JP7200562B2 - laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminate that achieves both flexibility and post-processability.

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

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

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

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

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

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

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

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

Silicone Handbook Nikkan Kogyo Shimbun 1990 Adhesives to learn from the basics - Why do they stick? why does it peel off? - Maruzen Publishing Co., Ltd.

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

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

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

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

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

In order to solve the above problems, the present inventors completed the following invention as a result of earnest research. That is, the present invention is as follows.
<1>
A laminate having a resin layer between two release films having a release layer on at least one surface of a supporting substrate, wherein the resin layer has a storage elastic modulus of 1 MPa or more and 100 MPa at a temperature of 25° C. and a frequency of 1 Hz. or less, a loss tangent of 0.5 or less, and different peeling forces of the two release films from the resin layer.
<2>
The laminate according to <1>, which satisfies Condition 1 below.

Condition 1: Regarding the peel strength between the resin layer and the two release films at a peel speed of 300 mm/min, the higher peel strength is 100 mN/50 mm or more and 1,000 mN/50 mm or less.
<3>
A laminate according to <1> or <2>, wherein one release film is removed.
<4>
A release film having a release layer on at least one surface of a supporting substrate, and a laminate having a resin layer that can be peeled off from the release film, wherein the resin layer has a segment represented by Chemical Formula 1 and / or Chemical Formula 2. A laminate, comprising: and satisfying condition 2 below.

Condition 2: The surface free energy S ₁ (mJ/m ² ) of the resin layer, the surface free energy S ₂ (mJ/m ² ) of the release layer, and the surface elastic modulus E ₂ ( MPa) satisfies the following formulas 1 and 2.

Equation 1: S ₁ - S ₂ < 60
Equation ₂ : E<2,000

R ₁ refers to hydrogen or a methyl group.

_R2 refers to any of the following:
A substituted or unsubstituted alkylene group A substituted or unsubstituted arylene group having an ether group, an ester group, or an amide group inside An alkylene group having an ether group, an ester group, or an amide group inside an arylene group An ether group, an ester group or an unsubstituted arylene group having an ether group, an ester group, or an amide group inside an unsubstituted alkylene group having an amide group

<5>
The laminate according to <4>, wherein the resin layer has a storage elastic modulus of 1 MPa or more and 100 MPa or less at a temperature of 25° C. and a frequency of 1 Hz.
<6>
The laminate according to <4> or <5>, wherein the resin layer has a loss tangent of 0.5 or less at a temperature of 25° C. and a frequency of 1 Hz.
<7>
Any one of <4> to <6>, wherein a protective layer having a different release force from the release layer is further provided on the surface of the resin layer opposite to the surface in contact with the release layer. Laminate as described.
<8>
The laminate according to any one of <1> to <7>, which satisfies condition 3 below.

Condition 3: Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) Strength of 1,000 or less.
<9>
The laminate according to any one of <1> to <8>, wherein the release layer includes segments having structures of chemical formulas 3 and 4.

R. ₁ ～R ₆ are each independently hydrogen, R _x OCH ₂ represents a group represented by - or a group derived from a melamine derivative represented by Chemical Formula 4; However, R _x represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

<10>
The laminate according to any one of <1> to <9>, wherein the resin layer contains a segment represented by Chemical Formula 5.

R ₁ is an alkyl group or alkylene group having 1 to 6 carbon atoms, and n is 2 to 50 carbon atoms.

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

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

Before describing embodiments of the present invention, the problem of the prior art, ie, compatibility between flexibility and transportability, will be considered from the viewpoint of the present inventor. In the following description, simply referring to the present invention means including both a laminate having a first configuration and a laminate having a second configuration, which will be described later.

[Comparison between the present invention and conventional technology]
In the prior art, there are materials exhibiting flexibility and stretchability, but due to their flexibility and stretchability, post-processability is insufficient. Therefore, even if the material is suitable from the viewpoint of flexibility and stretchability, it is often used after various post-processing in applications such as displays, devices, and sensors. Therefore, it was difficult to apply it in practice.

Materials exhibiting flexibility and stretchability (hereinafter referred to as flexible materials) are difficult to transport by themselves when applied to a continuous process such as Roll-to-Roll. In other words, it is necessary to apply tension to the material in order to convey it, and this tension causes deformation in the flexible material. In addition, by applying tension in the conveying direction, shrinkage occurs in the direction perpendicular to the conveying direction, causing wrinkles, and in such a state, the quality deteriorates. In addition, when wrinkles are generated, it is extremely difficult to apply and bond the adhesive and to form a circuit, and it cannot be practically used.

Therefore, flexible materials are used together with a supporting substrate (so-called carrier). Supporting substrates may be used on only one side of such materials, or on both sides. The problem here is that the supporting substrate is effective in improving the transportability of materials exhibiting flexibility and stretchability, but it can be peeled off without hindrance during post-processing or use. Desired. When peeling off the supporting substrate, since the flexible material and the supporting substrate are usually held while peeling, it is necessary to appropriately control the peeling force.

For example, if the peeling force is too high, if the supporting substrate cannot be peeled off from the flexible material well, if the force required for peeling is too strong and the flexible material is deformed or broken, or if the adhesive is formed on the flexible material. There is a possibility that the adhesive or the circuit may be destroyed. On the other hand, if the peeling force is too low, unintended peeling may occur. Further, in a situation where supporting substrates are used on both sides of the flexible material, if the peeling force is too heavy, the same problem as above may occur, and the release film may peel off from the side that is not desired to be peeled off. If the peeling force is too light, as described above, the release film on the side other than the side to be peeled may be peeled, or both may be partially peeled off.

In addition, regarding the laminate in the present invention, when focusing on the difference in behavior between the flexible material and the general-purpose adhesive material exemplified in Non-Patent Document 2, it was also found that different behaviors were exhibited with respect to peeling from the release film. rice field.

Specifically, when compared with the flexible materials dealt with in this application, even if the adhesive material unintentionally peels off the release film as described above, it is found that the unintended peeling does not grow easily. rice field. It is considered that this is because the adhesive material is inherently tacky, and if there is only a small amount of unintended peeling, it is likely that the adhesive material will be re-bonded during the transport process. In addition, flexible materials have a higher storage modulus than adhesive materials and are relatively self-supporting. Therefore, when unintended detachment occurs with a flexible material, the self-supporting property of the flexible material in the detached portion propagates the stress applied to detachment, and it is believed that unintended detachment is more likely to occur than with adhesive materials. . Therefore, we believe that a higher level of peel control is required for soft materials compared to conventional adhesive materials.

Here, as mentioned above, as a material used by using a support substrate on one side or both sides of the resin layer, an adhesive material is mentioned as a material close to a flexible material. For example, an adhesive tape or the like is provided as an adhesive material provided with a supporting substrate on one side thereof, and an optical adhesive sheet (OCA) or the like is provided as an adhesive material provided with a supporting substrate on both sides thereof. However, the flexible materials addressed in this application have different mechanical properties than the adhesive materials. In other words, the flexible material used in the present application may have, for example, a storage modulus of 1 MPa or more and 100 MPa or less, a loss tangent of 0.5 or less, or a material that satisfies both. In the adhesive material, these storage modulus and loss tangent have a great influence on the adhesive properties, and a material that satisfies the above properties cannot exhibit appropriate adhesive properties (ease of sticking, holding power, etc.). Therefore, the soft material dealt with in the present application belongs to a technical field different from that of the adhesive material. In addition, since flexible materials have the aforementioned storage elastic modulus and loss tangent, unlike adhesive materials, the force of adhesion to other materials is very weak (in other words, they cannot be said to have adhesiveness). With respect to the relationship between the release force and the release force of the release film, it is not possible to develop the conventional knowledge about the adhesive material and the release film as it is. In fact, when the inventors of the present invention conducted a detailed study of the peel strength between the flexible material and the release film, they found many tendencies that differed from the findings of the adhesive material.

