Laminate, laminate manufacturing method, resin film manufacturing method, plastic molded product, display, sensor, and manufacturing process material

Abstract

To provide a laminate with excellent transportability and being flexible.SOLUTION: There is provided a laminate having a resin layer on at least one surface of a supporting substrate, the laminate being characterized in that it satisfies all of the following conditions 1 to 5. Condition 1: 5% strain stress SF of a resin layer is 10 MPa or less. Condition 2: 5% strain stress SL of the laminate is 20 MPa or more. Condition 3: a peel strength Rb between the supporting substrate and the resin layer is 1,000 mN / 50 mm or less. Condition 4: A thermal shrinkage rate of the laminate in a longitudinal direction at 150°C is 2.0% or less. Condition 5: A haze of the laminate is 15% or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminate that is both flexible and easy to transport. [Background technology]

[0002] In recent years, display-equipped devices such as smartphones, tablets, personal computers, and LCD televisions, as well as various other devices, have become increasingly popular, and many of these devices use film and sheet materials made from synthetic resins, etc. In this context, research and development into flexible and wearable devices has been active in recent years, and progress is being made in the development of deformable devices and components.

[0003] Due to this situation, new technological fields are likely to emerge that are difficult to apply with the materials used in conventional displays and devices, and the need for new materials with high flexibility and stretchability is expected to increase.

[0004] On the other hand, as an example of an existing material that has flexibility and stretchability, Patent Document 1 proposes "a laminate having at least a layer made of a first polyethylene, a thermoplastic polyurethane layer laminated on the layer made of the first polyethylene, and a layer made of a second polyethylene laminated on the thermoplastic polyurethane layer, wherein the heat of crystallization of the first polyethylene is greater than the heat of crystallization of the second polyethylene."

[0005] Furthermore, Non-Patent Document 1 lists so-called "silicone materials," and proposes a sheet material using silicone rubber as an example of the silicone material.

[0006] Furthermore, Patent Document 2 proposes "an elastic film characterized by comprising an SBS resin composition prepared by mixing a styrene-butadiene-styrene copolymer (SBS-A) containing 65 to 95% by mass of a styrene component and a styrene-butadiene-styrene copolymer (SBS-B) containing 5 to 40% by mass of a styrene component in a composition ratio of (SBS-A) / (SBS-B) = 75 / 25 to 95 / 5, and a filler (C) blended in an amount of 20 to 45 parts by mass per 100 parts by mass of the SBS resin composition, and having a specific gravity of 1.10 to 1.32."

[0007] Furthermore, Patent Document 3 proposes "a foamed urethane sheet having a foam on a substrate, the foam being obtained by applying a mixture of urethane resin, organic solvent, water and fluorine-based surfactant to a substrate which is a polyethylene terephthalate film, a polypropylene film or a methylpentene polymer film and has an adhesive on one side, and then heating the applied mixture, wherein the organic solvent is a mixed solution of toluene and methyl ethyl ketone, and the foam is composed of fine cells with a continuous air permeability structure." [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-91223 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-88293 [Patent Document 3] Japanese Patent Application Laid-Open No. 2014-231170 [Non-patent literature]

[0009] [Non-Patent Document 1] Silicone Handbook, Nikkan Kogyo Shimbun, Ltd., 1990 Summary of the Invention [Problem to be solved by the invention]

[0010] However, when the inventors checked the material proposed in Patent Document 1, they found that although it had a certain degree of flexibility and stretchability, it lacked heat resistance at high temperatures and was therefore unsuitable for post-processing involving heating, which is necessary for application as a component for displays and devices.

[0011] Furthermore, the silicone rubber material proposed in Non-Patent Document 1 provides flexibility and stretchability, but has poor adhesion to different materials and is unsuitable for post-processing.

[0012] Next, it was found that the material proposed in Patent Document 2 had a certain degree of flexibility, but was insufficient in terms of stretchability and transparency.

[0013] Furthermore, although the material proposed in Patent Document 3 was confirmed to have a certain degree of flexibility and stretchability, it had insufficient transparency.In addition, due to the presence of foamed portions, it was found to be unsuitable for post-processing steps involving coating.

[0014] Therefore, an object of the present invention is to provide a laminate that has flexibility and stretchability and is also excellent in transportability. [Means for solving the problem]

[0015] In order to solve the above problems, the present inventors have conducted extensive research and have completed the following invention. <1> A laminate having a resin layer on at least one surface of a supporting substrate, characterized in that the laminate satisfies all of the following conditions 1 to 5: Condition 1: 5% strain stress S of the resin layer F is less than 10 MPa. Condition 2: 5% strain stress S of laminate L is 20 MPa or more. Condition 3: Peel force R between the support substrate and the resin layer b is less than 1,000mN / 50mm. Condition 4: The thermal shrinkage rate of the laminate in the longitudinal direction at 150°C is 2.0% or less. Condition 5: The haze of the laminate is 15% or less. <2> The following condition 6 is satisfied: <1> The laminate according to claim 1. Condition 6: The elastic recovery rate of the resin layer is 70% or more in a tensile test at a deformation of 20%. <3> The following conditions 7 and 8 are satisfied: <1> or <2> The laminate according to claim 1. Condition 7: In a stress relaxation test at 100% deformation, the stress retention rate F2 / F1 × 100, which is the ratio of the stress F1 when the resin layer is stretched to 100% strain to the stress F2 after maintaining that state for one hour, is 70% or more. Condition 8: In the hysteresis test method at 100% deformation, when the resin layer is stretched to 100% strain, held for 10 seconds, and then released, the hysteresis area enclosed by the stress-strain curves at the time of stretching and release is less than 1.0 MPa. <4> 4. The laminate according to claim 1, wherein the laminate satisfies the following condition 9: Condition 9: When the dimensions of the resin layer at 30°C are used as the standard, the absolute value of the dimensional change rate of the resin layer at 150°C is 10% or less. <5> The following condition 10 is satisfied: <1> from <4> The laminate according to any one of the preceding items. Condition 10: The glass transition temperature of the resin layer measured by the dynamic viscoelasticity method is 0°C or lower. <6> The following conditions 11 and 12 are satisfied: <1> from <5> The laminate according to any one of the preceding items. Requirement 11: The resin layer is a resin composition obtained by curing a 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 method for producing a laminate in which a resin layer is formed on at least one surface of a supporting substrate, the method being characterized by satisfying the following condition 13: <1> from <6> 10. A method for producing the laminate according to any one of the preceding claims. Condition 13: A resin layer is formed by applying the coating composition onto a supporting substrate. [Effects of the Invention]

[0016] According to the present invention, a laminate that is flexible and has good transportability can be obtained. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is an example of a laminate according to the present invention. [Figure 2] 1 is a cross-sectional view showing an example of a method for forming a resin layer in the present invention. [Figure 3] 1 is a cross-sectional view showing an example of a method for forming a resin layer in the present invention. [Figure 4] 1 is a cross-sectional view showing an example of a method for forming a resin layer in the present invention. [Figure 5] FIG. 2 is a diagram showing an example of a hysteresis area of ​​a resin layer in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] Before describing the embodiments of the present invention, the problem with the prior art, that is, the compatibility of flexibility and transportability, will be considered from the viewpoint of the inventor.

[0019] [Comparison of the present invention and the prior art] In conventional technology, there are materials that exhibit flexibility and stretchability, but due to this flexibility and stretchability, they lack transportability, heat resistance, optical properties, etc. Therefore, although they can be used for specific applications, in applications such as displays, devices, sensors, etc., film materials are often used after various post-processing processes, but conventional materials are not sufficiently suitable for post-processing, making them difficult to apply.

[0020] The reason for the lack of transportability, particularly for flexible materials, is that in continuous processes such as roll-to-roll processes, materials are transported under tension. This tension can cause deformation in flexible materials. Specifically, the material stretches or wrinkles, which can impede post-processing processes such as printing, laminating, and coating. Flexible materials are characterized by high mobility of their molecular structure near room temperature, but this makes it difficult to maintain their shape at high temperatures, resulting in poor heat resistance. Furthermore, poor optical properties (particularly transparency) can make it difficult to inspect post-processed products visually or using optical sensors, making it difficult to distinguish between good and bad products.

[0021] Therefore, the present inventors have focused on the layer structure of the laminate in their investigation into achieving both flexibility and transportability.

[0022] In applications such as display and device components, transportability is required during the component manufacturing process, but flexibility and stretchability are also considered necessary during use. Therefore, we conceived a method of imparting transportability to a laminate by combining a flexible resin layer with a transportable support substrate. In this case, by controlling the peel force between the support substrate and the resin layer to a certain level or less, it is possible to peel the support substrate at any time depending on the component manufacturing process and usage conditions. This configuration ensures transportability as a laminate structure during printing, laminating, and coating processes, and peels the support substrate at the time of use, thereby providing a flexible material with excellent post-processability. Furthermore, by ensuring the dimensional stability of the laminate at high temperatures, high-quality products can be obtained, especially during post-processing involving heating. Furthermore, increasing the transparency of the laminate improves inspectability after post-processing, thereby improving product productivity.

[0023] Specifically, the 5% strain stress S of the resin layer F is 10 MPa or less, and the 5% strain stress S LThe peel strength R between the support substrate and the resin layer is 20 MPa or more. b It is preferable that the thermal shrinkage of the laminate in the longitudinal direction at 150° C. is 2.0% or less, and the haze of the laminate is 15% or less.

[0024] Furthermore, in the method for producing the laminate of the present invention, methods other than the above-mentioned coating include, for example, 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 transported or heated, the adhesive may migrate to the resin layer (so-called adhesive residue), which may result in an unsuitable product. Furthermore, when lamination is performed without an adhesive, lamination is performed by heating or pressure, but if the resin layer is flexible, unintended deformation or thermal shrinkage may occur, which may cause wrinkles or a decrease in quality or may result in an unsuitable product.

[0025] Therefore, as a result of intensive research, the present inventors have found that, as a method for solving the above-mentioned problems, the method for producing a laminate of the present invention involves applying a coating composition to a support substrate to form a resin layer, thereby imparting transportability while minimizing the load on the resin layer. Furthermore, in the above-mentioned production method, by selecting the type of support substrate, it is also possible to control the peel force between the resin layer and the support substrate. It has also been found that obtaining the laminate of the present invention by coating can improve the smoothness of both the front and back surfaces of the resin layer.

[0026] Furthermore, in studying ways to improve the quality of laminates, the inventors focused on the deformability of the materials that make up the laminate. As mentioned above, materials that exhibit flexibility and stretchability can have insufficient conveyance, but there are also cases where the flexibility of the material makes it prone to deformation, which can be a problem. Specifically, during the conveyance process, fine irregularities, scratches, and unevenness can occur in the flexible resin layer, which can reduce the quality of the finished product or reduce the inspectability after post-processing.

[0027] On the other hand, in order to improve the conveyability of such flexible materials, conventionally, the conveyability has been improved by hardening or thickening the film within the range acceptable for the product. However, in the present invention, the conveyability can be improved by focusing on the layer structure of the laminate. Therefore, we conducted a detailed study on what would happen if the resin layer was made more flexible, which was difficult with conventional designs. As a result, we found that the quality of the laminate could be improved by making the resin layer extremely flexible.

