resin layer in the dynamic viscoelasticity method is preferably 0 ° C. or lower, more preferably -20 ° C. or lower, and particularly preferably - 30°C or less. By setting the glass transition temperature to a certain value or less, the quality of the laminate can be improved.

When the glass transition temperature of the resin layer takes a constant value, the quality is improved, which is preferable. If the glass transition temperature is low, the quality is improved, but if it is excessively low, the rigidity may be insufficient. On the other hand, if the glass transition temperature is higher than 0° C., the effect of improving the quality of the resin layer may be insufficient.

In order to keep the glass transition temperature of the resin layer within a certain range, for example, the resin contained in the resin layer can be selected from materials exemplified below.

Furthermore, from the viewpoint of quality, the laminate preferably satisfies Condition 11 and Condition 12 below.
Condition 11: The resin layer is a resin composition obtained by curing urethane acrylate having a number average molecular weight of 3,000 or more.
Condition 12: A release layer is provided on at least one surface of the supporting substrate, and the supporting substrate and the resin layer are in contact with each other via the release layer.

From the viewpoint of quality, the resin layer in the laminate of the present invention is preferably a resin composition obtained by curing urethane acrylate having a number average molecular weight of 3,000 or more, more preferably 5,000. That's it. By forming the resin layer from a resin composition obtained by curing urethane acrylate having a number-average molecular weight of at least a certain value, the aforementioned curing can improve the quality of the laminate.

When the number average molecular weight takes a constant value, the quality is improved, which is preferable. This effect increases as the number average molecular weight increases, but the upper limit is considered to be about 200,000 in consideration of the handling when the coating liquid is prepared. On the other hand, if the number average molecular weight is less than 3,000, the aforementioned effect of improving the quality may be insufficient.

In order to set the number average molecular weight to a constant value, for example, materials exemplified below can be selected as the resin contained in the resin layer and its precursor.

Furthermore, in the method for manufacturing the laminate, it is preferable that the following condition 13 is satisfied.
Condition 13: A resin layer is formed by applying the coating composition onto the supporting substrate.

As described above, from the viewpoint of the peel strength between the resin layer and the supporting substrate and the protection of the resin layer, the method for producing a laminate of the present invention is to apply the coating composition onto the supporting substrate to remove the resin. Layers are preferably formed.

[Laminate and resin layer]
The laminate of the present invention may be in a planar state or in a three-dimensional shape after molding as long as it has a resin layer exhibiting the physical properties described above. The number of layers of the resin layer is not particularly limited, and may be formed from one layer, or may be formed from two or more layers.

The thickness of the resin layer is not particularly limited, but the lower limit thereof is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. Further, the upper limit thereof is preferably 500 µm or less, more preferably 100 µm or less, still more preferably 50 µm or less, and particularly preferably 30 µm or less. The thickness of the resin layer can be selected according to the other functions described above.

In addition to flexibility and stretchability, which are the objects of the present invention, the resin layer has glossiness, fingerprint resistance, moldability, designability, scratch resistance, stain resistance, solvent resistance, antireflection, antistatic, It may have other functions such as electrical conductivity, heat reflection, near-infrared absorption, electromagnetic wave shielding, and easy adhesion.

In addition, one or more layers may be further formed on the resin layer, for example, a functional layer, an adhesive layer, an electronic circuit layer, a printed layer, an optical adjustment layer, etc., and other functional layers having the functions described above. may be provided.

[Support base material]
The resin constituting the supporting substrate used in the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homoresin, may be a copolymer or a blend of two or more types. good. It is preferable that the resin constituting the supporting substrate has good moldability, and from this point of view, a thermoplastic resin is more preferable.

Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyimide resins, polyester resins, polycarbonate resins, Fluorine such as polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene-hexafluoropropylene 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. From the viewpoint of strength, heat resistance, and transparency, the thermoplastic resin is more preferably polyester resin, polycarbonate resin, acrylic resin, or methacrylic resin.

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

Various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant 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.

Various surface treatments may be applied to the surface of the supporting substrate before forming the resin layer. Examples of surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred.

In addition to the resin layer of the present invention, functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, an ultraviolet absorption layer, and a release layer may be provided in advance on the surface of the support substrate. 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 support substrate and the resin layer.

Examples of films made of a polyester resin provided with the aforementioned release layer include "Therapeel" (registered trademark) manufactured by Toray Advanced Film Co., Ltd., "Unipeel" (registered trademark) manufactured by Unitika Ltd., Panac Co., Ltd. "PanaPeel" (registered trademark) manufactured by the company, "Toyobo Ester" (registered trademark) manufactured by Toyobo Co., Ltd., and "Purex" (registered trademark) manufactured by Teijin Limited can be mentioned, and these products are used. can do.

[Paint composition]
The method for producing the laminate of the present invention is not particularly limited, but the laminate of the present invention includes a step of applying a coating composition to at least one of the above-described supporting substrates, and a step of drying and curing as necessary. can be obtained through Here, the "coating composition" is a liquid consisting of a solvent and a solute, and a material capable of forming a resin layer by coating it on the above-mentioned supporting substrate, volatilizing the solvent in a drying process, removing it, and curing it. Point. Here, the “type” of the coating composition refers to liquids in which even a part of the type of solute constituting the coating composition is different. This solute includes resins or materials capable of forming them in the coating process (hereafter referred to as precursors), particles, and polymerization initiators, curing agents, catalysts, leveling agents, UV absorbers, antioxidants, etc. Consists of various additives.

Moreover, in the laminate of the present invention, it is preferable to form the resin layer by applying the coating composition A onto the supporting substrate.

[Paint composition A]
The coating composition A is a liquid containing a material suitable for forming the resin layer of the present invention, or a precursor that can be formed, and a resin containing the following segments (1) to (3) as a solute: Alternatively, it preferably contains a precursor.
(1) a segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment and a polyalkylene glycol segment (2) a urethane bond (3) from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment A segment containing at least one selected.

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

Further, the parts by mass of the above (1), (2), and (3) contained in the coating composition A are (1)/(2)/(3) = 95/5/1 to 50/50/15 is preferred, and (1)/(2)/(3)=90/10/1 to 60/40/10 is more preferred. 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 resin constituting the layer A on the surface of the resin layer has these segments, so that the stretchability and Flexibility can be improved.

Although the details of the urethane bond will be described later, the presence of this bond in the resin constituting layer A on the surface of the resin layer can improve the toughness and stretchability of the entire resin layer.

Details of the fluorine compound segment, the polysiloxane segment, and the polydimethylsiloxane segment will be described later, but by including these in the resin constituting the resin layer, 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 layer.