Therefore, the present inventors have studied the characteristics in detail in order to appropriately control the peeling force between the flexible material and the release film. First, in the configuration in which the support substrate is provided on both sides of the flexible material, the support substrate is a release film having a release layer, and the release film and the flexible material on both sides have different peeling forces, so that the It was found that when one of the release films is peeled off in a processing step or the like, the release film can be selectively peeled off. If the release force of each release film and flexible material is the same, when one is peeled off, the other may be partially or totally unintentionally peeled off, but if the release force of each is different. In particular, only the release film having a smaller release force can be selectively released.

Specifically, it is preferable that the two release films have different peel strengths from the resin layer.

Furthermore, when the present inventors examined the peeling force, it was found that it is effective to keep the peeling force between the resin layer and the release film within a certain range.

Considering only the peeling of the resin layer from the release film, the lower the peeling force, the easier the peeling. However, if the peeling is extremely light, unintended peeling as described above tends to occur. In particular, when two release films are laminated on both sides of the resin layer, it is necessary to peel off at least one of the release films laminated on the resin layer, and at this time, unintended peeling may occur. If it is put away, it may interfere with the subsequent post-processing steps.

Therefore, we examined the optimum range of the peeling force between the resin layer and the release film, and found that by keeping the peeling force within a certain range, the release film can be appropriately and selectively peeled off even in post-processing steps. have understood.

Specifically, with respect to the peeling force between the resin layer and the two release films at a peeling speed of 300 mm/min, the higher peeling force is preferably 100 mN/50 mm or more and 1,000 mN/50 mm or less.

In addition, in the structure having two release films on both sides of the resin layer, the resin layer can be exposed again by peeling off one of the release films. Therefore, various post-processing (printing processing, coating processing, bonding processing, vapor deposition processing, acid/alkali processing processing, etc.) can be performed on the resin layer.

Specifically, it is preferable to form a laminate by peeling off one of the two release films.

Furthermore, the present inventors focused on the properties of the release film and conducted detailed studies from the viewpoint of controlling the peeling force between the release film and the resin layer in the laminate. As a result, they have found that it is important that the difference in surface free energy between the release layer and the resin layer is less than a certain level and that the surface elastic modulus of the release layer is less than a certain level.

In general, when trying to lower the peeling force between an adherend and a release film, the material used for the release layer of the release film is often adjusted to lower the surface free energy of the release layer. However, although this tends to be qualitatively, there are many cases that do not match the tendency. Conversely, increasing the surface free energy does not necessarily increase the peel force.

Therefore, the present inventors paid attention not only to the release film but also to the surface free energy of the flexible material that serves as the adherend in the present invention, and examined the difference in detail. As a result, we found that the release force between the flexible material and the release film can be controlled by combining the difference in surface free energy and the surface elastic modulus of the release layer. This is because the difference in surface free energy controls the chemical affinity between the flexible material and the release film, and by lowering the surface elastic modulus of the release film, when the flexible material is peeled off from the release film, It is believed that this is because the release layer side actively deforms and the flexible material can be peeled off without excessive deformation.

Specifically, the surface free energy S ₁ (mJ/m ² ) of the resin layer, the surface free energy S ₂ (mJ/m ² ) of the release layer, and the surface elastic modulus E ₂ (MPa), it is preferable that the following formula holds.

Equation 1: S ₁ - S ₂ < 60
Equation ₂ : E2 < 1,000.

As described above, in order to appropriately control the release force of the flexible material and the release film, the present inventors have investigated various materials for the release layer. As a result, the inventors have found that there is a preferred material for the release layer, although it is not particularly limited.

In the flexible material exemplified in the present invention, from the viewpoint of controlling the surface free energy between the flexible material and the release layer, it is preferable that the components constituting the release layer contain, for example, a small amount of components derived from dimethylsiloxane. In addition, it has been found that there are other materials that are preferable as components for the release layer, as will be described later.

Specifically, Si(CH ₃ ) ⁺ fragment ions (M/Z = 43 ) is preferably 1,000 or less.

Also, the resin constituting the release layer preferably contains a segment having a structure represented by Chemical Formula 3 or Chemical Formula 4 described below.

Whether the resin constituting the release layer contains segments having the above structure can be examined by various analysis methods, but the method using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) is the most suitable. Easy. It can also be determined from the raw material that constitutes the release layer.

In addition, in the laminate exemplified above, in order to perform post-processing (printing processing, coating processing, bonding processing, vapor deposition processing, acid / alkali treatment processing, etc.) on the laminate, the resin layer and the release film It is preferable that one surface of the resin layer is exposed by being laminated. On the other hand, after forming the laminate in the present invention, it is necessary to perform packing and transportation in order to carry out the post-processing described above. However, the resin layer of the laminate in the present invention is very flexible as described above, and may be damaged or dented during handling such as packing or transportation, or may be mixed with foreign matter.

Therefore, in the laminate having the second configuration described later in the present invention, it is preferable to provide a protective layer on the surface of the resin layer opposite to the surface in contact with the release film (release layer). The protective layer is not particularly limited as long as it can protect the resin layer. For example, it is preferably a film, particularly a release film. Moreover, it is preferable that the release force between the release film provided as the protective layer and the resin layer is different from the release force of the release film provided on the opposite surface of the resin layer. This is because different peeling forces can prevent unintentional peeling as described above. When peeling off one of the release films as necessary, such as during post-processing, handling is facilitated, which is preferable.

Furthermore, when the present inventors examined long-term durability and peel strength, they found that a resin layer having high durability is more preferable.

As described above, it is assumed that the laminate of the present invention is subjected to post-processing, but due to manufacturing reasons, post-processing may be performed immediately after the laminate of the present invention is manufactured. is not limited. In that case, the laminate of the present invention will be stored until post-processing, but depending on the circumstances, it may be stored for a long period of time in a harsh environment such as high temperature and high humidity. Therefore, even if exposed to such a severe environment, if the resin layer and the release film in the laminate can be properly separated, it can be said that it is easier to handle as a product and more preferable.

The inventors of the present invention conducted studies from such a point of view and found that it is effective to increase the durability of the resin layer in particular. When the behavior of the resin layer was observed, it was speculated that if the resin layer had low durability, the resin layer deteriorated in a harsh environment. In this case, the resin layer becomes tacky (so-called sticky state), and as a result, it may not be possible to remove it from the release film.

Therefore, when the present inventors investigated the components that make up the resin layer, in addition to the segments of chemical formula 1 and chemical formula 2 described later, the resin layer has the segment of chemical formula 5, in addition to elasticity and toughness, It was found that the durability in such a severe environment can be enhanced.

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

In order to satisfy the above problems, that is, flexibility, stretchability, and post-processability, the laminate of the first configuration of the present invention includes two release films having a release layer on at least one surface of the support substrate. A laminate having a resin layer between them, wherein the storage elastic modulus of the resin layer is 1 MPa or more and 100 MPa or less and the loss tangent is 0.5 or less at a temperature of 25 ° C. and a frequency of 1 Hz, and two mold releases from the resin layer It is preferred that the peel forces of the films are different. Here, the different peeling forces of the two release films with respect to the resin layer means the peeling force when each of the two release films is peeled off by the measurement method described in the [Peeling Force] section of the Examples. (mN/50mm) is different.

