JP2019151815A - Laminate and resin film - Google Patents

Abstract

To provide a resin film and a laminate, achieving moisture heat resistance and post processing suitability while maintaining flexibility and high stability.SOLUTION: There is provided a resin film containing a polyether segment, a (meth)acryl segment, and an urethane segment, and satisfying following conditions 1 to 5. Condition 1; 5% strain stress is 10 MPa or less. Condition 2: Elastic recovery rate at deformation volume of 20% is 70% or more. Condition 3; An absolute value of dimensional change rate at 150°C is 10% or less. Condition 4; a ratio between the largest peak intensity P1 of peaks derived from a carbodiimide group and an isocyanate group in FT-IR spectrum and peak intensity P2 caused by NH stretching vibration of an urethane group, P1/P2 is 0.01 or less. Condition 5; a ratio between stress F4 when the resin film is stretched with strain amount of 100% at 23°C a stress F5 when the resin film is stretched with strain amount of 100% at 23°C after the lapse of 500 hr. at 85°C-85%,, F5/F4 is 0.4 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin film and a laminate that have both heat resistance and post-processing suitability while maintaining flexibility and high resilience.

  New devices such as smartphones and tablets have been born with thinner and lighter displays, and users can now freely use them wherever they like, from those that are used indoors in offices and homes. The shape can be changed from a square shape to a free shape, and it can be incorporated into various everyday life without any design restrictions. Furthermore, displays that can be bent and stretched freely are now being realized. If this is put into practical use, it is expected that a new device that has never existed will appear.

  Various sensors that can detect strain, minute pressure change, and temperature have been used for industrial and medical purposes. However, with the reduction in size and weight, mobile devices and various other things in daily life have been used. It can be attached to help improve convenience in daily life and avoid dangers. In the future, these sensors will be lighter and can be bent and stretched freely, so that they can be attached to the body without load, and it is expected to change our lives. ing.

  In the field of such displays and sensors, various resin films have been used so far to reduce weight and size. However, the material used so far is a film having a rigid chemical bond and strong crystallinity because of its durability and compatibility with post-processing steps, and can be bent freely but cannot be expanded or contracted. It was a film. Therefore, in the field of displays and sensors, there is a demand for a resin film that can be bent and stretched freely, and can be durable and can be used in post-processing steps.

  As an example of a resin film that can be bent and stretched freely, Patent Document 1 discloses "a layer made of a first polyethylene, a thermoplastic polyurethane layer laminated on the layer made of the first polyethylene, and the thermoplastic polyurethane layer. A layer of at least a second polyethylene layer, wherein the heat of crystallization of the first polyethylene is greater than the heat of crystallization of the second polyethylene. A laminate having a plastic polyurethane layer has been proposed.

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

  Further, as a resin material having both flexibility and durability, Patent Document 2 discloses that “the cyclic dicarbodiimide compound represented by the following formula (2) is 0.01 to 15 parts by weight relative to 100 parts by weight of the polyurethane elastomer. A urethane elastomer composition containing "has been proposed.

JP2013-91223A JP 2012-1613 A

Silicone Handbook Nikkan Kogyo Shimbun Co., Ltd. 1990

  In a resin film used for a display or a sensor, a film having a rigid chemical bond or high crystallinity is often used. The reason for this is that, as described above, since the process to become a product is long and complicated, a high level of thermal and chemical stability is required. It is also necessary that the functions of various electronic components are not affected in the various environments in which they are used.

  On the other hand, a highly flexible polymer material realizes its mechanical properties by including a highly flexible segment in the molecular structure. Therefore, as a compensation for a structure with a high degree of freedom, it is easy for gas and liquid to penetrate from the outside, and is also easily affected by heat and light, and has low thermal and chemical stability compared to hard materials. There are limited examples used for the above.