Another example of a preferred resin for the solute of the coating composition A is urethane acrylate. Various general-purpose products are available for urethane acrylate, and it is also possible to synthesize materials with various physical properties depending on the purpose.

In the present invention, one of the more preferred modes is a method of lowering the glass transition temperature of the resin layer, and one of the means for this is to select the type of urethane acrylate. Also, as one of the more preferable modes, it is possible to use a resin composition obtained by curing urethane acrylate having a certain number average molecular weight for the resin layer. can be selected.

Examples of commercially available urethane acrylates include urethane acrylate manufactured by Asia Industry Co., Ltd., urethane acrylate manufactured by Kyoeisha Chemical Co., Ltd., urethane acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., urethane acrylate manufactured by Taisei Fine Chemical Co., Ltd., and urethane acrylate manufactured by Taisei Fine Chemical Co., Ltd. "New Frontier" (registered trademark) manufactured by Ichi Kogyo Seiyaku, "EBECRYL" (registered trademark) manufactured by Daicel Allnex Co., Ltd., "Shiko" (registered trademark) manufactured by Nippon Gosei Co., Ltd., Urethane acrylate manufactured by DIC Corporation etc., and these products can be used.

[Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]
First, the polycaprolactone segment refers to the segment represented by Chemical Formula 1. Polycaprolactone 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 from 1 to 35.

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

As the resin containing polycaprolactone segments, polycaprolactone having di- or tri-functional hydroxyl groups is particularly preferred. Specifically, polycaprolactone diol represented by chemical formula 2,

Here, m+n is an integer of 4 to 35, m and n are each an integer of 1 to 34, 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 Chemical Formula 3,

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

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

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

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

Next, the polyalkylene glycol segment refers to the segment represented by Chemical Formula 5. Polyalkylene glycols include those having 2 (dimer) and 3 (trimer) repeating units of alkylene glycol, and oligomers having up to 11 repeating units of alkylene glycol.

n is an integer of 2-4 and m is an integer of 2-11.

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

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

Examples of the polyalkylene glycol (meth)acrylate contained in the coating composition used to form the resin layer include polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, and polybutylene glycol (meth)acrylate. . They are structures represented by the following chemical formulas 6, 7 and 8, respectively.

Polyethylene glycol (meth)acrylate:

Polypropylene glycol (meth)acrylate:

Polybutylene glycol (meth)acrylate:

In chemical formulas 6, 7 and 8, R is hydrogen (H) or a methyl group (--CH ₃ ), and m is an integer of 2-11.

In the present invention, preferably, a compound containing an isocyanate group, which will be described later, is reacted with a hydroxyl group of (poly)alkylene glycol (meth)acrylate and used as urethane (meth)acrylate in the resin layer, thereby forming the resin layer. However, it can have (2) a urethane bond and (3) a (poly)alkylene glycol segment, and as a result, it is possible to improve the toughness of the resin layer as well as the stretchability and flexibility, which is preferable.

Hydroxyalkyl (meth)acrylates to be blended at the same time during the urethanization reaction between the compound containing an isocyanate group and the 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 the segment represented by Chemical Formula 9. Polycarbonates include those having 2 (dimer), 3 (trimer) repeating carbonate units, and oligomers having up to 16 repeating carbonate units.

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

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

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

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

The polycarbonate diol may have any number of repetitions of carbonate units, but if the number of repetitions of carbonate units is too large, the strength of the cured product of urethane (meth)acrylate decreases, so the number of repetitions should be 10 or less. is preferred. The polycarbonate diol may be a mixture of two or more 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. If the number-average molecular weight is less than 500, it may be difficult to obtain suitable flexibility, and if the number-average molecular weight exceeds 10,000, the heat resistance and solvent resistance may decrease. is.

The polycarbonate diols used in the present invention include UH-CARB, UD-CARB, UC-CARB (Ube Industries, Ltd.), PLACCEL CD-PL, PLACCEL CD-H (DAICEL CHEMICAL INDUSTRIES, LTD.), and Kuraray Polyol C. Products such as the series (Kuraray Co., Ltd.) and the Duranol series (Asahi Kasei Chemicals Corporation) can be preferably exemplified. These polycarbonate diols can be used alone or in combination of two or more.

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

In the present invention, preferably, a compound containing an isocyanate group, which will be described later, is reacted with a hydroxyl group of a polycarbonate diol and used as a urethane (meth)acrylate for the resin layer, so that the resin constituting the resin layer is the above-mentioned (2). It can have a urethane bond and (1) a polycarbonate diol segment, and as a result, it is possible to improve the toughness of the resin layer as well as its stretchability and flexibility.

[Compound containing urethane bond and isocyanate group]
In the present invention, "urethane bond" refers to a bond represented by Chemical Formula 11.

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

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

In the present invention, it is preferable to introduce a urethane bond into the resin constituting the resin layer 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 and stretchability of the resin layer.

In the case of resins containing the above-mentioned polycaprolactone segment, polycarbonate segment, or polyalkylene glycol segment, or if they have hydroxyl groups, urethane bonds are generated between these resins and compounds containing isocyanate groups as precursors by heat or the like. It is also possible to let

When a resin layer is formed using a compound containing an isocyanate group, a resin containing a polysiloxane segment having a hydroxyl group described later, or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the toughness and elasticity of the resin layer are improved. In addition to this, it is possible to improve the slipperiness of the surface, 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, or a monomer or oligomer containing an isocyanate group. Compounds containing an isocyanate group include, for example, methylenebis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Examples include (poly)isocyanates such as isocyanurates, isocyanurates of hexamethylene diisocyanate, burettes of hexamethylene isocyanate, and blocked isocyanates.

Among these isocyanate group-containing compounds, aliphatic isocyanates are more preferable than alicyclic or aromatic isocyanates because of their high stretchability and flexibility. The compound containing isocyanate groups is more preferably hexamethylene diisocyanate. As for the isocyanate group-containing compound, an isocyanate having an isocyanurate ring is particularly preferable in terms of heat resistance, and an isocyanurate form of hexamethylene diisocyanate is most preferable. An isocyanate having an isocyanurate ring forms a resin layer having both stretchability and heat resistance.

[Fluorine compound segment, polysiloxane segment, polydimethylsiloxane segment]
In the laminate of the present invention, the resin constituting the resin layer preferably has a segment containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment.

Furthermore, a resin containing a segment containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment, or a paint composition A containing a precursor is added to the paint composition A that forms the resin layer. By using one, the resin constituting the resin layer can have these.