[0028] The inventors investigated this effect and found that, as mentioned above, soft materials are prone to developing irregularities, scratches, and unevenness, but that extremely soft materials tend to eliminate these irregularities during post-processing. This is believed to be because soft materials are prone to deformation, which makes them prone to developing irregularities, scratches, and unevenness. However, with extremely soft materials, once irregularities, scratches, and unevenness have been developed, they are smoothed and eliminated by heating and pressure during post-processing. This effect can improve the quality of the laminate. In particular, the deformability of the resin layer is temperature-dependent, and the inventors found that the aforementioned effect can be enhanced by lowering the glass transition temperature of the resin layer.

[0029] Specifically, it is preferable that the glass transition temperature of the resin layer be 0° C. or lower, as measured by a dynamic viscoelasticity method.

[0030] Furthermore, the present inventors conducted detailed studies on the laminate structure of the laminate and found that specific configurations between the support substrate and the resin layer can improve releasability and quality. One preferred laminate configuration of the present invention is a configuration in which a release layer is provided on the surface of the support substrate to improve the releasability between the resin layer and the support substrate. On the other hand, if the resin layer is flexible and therefore highly deformable, and the resin layer deforms significantly after laminating the support substrate and the resin layer, unintended partial peeling may occur during the conveying process. In particular, if the release layer provided on the surface of the support substrate has a formulation with very high releasability and the curing shrinkage that occurs when the resin layer hardens is extremely large, peeling may occur in part of the resin layer during hardening, or peeling may occur in part of the resin layer when further load is applied in a subsequent process, resulting in a deterioration in quality.

[0031] Therefore, we investigated methods for suppressing cure shrinkage of the resin layer and found that by setting the number average molecular weight of the resin composition used in the resin layer to a certain level or higher, it is possible to suppress the partial peeling described above and improve quality. This can be applied even when it becomes necessary to change the design of the release layer provided on the surface of the supporting substrate depending on the application (especially when improving releasability), and it is possible to improve the releasability of the resin layer and the quality of the laminate.

[0032] Specifically, it is preferable that the resin layer is a resin composition obtained by curing a urethane acrylate having a number average molecular weight of 3,000 or more, and that the support substrate has a release layer on at least one surface thereof, so that the support substrate and the resin layer are in contact with each other via the release layer.

[0033] Furthermore, it was found that conventional resin layers, after being subjected to strain for a long period of time, do not return to their original length even when the strain is released, resulting in sagging. Therefore, the inventors focused on the stress relaxation property of the resin layer in order to improve the restorability of the resin layer constituting the laminate after long-term deformation. It was found that, in conventional resin layers, high stress relaxation property, i.e., reduction of applied stress, results in small stress during restoration and poor restorability. Therefore, it was found that by setting the stress relaxation property of the resin layer within a specific range, high restorability can be achieved even when strain is continuously applied to the resin layer for a long period of time.

[0034] Specifically, in a stress relaxation test method at 100% deformation, the stress retention rate F2 / F1×100, which is the ratio of the stress F1 when the resin layer is stretched to 100% strain to the stress F2 after holding in that state for 1 hour, is preferably 70% or more, and in a hysteresis test method at 100% deformation, the resin layer is stretched to 100% strain, held for 10 seconds, and then released, and the hysteresis area surrounded by the stress-strain curves at stretching and release is preferably less than 1.0 MPa.

[0035] Furthermore, when examining the quality and post-processing suitability of the laminate, the inventors focused on the difference in deformation behavior between the resin layer and the supporting substrate upon heating. As mentioned above, examples of how the laminate of the present invention can be used include printing, laminating, and coating as post-processing steps, and these post-processing steps often involve heating. When observing the deformation behavior of the resin layer and the supporting substrate when this laminate is heated, it was found that if the deformation of the resin layer caused by heating is greater than the deformation of the supporting substrate caused by heating, the direction and magnitude of the deformation will differ depending on the thickness position of the laminate, resulting in internal stress. This internal stress can deteriorate the surface properties, and in extreme cases, can cause unintended peeling between the resin layer and the supporting substrate, resulting in deterioration of quality and post-processing suitability.

[0036] Therefore, we investigated ways to prevent unintended shrinkage due to such internal stress and found that it is effective to prevent dimensional change during heating, especially in the resin layer, which is prone to deformation. By preventing dimensional change during heating, it is possible to prevent the generation of unnecessary internal stress within the laminate, even when the laminate is subjected to various post-processing steps, thereby improving quality and post-processing suitability.

[0037] Specifically, when the dimensions of the resin layer at 30°C are used as a reference, the absolute value of the dimensional change rate of the resin layer at 200°C is preferably 10% or less.

[0038] Furthermore, when investigating laminates, the inventors also investigated thermoplastic urethane film (TPU). There are various commercially available thermoplastic urethane film products, and they exhibit certain characteristics in terms of transportability at room temperature. However, due to their thermoplastic properties, thermoplastic urethane films undergo deformation when exposed to temperatures above a certain level. In particular, when exposed to post-processing steps such as printing, laminating, and coating, the thermoplastic urethane film undergoes significant deformation, resulting in poor transportability. Furthermore, some thermoplastic urethane films have a supporting substrate, such as polyester film. However, as mentioned above, it was found that differences in deformation behavior occur between the thermoplastic urethane film and the supporting substrate when heated, resulting in deterioration of quality and poor post-processing suitability.

[0039] The present inventors also conducted detailed studies on the properties of thermoplastic urethane films (TPUs). As described above, in order to improve the recovery of the resin layer constituting the laminate of the present invention after long-term deformation, it is preferable to make the stress relaxation properties of the resin layer consistent as described above. However, due to the properties of thermoplastic urethane films, it is difficult to make the stress relaxation properties consistent as described above, and it was found that such films are unsuitable for the purposes of the present invention.

[0040] Thermoplastic urethane film, as its name suggests, is a thermoplastic material, but thermoplasticity means that it is prone to plastic deformation. Plastic deformation is a property inherent in the polymer structure that makes up the resin. Heating is a characteristic of thermoplasticity, but heating merely accelerates plastic deformation; plastic deformation can occur even at room temperature or in low-temperature environments. In particular, under conditions where external strain is applied for extended periods, plastic deformation can occur even without heating. Plastic deformation means that the resin layer will not return to its original shape even after stress is released, resulting in a loss of resilience. Therefore, thermoplastic urethane film is considered an unsuitable material for applications requiring high resilience in a variety of environments.

[0041] [Embodiments of the present invention] Hereinafter, embodiments of the present invention will be specifically described.

[0042] In order to achieve the above-mentioned objectives, i.e., 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 preferably satisfies all of the following conditions 1 to 5. Condition 1: 5% strain stress S of the resin layer F is less than 10 MPa. Condition 2: 5% strain stress S of laminate L is 20 MPa or more. Condition 3: The peel strength between the support substrate and the resin layer is 1,000 mN / 50 mm or less. Condition 4: The thermal shrinkage rate of the laminate in the longitudinal direction at 150°C is 2.0% or less. Condition 5: The haze of the laminate is 15% or less.

[0043] The methods for measuring the 5% strain stress, peel force, 150°C heat shrinkage rate, and haze will be described later. From the viewpoint of flexibility, the laminate of the present invention has a 5% strain stress S F is preferably 10 MPa or less, more preferably 5 MPa or less, and particularly preferably 3 MPa or less. F By placing the in a specific range, you can provide more flexibility.

[0044] 5% strain stress S of the resin layer F A specific range of S is preferable because it increases flexibility. F If S is low, flexibility improves, but if it is too low, rigidity may be insufficient, and the lower limit is thought to be around 0.01 MPa. F If the compressive strength is higher than 10 MPa, the flexibility of the resin layer decreases, which may make it unsuitable for the intended use.

[0045] The 5% strain stress S of the resin layer F In order to make the compressive strength 10 MPa or less, it is possible to select the resin contained in the resin layer from the materials exemplified below, for example.

[0046] From the viewpoint of transportability, the laminate of the present invention has a 5% strain stress S L It is preferable that the stress is 20 MPa or more. L By setting the thickness within a specific range, the transportability of the laminate can be improved.

[0047] 5% strain stress S of laminate L When S is in a specific range, the transportability is improved, which is preferable. L Higher S increases rigidity and improves transportability. L If the pressure is lower than 20 MPa, the laminate may lack rigidity, resulting in poor transportability and making it unsuitable for post-processing.

[0048] The 5% strain stress S L In order to make the compressive strength 20 MPa or more, for example, it is possible to select a resin contained in the supporting substrate from the materials exemplified below.

[0049] From the viewpoint of operability, the laminate of the present invention has a peel strength R between the supporting substrate and the resin layer. b The peel strength is preferably 1,000 mN / 50 mm or less, more preferably 800 mN / 50 mm or less. By setting the peel strength to a specific value or less, the support substrate can be peeled off as desired during the manufacturing process or use process of a product manufactured using the laminate of the present invention.

[0050] Peeling force R b When the peeling force R is low, the supporting substrate can be peeled off as desired in a product produced using the laminate of the present invention, which improves the operability of the product. b The lower the peel force R, the greater the effect, but if it is extremely low, peeling may occur at an unintended position or timing, making it unsuitable, so the lower limit is thought to be around 5mN / 50mm. b If the strength is higher than 1,000 mN / 50 mm, products manufactured using the laminate of the present invention may be unsuitable because peeling may be difficult or excessive load may be applied to the flexible resin layer during peeling, causing unintended deformation.

[0051] Peeling force R b In order to make the strength 1,000 mN / 50 mm or less, it is possible to do so by selecting a specific support substrate as described below.

[0052] From the viewpoint of transportability, the laminate of the present invention preferably has a longitudinal heat shrinkage rate of 2.0% or less, more preferably 1.0% or less, at 150° C. By setting the longitudinal heat shrinkage rate within a specific range, the transportability and post-processability of the laminate of the present invention can be improved.

[0053] By setting the longitudinal heat shrinkage at 150°C within the above range, unintended deformation can be suppressed during the transport process and post-processing process that involve heating, which is preferable because transportability and post-processability are improved. On the other hand, if the longitudinal heat shrinkage does not satisfy the above range, unevenness such as wrinkles and irregularities may occur in the film during so-called post-processing processes such as coating of a functional layer, which may make the film unsuitable as a product.

[0054] The longitudinal heat shrinkage rate can be set within the above range by, for example, selecting a specific supporting substrate as described below.

[0055] 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 within a specific range, it is possible to improve the optical quality of products using the laminate of the present invention and improve product inspectability during the manufacturing process.

[0056] The haze of the laminate can be set within the above range by, for example, selecting a specific resin as described below for the resin layer or by selecting a specific supporting substrate as described below.

[0057] Furthermore, from the viewpoint of stretchability, it is preferable that the laminate satisfy the following condition 6. Condition 6: The elastic recovery rate of the resin layer is 70% or more in a tensile test at a deformation of 20%.

[0058] The method for measuring the elastic recovery rate will be described later.

[0059] 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 indicates the restorability of the resin layer after strain is applied to the resin layer, and even if the flexible resin layer undergoes unintended deformation, it can recover to its original shape.

[0060] A high elastic recovery rate is preferable because, due to the aforementioned effect, the resin layer can recover to its original shape even when a large load is applied, improving operability. The higher the elastic recovery rate, the more preferable it is, with the upper limit being 100% in principle. On the other hand, if the elastic recovery rate is less than 70%, irreversible deformation may occur when a load is applied to the resin layer, making it unsuitable as a product.