  Regarding the material proposed in Patent Document 1, the present inventors have confirmed the above-mentioned viewpoints, but although certain flexibility and stretchability have been confirmed, the heat resistance at high temperatures is insufficient. In addition, the silicone rubber material proposed in Non-Patent Document 1 provides flexibility and stretchability, but has poor adhesion to different materials and requires a special material to ensure adhesion. Therefore, it was unsuitable for post-processing. The material proposed in Patent Document 2 is excellent in flexibility and heat-and-moisture resistance. However, when a thermosetting layer is laminated on the surface of the material by post-processing, the function of the post-processed layer is inhibited. There was a thing. From the above points, an object of the present invention is to achieve both heat and moisture resistance and suitability for post-processing while the resin film maintains flexibility and high resilience.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
1.
A resin film comprising a polyether segment, a (meth) acrylic segment, and a urethane segment,
A resin film characterized by satisfying all of the following conditions 1 to 4 and condition 6.

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

  Condition 2 The elastic recovery rate is 70% or more in the tensile test method when the deformation amount of the resin film is 20%.

  Condition 3 The absolute value of the dimensional change rate at 150 ° C. is 10% or less based on the size of the resin film at 30 ° C.

Condition 4 Among the peaks derived from the carbodiimide group of 2,100 to 2,200 cm ^{−1 and} the isocyanate group of 2,240 to 2,270 cm ⁻¹ in the FT-IR spectrum of the resin film, the intensity P1 of the one having the highest peak intensity And the ratio of the peak intensity P2 due to the NH stretching vibration of the urethane group of 3,000 cm ^{−1 to} 3,450 cm ⁻¹ , P1 / P2 is 0.01 or less.

Condition 6: Stress F4 when the resin film at 23 ° C. is stretched to 100% strain and stress F5 when the resin film at 23 ° C. is stretched to 100% strain after 500 hours at 85 ° C.-85%. Ratio, F5 / F4 is 0.4 or more.
2.
2. The resin film according to claim 1, wherein the resin film contains at least one antioxidant selected from the group consisting of hindered phenolic, semi-hindered phenolic, phosphite, and thioethers. .
3.
A laminate having a resin film comprising a polyether segment, a (meth) acrylic segment, and a urethane segment, and a support substrate that can be peeled on at least one surface of the resin film,
The said resin film satisfy | fills all the following conditions 1-5, The laminated body characterized by the above-mentioned.

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

  Condition 2 The elastic recovery rate is 70% or more in the tensile test method when the deformation amount of the resin film is 20%.

  Condition 3 The absolute value of the dimensional change rate at 150 ° C. is 10% or less based on the size of the resin film at 30 ° C.

Condition 4 Among the peaks derived from the carbodiimide group of 2,100 to 2,200 cm ^{−1 and} the isocyanate group of 2,240 to 2,270 cm ⁻¹ in the FT-IR spectrum of the resin film, the intensity P1 of the one having the highest peak intensity And the ratio of the peak intensity P2 due to the NH stretching vibration of the urethane group of 3,000 cm ^{−1 to} 3,450 cm ⁻¹ , P1 / P2 is 0.01 or less.

Condition 5 Stress F1 when the resin film at 23 ° C. is stretched to 100% strain, and after lapse of 500 hours at 85 ° C.-85% in the state of the laminate, the resin film at 23 ° C. is stretched to 100% strain. The ratio with the stress F3 when F3 / F1 is 0.5 or more.
4). 2. The resin film contains at least one antioxidant selected from the group consisting of hindered phenols, semi-hindered phenols, phosphites, and thioethers. The laminated body as described in.

  It is possible to provide a resin film and a laminate that have both heat and heat resistance and suitability for post-processing while maintaining flexibility and high resilience.

It is an example of the laminated body in this invention. It is an example of the laminated body in this invention. It is an example of the laminated body in this invention. It is an example of the laminated body in this invention. It is an example of the laminated body in this invention. It is an example of the laminated body in this invention. It is an example of the laminated body in this invention. It is an example of the laminated body in this invention.