The fluorine compound segment, polysiloxane segment, and polydimethylsiloxane segment are described below.

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

Here, the fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoroalkanediyl group, and fluorooxyalkanediyl group refer to hydrogen atoms of alkyl groups, oxyalkyl groups, alkenyl groups, alkanediyl groups, and oxyalkanediyl groups. A substituent partially or wholly substituted by fluorine, all of which are substituents mainly composed of fluorine atoms and carbon atoms, may have branches in the structure, and a structure having these sites Multiple linked dimers, trimers, oligomers and polymer structures may be formed.

Further, the fluorine compound segment is preferably a fluoropolyether segment, which is a site composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, etc., and is more preferably represented by chemical formulas 5 and 6. As already mentioned, it is a fluoropolyether segment.

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

Here, n1 is an integer of 1 to 3, n2 to n5 are integers of 1 or 2, k, m, p, and s are integers of 0 or more, and p+s is 1 or more. Preferably, n1 is 2 or more, n2 to n5 are integers of 1 or 2, more preferably n1 is 3, n2 and n4 are 2, and n3 and n5 are integers of 1 or 2.
The chain length of this fluoropolyether segment has a preferred range, and the number of carbon atoms is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. If the number of carbon atoms is 3 or less, the surface energy may not be sufficiently reduced, resulting in a decrease in oil repellency.

When the resin contained in this resin layer contains a fluorine compound segment, the coating composition A preferably contains the following fluorine compounds. This fluorine compound is a compound represented by Chemical Formula 14.

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

This reactive site refers to a site that reacts with other components by external energy such as heat or light. Examples of such reactive sites include alkoxysilyl groups and silanol groups obtained by hydrolyzing alkoxysilyl groups from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, methacryloyl groups, and the like. mentioned. Of these, vinyl groups, allyl groups, alkoxysilyl groups, silyl ether groups, silanol groups, epoxy groups, and acryloyl (methacryloyl) groups are preferred from the viewpoint of reactivity and handling.

An example of the fluorine compound is the compound shown below. 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropyltriisopropoxysilane, 3,3,3-trifluoropropyltrichlorosilane, 3,3,3-trifluoropropyltriisocyanatesilane, 2-perfluorooctyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethyltriisopropoxysilane, 2-perfluorooctylethyltri Chlorosilane, 2-perfluorooctyl isocyanate silane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluorobutyl -2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorohexyl-2-hydroxypropyl acrylate Fluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro- 5-methylhexyl-2-hydroxypropyl acrylate, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, dodecafluoroheptyl acrylate, hexadecafluorononyl acrylate, hexafluoro Butyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2 -perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2- Hydroxypropyl methacrylate, 2-perfluoro-5-methyl Hexylethyl methacrylate, 3-perfluoro-5-methylhexyl-2-hydroxypropyl methacrylate, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoro Pentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, triacryloyl-heptadecafluorononenyl-pentaerythritol and the like.

In addition, the fluorine compound may have a plurality of fluoropolyether moieties per molecule.
Commercially available examples of the fluorine compound include RS-75 (DIC Corporation), OPTOOL DAC-HP (Daikin Industries, Ltd.), C10GACRY, C8HGOL (Yushi Products Co., Ltd.), and the like. product can be used.

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

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

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

Although the details of the polysiloxane segment and the polydimethylsiloxane segment will be described later, the presence of these segments in the resin constituting the resin layer improves heat resistance and weather resistance, and improves slipperiness due to the lubricity of the resin layer. can be improved. More preferably, it contains a polydimethylsiloxane segment represented by Chemical Formula 16 described below from the viewpoint of lubricity.

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 is added with a polysiloxane segment. It can be used as a resin to be contained.

Resins containing polysiloxane segments include tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane. Complete or partial hydrolyzate of silane compound having hydrolyzable silyl group such as alkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, organosilica sol dispersed in organic solvent, hydrolyzable silyl group on surface of organosilica sol can be exemplified by addition of a hydrolyzed silane compound.

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

When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, the resin using a coating composition containing a resin (copolymer) containing a polysiloxane segment having a hydroxyl group and a compound containing an isocyanate group By forming the layer, a resin layer having polysiloxane segments and urethane bonds can be efficiently obtained.

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

m is an integer from 10 to 300;

When the resin constituting the resin layer has polydimethylsiloxane segments, the polydimethylsiloxane segments are coordinated to the surface of the resin layer. By coordinating the polydimethylsiloxane segment to the surface of the resin layer, the lubricity of the resin layer surface can be improved and the frictional resistance can be reduced. It is also preferable from the viewpoint of solvent resistance.

In the present invention, a copolymer obtained by copolymerizing a polydimethylsiloxane segment with a vinyl monomer is preferably used as the resin containing the polydimethylsiloxane segment.

For the purpose of improving the toughness of the resin layer, 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. When the resin layer is formed by using the above method, it is possible to efficiently obtain a resin layer having polydimethylsiloxane segments and urethane bonds.

When the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, it may be a block copolymer, a graft copolymer, or a random copolymer. When a resin containing polydimethylsiloxane segments is a copolymer with a vinyl monomer, it is called a polydimethylsiloxane-based copolymer. A polydimethylsiloxane copolymer can be produced by a living polymerization method, a polymer initiator method, a polymer chain transfer method, or the like. preferably used.

When the polymer initiator method is used, a polymer azo radical polymerization initiator represented by Chemical Formula 17 can be used for copolymerization with other vinyl monomers. In addition, a two-stage 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 the side chain, and the prepolymer is copolymerized with a vinyl monomer. can also be done.

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

When using the polymer chain transfer method, for example, HS—CH ₂ COOH, HS—CH ₂ CH ₂ COOH, or the like is added to the silicone oil represented by the chemical formula 18 to obtain a compound having an SH group, and then the SH group is added. A block copolymer can be synthesized by copolymerizing the silicone compound and a vinyl monomer using chain transfer.

m is an integer from 10 to 300;

To synthesize a polydimethylsiloxane-based graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound represented by Chemical Formula 19, that is, a methacrylic ester of polydimethylsiloxane or the like, with a vinyl monomer. can.

m is an integer from 10 to 300;

Vinyl monomers used in copolymers with polydimethylsiloxane include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-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-methylolacrylamide, N, N-dimethylacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, diacetitone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , allyl alcohol, and the like.

In addition, polydimethylsiloxane copolymers can be used in aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, isopropyl alcohol, and the like. is preferably produced by solution polymerization in an alcohol-based solvent or the like alone or in a mixed solvent.