[0061] In order to achieve an elastic recovery rate of 70% or more in a tensile test at a deformation of 20%, it is possible to achieve this, for example, by selecting a material for the resin contained in the resin layer that will be exemplified below.

[0062] Furthermore, from the viewpoint of restorability after long-term deformation, it is preferable that the laminate satisfy the following conditions 7 and 8. Condition 7: In a stress relaxation test at 100% deformation, the stress retention rate F2 / F1 × 100, which is the ratio of the stress F1 when the resin layer is stretched to 100% strain to the stress F2 after maintaining that state for one hour, is 70% or more. Condition 8: In the hysteresis test method at 100% deformation, when the resin layer is stretched to 100% strain, held for 10 seconds, and then released, the hysteresis area enclosed by the stress-strain curves at the time of stretching and release is less than 1.0 MPa.

[0063] In the following, the stress retention rate under condition 7 may be simply referred to as the stress retention rate, and the hysteresis area under condition 8 may be simply referred to as the hysteresis area.

[0064] The methods for measuring the stress retention rate and the hysteresis area will be described later.

[0065] 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 represents the ratio of the stress immediately after applying a certain strain to the resin layer to the stress after maintaining the certain strain for a long period of time, and is a parameter that indicates whether the resin layer can quickly recover to its original shape even after being deformed for a long period of time.

[0066] A high stress retention rate is preferable because, due to the aforementioned effect, the resin layer can quickly recover to its original shape even when a large load is applied for a long time, improving elasticity. The higher the stress retention rate, the more preferable it is, with the upper limit being 100% in principle. On the other hand, if the stress retention rate is less than 70%, irreversible deformation may occur when a load is applied to the resin layer for a long time, making it unsuitable for use as a product.

[0067] A stress retention rate of 70% or more can be achieved, for example, by selecting the resin contained in the resin layer from the materials exemplified below.

[0068] 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. The hysteresis area represents the difference in stress between when a certain strain is applied to the resin layer and when the strain is released, and is a parameter that indicates whether the resin layer can quickly recover to its original shape even when deformed.

[0069] A small hysteresis area is preferable because, due to the above-mentioned effect, the resin layer can quickly recover to its original shape even when a large load is applied, improving elasticity. The smaller the hysteresis area, the more preferable it is, and the lower limit is generally 0 MPa. On the other hand, if the hysteresis area is 1.0 MPa or more, deformation that cannot be quickly recovered occurs when a load is applied to the resin layer, which may make it unsuitable for use as a product.

[0070] The hysteresis area can be made less than 1.0 MPa by selecting the resin contained in the resin layer from the materials exemplified below.

[0071] Furthermore, from the viewpoint of quality and suitability for post-processing, it is preferable that the resin layer satisfy the following condition 9. Condition 9: When the dimensions of the resin layer at 30°C are used as the standard, the absolute value of the dimensional change rate of the resin layer at 200°C is 10% or less.

[0072] The dimensional change rate will be described in detail later.

[0073] From the viewpoint of quality and suitability for post-processing, 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% or less. By setting the absolute value of 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, which is preferable because it can improve the quality and suitability for post-processing.

[0074] It is preferable that the absolute value of the dimensional change rate is a certain value or less, because this improves the quality and post-processing suitability as described above. The smaller the dimensional change rate, the greater this effect. On the other hand, if the absolute value of the dimensional change rate exceeds 10%, the quality and post-processing suitability described above may become insufficient.

[0075] The absolute value of the dimensional change rate can be set to a certain value or less, for example, by selecting materials exemplified below as the resin and precursor contained in the resin layer.

[0076] Furthermore, from the viewpoint of quality, it is preferable that the laminate satisfy the following condition 10. Condition 10: The glass transition temperature of the resin layer measured by the dynamic viscoelastic method is 0°C or lower.

[0077] The dynamic viscoelasticity method will be described in detail later.

[0078] From the viewpoint of quality, in the laminate of the present invention, the glass transition temperature of the resin layer measured by a dynamic viscoelasticity method is preferably 0° C. or lower, more preferably −20° C. or lower, and particularly preferably −30° C. or lower. By setting the glass transition temperature at a certain value or lower, the quality of the laminate can be improved.

[0079] A certain glass transition temperature of the resin layer is preferable because it improves the quality. A low glass transition temperature improves the quality, but if it is too low, the rigidity may be insufficient, and the lower limit is thought to be around -150°C. 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.

[0080] The glass transition temperature of the resin layer can be set within a certain range, for example, by selecting the resin contained in the resin layer from the materials exemplified below.

[0081] Furthermore, from the viewpoint of quality, it is preferable that the laminate satisfy the following conditions 11 and 12. Requirement 11: The resin layer is a resin composition obtained by curing a 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.

[0082] From the viewpoint of quality, in the laminate of the present invention, the resin layer is preferably a resin composition obtained by curing a urethane acrylate having a number average molecular weight of 3,000 or more, more preferably a number average molecular weight of 5,000 or more. By using a resin composition obtained by curing a urethane acrylate having a number average molecular weight of a certain level or more, the quality of the laminate can be improved by the above-mentioned curing.

[0083] A certain number-average molecular weight is preferable because it improves the quality. The higher the number-average molecular weight, the greater this effect becomes, but considering handling when preparing a coating liquid, the upper limit is thought to be about 200,000. On the other hand, if the number-average molecular weight is less than 3,000, the effect of improving the quality may be insufficient.

[0084] In order to set the number average molecular weight to a certain value, for example, it is possible to select the materials exemplified below as the resin and its precursor contained in the resin layer.

[0085] Furthermore, in the method for producing the laminate, it is preferable that the following condition 13 be satisfied. Condition 13: A resin layer is formed by applying the coating composition onto a supporting substrate.

[0086] As described above, from the viewpoint of the peel strength between the resin layer and the supporting substrate, protection of the resin layer, etc., it is preferable that the method for producing the laminate of the present invention forms the resin layer by applying a coating composition onto the supporting substrate.

[0087] [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 above-mentioned physical properties. There is no particular limitation on the number of resin layers, and it may be formed from one layer or two or more layers.

[0088] The thickness of the resin layer is not particularly limited, but the lower limit is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. The upper limit is preferably 500 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 30 μm or less. The thickness of the resin layer can be selected depending on the other functions described above.

[0089] The resin layer may have other functions such as gloss, fingerprint resistance, moldability, designability, scratch resistance, stain resistance, solvent resistance, antireflection, antistatic properties, conductivity, heat ray reflection, near-infrared absorption, electromagnetic wave shielding, and easy adhesion, in addition to the flexibility and stretchability that are the object of the present invention.

[0090] Furthermore, one or more layers may be formed on the resin layer, such as a functional layer having the above-mentioned functions, an adhesive layer, an electronic circuit layer, a printing layer, an optical adjustment layer, or other functional layers.

[0091] [Supporting 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, and may be a homoresin, a copolymer, or a blend of two or more types. The resin constituting the supporting substrate is preferably one that has good moldability, and from this point of view, a thermoplastic resin is more preferred.

[0092] 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; polyarylate resins; polyacetal resins; polyphenylene sulfide resins; fluororesins such as tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, and vinylidene fluoride resin; acrylic resins; methacrylic resins; polyacetal resins; polyglycolic acid resins; and polylactic acid resins. Examples of thermosetting resins include phenolic resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, polyurethane resins, polyimide resins, and silicone resins. Thermoplastic resins with sufficient stretchability and conformability are preferred. From the viewpoints of strength, heat resistance, and transparency, the thermoplastic resin is more preferably a polyester resin, a polycarbonate resin, an acrylic resin, or a methacrylic resin.

[0093] In the present invention, polyester resin is a general term for polymers in which ester bonds are the main bonding chains in the main 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. These may also be copolymerized with other dicarboxylic acids and their esters or diol components as the acid component or diol component. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferred in terms of transparency, dimensional stability, heat resistance, and the like.

[0094] The support substrate may also contain various additives, such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, doping agents for adjusting the refractive index, etc. The support substrate may have either a single-layer structure or a multilayer structure.

[0095] The surface of the support substrate may be subjected to various surface treatments before the resin layer is formed. Examples of surface treatments 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.

[0096] Furthermore, it is also possible to provide a functional layer such as an easy-adhesion layer, an antistatic layer, an undercoat layer, an ultraviolet absorbing layer, or a release layer in advance on the surface of the support substrate, in addition to the resin layer of the present invention. In the laminate of the present invention, it is particularly preferable to provide a release layer in order to reduce the peel force between the support substrate and the resin layer.

[0097] Examples of films made of 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., "Panapeel" (registered trademark) manufactured by Panac Corporation, "Toyobo Ester" (registered trademark) manufactured by Toyobo Co., Ltd., and "Purex" (registered trademark) manufactured by Teijin Limited, and these products can be used.

[0098] [Paint composition] The method for producing the laminate of the present invention is not particularly limited, but the laminate of the present invention can be obtained by applying a coating composition to at least one of the aforementioned support substrates, followed by drying and curing steps as necessary. Here, the term "coating composition" refers to a liquid composed of a solvent and a solute, which can be applied to the aforementioned support substrate, and then the solvent is evaporated and removed in a drying step, followed by curing to form a resin layer. Here, the "type" of coating composition refers to a liquid in which the types of solutes constituting the coating composition are different, even if only partially. The solutes consist of resins or materials capable of forming them during the coating process (hereinafter referred to as precursors), particles, and various additives such as polymerization initiators, curing agents, catalysts, leveling agents, UV absorbers, and antioxidants.

[0099] In the laminate of the present invention, it is preferable to form a resin layer by using coating composition A and applying it onto a supporting substrate.

[0100] [Paint composition A] Coating composition A is a liquid containing a material suitable for forming the resin layer of the present invention, or a precursor capable of forming the resin layer, and preferably contains a resin or precursor containing the following segments (1) to (3) as a solute: (1) A segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment, and a polyalkylene glycol segment. (2) Urethane bond (3) A segment containing at least one selected from the group consisting of a fluorine compound segment, a polysiloxane segment, and a polydimethylsiloxane segment.

[0101] Each segment contained in the resin constituting the layer A on the surface of this resin layer can be confirmed by TOF-SIMS, FT-IR, or the like.

[0102] The parts by mass of (1), (2), and (3) contained in coating composition A are preferably (1) / (2) / (3) = 95 / 5 / 1 to 50 / 50 / 15, and more preferably (1) / (2) / (3) = 90 / 10 / 1 to 60 / 40 / 10. Details of (1), (2), and (3) are explained below.

[0103] Details of the (1) polycaprolactone segment, polycarbonate segment, and polyalkylene glycol segment will be described later, but by having these segments in the resin constituting layer A on the surface of the resin layer, the elasticity and flexibility of the resin layer can be improved.

[0104] The details of the urethane bond will be described later, but when the resin constituting the layer A on the surface of the resin layer has this bond, the toughness and stretchability of the entire resin layer can be improved.

[0105] The details of the fluorine compound segment, polysiloxane segment, and 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, thereby improving the solvent resistance of the resin layer.

[0106] Another example of a resin that is preferable as a solute for the coating composition A is urethane acrylate. A variety of general-purpose urethane acrylate products are available, and it is also possible to synthesize materials with various physical properties depending on the purpose.