  First, the present inventors consider the reason why the problems of the present invention cannot be solved by the prior art as follows.

  The resin material is required to have both a portion having a very high degree of freedom of deformation in order to exhibit flexibility and a portion having a low degree of freedom in order to exhibit high resilience. At this time, a portion having a low degree of freedom is often provided with a physical bond such as an interaction between aromatic rings or a hydrogen bond, and thereby a cohesive force is often expressed. On the other hand, since the cohesive force due to physical bonding decreases as the temperature increases, there is a problem that the heat resistance decreases, and the reason why the heat resistance is insufficient in Patent Document 1 is considered to be the cause. On the other hand, as a method for imparting heat resistance, the conventional technique solves the problem by introducing a segment having high heat resistance, but often has a trade-off relationship with flexibility and resilience.

  In addition, when hydrogen bonds are used to generate cohesive force in order to increase cohesive force, the water absorption of the material tends to increase, and as a result, there is a problem that hydrolysis tends to occur in a high temperature-high humidity environment. On the other hand, Patent Document 3 uses an additive that suppresses hydrolysis, and its mechanism of action is that the additive easily moves within the resin and is specifically generated at the end of hydrolysis. Is one that suppresses the progress of hydrolysis by easily reacting with a reactive terminal such as a carboxylic acid or a hydroxyl group.

  About the patent document 3, when the present inventors bonded and adhere | attached with another material, the reason for having influenced the hardening of the member processed later was the material which is easy to react with a reactive terminal to an adjacent material. It is thought that it was due to contact and movement.

  Therefore, in the present invention, among the above-mentioned problems, a method that does not rely on a segment with high heat resistance is used for the problem of improving heat resistance, which is a point, and a carboxylic acid, a hydroxyl group, or the like is used for hydrolysis. The inventors have devised a method that does not rely on a compound that easily reacts with a reactive terminal, and has solved the problems of the prior art. Details of the present invention will be described below.

As shown in FIG. 1, the laminate 1 of the present invention is preferably a laminate having a support base 3 that can be peeled off on at least one surface of a resin film 2.

  Here, when forming the laminate of the present invention, the support substrate is a resin film-forming coating composition formed by a laminate production method described later in providing a resin film on one surface thereof. An article that is flat in the in-plane direction and can be developed on the surface.

  And the support base material which can be peeled from the resin film means that when the support base material side is peeled in a state where the surface of the resin film without the support base material is fixed with an adhesive tape or the like, the support base material and the resin film It means that it can be peeled without any trouble.

  The reason why the support substrate is necessary in the laminate of the present invention is to add a liquid coating composition on the support substrate and form a resin film by curing, in the laminate production method described below, This is to ensure processability and transportability in the post-process where the resin film is processed. Therefore, it is not particularly limited as long as it can be peeled from the resin film and does not affect the functions including the post-processability of the resin film, but the release layer is formed between the laminate 4 and the resin film 5 as shown in FIG. It is preferable to have a supporting substrate 7 containing 6.

  Furthermore, when winding a laminated body in roll shape and making it an intermediate product, in order to stabilize the winding shape of a roll, as shown in FIG. 3, the laminated body 8 has the release layer 10 on the opposite side to the resin film 9. You may have the support base material 12 included. Of course, as shown in FIG. 4, the laminate 12 may have a support substrate 16 including a release layer 14 between the laminate 12 and the resin film 13 and a release layer 15 on the opposite side. In this case, the release layer 14 and the release layer 15 may be the same, but the release force between the resin film 9 and the release layer 15 when the laminate is unwound from the roll, and the resin film 13 in the subsequent step. Since it is necessary to adjust the peeling force between the release layer 14 and the release layer 14, a different one is preferable.