A polymerization initiator such as benzoyl peroxide or azobisisobutylnitrile is used in combination as necessary. The polymerization reaction is preferably carried out at 50-150° C. for 3-12 hours.

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

In the present invention, when a resin containing a polydimethylsiloxane segment is used as the coating composition used to form the resin layer, other segments or the like are contained (copolymerized) in addition to the polydimethylsiloxane segment. may For example, it may contain (copolymerize) a polycaprolactone segment or a polysiloxane segment.

The coating composition used for forming the resin layer includes copolymers of polycaprolactone segments and polydimethylsiloxane segments, copolymers of polycaprolactone segments and polysiloxane segments, polycaprolactone segments, polydimethylsiloxane segments and poly A copolymer with a siloxane segment or the like can be used. A resin layer obtained 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, the polycaprolactone, and the polysiloxane in the coating composition used to form the resin layer having the polycaprolactone segment, the polysiloxane segment, and the polydimethylsiloxane segment is the polydimethylsiloxane-based At the time of copolymer synthesis, a polycaprolactone segment and a polysiloxane segment can be appropriately added for copolymerization.

[solvent]
The coating composition may contain a solvent. The number of types of solvents is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 4.

As used herein, the term "solvent" refers to a substance that is liquid at normal temperature and normal pressure and can be almost completely evaporated in the drying process after application.

Here, the type of solvent is determined by the molecular structure that constitutes the solvent. That is, even if the elemental composition is the same and the type and number of functional groups are the same, the bonding relationship is different (structural isomers). Those that do not overlap exactly (stereoisomers) 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, the solvent preferably exhibits 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 n-butyl acetate as a solvent 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 greater than 0.4, the time required for the orientation of the polysiloxane segment and/or polydimethylsiloxane segment and the fluorine compound segment to the outermost surface in the resin layer is shortened. Therefore, the solvent resistance of the resin layer in the resulting laminate may be lowered. Further, the lower limit of the relative evaporation rate of the solvent is not a problem as long as the solvent can be evaporated and removed from the coating film in the drying process, and in a general coating process, it is sufficient if it is 0.005 or more.

As solvents, 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 the coating composition]
Moreover, the coating composition A preferably contains a polymerization initiator, a curing agent, and a catalyst. Polymerization initiators and catalysts are used to accelerate the curing of the resin layer. As the polymerization initiator, those capable of initiating or promoting the polymerization, condensation or crosslinking reaction of components contained in the coating composition by anionic, cationic or radical polymerization reactions are preferred.

Various polymerization initiators, curing agents and catalysts can be used. The polymerization initiator, curing agent and catalyst may be used singly, or multiple polymerization initiators, curing agents and catalysts may be used simultaneously. Furthermore, an acidic catalyst or a thermal polymerization initiator may be used in combination. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid, and the like. Examples of thermal polymerization initiators include peroxides and azo compounds. Examples of photopolymerization initiators include alkylphenone-based compounds, sulfur-containing compounds, acylphosphine oxide-based compounds, and amine-based compounds. Examples of cross-linking catalysts that promote the formation reaction of urethane bonds include dibutyltin dilaurate and dibutyltin diethylhexoate.

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

As the photopolymerization initiator, an alkylphenone-based compound is preferable from the viewpoint of curability. Specific examples of alkylphenone-type compounds 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-phenylketone, 2-methyl-1-phenylpropan-1-one, 1-[4-(2-ethoxy )-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, and high molecular weight products of these materials. .

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

[Laminate production method]
The resin layer formed on the supporting base material of the laminate of the present invention is preferably formed by coating the above-described resin layer coating composition on the above-described supporting base material, drying, and curing. Hereinafter, the process of applying the coating composition will be described as the coating process, the process of drying will be described as the drying process, and the process of curing will be described as the curing process. As the coating composition for the resin layer, two or more coating compositions may be applied successively or simultaneously to form a resin layer consisting of two or more layers.

Here, "sequentially applying" means that one type of coating composition is applied to the supporting substrate, dried and cured, and then another coating composition is applied and dried. , means that a resin layer consisting of two or more layers is formed by curing. By appropriately selecting the type of coating composition to be used, the magnitude and gradient of flexibility and stretchability between the resin layer side and the supporting base material side of the resin layer, the flexibility and stretchability of the supporting base material and the resin layer, etc. can be controlled. Furthermore, by appropriately selecting the type, composition, drying conditions, and curing conditions of the coating composition, the form of distribution of flexibility and stretchability in the resin layer can be controlled stepwise or continuously.

In addition, "coating at the same time" means that in the coating step, two or more types of coating compositions are simultaneously coated on a supporting substrate, followed by drying and curing.

In the coating step, the method of applying the coating composition is not particularly limited. It is preferable to apply to the supporting substrate by. Furthermore, among these coating methods, the gravure coating method or the die coating method is more preferable as the coating method.

When two or more coating compositions are applied simultaneously, methods such as multi-layer slide die coating, multi-layer slot die coating, and wet-on-wet coating can be used without particular limitation.

An example of multilayer slide die coating is shown in FIG. In multi-layer slide die coating, liquid films composed of two or more kinds of coating compositions are laminated in order using a multi-layer slide die 17, and then coated onto a support substrate.

An example of a multi-layer slot die coat is shown in FIG. In multi-layer slot die coating, a multi-layer slot die 18 is used to apply and simultaneously laminate liquid films composed of two or more types of coating compositions onto a support substrate.

An example of wet-on-wet coating is shown in FIG. In wet-on-wet coating, after forming a one-layer liquid film made of a coating composition discharged from a single-layer slot die 19 on a supporting substrate, the liquid film is in an undried state. A liquid film composed of another coating composition discharged from the single-layer slot die 19 is laminated.

Following the application step, the liquid film applied on the support substrate is dried in a drying step. From the viewpoint of completely removing the solvent from the resulting laminate, the drying step is preferably accompanied by heating of the liquid film.

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

The drying process of the liquid film in the drying process is generally divided into (A) constant rate drying period and (B) decreasing rate drying period. In the former, the rate of drying is controlled by the diffusion of solvent molecules into the atmosphere on the surface of the liquid film. , and the film surface temperature becomes constant at a value determined by the hot air temperature and the partial pressure of the evaporated solvent in the atmosphere. In the latter case, the diffusion of the solvent in the liquid film is rate-determining, so the drying rate does not show a constant value in this interval and continues to decrease. Rise. Here, the drying speed represents the amount of solvent evaporated per unit time and unit area, and has the dimension of g·m ⁻² ·s ⁻¹ .