[0107] In the present invention, a more preferred embodiment is a method for lowering the glass transition temperature of the resin layer, and one of the means for this is to select the type of urethane acrylate.Similarly, a more preferred embodiment is to use a resin composition obtained by curing a urethane acrylate having a certain number average molecular weight for the resin layer, and one of the means for this is to select the type of urethane acrylate.

[0108] Commercially available examples of urethane acrylates include urethane acrylates manufactured by Asia Kogyo Co., Ltd., urethane acrylates manufactured by Kyoeisha Chemical Co., Ltd., urethane acrylates manufactured by Shin-Nakamura Chemical Co., Ltd., urethane acrylates manufactured by Taisei Fine Chemical Co., Ltd., "New Frontier" (registered trademark) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "EBECRYL" (registered trademark) manufactured by Daicel-Allnex Co., Ltd., "Shiko" (registered trademark) manufactured by Nippon Gohsei Co., Ltd., and urethane acrylates manufactured by DIC Corporation, and these products can be used.

[0109] [Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment] First, a polycaprolactone segment refers to a segment shown in chemical formula 1. Polycaprolactone includes those in which the caprolactone repeating unit is 1 (monomer), 2 (dimer), or 3 (trimer), as well as oligomers with up to 35 caprolactone repeating units.

[0110] [ka]

[0111] Here, n is an integer from 1 to 35.

[0112] The resin containing the polycaprolactone segment preferably has at least one hydroxyl group, and the hydroxyl group is preferably located at the terminal of the resin containing the polycaprolactone segment.

[0113] As the resin containing a polycaprolactone segment, polycaprolactone having di- or tri-functional hydroxyl groups is particularly preferred. Specifically, polycaprolactone diol represented by Chemical Formula 2:

[0114] [ka]

[0115] Here, m+n is an integer between 4 and 35, m and n are each an integer between 1 and 34, and R is C2H4, C2H4OC2H4, or C(CH3)3(CH2)2 or a polycaprolactone triol represented by chemical formula 3:

[0116] [ka]

[0117] where l+m+n is an integer between 3 and 30, l, m, and n are each an integer between 1 and 28, and R is CH2CHCH2, CH3C(CH2)3, or CH3CH2C(CH2)3 Polycaprolactone polyols such as those listed above, and polycaprolactone-modified hydroxyethyl (meth)acrylates represented by chemical formula 4

[0118] [ka]

[0119] Here, n is an integer of 1 to 25, and R can be H or CH. Examples of other active energy ray-polymerizable caprolactones include polycaprolactone-modified hydroxypropyl (meth)acrylate and polycaprolactone-modified hydroxybutyl (meth)acrylate.

[0120] Furthermore, in the present invention, the resin containing a polycaprolactone segment may contain (or copolymerize) other segments or monomers in addition to the polycaprolactone segment, such as a polydimethylsiloxane segment, a polysiloxane segment, or a compound containing an isocyanate compound, as described below.

[0121] In the present invention, the weight-average molecular weight of the polycaprolactone segment in the resin containing the polycaprolactone segment is preferably 500 to 2,500, and more preferably 1,000 to 1,500. When the weight-average molecular weight of the polycaprolactone segment is 500 to 2,500, stretchability and flexibility are further improved, which is preferable.

[0122] Next, a polyalkylene glycol segment refers to a segment shown in chemical formula 5. Polyalkylene glycols include those with two (dimer) or three (trimer) alkylene glycol repeating units, as well as oligomers with up to 11 alkylene glycol repeating units.

[0123] [ka]

[0124] n is an integer of 2 to 4, and m is an integer of 2 to 11.

[0125] The resin containing the polyalkylene glycol segment preferably has at least one hydroxyl group, and the hydroxyl group is preferably located at the terminal of the resin containing the polyalkylene glycol segment.

[0126] The resin containing the polyalkylene glycol segment is preferably a polyalkylene glycol (meth)acrylate having an acrylate group at its terminal to impart elasticity. The number of acrylate functional groups (or methacrylate functional groups) in the polyalkylene glycol (meth)acrylate is not limited, but monofunctional groups are most preferred in terms of the elasticity and flexibility of the cured product.

[0127] Examples of polyalkylene glycol (meth)acrylates 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, which have structures represented by the following chemical formulas 6, 7, and 8, respectively.

[0128] Polyethylene glycol (meth)acrylate:

[0129] [ka]

[0130] Polypropylene glycol (meth)acrylate:

[0131] [ka]

[0132] Polybutylene glycol (meth)acrylate:

[0133] [ka]

[0134] In chemical formulas 6, 7, and 8, R is hydrogen (H) or a methyl group (-CH3), and m is an integer between 2 and 11.

[0135] In the present invention, it is preferable to use a urethane (meth)acrylate in the resin layer by reacting a compound containing an isocyanate group, which will be described later, with a hydroxyl group of a (poly)alkylene glycol (meth)acrylate, so that the resin constituting the resin layer has (2) a urethane bond and (3) a (poly)alkylene glycol segment, which results in improved toughness of the resin layer as well as improved stretchability and flexibility, which is preferable.

[0136] Examples of the hydroxyalkyl(meth)acrylate that is simultaneously blended during the urethane reaction of the compound containing an isocyanate group with the polyalkylene glycol(meth)acrylate include hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and hydroxybutyl(meth)acrylate.

[0137] Next, a polycarbonate segment refers to a segment represented by chemical formula 9. Polycarbonates include those with two (dimer) or three (trimer) carbonate repeating units, as well as oligomers with up to 16 carbonate repeating units.

[0138] [ka]

[0139] n is an integer from 2 to 16. R4 represents an alkylene group or cycloalkylene group having 1 to 8 carbon atoms.

[0140] The resin containing the polycarbonate segment preferably has at least one hydroxyl group, and the hydroxyl group is preferably located at the terminal of the resin containing the polycarbonate segment.

[0141] As a resin containing a polycarbonate segment, a polycarbonate diol having a bifunctional hydroxyl group is particularly preferred. Specifically, it is represented by Chemical Formula 10. Polycarbonate diol:

[0142] [ka]

[0143] n is an integer of 2 to 16. R represents an alkylene group or cycloalkylene group having 1 to 8 carbon atoms.

[0144] The polycarbonate diol may have any number of repeating carbonate units, but if the number of repeating carbonate units is too large, the strength of the cured product of the urethane (meth)acrylate will decrease, so the number of repeating carbonate units is preferably 10 or less. The polycarbonate diol may also be a mixture of two or more polycarbonate diols having different numbers of repeating carbonate units.

[0145] 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, heat resistance and solvent resistance may decrease, so those in the above range are preferred.

[0146] Suitable examples of 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.), Kuraray Polyol C Series (Kuraray Co., Ltd.), and Duranol Series (Asahi Kasei Chemicals Corporation). These polycarbonate diols can be used alone or in combination of two or more.

[0147] Furthermore, in the present invention, the resin containing a polycaprolactone segment may contain (or copolymerize) other segments or monomers in addition to the polycaprolactone segment, such as a polydimethylsiloxane segment, a polysiloxane segment, or a compound containing an isocyanate compound, as described below.

[0148] 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 to form a urethane (meth)acrylate, which is used in the resin layer. This allows the resin constituting the resin layer to have the above-mentioned (2) urethane bond and (1) polycarbonate diol segment, and as a result, the toughness of the resin layer can be improved, as well as the stretchability and flexibility.

[0149] [Compounds containing urethane bonds and isocyanate groups] In the present invention, the term "urethane bond" refers to a bond represented by chemical formula 11.

[0150] [ka]

[0151] When the resin constituting the resin layer has this bond, the toughness and stretchability of the entire resin layer can be improved.

[0152] The resin constituting the resin layer can have urethane bonds by including a commercially available urethane-modified resin in coating composition A. Furthermore, when forming the resin layer, coating composition A containing a compound containing an isocyanate group and a compound containing a hydroxyl group as precursors can be applied, dried, and cured to generate urethane bonds, allowing the resin layer to contain urethane bonds.

[0153] In the present invention, it is preferable to introduce a urethane bond into the resin constituting the resin layer by reacting an isocyanate group with a hydroxyl group to form a urethane bond, which can improve the toughness and stretchability of the resin layer.

[0154] Furthermore, in the case of a resin containing the above-mentioned polycaprolactone segment, polycarbonate segment, or polyalkylene glycol segment, or in the case of a resin having a hydroxyl group, it is also possible to form a urethane bond between this resin and a compound containing an isocyanate group as a precursor by heat or the like.

[0155] Forming a resin layer using a compound containing an isocyanate group and a resin containing a polysiloxane segment having a hydroxyl group, as described below, or a resin containing a polydimethylsiloxane segment having a hydroxyl group, can improve the toughness and elasticity of the resin layer, as well as the slipperiness of the surface, and is also more preferable from the viewpoint of solvent resistance.

[0156] 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. Examples of the compound containing an isocyanate group include (poly)isocyanates such as methylenebis-4-cyclohexyl isocyanate, a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, a trimethylolpropane adduct of isophorone diisocyanate, an isocyanurate of tolylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, and a biuret of hexamethylene isocyanate, as well as blocked compounds of the above isocyanates.

[0157] Among these compounds containing an isocyanate group, aliphatic isocyanates are preferred because they have higher elasticity and flexibility than alicyclic or aromatic isocyanates. Hexamethylene diisocyanate is a more preferred compound containing an isocyanate group. Furthermore, isocyanates having an isocyanurate ring are particularly preferred as compounds containing an isocyanate group in terms of heat resistance, with the isocyanurate of hexamethylene diisocyanate being most preferred. Isocyanates having an isocyanurate ring form a resin layer that combines elasticity and heat resistance.

[0158] [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.

[0159] Furthermore, by using 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 coating composition A containing a precursor thereof, as one of the coating precursors that form the resin layer, the resin that constitutes the resin layer can have these.

[0160] The fluorine compound segment, polysiloxane segment, and polydimethylsiloxane segment will be explained below.

[0161] First, the fluorine compound segment refers to a segment containing at least one selected from the group consisting of a fluoroalkyl group, a fluorooxyalkyl group, a fluoroalkenyl group, a fluoroalkanediyl group, and a fluorooxyalkanediyl group.

[0162] Here, the fluoroalkyl group, fluorooxyalkyl group, fluoroalkenyl group, fluoroalkanediyl group, and fluorooxyalkanediyl group are substituents in which some or all of the hydrogen atoms in an alkyl group, oxyalkyl group, alkenyl group, alkanediyl group, or oxyalkanediyl group have been replaced with fluorine, and all of these are substituents mainly composed of fluorine atoms and carbon atoms, and the structure may be branched, or a dimer, trimer, oligomer, or polymer structure may be formed in which multiple structures having these moieties are linked together.

[0163] As already mentioned, the fluorine compound segment is preferably a fluoropolyether segment, which is a moiety consisting of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, or the like, and more preferably a fluoropolyether segment represented by Chemical Formula 5 or Chemical Formula 6.

[0164] The fluoropolyether segment is a segment consisting of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, or the like, and has a structure represented by Chemical Formula 12 or Chemical Formula 13.

[0165] [ka]

[0166] [ka]

[0167] Here, n1 is an integer of 1 to 3, n2 to n5 are each an integer of 1 or 2, k, m, p, and s are each an integer of 0 or greater, and p+s is greater than or equal to 1. Preferably, n1 is 2 or greater, and n2 to n5 are each an integer of 1 or 2, and more preferably, n1 is 3, n2 and n4 are each 2, and n3 and n5 are each an integer of 1 or 2.