Methods for measuring the storage modulus and the peel strength will be described later.

From the viewpoint of flexibility and stretchability, the laminate of the present invention preferably has a storage elastic modulus of 1 MPa or more and 100 MPa or less at a temperature of 25° C. and a frequency of 1 Hz, more preferably 50 MPa or less. , particularly preferably 30 MPa or less. Flexibility can be enhanced by setting the storage modulus within a specific range. The point that the storage elastic modulus of the resin layer is preferably 1 MPa or more and 100 MPa or less is the same not only for the laminate having the first configuration but also for the laminate having the second configuration described later. It can also have excellent effects on the body.

When the storage elastic modulus of the resin layer is within a specific range, flexibility is improved, which is preferable. If the storage elastic modulus is low, the flexibility is improved, but if it is excessively low, the rigidity may be insufficient, and the lower limit is considered to be about 1 MPa. On the other hand, when the storage elastic modulus is higher than 100 MPa, the flexibility of the resin layer is lowered, which may make it unsuitable for the intended use.

In order to set the storage elastic modulus of the resin layer to 1 MPa or more and 100 MPa or less, it is possible, for example, by selecting a material exemplified later for the resin contained in the resin layer.

From the viewpoint of stretchability, the laminate of the present invention preferably has a loss tangent of the resin layer of 0.5 or less at a temperature of 25° C. and a frequency of 1 Hz. By setting the loss tangent to a certain value or less, the stretchability of the resin layer can be enhanced. The point that the loss tangent of the resin layer is preferably 0.5 or less is the same not only for the laminate having the first configuration, but also for the laminate having the second configuration described later, and the laminate having the second configuration An excellent effect can be obtained also in

When the loss tangent of the resin layer is 0.5 or less, the stretchability is improved, which is preferable. On the other hand, if the loss tangent is higher than 0.5, the elasticity of the resin layer may be insufficient and the product may be unsuitable. Also, if the loss tangent is high, the resin layer becomes sticky, which may be unsuitable for some applications.

In order to set the storage elastic modulus of the resin layer to 1 MPa or more and 100 MPa or less, it is possible, for example, by selecting a material exemplified later for the resin contained in the resin layer.

From the viewpoint of releasability, it is preferable that the laminate of the present invention has different releasability between the two release films with respect to the resin layer. If the two release films have different peeling forces from the resin layer, only the release film can be selectively peeled when the release film having the smaller peeling force is peeled off. On the other hand, if the two release films have the same peel force against the resin layer, when one release film is peeled off, the other release film partially or entirely unintentionally peels off. There are cases where the release film cannot be selectively peeled off.

In order to make the peel strength of the two release films different from the resin layer, it is possible, for example, by selecting different release films. Regarding the two release films in the present invention, one release film may be referred to as "release film (coating side)" and the other release film may be referred to as "release film (bonding side)".

Furthermore, from the viewpoint of post-processing, the laminate having the first configuration preferably satisfies Condition 1 below.

Condition 1: With respect to the peel strength between the resin layer and the two release films at a peel speed of 300 mm/min, the peel strength of the higher peel strength is 100 mN/50 mm or more and 1,000 mN/50 mm or less.

A method for measuring the peel force will be described later.

From the viewpoint of post-processability, in the laminate of the present invention, with respect to the peel strength between the resin layer and the two release films at a peel rate of 300 mm/min, the peel strength of the higher peel strength is 100 mN/50 mm or more. ,000 mN/50 mm or less, more preferably 100 mN/50 mm or more and 800 mN/50 mm or less, and particularly preferably 100 mN/50 mm or more and 500 mN/50 mm or less. The peel strength represents the ease with which the release film and the resin layer can be peeled off.

Regarding the peeling force between the resin layer and the two release films, if the peeling force of the higher peeling force is within a specific range, one of the release films can be selectively peeled due to the above effect, This is preferable because it improves operability. If the release force of both the resin layer and the two release films is less than 100 mN / 50 mm, the release film will be too easy to peel from the resin layer, and when one is peeled off, the other will also peel off. It may not be possible to peel off effectively. In addition, if the peel force exceeds 1,000 mN/50 mm, peeling may not be possible, or selective peeling may not be possible because a large force is required for peeling.

In order to set the peel force of at least one of the resin layer and the two release films to 100 mN / 50 mm or more and 1,000 mN / 50 mm or less at a peel speed of 300 mm / min, for example, conditions 5 and 6 described later or by satisfying one or more of Condition 9, Condition 10, or Condition 11.

Further, from the viewpoint of post-processability including peelability, the laminate of the second configuration of the present invention includes a release film having a release layer on at least one surface of the support substrate, and a release film that can be peeled off from the release film. It is preferable that the laminate has a resin layer, the resin layer contains segments represented by chemical formula 1 and/or chemical formula 2, and satisfies condition 2 below.

Condition 2: Regarding the surface free energy S ₁ (mJ/m ² ) of the resin layer, the surface free energy S ₂ (mJ/m ² ) of the release layer, and the surface elastic modulus E ₂ (MPa) by atomic force microscope , satisfies Equations 1 and 2 below.

Equation 1: S ₁ - S ₂ < 60
Equation ₂ : E<2,000
In Chemical Formula 1, R ₁ is hydrogen or a methyl group.

In Chemical Formula 1, R ₂ refers to any of the following.
A substituted or unsubstituted alkylene group A substituted or unsubstituted arylene group having an ether group, an ester group, or an amide group inside An alkylene group having an ether group, an ester group, or an amide group inside an arylene group An ether group, an ester group or an unsubstituted arylene group having an ether group, an ester group, or an amide group inside an unsubstituted alkylene group having an amide group. Methods for measuring surface free energy and surface elastic modulus will be described later.

Formula 1 represents groups derived from acrylate and/or methacrylate. In order for the resin layer to include the segment represented by Chemical Formula 1, it is possible to use a commercially available acrylate material or methacrylate material, or an acrylate material or methacrylate material to be described later, for the resin layer and perform a curing process. For example, as described later, the above-described acrylate material or methacrylate material is used in the coating composition used to form the resin layer, and the coating composition is applied on the support substrate or release film, dried, and cured. A method of forming a resin layer is exemplified.

From the viewpoint of the stretchability and toughness of the resin layer, it is preferable that the resin layer contains segments of Chemical Formula 1 and/or Chemical Formula 2. Moreover, it is more preferable that the resin layer includes both segments of Chemical Formula 1 and Chemical Formula 2.

From the viewpoint of flexibility and stretchability, it is preferable to satisfy Formulas 1 and 2. Formula 1 expresses the chemical affinity between the resin layer and the release layer. In addition, as described above, the surface elastic modulus of the release layer affects the release force.

When formulas 1 and 2 are satisfied, as described above, the peeling force between the resin layer and the release film can be kept above a certain level, which is preferable. On the other hand, when at least one of the formulas 1 and 2 is not satisfied, the peeling force between the resin layer and the release film becomes excessively small, and unintended peeling may occur. In addition, in the case of a configuration in which release films are provided on both surfaces of the resin layer, it may be difficult to selectively release one of the release films because the release force is excessively low.

In order to satisfy Formulas 1 and 2, for example, the release layer can contain segments having structures of Chemical Formulas 3 and 4 described below.