The drying rate is preferably 0.1 g·m ⁻² ·s ⁻¹ or more and 10 g·m ⁻² ·s ⁻¹ or less, and 0.1 g·m ⁻² ·s ⁻¹ or more and 5 g·m ⁻² · s ⁻¹ or less is more preferable. By setting the drying speed in the constant rate drying section within this range, it is possible to prevent unevenness caused by non-uniformity of the drying speed.

Although it is not particularly limited as long as a preferable drying speed can be obtained, the temperature is preferably 15° C. to 129° C., more preferably 50° C. to 129° C., more preferably 50° C. in order to obtain the above drying speed. to 99°C is particularly preferred.

During the declining rate drying period, the remaining solvent evaporates and the polysiloxane segment and/or the polydimethylsiloxane segment and/or the fluorine compound segment are oriented. Since this process requires time for orientation, the film surface temperature rise rate during the declining rate drying period is preferably 5° C./second or less, more preferably 1° C./second or less.

The drying step may be followed by a further curing operation (curing step) by irradiating heat or active energy rays.

As the active energy rays, electron beams (EB rays) and/or ultraviolet rays (UV rays) are preferable from the viewpoint of versatility. When curing with ultraviolet rays, the oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable. When the oxygen concentration is high, the hardening of the outermost surface is inhibited, the hardening of the surface becomes weak, and the toughness may decrease. Further, the types of ultraviolet lamps used for irradiating ultraviolet rays include, for example, a discharge lamp method, a flash method, a laser method, an electrodeless lamp method, and the like. When a discharge lamp type high-pressure mercury lamp is used, the ultraviolet illuminance is preferably 100 to 3,000 mW/cm ² , more preferably 200 to 2,000 mW/cm ² , still more preferably 300 to 1,500 mW/cm ² . UV irradiation is preferably performed under the following conditions. Ultraviolet irradiation can be carried out under the condition that the integrated amount of ultraviolet light is preferably 100 to 3,000 mJ/cm ² , more preferably 200 to 2,000 mJ/cm ² , and still more preferably 300 to 1,500 mJ/cm ² . preferable. Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and varies depending on the lamp output, the emission spectral efficiency, the diameter of the light-emitting bulb, the design of the reflecting mirror, and the distance from the light source to the irradiated object. However, the illuminance does not change with the transport speed. Further, the cumulative amount of ultraviolet light is the irradiation energy received per unit area, and is the total amount of photons that reach the surface. The integrated amount of light is inversely proportional to the irradiation speed passing under the light source, and proportional to the number of times of irradiation and the number of lamp lights.

[Example of use]
The laminate of the present invention can be suitably used for applications that require particularly high flexibility and stretchability, taking advantage of the advantages of excellent optical properties, flexibility, stretchability and transportability.

Examples include glasses/sunglasses, cosmetic boxes, plastic molded products such as food containers, water tanks, showcases for exhibitions, etc., smartphone housings, touch panels, color filters, flat panel displays, flexible displays, flexible devices, and wearables. Devices, sensors, circuit materials, electrical and electronic applications, home appliances such as keyboards, TV/air conditioner remote controls, mirrors, window glass, buildings, dashboards, car navigation/touch panels, vehicle parts such as rearview mirrors and windows, etc. printed matter, medical film, sanitary material film, medical film, agricultural film, building material film, etc., can be suitably used for each surface material, internal material, constituent material, and manufacturing process material.

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

[Urethane (meth)acrylate A]
[Synthesis of urethane (meth)acrylate A1]
50 parts by mass of toluene, isocyanurate-modified type of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.) 50 parts by mass, polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA5 manufactured by Daicel Chemical Industries, Ltd.) 76 parts by mass, 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and maintained at 70° C. for 5 hours. After that, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth)acrylate A1 with a solid content concentration of 50% by mass. Urethane (meth)acrylate A1 had a number average molecular weight of 2,000.

[Urethane (meth)acrylate B]
[Synthesis of urethane (meth)acrylate B1]
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Hakko Kirin Co., Ltd.) and 119 parts by mass of polycarbonate diol (“PLAXEL” (registered trademark) CD-210HL manufactured by Daicel Chemical Industries, Ltd.) The parts were mixed, heated to 40° C. and held 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 holding the mixture at 70°C for 30 minutes, 0.02 parts by mass of dibutyl tin laurate was added and the mixture was held at 80°C for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane (meth)acrylate B1 with a solid content concentration of 50% by mass. Urethane (meth)acrylate B1 had a number average molecular weight of 5,800.

[Urethane (meth)acrylate C]
[Synthesis of urethane (meth)acrylate C1]
Isocyanurate modified form of hexamethylene diisocyanate ("Takenate" (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc., isocyanate group content: 20.9% by mass) 50 parts by mass, polyethylene glycol monoacrylate (manufactured by NOF Corporation 53 parts by weight of "Blemmer" (registered trademark) AE-150, hydroxyl value: 264 (mgKOH/g)), 0.02 parts by weight of dibutyltin laurate and 0.02 parts by weight of hydroquinone monomethyl ether were charged. Then, the reaction was carried out by holding at 70° C. for 5 hours. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter also referred to as MEK) was added to the reaction solution to obtain urethane (meth)acrylate C1 with a solid content concentration of 50% by mass. Urethane (meth)acrylate C1 had a number average molecular weight of 2,000.

[Urethane (meth)acrylate D]
[Urethane (meth)acrylate D1]
SUA-017 (manufactured by Asia Industry Co., Ltd., solid content concentration 100% by mass) having a number average molecular weight of 4,600 was used as urethane (meth)acrylate D1.

[Urethane (meth)acrylate E]
[Urethane (meth)acrylate E1]
As urethane (meth)acrylate E1, UV-3500BA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 70% by mass) having a number average molecular weight of 13,000 was used.

[Polyol compound]
[Polyol compound 1]
As the polyol compound 1, "PLAXEL" (registered trademark) 210CP (manufactured by Daicel Chemical Industries, Ltd., solid content concentration 100% by mass) was used.

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

[Radical photopolymerization initiator]
[Radical photopolymerization initiator 1]
As the radical photopolymerization initiator 1, "Irgacure" (registered trademark) 184 (manufactured by BASF Japan Ltd., solid concentration: 100% by mass) was used.

[Preparation of coating composition A]
[Paint composition A1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate A1 solution (solid content concentration: 50% by mass) 100 parts by mass ・Photoradical polymerization initiator 1 1.5 parts by mass.

[Paint composition A2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate B1 solution (solid concentration: 50% by mass): 100 parts by mass ・Photoradical polymerization initiator 1: 1.5 parts by mass.