[0168] There is a preferred range for the chain length of this fluoropolyether segment, with the number of carbon atoms being preferably 4 to 12, more preferably 4 to 10, and particularly preferably 6 to 8. If the number of carbon atoms is 3 or less, the surface energy may not be sufficiently reduced, resulting in reduced oil repellency, while if the number of carbon atoms is 13 or more, the solubility in solvents may decrease, resulting in reduced quality of the resin layer.

[0169] When the resin contained in this resin layer contains a fluorine compound segment, the above-mentioned coating composition A preferably contains the following fluorine compound. This fluorine compound is a compound represented by chemical formula 14.

[0170] [ka]

[0171] where R f1 represents a fluorine compound segment, R7 represents an alkanediyl group, an alkanetriyl group, and an ester structure, a urethane structure, an ether structure, or a triazine structure derived therefrom, D 1 indicates a reactive site.

[0172] The reactive site refers to a site that reacts with other components due to external energy such as heat or light. From the viewpoint of reactivity, examples of such reactive sites include alkoxysilyl groups and silanol groups formed by hydrolysis of alkoxysilyl groups, as well as carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, and methacryloyl groups. Among these, from the viewpoints of reactivity and handleability, vinyl groups, allyl groups, alkoxysilyl groups, silyl ether groups, or silanol groups, epoxy groups, and acryloyl (methacryloyl) groups are preferred.

[0173] Examples of the fluorine compound are the following compounds: 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-perfluorooctylethyltrichlorosilane, 2-perfluorooctylisocyanatesilane, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexyl ... Perfluorohexyl-2-hydroxypropyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecylethyl 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, hexafluorobutyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-Pentafluoropropyl methacrylate, 2-perfluorobutylethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-perfluorooctylethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecylethyl methacrylate, 2-perfluoro-3-methylbutylethyl methacrylate, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexylethyl methacrylate, 3-perfluoro-5-methylhexyl Examples of perfluoro-2-hydroxypropyl methacrylate include 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-6-methyloctyl methacrylate, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorononyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate, hexafluorobutyl methacrylate, and triacryloyl-heptadecafluorononenyl-pentaerythritol.

[0174] The fluorine compound may have a plurality of fluoropolyether moieties per molecule.

[0175] Commercially available examples of the above fluorine compounds include RS-75 (DIC Corporation), Optool DAC-HP (Daikin Industries, Ltd.), C10GACRY, C8HGOL (Yushi Seihin Co., Ltd.), and the like, and these products can be used.

[0176] Next, the polysiloxane segment will be described. In the present invention, the polysiloxane segment refers to a segment represented by Chemical Formula 15, which will be described later.

[0177] Here, polysiloxane includes both low molecular weight ones (so-called oligomers) with about 100 siloxane repeating units, and high molecular weight ones (so-called polymers) with more than 100 siloxane repeating units.

[0178] [ka]

[0179] R1 and R2 are either a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and the formula has at least one of each; n is an integer of 100 to 300.

[0180] The details of the polysiloxane segment and polydimethylsiloxane segment will be described later, but the inclusion of these segments in the resin constituting the resin layer can improve heat resistance and weather resistance, and can also improve the slipperiness due to the lubricity of the resin layer. More preferably, from the viewpoint of lubricity, the resin layer contains a polydimethylsiloxane segment represented by Chemical Formula 16, which will be described later.

[0181] In the present invention, a partial hydrolyzate of a silane compound containing a hydrolyzable silyl group, an organosilica sol, or a coating composition in which a hydrolyzable silane compound having a radical polymer is added to the organosilica sol can be used as the resin containing a polysiloxane segment.

[0182] Examples of resins containing polysiloxane segments include complete or partial hydrolysates of silane compounds having hydrolyzable silyl groups, such as tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, and γ-methacryloxypropylalkyldialkoxysilane; organosilica sols dispersed in organic solvents; and organosilica sols to which hydrolyzed silane compounds having hydrolyzable silyl groups have been added on their surfaces.

[0183] In the present invention, the resin containing a polysiloxane segment may contain (copolymerize) other segments in addition to the polysiloxane segment, such as a monomer component having a polycaprolactone segment or a polydimethylsiloxane segment.

[0184] When the resin containing polysiloxane segments is a copolymer having hydroxyl groups, a resin layer can be formed efficiently using a coating composition containing a resin (copolymer) containing polysiloxane segments having hydroxyl groups and a compound containing an isocyanate group, thereby making it possible to obtain a resin layer having polysiloxane segments and urethane bonds.

[0185] Next, the polydimethylsiloxane segment will be described. In the present invention, the polydimethylsiloxane segment refers to a segment represented by chemical formula 16. Polydimethylsiloxane includes both low molecular weight ones (so-called oligomers) with 10 to 100 dimethylsiloxane repeating units and high molecular weight ones (so-called polymers) with more than 100 dimethylsiloxane repeating units.

[0186] [ka]

[0187] m is an integer from 10 to 300.

[0188] When the resin constituting the resin layer has a polydimethylsiloxane segment, the polydimethylsiloxane segment is coordinated on the surface of the resin layer. By coordinating the polydimethylsiloxane segment on the surface of the resin layer, the lubricity of the surface of the resin layer is improved and frictional resistance can be reduced. This is also preferable from the viewpoint of solvent resistance.

[0189] In the present invention, it is preferable to use a copolymer in which a vinyl monomer is copolymerized with a polydimethylsiloxane segment as the resin containing the polydimethylsiloxane segment.

[0190] For the purpose of improving the toughness of the resin layer, it is preferable that the resin containing the polydimethylsiloxane segment is copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group.

[0191] When the resin containing polydimethylsiloxane segments is a copolymer having hydroxyl groups, a resin layer having polydimethylsiloxane segments and urethane bonds can be efficiently obtained by forming the resin layer using a coating composition containing a resin (copolymer) containing polydimethylsiloxane segments having hydroxyl groups and a compound containing an isocyanate group.

[0192] When the resin containing polydimethylsiloxane segments is a copolymer with a vinyl monomer, it may be a block copolymer, a graft copolymer, or a random copolymer. When the resin containing polydimethylsiloxane segments is a copolymer with a vinyl monomer, it is called a polydimethylsiloxane copolymer. Polydimethylsiloxane copolymers can be produced by living polymerization, polymer initiator methods, polymer chain transfer methods, etc., but in consideration of productivity, the polymer initiator method and polymer chain transfer method are preferably used.

[0193] When using the polymeric initiator method, copolymerization with other vinyl monomers can be performed using a polymeric azo-based radical polymerization initiator represented by Chemical Formula 17. Alternatively, a two-step polymerization can be performed in which a peroxy monomer and a polydimethylsiloxane having an unsaturated group are copolymerized at low temperature to synthesize a prepolymer with a peroxide group introduced into the side chain, and this prepolymer is then copolymerized with a vinyl monomer.

[0194] [ka]

[0195] m is an integer of 10 to 300, and n is an integer of 1 to 50.

[0196] When using the polymer chain transfer method, for example, HS-CH2COOH, HS-CH2CH2COOH, or the like is added to the silicone oil shown in Chemical Formula 18 to form a compound having an SH group, and then the silicone compound is copolymerized with a vinyl monomer by utilizing chain transfer of the SH group to synthesize a block copolymer.

[0197] [ka]

[0198] m is an integer from 10 to 300.

[0199] To synthesize a polydimethylsiloxane-based graft copolymer, for example, a compound shown in Chemical Formula 19, i.e., a methacrylic ester of polydimethylsiloxane, can be copolymerized with a vinyl monomer to easily obtain the graft copolymer.

[0200] [ka]

[0201] m is an integer from 10 to 300.

[0202] Examples of vinyl monomers used in copolymers with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, and vinyl chloride. Examples of the vinyl acrylate copolymer include vinylidene 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, diacetone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and allyl alcohol.

[0203] Furthermore, the polydimethylsiloxane copolymer is preferably produced by solution polymerization in a solvent selected from the group consisting of 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, and alcohol solvents such as ethanol and isopropyl alcohol, either alone or in a mixture thereof.

[0204] If necessary, a polymerization initiator such as benzoyl peroxide, azobisisobutylnitrile, etc. is used in combination. The polymerization reaction is preferably carried out at 50 to 150°C for 3 to 12 hours.

[0205] In view of the lubricity and solvent resistance of the resin layer, the amount of polydimethylsiloxane segments in the polydimethylsiloxane copolymer of the present invention is preferably 1 to 30 mass % relative to 100 mass % of all components of the polydimethylsiloxane copolymer, and the weight average molecular weight of the polydimethylsiloxane segments is preferably 1,000 to 30,000.

[0206] 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 may be contained (copolymerized) in addition to the polydimethylsiloxane segment, such as a polycaprolactone segment or a polysiloxane segment.

[0207] The coating composition used to form the resin layer can be a copolymer of a polycaprolactone segment and a polydimethylsiloxane segment, a copolymer of a polycaprolactone segment and a polysiloxane segment, a copolymer of a polycaprolactone segment, a polydimethylsiloxane segment and a polysiloxane segment, etc. The resin layer obtained using such a coating composition can have a polycaprolactone segment and a polydimethylsiloxane segment and / or a polysiloxane segment.

[0208] The reaction of the polydimethylsiloxane-based copolymer, polycaprolactone, and polysiloxane in the coating composition used to form a resin layer having polycaprolactone segments, polysiloxane segments, and polydimethylsiloxane segments can be copolymerized by adding the polycaprolactone segments and polysiloxane segments as appropriate during the synthesis of the polydimethylsiloxane-based copolymer.

[0209] [solvent] The coating composition may contain a solvent, and the number of types of solvents is preferably from 1 to 20, more preferably from 1 to 10, even more preferably from 1 to 6, and particularly preferably from 1 to 4.

[0210] Here, the term "solvent" refers to a substance that is liquid at room temperature and pressure and can be evaporated almost entirely in the drying process after application.

[0211] Here, the type of solvent is determined by the molecular structure that makes up the solvent. In other words, solvents that have the same elemental composition and the same type and number of functional groups but different bonding relationships (structural isomers) and solvents that are not structural isomers but do not perfectly overlap in three-dimensional space no matter what conformation they take (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are treated as different solvents.

[0212] Furthermore, when a solvent is contained, it is preferable that the solvent exhibits the following properties.

[0213] Condition 1: When solvent B is the solvent with the lowest relative evaporation rate (ASTM D3539-87(2004)) based on n-butyl acetate, the relative evaporation rate of solvent B must be 0.4 or less.

[0214] Here, the relative evaporation rate based on the solvent n-butyl acetate is the evaporation rate measured in accordance with ASTM D3539-87 (2004). Specifically, it is a value defined as the relative value of the evaporation rate based on the time required for 90% by mass of n-butyl acetate to evaporate in dry air.

[0215] If the relative evaporation rate of the solvent is greater than 0.4, the time required for the aforementioned polysiloxane segments and / or polydimethylsiloxane segments and fluorine compound segments to be oriented to the outermost surface of the resin layer will be shortened, which may result in a decrease in the solvent resistance of the resin layer in the resulting laminate. Furthermore, the lower limit of the relative evaporation rate of the solvent is acceptable as long as it is a solvent that can be evaporated and removed from the coating film in the drying process, and in a typical coating process, a value of 0.005 or more will suffice.