  Furthermore, in order to improve the transportability in the process of the resin film and to prevent damage, the laminate 17 has a support base 19 that can be peeled off on one side of the resin film 18 as shown in FIG. You may have a peelable protective material. The protective material and the supporting base material may be the same, but as shown in FIG. 6, the laminate 21 includes a supporting base material 24 including a release layer 23 between the resin film 22 and a protective material 25. As shown in FIG. 7, the laminate 26 may include a support base material 29 including a release layer 28 and a protective material 31 including a release layer 30 between the resin film 27 and the laminate 26. As shown in FIG. 8, the laminate 32 may have a support base 35 including a release layer 34 and a protective material 37 including an adhesive layer 36 between the resin film 33. Whether the laminate has a protective material having an adhesive layer or a protective material using a release layer is selected as appropriate from the suitability of subsequent processes and the physical properties of the resin film.

  In the laminate of the present invention, the resin film preferably includes a polyether segment, a (meth) acrylic segment, and a urethane segment. Here, the (meth) acryl segment is represented by the chemical formula 1, the polyether segment is represented by the chemical formula 2, and the urethane segment is represented by the chemical formula 3.

Here, R ¹ is hydrogen or a methyl group. R ² is (1) a substituted or unsubstituted alkylene group or arylene group, and (2) a substituted or unsubstituted alkylene group or arylene group having an ether group, ester group, or amide group inside. R ³ is an alkyl or alkylene group having 1 to 6 carbon atoms. n is an integer of 2 to 50.

It is preferable that the resin film includes a polyether segment in order to impart high flexibility and hydrolysis resistance. In Chemical Formula 2, R ³ is an alkyl group or alkylene group having 2 to 4 carbon atoms, n is more preferably an integer of 10 to 40.

  It is preferable that the resin film contains a (meth) acrylic segment in order to have heat resistance and restorability, and the (meth) acrylic segment has a crosslinked structure by ultraviolet curing or the like in the resin film forming step of the present invention. It is more preferable to make it. The (meth) acrylic segment functions as a site with low heat-resistance when the resin film generates resilience, and at the same time, it can further improve heat resistance by creating a crosslinked structure.

  Whether or not the resin film contains the segments represented by Chemical Formulas 1 to 3 can be examined by various analysis methods, but the method using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) is the easiest. . Moreover, it can also judge from the raw material which forms a mold release layer or a resin film.

In addition, the resin film preferably has specific mechanical properties and dimensional stability. Specifically, the resin film preferably satisfies the following condition 1, condition 2, and condition 3, and the following condition 1-2 and condition: It is more preferable to satisfy 2-2 and condition 3-2.
Condition 1 The 5% strain stress of the resin film is 10 MPa or less.
Condition 2 The elastic recovery rate is 70% or more in the tensile test method when the deformation amount of the resin film is 20%.
Condition 3 The absolute value of the dimensional change rate at 150 ° C. is 10% or less, based on the dimensions at 30 ° C. of the resin film. Condition 1-2 The 5% strain stress of the resin film is 5 MPa or less. Condition 2-2. In the tensile test method, the elastic recovery rate of the resin film is 80% or more. Condition 3-2 The absolute value of the dimensional change rate at 150 ° C. is 5% or less based on the size of the resin film at 30 ° C.

  It is preferable that the 5% strain stress of the resin film is within a specific range because flexibility is improved. If the 5% strain stress of the resin film 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 0.01 MPa. On the other hand, when the 5% strain stress of the resin film is higher than 10 MPa, the flexibility of the resin film is lowered, which may be unsuitable for the intended use. In order to set the 5% strain stress of the resin film to 10 MPa or less, for example, the resin included in the resin film can be selected by selecting a material exemplified below. Moreover, in a region larger than the range of Condition 1, the flexibility is insufficient. The measurement conditions for the 5% strain stress of the resin film will be described later.