Furthermore, from the viewpoint of releasability, the laminate having the second configuration preferably satisfies Condition 3 below.

Condition 3: Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) Strength of 1,000 or less.

Details of the time-of-flight secondary ion mass spectrometer (TOF-SIMS) will be described later.

The intensity of Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer represents the intensity of uneven distribution of the dimethylsiloxane component on the surface of the release layer.

From the viewpoint of releasability, the intensity of Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer is preferably 1,000 or less.

When the intensity of Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer is 1,000 or less, the release force between the resin layer and the release film is improved. preferable. On the other hand, when the intensity of Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer exceeds 1,000, the release force between the resin layer and the release film is excessive. too low and unintentional delamination may occur. In addition, in the case of a configuration in which release films are provided on both surfaces of the resin layer, it may be difficult to selectively release one of the release films because the release force is excessively low.

In order to set the intensity of Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer to 1,000 or less, for example, the release layer has chemical formula 3 and chemical formula This is possible by including a segment having a structure of 4 and by not using materials derived from silicone such as dimethylsiloxane.

In Chemical Formula 4 , R ₁ to R ₆ each independently represent hydrogen, a group represented by R _x OCH ₂ —, or a group derived from a melamine derivative represented by Chemical Formula 4. However, R _x represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

Furthermore, from the viewpoint of long-term durability, it is preferable that the resin layer contains a segment represented by Chemical Formula 5.

In Chemical Formula 5, R ₁ is an alkyl group or alkylene group having 1 to 6 carbon atoms, and n is 2 to 50 carbon atoms. More preferably, R ₁ is an alkyl group or alkylene group having 2 or more and 4 or less carbon atoms, and n is 10 or more and 40 or less.

From the viewpoint of long-term durability of the laminate, it is preferable that the resin layer contains a segment represented by Chemical Formula 5. When the resin layer contains the segment represented by the chemical formula 5, the durability of the resin layer is improved, and the laminate can be made easier to handle even when stored for a long period of time in a harsh environment as described above.

[Release film, release layer]
The release layer in the release film of the present invention is used by providing a resin layer on at least one surface of the support substrate and on the surface of the release layer opposite to the support substrate. The release layer may be composed of a plurality of layers from the viewpoint of imparting adhesiveness, antistatic properties, solvent resistance, etc., and may be present on both sides of the support substrate.

Here, the term "layer" refers to a portion having a boundary surface distinguishable from adjacent portions and having a finite thickness in the thickness direction from the surface side. More specifically, when the cross section of the release layer is observed with an electron microscope (transmission type, scanning type) or an optical microscope, it refers to the presence or absence of a discontinuous interface. Even if the composition changes in the thickness direction of the release layer, if there is no boundary surface between them, it is treated as one layer.

The thickness of the release layer is not particularly limited as long as the surface on which the resin layer is provided has the standard deviation and average value of the above-mentioned specific elastic modulus distribution, but the in-plane uniformity and quality of the release layer , the thickness is preferably 10 nm or more and 500 nm or less, more preferably 20 nm or more and 300 nm or less, from the viewpoint of peel strength.

_The material of the release layer is not particularly limited as long as the surface free energy S1 and the surface elastic modulus E2 measured by _an atomic force microscope satisfy the above ranges, but the release layer coating composition described below is used. It is preferably formed on the surface of the supporting substrate by applying, drying, and curing by the manufacturing method of the release layer described below.

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

Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyimide resins, polyester resins, polycarbonate resins, Fluorine such as polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene chloride resin, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride resin, etc. Resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. Examples of thermosetting resins that can be used include phenol resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, polyurethane resins, polyimide resins, and silicone resins. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. From the viewpoint of strength, heat resistance, and transparency, the thermoplastic resin is more preferably polyester resin, polycarbonate resin, acrylic resin, or methacrylic resin.

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

Various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant or the like for adjusting the refractive index may be added. The supporting substrate may have either a single-layer structure or a laminated structure.

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

In addition to the resin layer of the present invention, functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, an ultraviolet absorption layer, and a release layer may be provided in advance on the surface of the support substrate. In the laminate of the present invention, it is particularly preferable to provide a release layer in order to reduce the peeling force between the support substrate and the resin layer.

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

[Release layer coating composition]
If the release layer coating composition satisfies the elastic modulus and surface free energy determined by an atomic force microscope when the release layer is formed on the supporting substrate by the above-described method for producing a release film, The material is not particularly limited, but when the release layer is placed on the supporting substrate, it is preferable that the resin constituting the release layer is composed of a component capable of containing segments having the structure described above.

Compounds containing a segment having the structure of Chemical Formula 3 include polyester compounds and their derivatives and precursors, and alkyd compounds and their derivatives and precursors are particularly preferred. Further, examples of compounds containing a segment having the structure of Chemical Formula 4 include melamine compounds and their derivatives and precursors.

A melamine compound is a compound having a melamine skeleton in the compound. Examples thereof include alkylolated melamine derivatives and compounds obtained by reacting alkylolated melamine derivatives with alcohol to partially or completely etherify them. Examples of alkylolation include methylolation, ethylolation, isopropylolation, n-butyrolation, and isobutyrolation. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol and isobutanol. The melamine compound may be a monomer, a polymer of dimers or higher, or a mixture thereof. Also, urea or the like may be co-condensed with a part of melamine, or a catalyst may be used to improve the reactivity of the melamine compound.

It may also contain a compound having a long-chain alkyl group. Examples of compounds having long-chain alkyl groups include acrylic monomers having long-chain alkyl groups. Examples of acrylic monomers having long-chain alkyl groups include decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadechyl (meth)acrylate, icosyl (meth)acrylate, henicosyl (meth)acrylate, triacontyl (meth)acrylate.

In addition to the above materials, acrylic resins such as acrylic polyol, polyester resins, epoxy resins, urethane resins, and their precursors may be included.

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

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

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

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

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

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

Furthermore, in the laminate of the present invention, from the viewpoint of long-term durability, it is preferable to form a resin layer by applying the following resin layer coating composition B on a release film.

[Resin layer coating composition A]
The resin layer coating composition A is a liquid containing a material suitable for forming the resin layer of the present invention, or containing a precursor capable of being formed, and the following segments (1) to (2) as a solute: It is preferable to include a resin or precursor containing It may also contain a resin or precursor containing the segment (3).
(1) a segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment and a polyalkylene glycol segment (2) a urethane bond (3) from the group consisting of a fluorine compound segment, a polysiloxane segment and a polydimethylsiloxane segment A segment containing at least one selected.

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

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

The details of the (1) polycaprolactone segment, polycarbonate segment and polyalkylene glycol segment will be described later, but the resin constituting the resin layer has these segments, so that the stretchability and flexibility of the resin layer are improved. be able to. Moreover, from the viewpoint of durability of the resin layer, it is particularly preferable that the resin constituting the resin layer has a polyalkylene glycol segment.

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

Details of the fluorine compound segment, the polysiloxane segment, and the polydimethylsiloxane segment will be described later, but by including these in the resin constituting the resin layer, molecules exhibiting low surface energy can be present at a high density on the outermost surface. It is possible to improve the solvent resistance of the resin layer.

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

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

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

[Resin layer coating composition B]
The resin layer coating composition B is a liquid containing a material suitable for forming the resin layer of the present invention, or containing a precursor capable of being formed, and contains the polyether segment of Chemical Formula 5 and the ( It preferably contains a resin or precursor containing a meth)acrylic segment and a urethane segment of formula (2). These may all be present in one type of polymer or oligomer, or may be a mixture of different polymers or oligomers containing each.