[0216] Solvents include 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), and cyclohexanone (relative evaporation rate: 0.32).

[0217] [Other components in the coating composition] The coating composition A preferably contains a polymerization initiator, a curing agent, and a catalyst. The polymerization initiator and catalyst are used to promote curing of the resin layer. The polymerization initiator is preferably one that can initiate or promote polymerization, condensation, or crosslinking reactions of the components contained in the coating composition through anionic, cationic, or radical polymerization reactions.

[0218] Various polymerization initiators, curing agents, and catalysts can be used. The polymerization initiators, curing agents, and catalysts may be used alone, 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, and acetic acid. Examples of thermal polymerization initiators include peroxides and azo compounds. Examples of photopolymerization initiators include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, and amine compounds. Examples of crosslinking catalysts that promote the urethane bond-forming reaction include dibutyltin dilaurate and dibutyltin diethylhexoate.

[0219] The coating composition may also contain other crosslinkers, such as melamine crosslinkers, such as alkoxymethylol melamine, acid anhydride crosslinkers, such as 3-methyl-hexahydrophthalic anhydride, and amine crosslinkers, such as diethylaminopropylamine.

[0220] As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-phenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-phenyl)-1-butane, 2-benzyl-2-dimethylamino-1-(4- Examples include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1-[4-(2-ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxybisethylene, and polymerized versions of these materials.

[0221] Furthermore, as long as the effects of the present invention are not impaired, leveling agents, UV absorbers, lubricants, antistatic agents, etc. may be added to the coating composition used to form the resin layer. This allows the resin layer to contain leveling agents, UV absorbers, lubricants, antistatic agents, etc. Examples of leveling agents include acrylic copolymers, silicone-based, and fluorine-based leveling agents. Specific examples of UV absorbers include benzophenone-based, benzotriazole-based, oxalic acid anilide-based, triazine-based, and hindered amine-based UV absorbers. Examples of antistatic agents include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.

[0222] [Method of manufacturing laminate] The resin layer formed on the support substrate of the laminate of the present invention is preferably formed by applying the above-mentioned coating composition for the resin layer to the support substrate, drying, and curing. Hereinafter, the process of applying the coating composition will be referred to as the coating process, the drying process will be referred to as the drying process, and the curing process will be referred to as the curing process. Two or more coating compositions for the resin layer may be applied sequentially or simultaneously to form a resin layer consisting of two or more layers.

[0223] Here, "sequential application" means that one type of coating composition is applied to a support substrate, dried, and cured, and then another coating composition is applied thereon, dried, and cured to form a resin layer consisting of two or more layers. By appropriately selecting the type of coating composition used, it is possible to control the magnitude and gradient of the flexibility and stretchability of the resin layer on the resin layer side and the support substrate side, as well as the magnitude and stretchability of the support substrate and the resin layer. Furthermore, by appropriately selecting the type, composition, drying conditions, and curing conditions of the coating composition, it is possible to control the distribution of flexibility and stretchability within the resin layer in a stepwise or continuous manner.

[0224] Furthermore, "coating simultaneously" means that two or more types of coating compositions are simultaneously coated onto a supporting substrate in the coating step, and then dried and cured.

[0225] In the coating step, the method for applying the coating composition is not particularly limited, but it is preferable to apply the coating composition to the supporting substrate by a dip coating method, roller coating method, wire bar coating method, gravure coating method, die coating method (U.S. Pat. No. 2,681,294), etc. Furthermore, among these coating methods, gravure coating method or die coating method is more preferable as the coating method.

[0226] When two or more types of 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, although there are no particular limitations.

[0227] An example of multilayer slide die coating is shown in Figure 2. In multilayer slide die coating, liquid films consisting of two or more types of coating compositions are laminated in order using a multilayer slide die 17, and then coated onto a supporting substrate.

[0228] An example of multilayer slot die coating is shown in Figure 3. In multilayer slot die coating, a liquid film consisting of two or more types of coating compositions is applied and simultaneously laminated onto a supporting substrate using a multilayer slot die 18.

[0229] An example of wet-on-wet coating is shown in Figure 4. In wet-on-wet coating, one layer of liquid film made of a coating composition discharged from a single-layer slot die 19 is formed on a supporting substrate, and then, while the liquid film is still wet, another liquid film made of a different coating composition discharged from another single-layer slot die 19 is laminated on top of the first liquid film.

[0230] Following the coating step, the liquid film coated 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 preferably involves heating the liquid film.

[0231] Heating methods used in the drying process include heat transfer drying (contact with a hot object), convection heat transfer (hot air), radiation heat transfer (infrared rays), and others (microwaves, induction heating). Of these, methods using convection heat transfer or radiation heat transfer are preferred because of the need to precisely uniform the drying speed in the width direction.

[0232] The drying process of a liquid film in the drying step is generally divided into (A) a constant rate drying period and (B) a falling rate drying period. In the former, the rate-limiting factor for drying is the diffusion of solvent molecules into the atmosphere on the liquid film surface, so the drying rate is constant in this period and is governed by the partial pressure of the solvent to be evaporated in the atmosphere, the air speed, and the temperature, and the film surface temperature is constant at a value determined by the hot air temperature and the partial pressure of the solvent to be evaporated in the atmosphere. In the latter, the rate-limiting factor is the diffusion of the solvent in the liquid film, so the drying rate does not remain constant in this period but continues to decrease, and is governed by the diffusion coefficient of the solvent in the liquid film, and the film surface temperature gradually rises. Here, the drying rate represents the amount of solvent evaporated per unit time and unit area, and is expressed in g·m -2 ·s -1 It consists of dimensions.

[0233] The drying rate is 0.1 g m -2 ·s -1 More than 10g m -2 ·s -1 Preferably, it is 0.1 g m or less. -2 ·s -1 More than 5g m -2 ·s -1 By setting the drying rate in the constant rate drying section within this range, unevenness due to non-uniformity in the drying rate can be prevented.

[0234] There are no particular limitations as long as a desirable drying rate is obtained, but to achieve the above drying rate, the temperature is preferably 15°C to 129°C, more preferably 50°C to 129°C, and particularly preferably 50°C to 99°C.

[0235] During the falling-rate drying period, the remaining solvent evaporates and the aforementioned polysiloxane segments and / or polydimethylsiloxane segments and fluorine compound segments are oriented. Because this process requires time for orientation, the rate of temperature rise on the film surface during the falling-rate drying period is preferably 5°C / sec or less, and more preferably 1°C / sec or less.

[0236] The drying step may be followed by a further curing operation (curing step) by irradiation with heat or active energy rays.

[0237] As the active energy ray, electron beams (EB rays) and / or ultraviolet rays (UV rays) are preferred from the viewpoint of versatility. When curing with ultraviolet rays, it is preferable to keep the oxygen concentration as low as possible to prevent oxygen inhibition, and it is more preferable to cure in a nitrogen atmosphere (nitrogen purging). If the oxygen concentration is high, curing of the outermost surface may be inhibited, resulting in weak surface curing and reduced toughness. In addition, the type of ultraviolet lamp used for irradiating ultraviolet rays may include, for example, a discharge lamp type, a flash type, a laser type, an electrodeless lamp type, etc. When using a high-pressure mercury lamp that is a discharge lamp type, the illuminance of the ultraviolet rays is preferably 100 to 3,000 mW / cm. 2 , more preferably 200 to 2,000 mW / cm 2 , and more preferably 300 to 1,500 mW / cm 2 It is preferable to perform ultraviolet irradiation under the conditions that the integrated light amount of ultraviolet light is preferably 100 to 3,000 mJ / cm 2 2 , more preferably 200 to 2,000 mJ / cm 2 , and more preferably 300 to 1,500 mJ / cm 2It is preferable to perform ultraviolet irradiation under the following conditions. Here, ultraviolet irradiance refers to the irradiation intensity per unit area, and varies depending on the lamp output, light-emitting spectral efficiency, diameter of the light-emitting bulb, design of the reflector, and the distance between the irradiated object and the light source. However, irradiance does not vary depending on the transport speed. Furthermore, the integrated amount of ultraviolet light refers to the irradiation energy 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 irradiations and the number of lamps.

[0238] [Application example] The laminate of the present invention has advantages such as excellent optical properties, flexibility, stretchability, and transportability, and can be suitably used in applications where particularly high flexibility and stretchability are required.

[0239] To give just a few examples, it can be suitably used for surface materials, internal materials, constituent materials, and manufacturing process materials in plastic molded products such as eyeglasses and sunglasses, cosmetic cases, and food containers, aquariums, showcases for exhibitions, smartphone housings, touch panels, color filters, flat panel displays, flexible displays, flexible devices, wearable devices, sensors, circuit materials, electrical and electronic applications, home appliances such as keyboards and TV and air conditioner remote controls, mirrors, window glass, buildings, dashboards, car navigation systems and touch panels, vehicle parts such as rearview mirrors and windows, and various printed materials, medical films, sanitary material films, medical films, agricultural films, and building material films. [Example]

[0240] Next, the present invention will be described based on examples, but the present invention is not necessarily limited to these. In the following, Examples 1 to 6 and 10 will be read as Reference Examples 1 to 6 and 10.

[0241] [Urethane (meth)acrylate A] [Synthesis of urethane (meth)acrylate A1] 50 parts by weight of toluene, 50 parts by weight of isocyanurate-modified hexamethylene diisocyanate ("Takenate" (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.), 76 parts by weight of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.), 0.02 parts by weight of dibutyltin laurate, and 0.02 parts by weight of hydroquinone monomethyl ether were mixed and maintained at 70°C for 5 hours. Subsequently, 79 parts by weight of toluene was added to obtain a toluene solution of urethane (meth)acrylate A1 with a solids concentration of 50% by weight. The number average molecular weight of urethane (meth)acrylate A1 was 2,000.

[0242] [Urethane (meth)acrylate B] [Synthesis of urethane (meth)acrylate B1] 100 parts by weight of toluene, 50 parts by weight of methyl-2,6-diisocyanate hexanoate (LDI, manufactured by Kyowa Hakko Kirin Co., Ltd.), and 119 parts by weight of polycarbonate diol (Placcel® CD-210HL, manufactured by Daicel Chemical Industries, Ltd.) were mixed, heated to 40°C, and maintained for 8 hours. Next, 28 parts by weight of 2-hydroxyethyl acrylate (Light Ester HOA, manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by weight of dipentaerythritol hexaacrylate (M-400, manufactured by Toagosei Co., Ltd.), and 0.02 parts by weight of hydroquinone monomethyl ether were added, and the mixture was maintained at 70°C for 30 minutes. Then, 0.02 parts by weight of dibutyltin laurate was added, and the mixture was maintained at 80°C for 6 hours. Finally, 97 parts by weight of toluene was added to obtain a toluene solution of urethane (meth)acrylate B1 with a solids concentration of 50% by weight. The number average molecular weight of urethane (meth)acrylate B1 was 5,800.

[0243] [Urethane (meth)acrylate C] [Synthesis of urethane (meth)acrylate C1] 50 parts by mass of an isocyanurate-modified hexamethylene diisocyanate (Mitsui Chemicals, Inc., "Takenate" (registered trademark) D-170N, isocyanate group content: 20.9% by mass), 53 parts by mass of polyethylene glycol monoacrylate (NOF Corporation, "Blemmer" (registered trademark) AE-150, hydroxyl value: 264 (mgKOH / g)), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were charged. The mixture was then maintained at 70°C for 5 hours to carry out the reaction. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter sometimes referred to as MEK) was added to the reaction solution to obtain urethane (meth)acrylate C1 with a solids concentration of 50% by mass. The number average molecular weight of the urethane (meth)acrylate C1 was 2,000.