  When the elastic recovery rate when the deformation amount of the resin film is 20% falls within a specific range, it is preferable that the recovery property is improved. The higher the elastic recovery rate is, the more preferable, ideally 100%. When the elastic restoration rate is lower than 70%, the restoration property of the resin film is lowered, which may be unsuitable for the intended use. A method for measuring the elastic recovery rate will be described later.

  By making the absolute value of the dimensional change rate of the resin film below a certain value, it is preferable because unintended deformation hardly occurs even when the laminate of the present invention is exposed to heating, and the quality and suitability for post-processing can be improved.

  It is preferable that the absolute value of the dimensional change rate is a certain value or less because the quality and post-processing suitability can be improved as described above. This effect increases as the dimensional change rate of the dimensional change rate decreases. On the other hand, when the absolute value of the dimensional change rate exceeds 10%, the above-described quality and post-processing suitability may be insufficient. A method for measuring the dimensional change rate will be described later. The absolute value of the dimensional change rate is preferably as low as possible, and ideally 0%.

  In order to set the absolute value of the 5% strain stress of the resin film, the elastic recovery rate when the deformation amount of the resin film is 20%, and the dimensional change rate to a certain value or less, for example, the resin contained in the resin film and its This can be achieved by selecting a material described later as the precursor.

  In the laminate of the present invention and the resin film of the present invention, from the viewpoint of securing the above-mentioned post-processing suitability, the resin film is an additive that easily reacts with a reactive terminal such as carboxylic acid or hydroxyl group, that is, carboxylic acid or It is preferable not to include a compound having a carbodiimide group and an isocyanate group that easily react with a hydroxyl group. Therefore, it is preferable that the FT-IR spectrum of the resin film shows a specific peak intensity relationship under the following condition 4.

Condition 4 Among the peaks derived from the carbodiimide group of 2,100 to 2,200 cm ^{−1 and} the isocyanate group of 2,240 to 2,270 cm ⁻¹ in the FT-IR spectrum of the resin film, the intensity P1 of the one having the highest peak intensity And the ratio P1 / P2 (hereinafter sometimes simply referred to as P1 / P2) of the peak intensity P2 resulting from NH stretching vibration of urethane groups of 3,000 cm ^{−1 to} 3,450 cm ⁻¹ is 0. 01 or less.

In condition 4, P1 is a FT-IR spectrum peak intensity corresponding to a carbodiimide group or an isocyanate group, and is a parameter proportional to the content of the carbodiimide group and the isocyanate group in the resin film. By the composition of the resin film, the peak of 2,240～2,270Cm ^-1 corresponding to antisymmetric stretching vibration of the isocyanate groups, corresponding to the carbodiimide group, the peak of ^{cm -1} of 2,100～2,200 Both may appear, and in this case, the peak having the highest peak intensity is selected as P1. P2 is the peak intensity of the FT-IR spectrum corresponding to the urethane group, and is proportional to the urethane group content in the resin film. The NH of the urethane group is hydrogen bonded to the ether bond and ester bond contained in the residue of the urethane group, which is the acceptor urethane group, and therefore the wave number of the stretching vibration of NH shifts to 3,000 cm ⁻¹ to It appears in the range of 3,450 cm ⁻¹ , and a plurality of peaks may appear depending on the structure of the polymer. In that case, the peak having the highest peak intensity is selected as P2. P1 / P2 indicates how much a carbodiimide group or an isocyanate group, which lowers post-processing suitability, is contained in the main polymer, and is preferably 0.01 or less. A specific method for measuring the FT-IR spectrum of the resin film will be described later. P1 / P2 is preferably as small as possible, and is particularly preferably 0.

  In the laminate of the present invention, the resin film preferably has a specific change in stress change before and after wet heat storage. Specifically, the following condition 5 is preferably satisfied, and more preferably the following condition 5-2 is satisfied.

Condition 5 Stress F1 when the resin film at 23 ° C. is stretched to 100% strain, and stress F3 when the resin film at 23 ° C. is stretched to 100% strain after 500 hours at 85 ° C.-85%. The ratio of F3 / F1 (hereinafter sometimes simply referred to as F3 / F1) is 0.5 or more. Condition 5-2 0.8 <F3 / F1 <1.