In the laminate of the present invention, mechanical properties such as flexibility and restorability of the resin layer are important. Therefore, a method capable of controlling the structure of the polymer forming the resin layer is preferred. In the laminate of the present invention, the resin layer is required to have a high level of appearance quality and thickness smoothness. has a preferred range. Furthermore, since the laminate of the present invention is processed in a post-process, it is preferable that the laminate have as much resistance to solvents and the like as possible.

Therefore, the resin layer coating composition B is prepared by polymerizing a precursor containing a polyether segment represented by Chemical Formula 5, a (meth)acrylic segment represented by Chemical Formula 1, and a urethane segment represented by Chemical Formula 2 in such a manner that the molecular weight can be controlled to form an oligomer. , Various additives are added to this to prepare a resin film-forming coating composition, and in the method for producing a laminate described later, this is applied on a supporting substrate and crosslinked to form a resin film. is preferred.

Specifically, a polyether polyol and a compound containing an isocyanate group and a hydroxyalkyl (meth)acrylate or an acrylic-modified polyether polyol and a compound containing an isocyanate group are polymerized in advance to make a urethane acrylate oligomer. It is preferable to add additives as appropriate to the resin film-forming coating composition.

Polyether polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and various derivatives thereof.

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

[Polycaprolactone segment, polycarbonate segment, polyalkylene glycol segment]
First, the polycaprolactone segment refers to the segment represented by Chemical Formula 6. Polycaprolactone includes those having 1 (monomer), 2 (dimer), 3 (trimer) repeating units of caprolactone, and oligomers having up to 35 repeating units of caprolactone.

Here, n is an integer from 1 to 35.

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

As the resin containing polycaprolactone segments, polycaprolactone having di- or tri-functional hydroxyl groups is particularly preferred. Specifically, polycaprolactone diol represented by Chemical Formula 7,

Here, m+n is an integer of 4 to 35, m and n are each an integer of 1 to 34, R is C ₂ H ₄ , C ₂ H ₄ OC ₂ H ₄ or C(CH ₃ ) ₃ (CH ₂ ) ₂
or polycaprolactone triol represented by Chemical Formula 8,

Here, l+m+n is an integer of 3 to 30, l, m and n are integers of 1 to 28, respectively, and R is CH ₂ CHCH ₂ , CH ₃ C(CH ₂ ) ₃ or CH ₃ CH ₂ C(CH ₂ ) ₃
Polycaprolactone polyol such as polycaprolactone modified hydroxyethyl (meth) acrylate represented by the chemical formula 9

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

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

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

Next, the polyalkylene glycol segment refers to the segment represented by Chemical Formula 10. Polyalkylene glycols include those having 2 (dimer) and 3 (trimer) repeating units of alkylene glycol, and oligomers having up to 11 repeating units of alkylene glycol.

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

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

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

Examples of the polyalkylene glycol (meth)acrylate contained in the coating composition used to form the resin layer include polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, and polybutylene glycol (meth)acrylate. . They are structures represented by the following chemical formulas 11, 12 and 13, respectively.

Polyethylene glycol (meth)acrylate:

Polypropylene glycol (meth)acrylate:

Polybutylene glycol (meth)acrylate:

In chemical formulas 11, 12, and 13, R is hydrogen (H) or a methyl group (--CH ₃ ), and m is an integer of 2-11.

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

Hydroxyalkyl (meth)acrylates that are simultaneously blended during the urethanization reaction between the compound containing an isocyanate group and the polyalkylene glycol (meth)acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl. (Meth)acrylate and the like are exemplified.

Next, the polycarbonate segment refers to the segment represented by Chemical Formula 14. Polycarbonates include those having 2 (dimer), 3 (trimer) repeating carbonate units, and oligomers having up to 16 repeating carbonate units.

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

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

A polycarbonate diol having a bifunctional hydroxyl group is particularly preferable as the resin containing a polycarbonate segment. Specifically, it is represented by chemical formula 15.
Polycarbonate Diol:

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

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

The polycarbonate diol preferably has a number average molecular weight of 500 to 10,000, more preferably 1,000 to 5,000. If the number-average molecular weight is less than 500, it may be difficult to obtain suitable flexibility, and if the number-average molecular weight exceeds 10,000, the heat resistance and solvent resistance may decrease. is.

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

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

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

[Compound containing urethane bond and isocyanate group]
In the present invention, the "urethane bond" refers to the bond represented by Chemical Formula 2 above.

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

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

In the present invention, it is preferable to introduce a urethane bond into the resin constituting the resin layer by reacting an isocyanate group and a hydroxyl group to generate a urethane bond. By reacting an isocyanate group and a hydroxyl group to generate a urethane bond, it is possible to improve the toughness and stretchability of the resin layer.

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

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

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

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

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

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

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

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

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

Further, the fluorine compound segment is preferably a fluoropolyether segment, which is a site composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, or the like.

The fluoropolyether segment is a segment composed of a fluoroalkyl group, an oxyfluoroalkyl group, an oxyfluoroalkanediyl group, or the like, and has a structure represented by chemical formulas 16 and 17.

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

The chain length of this fluoropolyether segment has a preferred range, and the number of carbon atoms is preferably 4 or more and 12 or less, more preferably 4 or more and 10 or less, and particularly preferably 6 or more and 8 or less. If the number of carbon atoms is 3 or less, the surface energy may not be sufficiently reduced, resulting in a decrease in oil repellency.

When the resin contained in this resin layer contains a fluorine compound segment, the coating composition A preferably contains the following fluorine compounds. This fluorine compound is a compound represented by Chemical Formula 18.

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

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

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

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

Next, the polysiloxane segment will be described. In the present invention, the polysiloxane segment refers to a segment represented by chemical formula 19 below.

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

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

Although the details of the polysiloxane segment and the polydimethylsiloxane segment will be described later, the presence of these segments in the resin constituting the resin layer improves heat resistance and weather resistance, and improves slipperiness due to the lubricity of the resin layer. can be improved. More preferably, it contains a polydimethylsiloxane segment represented by Chemical Formula 20 described below from the viewpoint of lubricity.

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

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

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

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

Next, the polydimethylsiloxane segment will be described. In the present invention, the polydimethylsiloxane segment refers to the segment represented by Chemical Formula 20. Polydimethylsiloxane includes both low-molecular-weight dimethylsiloxane repeating units of 10 to 100 (so-called oligomers) and high-molecular-weight dimethylsiloxane repeating units of more than 100 (so-called polymers).

m is an integer from 10 to 300;

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

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

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

When the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, a coating composition containing a resin (copolymer) containing a polydimethylsiloxane segment having a hydroxyl group and a compound containing an isocyanate group is used. When the resin layer is formed by using the above method, it is possible to efficiently obtain a resin layer having polydimethylsiloxane segments and urethane bonds.

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

When the polymer initiator method is used, a polymer azo radical polymerization initiator represented by Chemical Formula 21 can be used for copolymerization with other vinyl monomers. In addition, a two-stage polymerization in which a peroxy monomer and a polydimethylsiloxane having an unsaturated group are copolymerized at a low temperature to synthesize a prepolymer in which a peroxide group is introduced into the side chain, and the prepolymer is copolymerized with a vinyl monomer. can also be done.