[0244] [Urethane (meth)acrylate D] [Urethane (meth)acrylate D1] As the urethane (meth)acrylate D1, SUA-017 (manufactured by Asia Industries Co., Ltd., solid content concentration 100% by mass) having a number average molecular weight of 4,600 was used.

[0245] [Urethane (meth)acrylate E] [Urethane (meth)acrylate E1] As the 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.

[0246] [Polyol compounds] [Polyol Compound 1] As polyol compound 1, "Placcel" (registered trademark) 210CP (manufactured by Daicel Chemical Industries, Ltd., solid content concentration 100% by mass) was used.

[0247] [Fluorine compounds] [Fluorine Compound 1] As the fluorine compound 1, an acrylate compound containing a fluoropolyether segment ("Megafac" (registered trademark) RS-75 manufactured by DIC Corporation, solid content concentration 40 mass %, solvent (toluene and methyl ethyl ketone) 60 mass %) was used.

[0248] [Photoradical polymerization initiator] [Photoradical polymerization initiator 1] As the photoradical polymerization initiator 1, "Irgacure" (registered trademark) 184 (manufactured by BASF Japan Ltd., solid content concentration 100% by mass) was used.

[0249] [Formulation of Paint Composition A] [Coating composition A1] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A1 with a solids concentration of 30 mass %. Urethane (meth)acrylate A1 solution (solid content concentration 50% by mass) 100 parts by mass 1.5 parts by mass of photoradical polymerization initiator 1

[0250] [Coating composition A2] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A2 with a solids concentration of 30 mass %. Urethane (meth)acrylate B1 solution (solid content concentration 50% by mass) 100 parts by mass 1.5 parts by mass of photoradical polymerization initiator 1

[0251] [Coating composition A3] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A3 with a solids concentration of 30 mass %. Urethane (meth)acrylate C1 solution (solid content concentration 50% by mass) 100 parts by mass Fluorine compound 1 solution (solid concentration 40% by mass) 3.8 parts by mass Photoradical polymerization initiator 1 1.5 parts by mass Ethylene glycol monobutyl ether 10 parts by mass.

[0252] [Paint composition A4] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A4 with a solids concentration of 30 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 by mass Fluorine compound 1 solution (solid concentration 40% by mass) 3.8 parts by mass Photoradical polymerization initiator 1 1.5 parts by mass Ethylene glycol monobutyl ether 10 parts by mass.

[0253] [Paint composition A5] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A5 with a solids concentration of 30 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 1.5 parts by mass of photoradical polymerization initiator 1

[0254] [Coating composition A6] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A6 with a solids concentration of 30 mass %. Urethane (meth)acrylate D1 (solid content concentration 100% by mass) 50 parts by mass 1.5 parts by mass of photoradical polymerization initiator 1

[0255] [Coating composition A7] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A7 with a solids concentration of 30 mass %. Urethane (meth)acrylate B1 (solid content concentration 100% by mass) 90 parts by mass Polyol compound 1 (solid content concentration 100% by mass) 5 parts by mass 1.5 parts by mass of photoradical polymerization initiator 1

[0256] [Coating composition A8] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A8 with a solids concentration of 30 mass %. Urethane (meth)acrylate D1 (solid content concentration 100% by mass) 45 parts by mass Urethane (meth)acrylate A1 solution (solid content concentration 50% by mass) 10 parts by mass 1.5 parts by mass of photoradical polymerization initiator 1

[0257] [Coating composition A9] The following materials were mixed and diluted with methyl ethyl ketone to obtain a coating composition A9 with a solids concentration of 30 mass %. Urethane (meth)acrylate E1 (solid content concentration 70% by mass) 71 parts by mass 1.5 parts by mass of photoradical polymerization initiator 1

[0258] [Supporting base material] [Support base material A1] As the supporting substrate A1, "Cerapeel" (registered trademark) SY (thickness 38 μm, manufactured by Toray Advanced Film Co., Ltd.) was used.

[0259] [Support base material B1] As the supporting substrate B1, "Lumirror" (registered trademark) U48 (thickness: 50 μm, manufactured by Toray Industries, Inc.) was used.

[0260] [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.

[0261] Furthermore, when the composition of "ESMER" (registered trademark) URS PX98 was confirmed, it was found to be composed of a 50 μm thick polyester film layer, a 150 μm thick thermoplastic urethane film layer, and a 75 μm thick polyester film layer laminated in that order. 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 and designated Reference Example 1.

[0262] [Method of manufacturing laminate and resin film] [Preparation of Laminate] The coating composition A was applied onto a supporting substrate using a continuous coating device with a slot die coater, adjusting the discharge flow rate from the slot so that the resin layer would have a specified thickness after drying. The conditions of the drying air that hit the liquid film from coating to drying and curing were as follows:

[0263] [Drying process] Air temperature and humidity: Temperature: 80°C, Relative humidity: 1% or less Wind speed: Coating side: 5m / sec, non-coating side: 5m / sec Wind direction: Coated side: parallel to the surface of the substrate, non-coated side: perpendicular to the surface of the substrate Dwell time: 2 minutes

[0264] [Curing process] Irradiation output: 400W / cm 2 Accumulated light intensity: 120mJ / cm 2 Oxygen concentration: 0.1% by volume.

[0265] [Preparation of resin film] The coating composition A was applied onto a supporting substrate using a continuous coating device with a slot die coater, adjusting the discharge flow rate from the slot so that the resin layer would have a specified thickness after drying. The conditions of the drying air that hit the liquid film from coating to drying and curing were as follows:

[0266] Furthermore, the resin layer was peeled off from the supporting substrate, treated as a resin film, and evaluated in the same manner as the laminate and resin layer.

[0267] [Drying process] Air temperature and humidity: Temperature: 80°C, Relative humidity: 1% or less Wind speed: Coating side: 5m / sec, non-coating side: 5m / sec Wind direction: Coated side: parallel to the surface of the substrate, non-coated side: perpendicular to the surface of the substrate Dwell time: 2 minutes

[0268] [Curing process] Irradiation output: 400W / cm 2 Accumulated light intensity: 120mJ / cm 2 Oxygen concentration: 0.1% by volume.

[0269] By the above methods, laminates and resin films were prepared in Examples 1 to 10 and Comparative Examples 1 and 2. The methods for preparing the laminates and resin films corresponding to each Example and Comparative Example, and the film thickness of each layer, are shown in Table 2 below.

[0270] [Table 1]

[0271] [Evaluation of laminates, resin layers, and resin films] The laminate, resin layer, and resin film were subjected to the following performance evaluations, and the results are shown in Table 2. Unless otherwise specified, measurements were taken three times for one sample in each Example and Comparative Example at different locations, and the average value was used.

[0272] The resin film was considered to be equivalent to the laminate and the resin layer, and was evaluated in the same manner.

[0273] In addition, for Comparative Examples 1 and 2, some of the evaluation results were judged to be clearly inappropriate, so some of the evaluation was omitted.

[0274] [Thickness of Laminate, Resin Layer, and Resin Film] The thickness of the laminate, resin layer, and 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 cross-sectional slices of the laminate, resin layer, and resin film were photographed with an SEM at 3,000x magnification, and the thickness of each layer was read using software (image processing software ImageJ). The layer thickness was measured at a total of 30 points, and the average value obtained was used as the measured value.

[0275] [5% strain stress] For evaluation of the laminate, the laminate was cut into a rectangular shape measuring 10 mm wide x 150 mm long to prepare a test specimen. For evaluation of the resin layer and resin film, the laminate was cut into a rectangular shape measuring 10 mm wide x 150 mm long, and the resin layer was then peeled off from the support substrate to prepare a test specimen. The 150 mm length of each specimen was aligned with the longitudinal direction of the laminate. Using a tensile tester (Orientec Tensilon UCT-100), the tensile test was performed at a temperature of 23°C, with an initial tensile chuck distance of 50 mm and a tensile speed of 300 mm / min.

[0276] Read the load b (N) applied to the sample when the chuck distance is a (mm), and use the following formula to calculate the strain x (%) and stress y (N / mm 2 ) was calculated, where the sample thickness before the test is k (mm). Strain amount: x = ((a-50) / 50) x 100 Stress: y=b / (k×10).

[0277] Of the data obtained above, the stress at a strain of 5% was defined as the 5% strain stress.

[0278] [Peeling force R b 〕 The support substrate and resin layer of the laminate were previously peeled slightly from the edge to form a grip for measurement with a tensile tester. The resistance (N) was then measured at 180° peeling at a rate of 300 mm / min using a tensile tester under an environment of 23°C and 65% RH. The resistance (N) was divided by the width (mm) of the support substrate and resin layer, then multiplied by 50 to convert it into a peel force (mN / 50 mm) equivalent to a width of 50 mm.

[0279] [Heat shrinkage rate] The laminate was cut into a rectangular shape measuring 10 mm wide and 200 mm long to prepare a test piece. The test piece was prepared with the 200 mm length aligned with the longitudinal direction of the laminate, and the longitudinal heat shrinkage rate was measured.

[0280] First, in the 200 mm length direction of the cut test piece, a gauge line was drawn across the width at a position 25 mm from each end, so that the distance between each gauge line 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 that a load of 3 g was applied. The hot air oven was preheated to 150°C, and the test piece was placed in the hot air oven and subjected to heat treatment for 30 minutes. After that, the test piece was removed from the hot air oven, and after confirming that the test piece had cooled to room temperature, the distance x (mm) between each gauge line drawn before the heat treatment was measured.

[0281] Using the obtained values, the heat shrinkage rate (%) at 150°C was calculated using the following formula. (Heat shrinkage rate) = ((150-x) / 150) x 100.

[0282] [Hayes] The laminate was cut into a 100 mm wide x 100 mm long specimen, and the haze was measured using a haze meter (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136 (2000).

[0283] [Elastic recovery rate] The resin layer and resin film were cut into rectangular specimens measuring 10 mm wide and 150 mm long to prepare test pieces. The 150 mm length of each specimen was aligned with the longitudinal direction of the laminate. Using a tensile tester (Orientec Tensilon UCT-100), the initial tensile chuck distance was set to 50 mm, the tensile speed was set to 50 mm / min, and the test temperature was 23°C. After the sample was stretched to a strain of 10 mm (= 20%), the tensile load on the sample was released. This test method is referred to as the tensile test method at a strain of 20%.

[0284] The distance marked as the initial test length before the measurement was measured and defined as L mm, and the elastic recovery rate z % was calculated using the following formula. Elastic recovery rate: z = (1-(L-50) / 20) x 100 (%).

[0285] [Stress retention rate] The resin layer was cut into a rectangular shape measuring 10 mm wide x 120 mm long to prepare a test specimen. In Comparative Example 2, the test specimen was a resin film alone. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec), the tensile test was performed at a temperature of 23°C, with an initial tensile chuck distance of 20 mm and a tensile speed of 300 mm / min. The sample was stretched to a strain of 20 mm (=100%) and held in that state for 1 hour. The stress was measured every 1 second from the start of stretching until the strain was held at 100% for 1 hour. This test method is referred to as a stress relaxation test method at 100% deformation.