  Furthermore, as in the case of the laminate, in the resin film of the present invention that does not have a peelable support substrate, the resin film preferably has a specific change in stress before and after wet heat storage. Specifically, it is preferable to satisfy the following condition 6, and it is more preferable to satisfy the following condition 6-2.

Condition 6: Stress F4 when the resin film at 23 ° C. is stretched to 100% strain and stress F5 when the resin film at 23 ° C. is stretched to 100% strain after 500 hours at 85 ° C.-85%. The ratio of F5 / F4 (hereinafter sometimes simply referred to as F5 / F4) is 0.4 or more. Condition 6-2 0.7 <F5 / F4 <1.

  Here, when F3 / F1 in the above-mentioned laminated body is smaller than 0.5, there is a possibility that the recoverability is lowered. F3 / F1 of the laminate is preferably less than 1 at the maximum. That F3 / F1 of the laminated body exceeds 1, that is, it means that the stress becomes high in storage with wet heat, and the flexibility of the resin film may not be maintained. A method for measuring the stress change before and after wet heat storage will be described later.

  Moreover, when F5 / F4 in the resin film of the present invention that does not have a peelable support substrate is smaller than 0.4, there is a possibility that the recoverability is lowered. The F5 / F4 of the resin film is preferably less than 1 at the maximum. That F5 / F4 in the resin film is 1 or more indicates that the stress becomes high during storage with wet heat, and the flexibility of the resin film may not be maintained. A method for measuring the stress change before and after wet heat storage will be described later.

  In the laminate of the present invention, the resin film preferably contains an antioxidant. By containing an antioxidant, it is possible to suppress oxidative deterioration of the polyether segment due to heat, which is effective for improving heat resistance and moist heat resistance. Here, the antioxidant is a chain reaction in which the polymer compound constituting the resin film is started by heat, light, metal, etc., and the generated radicals react while taking in oxygen, so-called oxidative degradation is prevented. It is an additive. Antioxidants are broadly classified into radical chain initiators, radical scavengers, and peroxide decomposers based on their mechanism of action, and any of these is a problem to be solved by the present invention for suppressing deterioration under high temperature conditions. However, although the effects of the present invention can be obtained, radical scavengers or peroxide decomposers are more preferred, hindered phenol-based, semi-hindered phenol-based radical scavengers, or phosphite-based, thioether-based peroxides. Decomposing agents are particularly preferred. That is, the resin film preferably contains at least one antioxidant selected from the group consisting of hindered phenols, semi-hindered phenols, phosphites, and thioethers.

  Even if these antioxidants are pasted or bonded to other members in the post-processing step, and the antioxidant is transferred to other members, the reactive sites of the other members are directly Since it is difficult to react, it hardly affects the post-processing process.

  Whether or not the resin film contains the above-mentioned antioxidant can be examined by various analysis methods, but the method using a time-of-flight secondary ion mass spectrometer (TOF-SIMS) is the easiest. Moreover, it can also judge from the raw material which forms a mold release layer or a resin film.

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

[Laminate]
If the laminate of the present invention has a resin film exhibiting the above-mentioned physical properties and has a supporting substrate that can be peeled from the resin film on at least one surface thereof, it is in a flat state or after being molded Any of the three-dimensional shapes may be used.

[Resin film]
The number of layers in the resin film of the present invention is not particularly limited, and it may be formed from one layer or may be formed from two or more layers. Here, the layer refers to a portion having a boundary surface that can be distinguished from an adjacent portion in the thickness direction from the surface side and having a finite thickness. More specifically, when the cross section of the mold release layer is observed with an electron microscope (transmission type, scanning type) or an optical microscope, it refers to what is distinguished by the presence or absence of a discontinuous boundary surface. Even if the composition changes in the thickness direction of the release layer, if there is no boundary surface between them, it is handled as one layer.