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

When using the polymer chain transfer method, for example, HS—CH ₂ COOH, HS—CH ₂ CH ₂ COOH, or the like is added to the silicone oil represented by the chemical formula 22 to obtain a compound having an SH group, and then the SH group is added. A block copolymer can be synthesized by copolymerizing the silicone compound and a vinyl monomer using chain transfer.

m is an integer from 10 to 300;

To synthesize a polydimethylsiloxane-based graft copolymer, for example, a graft copolymer can be easily obtained by copolymerizing a compound represented by Chemical Formula 23, that is, a methacrylic ester of polydimethylsiloxane or the like, with a vinyl monomer. can.

m is an integer from 10 to 300;

Vinyl monomers used in copolymers with polydimethylsiloxane include, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride , vinyl fluoride, vinylidene fluoride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, diacetitone acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , allyl alcohol, and the like.

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

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

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

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

The coating composition used to form the resin layer includes copolymers of polycaprolactone segments and polydimethylsiloxane segments, copolymers of polycaprolactone segments and polysiloxane segments, polycaprolactone segments, polydimethylsiloxane segments and poly A copolymer with a siloxane segment or the like can be used. A resin layer obtained using such a coating composition can have a polycaprolactone segment and a polydimethylsiloxane segment and/or a polysiloxane segment.

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

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

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

Here, the type of solvent is determined by the molecular structure that constitutes the solvent. That is, even if the elemental composition is the same and the type and number of functional groups are the same, the bonding relationship is different (structural isomers). Those that do not overlap exactly (stereoisomers) are treated as different kinds of solvents. For example, 2-propanol and n-propanol are treated as different solvents.

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

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

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

When the relative evaporation rate of the solvent is greater than 0.4, the time required for the orientation of the polysiloxane segment and/or polydimethylsiloxane segment and the fluorine compound segment to the outermost surface in the resin layer is shortened. Therefore, the solvent resistance of the resin layer in the resulting laminate may be lowered. Further, the lower limit of the relative evaporation rate of the solvent is not a problem as long as the solvent can be evaporated and removed from the coating film in the drying process, and in a general coating process, it is sufficient if it is 0.005 or more.

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

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

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

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

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

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

[Release film, manufacturing method of laminate]
The method for producing the release film and the laminate of the present invention is not particularly limited. It is preferably formed by coating, drying and curing on the release film. Hereinafter, the process of applying each coating composition is described as the coating process, the process of drying is described as the drying process, and the process of curing is described as the curing process. As each coating composition, two or more coating compositions may be applied sequentially or simultaneously to form a resin layer composed of two or more layers.

Here, "sequentially applied" means that one type of coating composition is applied to the supporting substrate or release film, dried and cured, and then another coating composition is applied. It means forming a release layer or a resin layer consisting of two or more layers by drying and curing. By appropriately selecting the type of coating composition to be used, the release layer side of the release layer - support substrate side flexibility and purchase of surface free energy, resin layer side of the resin layer - release film side flexibility It is possible to control the degree and gradient of stretchability, and the degree of flexibility and stretchability of the release film and resin layer. Furthermore, by appropriately selecting the type, composition, drying conditions, and curing conditions of the coating composition, the shape of the distribution of flexibility and stretchability in the release layer and the resin layer can be controlled stepwise or continuously. can be done.

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

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

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

An example of multilayer slide die coating is shown in FIG. In multi-layer slide die coating, liquid films composed of two or more types of coating compositions are sequentially laminated using a multi-layer slide die 6, and then coated onto a support substrate or release film.

An example of a multi-layer slot die coat is shown in FIG. In multi-layer slot die coating, a multi-layer slot die 7 is used to apply and simultaneously laminate liquid films composed of two or more types of coating compositions on a support substrate or a release film.

An example of wet-on-wet coating is shown in FIG. In wet-on-wet coating, after forming a one-layer liquid film made of a coating composition discharged from a single-layer slot die 8 on a support substrate, the liquid film is in an undried state. A liquid film composed of another coating composition discharged from the single-layer slot die 8 is laminated.

Following the coating step, the liquid film applied on the supporting substrate or the release film is dried in the drying step. From the viewpoint of completely removing the solvent from the resulting laminate, the drying step is preferably accompanied by heating of the liquid film.

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

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

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

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

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

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

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

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

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

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

[Alkyd compound]
[Alkyd compound 1]
As the alkyd compound 1, Haliftal KV-905 (manufactured by Harima Kasei Co., Ltd., solid content concentration 53% by mass), which is an acrylic-modified alkyd resin, was used.

[Melamine compound]
[Melamine compound 1]
As melamine compound 1, Melan 2650L (manufactured by Hitachi Chemical Co., Ltd., solid content concentration 60% by mass), which is an isobutyl alcohol-modified melamine resin, was used.

[Melamine compound 2]
As the melamine compound 2, RP-50 (manufactured by Miwa Laboratory), which is a butylated melamine formaldehyde, was used.

[Phosphite compound]
[Phosphite ester compound 1]
As the phosphite ester compound 1, a phosphite ester, Plascoat DEP Clear (manufactured by Washin Chemical Industry Co., Ltd.) was used.

[Urethane compound]
[Urethane compound 1]
As urethane compound 1, RP-20 (manufactured by Nippon Shokubai Co., Ltd.), which is an alkyl-modified polyurethane resin, was used.

[Silicone compound]
[Silicone compound 1]
As silicone compound 1, X-22-4015 (Shin-Etsu Chemical Co., Ltd. active ingredient: 100% by mass), which is a side chain modified reactive silicone oil, was used.

[Silicone resin precursor]
[Silicone resin precursor 1]
As silicone resin precursor 1, KS847H (manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

[Platinum catalyst]
[Platinum catalyst 1]
As platinum catalyst 1, PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

[Urethane (meth)acrylate]
[Synthesis of urethane (meth)acrylate 1]
100 parts by mass of toluene, 50 parts by mass of methyl-2,6-diisocyanate hexanoate (LDI manufactured by Kyowa Hakko Kirin Co., Ltd.) and 119 parts by mass of polycarbonate diol (“PLAXEL” (registered trademark) CD-210HL manufactured by Daicel Chemical Industries, Ltd.) The parts were mixed, heated to 40° C. and held for 8 hours. Then, 28 parts by mass of 2-hydroxyethyl acrylate (light ester HOA manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate (M-400 manufactured by Toagosei Co., Ltd.), and 0.02 parts by mass of hydroquinone monomethyl ether were added. After holding the mixture at 70°C for 30 minutes, 0.02 parts by mass of dibutyl tin laurate was added and the mixture was held at 80°C for 6 hours. Finally, 97 parts by mass of toluene was added to obtain a toluene solution of urethane (meth)acrylate 1 with a solid content concentration of 50% by mass. Urethane (meth)acrylate 1 had a number average molecular weight of 5,800.

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

[Oligomer]
[Synthesis of oligomer A]
After mixing 1 to 7 below, the mixture was kept at 70° C. for 5 hours and then diluted with toluene to obtain a toluene solution of oligomer A with a solid content concentration of 60% by mass.

1. Toluene: 50 parts by mass 2. Polytetramethylene glycol (PTMG2000 manufactured by Mitsubishi Chemical Corporation): 330 parts by mass3. Hexamethylene diisocyanate: 50 parts by mass4. 5. Hexamethylene diisocyanate isocyanurate-modified type ("Takenate" (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass. Dibutyl tin laurate: 0.02 parts by mass6. Hydroquinone monomethyl ether: 0.02 parts by mass 7.2-Hydroxyethyl acrylate: 11 parts by mass.