[Paint composition A3]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate C1 solution (solid content concentration 50 mass%) 100 mass parts ・Fluorine compound 1 solution (solid content concentration 40 mass%) 3.8 mass parts ・Photoradical polymerization initiator 1 1.5 mass parts ・Ethylene glycol monobutyl ether 10 parts by mass.

[Paint composition A4]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate A1 solution (solid content concentration 50% by mass) 50 parts by mass ・Urethane (meth)acrylate B1 solution (solid content concentration 50% by mass) 50 parts ・Fluorine compound 1 solution (solid content concentration 40% by mass) ) 3.8 parts by mass, photoradical polymerization initiator 1 1.5 parts by mass, and 10 parts by mass of ethylene glycol monobutyl ether.

[Paint composition A5]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate B1 solution (solid content concentration 50% by mass) 50 parts by mass ・Urethane (meth)acrylate C1 solution (solid content concentration 50% by mass) 50 parts by mass ・Photoradical polymerization initiator 1 1.5 parts by mass .

[Paint composition A6]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate D1 (solid concentration: 100% by mass) 50 parts by mass ・Photoradical polymerization initiator 1 1.5 parts by mass.

[Paint composition A7]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate B1 (solid concentration: 100% by mass) 90 parts by mass ・Polyol compound 1 (solid concentration: 100% by mass) 5 parts by mass ・Photoradical polymerization initiator 1: 1.5 parts by mass.

[Paint composition A8]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate D1 (solid concentration: 100% by mass) 45 parts by mass ・Urethane (meth)acrylate A1 solution (solids concentration: 50% by mass) 10 parts by mass ・Photoradical polymerization initiator 1: 1.5 parts by mass.

[Paint composition A9]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 having a solid concentration of 30% by mass.
・Urethane (meth)acrylate E1 (solid concentration: 70% by mass) 71 parts by mass ・Photoradical polymerization initiator 1: 1.5 parts by mass.

[Support base material]
[Support base material A1]
"Therapeal" (registered trademark) SY (thickness: 38 µm, manufactured by Toray Advanced Film Co., Ltd.) was used as the supporting substrate A1.

[Support base material B1]
As the supporting substrate B1, "Lumirror" (registered trademark) U48 (thickness: 50 µm, manufactured by Toray Industries, Inc.) was used.

[Thermoplastic urethane film]
[Thermoplastic urethane film 1]
As the thermoplastic urethane film 1, "Esmer" (registered trademark) URS PX98 (thickness: 150 µm, manufactured by Nihon Matai Co., Ltd.) was used.

As a result of confirming the structure of "ESMER" (registered trademark) URS PX98, a layer of polyester film with a thickness of 50 μm, a layer of thermoplastic urethane film with a thickness of 150 μm, and a layer of polyester film with a thickness of 75 μm were laminated in this order. was the configuration. Therefore, the 50 μm polyester film was peeled off, and the state in which the thermoplastic urethane film and the 75 μm polyester film were laminated was treated as a laminate, which was referred to as Reference Example 1.

[Method for producing laminate and resin film]
[Production of laminate]
The coating composition A was applied onto the supporting substrate using a slot die coater and a continuous coating device, adjusting the discharge flow rate from the slot so that the thickness of the resin layer after drying would be the specified thickness. The conditions for the drying air that hits the liquid film during the period from application to drying and curing are as follows.

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

[Preparation of resin film]
The coating composition A was applied onto the supporting substrate using a slot die coater and a continuous coating device, adjusting the discharge flow rate from the slot so that the thickness of the resin layer after drying would be the specified thickness. The conditions for the drying air that hits the liquid film during the period from application to drying and curing are as follows.

Furthermore, the resin layer was peeled off from the support substrate, treated as a resin film, and evaluated in the same manner as the laminate and the resin layer.

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

Laminates and resin films of Examples 1 to 10 and Comparative Examples 1 and 2 were prepared by the above method. The method for producing the laminate and the resin film corresponding to each example and comparative example, and the film thickness of each layer are shown in Table 2 below.

[Evaluation of laminate, resin layer, and resin film]
The laminate, resin layer, and resin film were subjected to the following performance evaluations, and the results obtained are shown in Table 2. Unless otherwise specified, the measurement was performed three times for each sample in each example and comparative example at different locations, and the average value was used.

The resin film was regarded as equivalent to the laminate and the resin layer, and was evaluated in the same manner.

Some of the evaluation results of Comparative Examples 1 and 2 were omitted because they were clearly judged to be unsuitable.

[Laminate, resin layer, thickness of resin film]
The thickness of the laminate, the resin layer, 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 using software (image processing software ImageJ) from images of cross-sectional sections of the laminate, the resin layer, and the resin film taken by SEM at a magnification of 3,000. The average value obtained by measuring the layer thickness at a total of 30 points was used as the measured value.

[5% strain stress]
In the evaluation of the laminate, a rectangular test piece of 10 mm width×150 mm length was cut out from the laminate. In the evaluation of the resin layer and the resin film, the laminate was cut into a rectangle having a width of 10 mm and a length of 150 mm, and then the resin layer was peeled off from the support substrate to obtain a test piece. The direction of each 150 mm length was aligned with the longitudinal direction of the laminate. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec Co., Ltd.), a tensile test was performed at a measurement temperature of 23° C. with an initial tension chuck distance of 50 mm and a tensile speed of 300 mm/min.

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

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

[Peeling force R _b ]
In the laminate, the supporting substrate and the resin layer were slightly peeled off from the ends in advance to form gripping margins for measurement with a tensile tester. Next, the resistance value (N) was measured at 180° peeling at a speed of 300 (mm/min) using a tensile tester under an environment of 23°C and 65% RH. The resistance value (N) was divided by the width (mm) of the support base material and the resin layer, multiplied by 50, and converted into a peel force (mN/50 mm) corresponding to a width of 50 mm.

[Heat shrinkage rate]
The laminate was cut into a rectangle of 10 mm width×200 mm length to obtain a test piece. A test piece with a length of 200 mm aligned with the longitudinal direction of the laminate was prepared, and the thermal shrinkage rate in the longitudinal direction was obtained.

First, in the 200 mm length direction of the cut test piece, marked lines were drawn in the width direction at positions 25 mm from each end so that the distance between the marked lines was 150 mm. Next, one end of the test piece was fixed in a hot air oven, and a weight was attached to the other end so as to apply a load of 3 g. The hot air oven was preheated to 150° C., and heat treatment was performed for 30 minutes while the test piece was placed. After that, the test piece was taken out from the hot air oven, and after confirming that the test piece had cooled to room temperature, the distance x (mm) between each marked line attached before the heat treatment was measured.