  In addition to flexibility and stretchability, which are the subject of the present invention, glossiness, fingerprint resistance, moldability, designability, scratch resistance, antifouling properties, solvent resistance, antireflection, antistatic properties, electrical conductivity, heat ray reflection , May have other functions such as near-infrared absorption, electromagnetic wave shielding, and easy adhesion, and in that case, one or more layers may be further formed. For example, a functional layer or an adhesive layer having the above-described functions Further, an electronic circuit layer, a printed layer, an optical adjustment layer, and other functional layers may be provided.

  The thickness of the resin film is not particularly limited and is appropriately selected depending on the application. The lower limit of the thickness of the resin film is affected by the elastic modulus of the resin film itself, the elongation at break, the peel force from the laminate, the peel angle, etc. When using the same physical property as that of a general flexible material, the lower limit is about several μm.

[Supporting substrate]
The support substrate used in the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, may be a copolymer or a blend of two or more types. . The resin constituting the supporting base material is preferable if the moldability is good, and a thermoplastic resin is more preferable in that respect.

  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-6 fluoropropylene copolymer, vinylidene fluoride resin Resins, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. As examples of the thermosetting resin, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, polyurethane resin, polyimide resin, silicone resin, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is more preferably a polyester resin, a polycarbonate resin, an acrylic resin, or a methacrylic resin from the viewpoint of strength, heat resistance, and transparency.

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

  In addition, for the support substrate, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant for adjusting the refractive index may be added. The support substrate may be either a single layer configuration or a laminated configuration.

  In addition to the resin film 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 can be provided in advance on the surface of the support substrate. In the laminate of the present invention, it is preferable to provide a release layer in order to reduce the peeling force between the support substrate and the resin film. Details of the release layer will be described later.

  Examples of support substrates provided with a release layer include “Therapel” (registered trademark) manufactured by Toray Film Processing Co., Ltd., “Unipeel” (registered trademark) manufactured by Unitika Co., Ltd., “Panapill” manufactured by Panac Corporation (Registered trademark), “Toyobo Ester” (registered trademark) manufactured by Toyobo Co., Ltd., “Purex” (registered trademark) manufactured by Teijin Limited, and the like, and these products can also be used.

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

[Release layer]
As described above, the support base material used in the laminate of the present invention preferably has a release layer. The support base material which has a release layer is also called a release film. The release layer may be composed of a plurality of layers from the viewpoint of imparting adhesion, antistatic properties, solvent resistance, etc., and may be on both sides of the support substrate.

  The composition and thickness of the release layer are not particularly limited as long as the peeling force from the resin film can be within the above-mentioned preferable range, but it is 10 to 500 nm from the viewpoint of in-plane uniformity, quality, and peeling force of the release layer. It is preferable that it is 20-300 nm.

[Protective materials]
The laminate of the present invention may have a protective material on the surface of the resin film opposite to the support base as shown in FIG. The protective material may be the same as or different from the above-mentioned support base material, but it is preferable to have a difference in peeling force from the above-mentioned support base material in use in the subsequent step. The magnitude relationship between the peel strength of the protective material and the support substrate from the resin film is appropriately selected according to the method of use in the subsequent step. Therefore, the protective material may have a release layer as shown in FIG. 7 described above, may have an adhesive layer as shown in FIG. 8, or may not have a layer as shown in FIG. .

[Coating composition for forming resin film]
Although the manufacturing method of the laminated body of this invention is not specifically limited, The laminated body of this invention is the process of apply | coating the coating composition for resin film formation mentioned later to one side of the above-mentioned support base material, and as needed. It is preferable to make it through a drying process and a curing process.