[Synthesis of oligomer B]
After mixing 1 to 7 below, the mixture was kept at 70° C. for 5 hours and then diluted with toluene to obtain a toluene solution of oligomer B with a solid content concentration of 60% by mass.

1. Toluene: 50 parts by mass 2. Polytetramethylene glycol (PTM G 1300 manufactured by Mitsubishi Chemical Corporation): 220 parts by mass3. Hexamethylene diisocyanate: 50 parts by mass4. 5. Hexamethylene diisocyanate isocyanurate-modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass. Dibutyl tin laurate: 0.02 parts by mass6. Hydroquinone monomethyl ether 0.02 parts by mass 7.2-Hydroxyethyl acrylate: 11 parts by mass.

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

[Preparation of coating composition for release layer]
[Release layer coating composition A1]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition A1 having a solid content concentration of 5% by mass.

- Alkyd compound 1: 100 parts by mass - Melamine compound 1: 20 parts by mass - Paratoluenesulfonic acid: 5 parts by mass.

[Release layer coating composition A2]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition A2 having a solid content concentration of 5% by mass.

Alkyd compound 1: 100 parts by mass Melamine compound 1: 20 parts by mass Para-toluenesulfonic acid: 5 parts by mass 4-hydroxybutyl acrylate: 5 parts by mass.

[Release layer coating composition A3]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition A3 having a solid content concentration of 5% by mass.

Alkyd compound 1: 100 parts by mass Melamine compound 1: 20 parts by mass Para-toluenesulfonic acid: 5 parts by mass 4-hydroxypropyl acrylate: 5 parts by mass.

[Release layer coating composition A4]
The following materials were mixed and diluted with a toluene/heptane mixed solvent (mixing ratio by mass: 50/50) to obtain a release layer coating composition A4 having a solid concentration of 2% by mass.

・Silicone resin precursor 1: 100 parts by mass ・Platinum catalyst 1: 1 part by mass.

[Release layer coating composition A5]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition A5 having a solid content concentration of 5% by mass.

- Alkyd compound 1: 100 parts by mass - Melamine compound 1: 20 parts by mass - Paratoluenesulfonic acid: 5 parts by mass - Silicone compound 1: 5 parts by mass.

[Release layer coating composition A6]
The following materials were mixed and diluted with a mixed solvent of methyl ethyl ketone/isopropyl alcohol (mixing ratio by mass: 50/50) to obtain a release layer coating composition A6 having a solid content concentration of 5% by mass.

- Melamine compound 1: 20 parts by mass - Urethane compound 1: 0.3 parts by mass - Phosphite ester compound 1: 4 parts by mass.

[Support base material]
[Support base material 1]
As the supporting substrate 1, “Lumirror” (registered trademark) R60R (thickness: 38 μm, manufactured by Toray Industries, Inc.) was used.

[Release film]
[Release films 1 to 6]
Release films 1 to 6 were prepared by forming a release layer by the following method using the release layer coating composition and the support substrate described above. Combinations of the release layer coating composition to be used are as shown in Table 1.

[Preparation of release film 1]
Using a coating device with a small-diameter gravure coater, the number of gravure lines, peripheral speed, solid The concentration was adjusted and applied.

Then, the film was dried and cured by holding it at a hot air temperature of 140° C. for 30 seconds to obtain a release film.

[Preparation of release film 2]
Using a coating device with a small-diameter gravure coater, the number of gravure lines, peripheral speed, solid The concentration was adjusted and applied.

Then, the film was dried and cured by holding it at a hot air temperature of 120° C. for 30 seconds to obtain a release film.

[Lamination side release film 7]
"Therapeal" (registered trademark) MDA (thickness: 38 µm, manufactured by Toray Advanced Film Co., Ltd.) was used as the lamination-side release film 7 (hereinafter sometimes simply referred to as the release film 7).

[Preparation of coating composition for resin layer]
[Resin layer coating composition B1]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition B1 having a solid content concentration of 30% by mass.

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

[Resin layer coating composition B2]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition B2 having a solid content concentration of 30% by mass.

・Urethane (meth)acrylate 2 solution: 50 parts by mass ・Photoradical polymerization initiator 1: 1.5 parts by mass.

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

- Oligomer A solution: 100 parts by mass - Photoradical polymerization initiator 1: 1.5 parts by mass.

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

- Oligomer B solution: 100 parts by mass - Photoradical polymerization initiator 1: 1.5 parts by mass.

[Laminate production method]
[Production of laminate 1]
On the release films 1 to 6, the coating composition for the resin layer is continuously applied using a slot die coater, and the discharge flow rate from the slot is adjusted so that the thickness of the resin layer after drying becomes the specified thickness. and applied. Combinations of coating compositions for the resin layer to be used are as shown in Table 2.

The conditions for the drying air that hits the liquid film during the period from application to drying and curing are as follows.

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

[Preparation of laminate 2]
With respect to the laminate prepared in [Preparation of Laminate 1], a release film 7 was attached to the surface of the resin layer with a load of 1 g/mm using a hand roller. The release film 7 was laminated so that the surface provided with the release layer was in contact with the surface of the resin layer.

Laminates of Examples 1 to 8 and Comparative Examples 1 to 4 were produced by the above method. The method of producing the above-described laminate corresponding to each example and comparative example, and the film thickness of each layer are shown in Tables 3 to 5 below.

Since two release films are provided in Examples and Comparative Examples, release films 1 to 6 are release films (applied side), and release film 7 is a release film (adhesion side). side).

[Evaluation of release layer of laminate, resin layer and release film]
The laminate, the resin layer, and the release layer of the release film were subjected to the following performance evaluations, and Tables 2 to 6 show the results obtained. Unless otherwise specified, the measurement was performed three times for each sample in each example and comparative example at different locations, and the average value was used.

In addition, for the laminates obtained in Examples 5 to 6 and Comparative Example 4, each evaluation was performed in a state in which the lamination side release film was peeled from the laminate, except for the evaluation of peel strength and peeling selection system described later. went.

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

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

[Storage modulus]
Based on the tensile vibration-nonresonance method of JIS K7244 (1998) (this is referred to as a dynamic viscoelasticity method), the storage elastic modulus of the resin layer is measured using a dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Inc. and loss modulus.
Measurement mode: Distance between tensile chucks: 20mm
Width of test piece: 10 mm
Frequency: 1Hz
Strain amplitude: 10 μm
Force amplitude initial value: 40mN
Measurement temperature: from −100° C. to 100° C. Heating rate: 5° C./min Loss tangent: (loss modulus)/(storage modulus).

[Surface elastic modulus (atomic force microscope)]
The surface of the release layer is measured in PeakForceQNM mode using AFM (DimensionIcon manufactured by Burker Corporation), and the resulting force curve is analyzed using the attached analysis software "NanoScope Analysis V1.40" to JKR contact theory. The elastic modulus distribution was obtained by performing an analysis based on the results.

Specifically, after calibrating the warp sensitivity, spring constant, and tip curvature of the cantilever according to the PeakForceQNM mode manual, measurement was performed under the following conditions. adopted as. The spring constant and the tip curvature vary depending on the individual cantilever, but the range that does not affect the measurement is a spring constant of 0.3 (N/m) or more and 0.5 (N/m) or less, and a tip curvature radius of 15 ( nm) A cantilever that satisfies the following conditions was adopted and used for measurement.