Using the obtained values, the thermal shrinkage rate (%) at 150° C. was calculated by the following formula.

(Thermal shrinkage rate) = ((150-x)/150) x 100.

[Haze]
A piece of 100 mm width×100 mm length was cut from the laminate to obtain a test piece. Haze was measured using a haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K 7136 (2000).

[Elastic recovery rate]
The resin layer and the resin film were cut into a rectangle of 10 mm width×150 mm length to obtain a test piece. The direction of each 150 mm length was aligned with the longitudinal direction of the laminate. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec), a tensile test was performed at a measurement temperature of 23° C. with an initial tension chuck distance of 50 mm and a tensile speed of 50 mm/min. At that time, after stretching the sample to a strain amount of 10 mm (=20%), the tensile load on the sample was released. This test method is referred to as a tensile test method with a deformation amount of 20%.

The distance marked as the initial test length before the measurement was measured as L mm, and the elastic recovery rate z% was calculated from the following formula.
Elastic recovery rate: z=(1-(L-50)/20)×100 (%).

[Stress retention rate]
A rectangular specimen of 10 mm width×120 mm length was cut out of the resin layer and used as a test piece. In Comparative Example 2, a single resin film was used as a test piece. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec), a tensile test was performed at a measurement temperature of 23° C. with an initial tension chuck distance of 20 mm and a tensile speed of 300 mm/min. At that time, the sample was stretched to a strain amount of 20 mm (=100%) and held in that state for 1 hour. The stress was measured at intervals of 1 second while the strain was held at 100% for 1 hour from the start of stretching. This test method is referred to as a stress relaxation test method with a deformation amount of 100%.

The stress retention rate F ₂ /F ₁ ×100 was calculated with F ₁ being the stress when the strain amount reached 100% from the start of stretching and F ₂ being the stress when the strain amount was held at 100% for 1 hour.

[Hysteresis area]
A rectangular specimen of 10 mm width×120 mm length was cut out of the resin layer and used as a test piece. In Comparative Example 2, a single resin film was used as a test piece. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec), a tensile test was performed at a measurement temperature of 23° C. with an initial tension chuck distance of 20 mm and a tensile speed of 300 mm/min. At that time, the sample was stretched to a strain amount of 20 mm (=100%), held in that state for 10 seconds, and then similarly restored to a strain amount of 0 mm (=0%) at a tensile speed of 300 mm/min. A strain amount of 100% was maintained for 10 seconds from the start of stretching, and the stress was measured at intervals of 0.01 seconds while the strain amount was restored to 0%. This test method is referred to as a hysteresis test method with a deformation amount of 100%.

From the start of stretching, the stress-strain curve obtained while the strain amount reaches 100%, and the stress-strain curve obtained while the strain amount is restored to 0% after holding the strain amount of 100% for 10 seconds. Surrounded by the strain curve. The hysteresis area (MPa) was calculated.

An example of the hysteresis area is shown in FIG. The shaded area surrounded by the stress-strain curve is the hysteresis area (MPa).

[Dimensional change rate]
In the evaluation of the resin layer and the resin film, after cutting the laminate into a rectangle with a width of 10 mm, the resin layer was peeled off from the support substrate to obtain a test piece.

Based on the tensile vibration-nonresonance method of JIS K7244 (1998) (this is referred to as a dynamic viscoelasticity method), the storage elastic modulus of the resin layer is measured using a dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Inc. and loss modulus.
Measurement mode: Distance between tensile chucks: 20mm
Width of test piece: 10 mm
Frequency: 1Hz
Strain amplitude: 10 μm
Minimum tension: 20mN
Force amplitude initial value: 40mN
Measurement temperature: from -100 ° C. to 200 ° C. Heating rate: 5 ° C./min At this time, the dL value (LVDT (Linear Variable Differential Transformer) output value) is obtained at the same time as the storage modulus and loss modulus are measured. This represents the value corresponding to the dimensions of the test piece at the time of measurement. The dL value at 30° C. was defined as a ₃₀ (μm), and the dL value at 150° C. as a ₁₅₀ (μm).
(Dimensional change rate) = (( _a150 - _a30 )/20,000) x 100
Furthermore, the absolute value of the dimensional change rate obtained by the above formula was calculated.

〔Glass-transition temperature〕
Based on the tensile vibration-nonresonance method of JIS K7244 (1998) (this is referred to as a dynamic viscoelasticity method), the storage elastic modulus of the resin layer is measured using a dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Inc. and loss modulus. A loss tangent was calculated from the obtained value, and a temperature vs. loss tangent curve was plotted, and the temperature at which the loss tangent showed a maximum value was taken as the glass transition temperature.

In the case where there are multiple temperatures at which the loss tangent shows a maximum value, the temperature showing the maximum loss tangent value that appears in the temperature range where the storage modulus is 10 MPa or more is given priority as the glass transition temperature, and the loss tangent is still the maximum value. When the temperature indicating the is not fixed at one point, the temperature indicating the maximum value of the loss tangent value was given priority as the glass transition temperature.
Measurement mode: Distance between tensile chucks: 20mm
Width of test piece: 10 mm
Frequency: 1Hz
Strain amplitude: 10 μm
Force amplitude initial value: 40mN
Measurement temperature: from −100° C. to 100° C. Heating rate: 5° C./min Loss tangent: (loss modulus)/(storage modulus).

[Evaluation of transportability]
The laminate and the resin film were cut into pieces of 150 mm width×250 mm length, and this sample was placed in a hot air oven adjusted to 180° C. and allowed to stand still for 1 minute. After that, the sample was taken out from the hot air oven, and the state of wrinkles and unevenness generated in the laminate was visually observed, and judged according to the following criteria.
10 points: No wrinkles, irregularities, or curls.
7 points: Slight wrinkles, irregularities, and curls.
4 points: Small wrinkles, irregularities, and curls are generated.
1 point: Others (large wrinkles, irregularities, curls, etc.).

[Evaluation of peelability]
In the laminate, the supporting base material and the resin layer are slightly peeled from the edge in advance, and the supporting base material and the resin layer are peeled by hand in a 180-degree direction by grasping the peeled part, and judgment is made according to the following criteria. gone.
10 points: The film can be peeled off without feeling stickiness.
7 points: Slight stickiness is felt at the time of peeling.
4 points: Strong stickiness is felt during peeling.
1 point: Others (cannot be peeled off, etc.).