[0286] The stress when the strain reached 100% from the start of elongation was defined as F1, and the stress when the strain was maintained at 100% for 1 hour was defined as F2, and the stress retention rate F2 / F1×100 was calculated.

[0287] [Hysteresis area] The resin layer was cut into a rectangular shape measuring 10 mm wide x 120 mm long to prepare a test specimen. In Comparative Example 2, a resin film alone was used as the test specimen. Using a tensile tester (Tensilon UCT-100 manufactured by Orientec), the tensile test was performed at a temperature of 23°C, with an initial tensile chuck distance of 20 mm, a tensile speed of 300 mm / min, and a test temperature of 23°C. The sample was stretched to a strain of 20 mm (=100%), held in that state for 10 seconds, and then restored to a strain of 0 mm (=0%) at a tensile speed of 300 mm / min. The stress during the 100% strain hold from the start of stretching until the sample was restored to a strain of 0% was measured every 0.01 seconds. This test method is referred to as a hysteresis test method at 100% deformation.

[0288] The hysteresis area (MPa) enclosed by the stress-strain curve obtained from the start of elongation until the strain reached 100% and the stress-strain curve obtained from holding the strain at 100% for 10 seconds until the strain returned to 0% was calculated.

[0289] An example of the hysteresis area is shown in Figure 5. The area of ​​the shaded area enclosed by the stress-strain curve is the hysteresis area (MPa).

[0290] [Dimensional change rate] 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 then the resin layer was peeled off from the supporting substrate to prepare a test piece.

[0291] Based on the tensile vibration-non-resonance method of JIS K7244 (1998) (this is called the dynamic viscoelasticity method), the storage modulus and loss modulus of the resin layer were determined using a dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Inc. Measurement mode: Tensile Chuck distance: 20mm Test piece width: 10 mm Frequency: 1Hz Distortion amplitude: 10μm Minimum tension: 20mN Initial force amplitude: 40 mN Measurement temperature: -100℃ to 200℃ Heating rate: 5°C / min

[0292] At this time, the dL value (output value of LVDT (Linear Variable Differential Transformer)) is obtained simultaneously with the measurement of the storage modulus and loss modulus, and this value represents the value corresponding to the dimension of the test piece at the time of measurement. The dL value at 30°C is a 30 (μm), and the dL value at 150°C is a 150 The dimensional change rate was calculated using the following formula: (Dimensional change rate) = ((a 150 -a 30 ) / 20,000)×100

[0293] Furthermore, the absolute value of the dimensional change rate obtained by the above formula was calculated.

[0294] [Glass transition temperature] Based on the tensile vibration-non-resonance method of JIS K7244 (1998) (this is called the dynamic viscoelasticity method), the storage modulus and loss modulus of the resin layer were determined using a dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Inc. The loss tangent was calculated from the obtained values, and a curve of temperature vs. loss tangent was plotted. The temperature at which the loss tangent reached its maximum value was determined as the glass transition temperature.

[0295] In addition, when there are multiple temperatures at which the loss tangent shows a maximum value, the temperature at which the loss tangent shows a maximum value in the temperature range where the storage modulus is 10 MPa or more is prioritized as the glass transition temperature, and when the temperature at which the loss tangent shows a maximum value cannot be determined at a single point, the temperature at which the loss tangent shows the largest value is prioritized as the glass transition temperature. Measurement mode: Tensile Chuck distance: 20mm Test piece width: 10 mm Frequency: 1Hz Distortion amplitude: 10μm Initial force amplitude: 40 mN Measurement temperature: -100℃ to 100℃ Heating rate: 5°C / min Loss tangent: (loss modulus) / (storage modulus).

[0296] [Evaluation of transportability] The laminate and resin film were cut into a 150 mm wide x 250 mm long sample, and the sample was placed in a hot air oven adjusted to 180°C and left to stand for 1 minute. The sample was then removed from the hot air oven and visually inspected for wrinkles and unevenness on the laminate, and judged according to the following criteria. 10 points: No wrinkles, unevenness or curling. 7 points: Slight wrinkles, unevenness, or curling occurs. 4 points: Small wrinkles, unevenness, or curling occurs. 1 point: Other (large wrinkles, unevenness, curling, etc.).

[0297] [Evaluation of peelability] In the laminate, the support substrate and resin layer were previously peeled slightly from the edge, and the peeled portion was grasped and the support substrate and resin layer were peeled by hand in a 180-degree direction, and evaluation was made according to the following criteria. 10 points: Can be peeled off without any feeling of resistance. 7 points: There is a slight feeling of resistance when peeling off. 4 points: There is a strong feeling of resistance when peeling off. 1 point: Other (cannot be peeled off, etc.).

[0298] [Flexibility evaluation] In the laminate, the resin layer was peeled off from the supporting substrate, and then the resin layer was pulled by hand and evaluated according to the following criteria: Furthermore, the resin film was evaluated in the same manner as the resin layer and evaluated according to the following criteria. 10 points: Can be transformed with very little force. 7 points: Can be deformed with light force. 4 points: Can be deformed with a moderate amount of force. 1 point: Other (requires a strong force to transform, etc.).

[0299] [Evaluation of Stretchability] In the laminate, the resin layer was peeled off from the supporting substrate, and then the resin layer was subjected to tensile deformation by applying a light force by hand, and the evaluation was performed according to the following criteria. The resin film was also evaluated in the same manner as the resin layer, and the evaluation was performed according to the following criteria. 10 points: After deformation, the material returns to its original shape when the load is removed. 7 points: After deformation, when the load is removed, the material returns to almost its original shape. 4 points: After deformation, when the load is removed, the material returns to its original shape slightly. 1 point: Other (no restoration at all, etc.).

[0300] [Evaluation of quality recovery] In this evaluation, the laminate was subjected to load during transportation, etc., causing deformation such as unevenness in the resin layer, and it was evaluated whether the deformation such as unevenness was restored in the post-processing step, and whether the final quality was good.

[0301] In the laminate, with the support substrate and resin layer stacked, the surface of the resin layer was lightly pressed with tweezers to make multiple indentations. The indented laminate was then placed in a hot air oven preheated to 50°C for 5 minutes. The laminate was then removed, and the surface condition of the resin layer was visually observed and evaluated according to the following criteria. 10 points: No dents remain. 7 points: A slight dent remains. 4 points: A few dents remain. 1 point: Other (many dents remain, all dents remain, etc.).

[0302] [Evaluation of quality under severe conditions] In this evaluation, we evaluated whether the laminate would lose quality due to peeling or other reasons when subjected to severe stress during transportation or post-processing.

[0303] In the laminate, with the support substrate and the resin layer stacked, the surface of the resin layer was rubbed with gauze ("Hyse" (registered trademark) Gauze NT-4 manufactured by Kawamoto Sangyo Co., Ltd.) 10 times. The state of peeling of the resin layer from the support substrate was then visually observed and evaluated according to the following criteria. 10 points: No or very little peeling occurs. 7 points: Slight peeling occurs. 4 points: Severe peeling occurs. 1 point: Other (very strong peeling, etc.)

[0304] [Evaluation of restorability after long-term deformation] In the laminate, the resin layer was peeled off from the supporting substrate, and then the resin layer was manually subjected to tensile deformation of 100% strain and held for 1 minute, and evaluated according to the following criteria. 10 points: After deformation, if the load is removed, the material will return to its original shape within 1 second. 7 points: After deformation, the material returns to its original shape within 5 seconds and more than 1 second when the load is removed. 5 points: After deformation, the material returns to its original shape within 5 seconds and 10 seconds after the load is removed. 3 points: After deformation, the material returns to its original shape within 10 seconds but not more than 30 seconds after the load is removed. 1 point: After deformation, the material returns to its original shape after removal of the load in more than 30 seconds, or other (e.g., does not return to its original shape at all).

[0305] Tables 2 and 3 summarize the evaluation results of the final laminate.

[0306] [Table 2]

[0307] [Table 3] [Explanation of symbols]

[0308] 1 resin layer 2 Supporting base material 3 Multi-layer slide die 4 Multi-layer slot die 5 Single layer slot die [Industrial Applicability]

[0309] The laminate of the present invention has advantages such as excellent optical properties, flexibility, stretchability, and transportability, and can be suitably used in applications where particularly high flexibility and stretchability are required.

[0310] To give just a few examples, it can be suitably used for surface materials, internal materials, constituent materials, and manufacturing process materials in plastic molded products such as eyeglasses and sunglasses, cosmetic cases, and food containers, aquariums, showcases for exhibitions, smartphone housings, touch panels, color filters, flat panel displays, flexible displays, flexible devices, wearable devices, sensors, circuit materials, electrical and electronic applications, home appliances such as keyboards and TV and air conditioner remote controls, mirrors, window glass, buildings, dashboards, car navigation systems and touch panels, vehicle parts such as rearview mirrors and windows, and various printed materials, medical films, sanitary material films, medical films, agricultural films, and building material films.

Claims

1. A laminate having a resin layer on at least one surface of a supporting substrate, characterized in that the laminate satisfies all of the following conditions 1 to 4, 10, and 11-2. Condition 1: The 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 strength Rb between the supporting substrate and the resin layer is 1,000 mN / 50 mm or less. Condition 4: The thermal shrinkage rate of the laminate in the longitudinal direction at 150°C is 2.0% or less. Condition 10: The glass transition temperature of the resin layer is 0° C. or lower in a dynamic viscoelasticity method. Condition 11-2: The resin layer is a resin composition obtained by curing urethane (meth)acrylate.

2. 2. The laminate according to claim 1, wherein the laminate satisfies the following condition 6: Condition 6: The elastic recovery rate of the resin layer is 70% or more in a tensile test at a deformation amount of 20%.

3. 3. The laminate according to claim 1, wherein the laminate satisfies the following conditions 7 and 8: Condition 7: Stress F when the resin layer is stretched to 100% strain in a stress relaxation test method at 100% deformation １ and the stress F after holding it in that state for 1 hour ２ The stress retention rate F is the ratio of ２ / F １ ×100 is 70% or more. Condition 8: In a hysteresis test at 100% deformation, the resin layer is stretched to a strain of 100%, held for 10 seconds, and then released. The hysteresis area enclosed by the stress-strain curves at the time of stretching and at the time of release is less than 1.0 MPa.

4. 4. The laminate according to claim 1, wherein the laminate satisfies the following condition 9: Condition 9: When the dimensions of the resin layer at 30°C are used as a reference, the absolute value of the dimensional change rate of the resin layer at 150°C is 10% or less.

5. 5. The laminate according to claim 1, wherein the urethane (meth)acrylate has a number average molecular weight of 3,000 or more.

6. 6. The laminate according to claim 1, wherein the laminate satisfies the following condition 12: 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. 7. A method for producing a laminate according to claim 1, wherein a resin layer is formed on at least one surface of a supporting substrate, and the method satisfies the following condition 13: Condition 13: A resin layer is formed by applying the coating composition onto a supporting substrate.

8. A method for producing a resin film, comprising a step of peeling off the supporting substrate from the laminate according to any one of claims 1 to 6.

9. A plastic molded product using the laminate according to any one of claims 1 to 6.

10. A display using the laminate according to any one of claims 1 to 6.

11. A sensor using the laminate according to any one of claims 1 to 6.

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