Measurement conditions are shown below.
Measuring device: Burker Corporation atomic force microscope (AFM)
Measurement mode: PeakForceQNM (force curve method)
Cantilever: SCANASYST-AIR manufactured by Bruker AXS
(Material: Si, spring constant K: 0.4 (N/m), tip curvature radius R: 2 (nm))
Measurement atmosphere: 23°C, in air Measurement range: 3 (μm) Square resolution: 512 x 512
Cantilever moving speed: 10 (μm/s)
Maximum push load: 10 (nN)
Next, the obtained DMT Modulus channel data was analyzed with the analysis software "NanoScope Analysis V1.40" and processed with Roughness. rate.

[Surface free energy]
The surface free energies S ₁ and S ₂ of the release layer and the resin layer are measured by determining the static contact angle at 25°C with water, ethylene glycol, formamide, and diiodomethane on the release layer surface and the resin layer surface. The static contact angle with each liquid and J.P. Panzer: J.P. Colloid Interface Sci. , 44, 142 (1973). The surface free energy dispersion term, polar term, and hydrogen bond term of each liquid described in No. Kitazaki, Toshio Hata: Japan Adhesion Association Paper, 8, (3) 131 (1972). was introduced into the "Hata and Kitazaki's Extended Hawkes Equation" described in , and was obtained by solving the simultaneous equations.

The static contact angle was measured after the sample was left in an environment of 25°C for 12 hours in advance. Kyowa Interface Science Drop Master DM-501 was used, and droplets were prepared under conditions that would allow droplets to be as small as possible without creeping up the needle. The static contact angle was calculated by the θ/2 method using an image taken 5 seconds after the droplet was deposited on the release layer surface.

[Time-of-flight secondary ion mass spectrometry (TOF-SIMS)]
Using a time-of-flight secondary ion mass spectrometer TOF-SIMS 5 and measurement software SURFACE LAB 6 manufactured by ION TOF, the surface of the release layer is measured by secondary ion mass spectrometry, Si (CH ₃ ) ⁺ fragment ion intensity was calculated. The measurement conditions are as follows.
Primary ion species: Bi ₃ ⁺⁺
Primary ion acceleration voltage: 25 kV
Pulse width: 7.4ns
Mass range (m/z): 0-1,500
Detection ion polarity: positive (Si(CH ₃ ) ⁺ )
Raster size: 300 μm × 300 μm
Number of scans: 12 Number of pixels: 256×256.

[Evaluation of peeling selectivity]
A laminate having a resin layer between two release films was cut into two pieces each having a width of 100 mm and a length of 200 mm to obtain a test piece. Next, for the first test piece, one of the release films was peeled off from the resin layer, and the peelability was observed. Furthermore, for the second test piece, the release film on the opposite side of the one peeled off in the first test piece was peeled off from the resin layer, and the peelability was observed.

The releasability of each release film was evaluated according to the following criteria.

Since the release films to be peeled off are different between the two test pieces, different evaluation results may be obtained. In that case, the evaluation result with the higher score in the following criteria was given priority and adopted as the final evaluation result (e.g., one release film was peeled off, one point, and the other release film was peeled off. If the evaluation result was 4 points, the evaluation result was 4 points).
10 points: When one release film is peeled off, the other release film does not float.
7 points: When one release film is peeled off, the other release film is slightly lifted.
4 points: When one release film is peeled off, the other release film is lifted.
1 point: Others (When one release film is peeled off, the other release film is largely peeled off, or when one release film is peeled off, the release film that is about to be peeled off or the release film cannot be peeled off).

[Evaluation of peeling durability]
A 100 mm wide×200 mm long piece was cut from the laminate to obtain a test piece. Next, the release film and the resin layer were slightly peeled off from the ends in advance, and only the exposed release film was grasped and wound around a cylinder with a diameter of 30 mm. At this time, the winding force was repeatedly strengthened and weakened 10 times to apply a load to the laminate. After that, the state of separation between the resin layer and the release film in the laminate was observed, and judgment was made according to the following criteria.
10 points: No change from before the load was applied.
7 points: The peeled portion spreads slightly.
4 points: The peeled portion spreads.
1 point: Others (exfoliated portion is widely spread, etc.).

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

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

[Evaluation after long-term storage in a harsh environment]
Two sheets of 100 mm width×200 mm length were cut from the laminate to obtain test pieces. One test piece was allowed to stand still for 500 hours in a room temperature environment. The other test piece was allowed to stand still for 500 hours in a constant temperature and humidity chamber adjusted to a temperature of 85% and a humidity of 85%. After that, both test pieces were leveled for 1 hour in a room temperature environment. Next, each test piece was peeled off from the release film, the change in the resin layer was evaluated, and judgment was made according to the following criteria.
10 points: No change at all.
7 points: Slightly increased stickiness, but almost no difference.
4 points: The stickiness is clearly increased.
1 point: Others (resin layer cannot be peeled off, resin layer is clearly dissolved, etc.).

Tables 3 to 6 summarize the evaluation results of the laminates finally obtained.

1 resin layer 2 release film 3 release film 4 resin layer 5 release film 6 multilayer slide die 7 multilayer slot die 8 single layer slot die

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

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

Claims (7)

A release film having a release layer on at least one surface of a supporting substrate, and a laminate having a resin layer that can be peeled off from the release film, wherein the resin layer has a segment represented by Chemical Formula 1 and / or Chemical Formula 2. A laminate, comprising: and satisfying condition 2 below.
Condition 2: The surface free energy S ₁ (mJ/m ² ) of the resin layer, the surface free energy S ₂ (mJ/m ² ) of the release layer, and the surface elastic modulus E ₂ ( MPa) satisfies the following formulas 1 and 2.
Equation 1: S ₁ - S ₂ < 60
Equation ₂ : E<2,000

R ₁ refers to hydrogen or a methyl group.
_R2 refers to any of the following:
A substituted or unsubstituted alkylene group A substituted or unsubstituted arylene group having an ether group, an ester group, or an amide group inside An alkylene group having an ether group, an ester group, or an amide group inside an arylene group An ether group, an ester group unsubstituted arylene group having an ether group, an ester group, or an amide group inside a group or an unsubstituted alkylene group having an amide group

The laminate according to claim 1 , wherein the resin layer has a storage elastic modulus of 1 MPa or more and 100 MPa or less under conditions of a temperature of 25°C and a frequency of 1 Hz. 3. The laminate according to claim 1 , wherein the resin layer has a loss tangent of 0.5 or less at a temperature of 25[deg.] C. and a frequency of 1 Hz. 4. The protective layer according to any one of claims 1 to 3 , further comprising a protective layer having a peeling force different from that of the release layer on the surface of the resin layer opposite to the surface in contact with the release layer. Laminate as described. 5. The laminate according to any one of claims 1 to 4 , wherein the following condition 3 is satisfied.
Condition 3: Si(CH ₃ ) ⁺ fragment ions (M/Z=43) derived from dimethylsiloxane on the surface of the release layer measured by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) Strength of 1,000 or less. 6. The laminate according to any one of claims 1 to 5 , wherein the release layer includes segments having structures of chemical formulas 3 and 4.

Each of R ₁ to R ₆ independently represents hydrogen, a group represented by R _x OCH ₂ —, or a group derived from a melamine derivative represented by Chemical Formula 4. However, R _x represents hydrogen or an alkyl group having 1 to 4 carbon atoms. 7. The laminate according to any one of claims 1 to 6 , wherein the resin layer contains segments of chemical formula 5.

R ₁ is an alkyl group or alkylene group having 1 to 6 carbon atoms, and n is 2 to 50 carbon atoms.

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