[Evaluation of flexibility]
In the laminate, after the resin layer was peeled off from the supporting base material, the resin layer was pulled by hand and evaluated according to the following criteria. Also, the resin film was evaluated in the same manner as the resin layer, and was judged according to the following criteria.
10 points: Can be deformed with a very light force.
7 points: It can be transformed by applying a light force.
4 points: It can be transformed by applying a slightly strong force.
1 point: Other (strong force is required to transform, etc.).

[Evaluation of elasticity]
In the laminate, after the resin layer was peeled off from the supporting substrate, a light force was applied to the resin layer by hand to give tensile deformation, and the evaluation was made according to the following criteria. Also, the resin film was evaluated in the same manner as the resin layer, and was judged according to the following criteria.
10 points: If the load is removed after deformation, the original shape is restored.
7 points: Almost restored to the original shape if the load is removed after deformation.
4 points: If the load is removed after deformation, the original shape is slightly restored.
1 point: Others (not restored at all, etc.).

[Evaluation of recoverability of quality]
In this evaluation, the laminate was subjected to a load during transportation, etc., and deformation such as unevenness occurred in the resin layer.

In the laminate, in a state in which the support substrate and the resin layer were laminated, the surface of the resin layer was lightly pressed with tweezers to form a plurality of dents. The dented laminate was then placed in a hot air oven preheated to 50° C. for 5 minutes. After that, the laminate was taken out, and the surface state of the resin layer was visually observed, and judged according to the following criteria.
10 points: No dent remains.
7 points: Slight dents remain.
4 points: A few dents remain.
1 point: Others (many dents remain, all dents remain, etc.).

[Evaluation of quality under severe conditions]
In this evaluation, it was evaluated whether or not the quality would deteriorate due to peeling or the like when the laminate was subjected to a severe load during transportation or in post-processing steps.

In the laminated body, in a state in which the support base material and the resin layer are laminated, the surface of the resin layer was rubbed with gauze ("Haise" (registered trademark) gauze NT-4 manufactured by Kawamoto Sangyo Co., Ltd.) 10 times. . Next, the peeling state of the resin layer from the supporting substrate was visually observed, and judgment was made according to the following criteria.
10 points: No peeling occurred, or almost no peeling occurred.
7 points: Slight peeling occurs.
4 points: Strong peeling occurs.
1 point: Others (very strong peeling occurs, etc.)
[Evaluation of restorability after long-term deformation]
In the laminate, after the resin layer was peeled off from the supporting substrate, the resin layer was manually held in tensile deformation with a strain amount of 100% for 1 minute, and the evaluation was made according to the following criteria.
10 points: If the load is removed after deformation, the original shape is restored within 1 second.
7 points: If the load is removed after deformation, the original shape is restored within 5 seconds exceeding 1 second.
5 points: If the load is removed after deformation, the original shape is restored within 10 seconds exceeding 5 seconds.
3 points: If the load is removed after deformation, the original shape is restored within 30 seconds exceeding 10 seconds.
1 point: Recovers to its original shape for more than 30 seconds after deformation, if the load is removed, or else (no recovery at all, etc.).

Tables 2 and 3 summarize the evaluation results of the finally obtained laminate.

REFERENCE SIGNS LIST 1 resin layer 2 support base 3 multi-layer slide die 4 multi-layer slot die 5 single-layer slot die

The laminate of the present invention can be suitably used for applications that require particularly high flexibility and stretchability, taking advantage of the advantages of excellent optical properties, flexibility, stretchability and transportability.

Examples include glasses/sunglasses, cosmetic boxes, plastic molded products such as food containers, water tanks, showcases for exhibitions, etc., smartphone housings, touch panels, color filters, flat panel displays, flexible displays, flexible devices, and wearables. Devices, sensors, circuit materials, electrical and electronic applications, home appliances such as keyboards, TV/air conditioner remote controls, mirrors, window glass, buildings, dashboards, car navigation/touch panels, vehicle parts such as rearview mirrors and windows, etc. printed matter, medical film, sanitary material film, medical film, agricultural film, building material film, etc., can be suitably used for each surface material, internal material, constituent material, and manufacturing process material.

EXAMPLES Next, the present invention will be described based on Examples, but the present invention is not necessarily limited to these. Hereinafter, Examples 1 to 6 and 10 shall be read as Reference Examples 1 to 6 and 10.

Claims (7)

A laminate having a resin layer on at least one surface of a supporting substrate, wherein the laminate satisfies all of the following conditions 1 to 5.
Condition 1: 5% strain stress SF of the resin layer is 10 _MPa or less.
Condition 2: The 5% strain stress _SL of the laminate is 20 MPa or more.
Condition 3: The peel force _Rb between the supporting substrate and the resin layer is 1,000 mN/50 mm or less.
Condition 4: The longitudinal heat shrinkage of the laminate at 150°C is 2.0% or less.
Condition 5: The laminate has a haze of 15% or less. 2. The laminate according to claim 1, which satisfies condition 6 below.
Condition 6: The elastic recovery rate of the resin layer is 70% or more in a tensile test method with a deformation amount of 20%. 3. The laminate according to claim 1, which satisfies the following conditions 7 and 8.
Condition 7: Stress retention rate, which is the ratio of the stress F1 when the resin layer is stretched to a strain of 100% and the stress F2 after being held in that state for _{1 hour} in the stress relaxation test method at a deformation of 100%. F ₂ /F ₁ ×100 is 70% or more.
Condition 8: In the hysteresis test method with a deformation amount of 100%, the resin layer is stretched to a strain amount of 100%, held for 10 seconds, and then released. , is less than 1.0 MPa. 4. The laminate according to any one of claims 1 to 3, which satisfies condition 9 below.
Condition 9: The absolute value of the dimensional change rate of the resin layer at 150°C is 10% or less with respect to the dimension of the resin layer at 30°C. 5. The laminate according to any one of claims 1 to 4, wherein the following condition 10 is satisfied.
Condition 10: The glass transition temperature of the resin layer is 0° C. or lower in the dynamic viscoelasticity method. 6. The laminate according to any one of claims 1 to 5, which satisfies the following conditions 11 and 12.
Condition 11: The resin layer is a resin composition obtained by curing urethane acrylate having a number average molecular weight of 3,000 or more.
Condition 12: A release layer is provided on at least one surface of the supporting substrate, and the supporting substrate and the resin layer are in contact with each other via the release layer. A laminate according to any one of claims 1 to 6, wherein a resin layer is formed on at least one surface of a supporting substrate, wherein the laminate satisfies the following condition 13. body manufacturing method.
Condition 13: A resin layer is formed by applying the coating composition onto the supporting substrate.

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