  Here, the “coating composition” is not particularly limited as long as it can be uniformly applied on the above-mentioned supporting substrate and can form a resin film, but in order to form a resin film having the above-mentioned physical properties, It is preferable to perform curing after application or by irradiation with ionizing radiation. Further, from the viewpoint of the quality of the resin film and the suitability for production, a solvent may be included. In that case, it is preferable to perform drying to remove the solvent between coating and curing.

  The solid content of the coating composition is a resin or a material capable of forming them in the coating process (hereinafter referred to as a precursor), particles, and a polymerization initiator, a curing agent, a catalyst, a leveling agent, an ultraviolet absorber, Consists of various additives such as antioxidants.

  The coating composition for forming a resin film is a liquid containing a material suitable for constituting the resin film of the present invention or containing a formable precursor, and includes a polyether segment, a (meth) acrylic segment, and urethane as solutes. It is preferable to include a resin or a precursor containing a segment. These may be all present in one type of polymer or oligomer, or may be a mixture of another polymer or oligomer containing each.

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

  Therefore, the coating composition for forming a resin film makes an oligomer obtained by polymerizing a precursor containing a polyether segment, a (meth) acrylic segment, and a urethane segment in a state in which the molecular weight can be controlled, and then various additives are added thereto. Then, it is preferable to prepare a resin film-forming coating composition and apply it to a support substrate and cross-link it on a support substrate in a method for producing a laminate to be described later, thereby forming a resin film.

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

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

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

  The compound containing an isocyanate group refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Examples include isocyanurate bodies, isocyanurate bodies of hexamethylene diisocyanate, (poly) isocyanates such as biuret bodies of hexamethylene isocyanate, and block bodies of the above isocyanates.

  Of these isocyanate group-containing compounds, aliphatic isocyanates are preferred because of their high stretchability and flexibility as compared with alicyclic and aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. The isocyanate group-containing compound is particularly preferably an isocyanate having an isocyanurate ring from the viewpoint of heat resistance, and most preferably an isocyanurate of hexamethylene diisocyanate. An isocyanate having an isocyanurate ring forms a resin film having both stretchability and heat resistance.

  Examples of commercially available urethane acrylates include urethane acrylate manufactured by Asia Kogyo Co., Ltd., urethane acrylate manufactured by Kyoeisha Chemical Co., Ltd., urethane acrylate manufactured by Shinnakamura Chemical Co., Ltd., urethane acrylate manufactured by Taisei Fine Chemical Co., Ltd. "New Frontier" (registered trademark) manufactured by Ichi Kogyo Seiyaku Co., Ltd. "EBECRYL" (registered trademark) manufactured by Daicel Ornex Co., Ltd. These products can be used.

[Antioxidant]
The resin film preferably contains an antioxidant. By containing an antioxidant, it is possible to suppress oxidative deterioration of the polyether segment due to heat, which is effective for improving heat resistance and moist heat resistance. Here, the antioxidant is a chain reaction in which the polymer compound constituting the resin film is started by heat, light, metal, etc., and the generated radicals react while taking in oxygen, so-called oxidative degradation is prevented. It is an additive. Antioxidants are broadly classified into radical chain initiators, radical scavengers, and peroxide decomposers based on their mechanism of action, and any of these is a problem to be solved by the present invention for suppressing deterioration under high temperature conditions. However, although the effects of the present invention can be obtained, radical scavengers or peroxide decomposers are more preferred. Hindered phenol-based, semi-hindered phenol-based radical scavengers, or phosphite-based, thioether-based peroxide decomposers. Agents are particularly preferred.

[solvent]
The coating composition for a resin film of the present invention may contain a solvent, and in order to form the coating layer uniformly in the plane, it is preferable to contain a solvent. The number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, still more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

  Here, the “solvent” refers to a substance that is liquid at normal temperature and normal pressure, which can be evaporated almost entirely in the aforementioned drying step.

  Here, the kind of solvent is determined by the molecular structure constituting the solvent. That is, the same elemental composition and the same type and number of functional groups have different bond relationships (structural isomers), which are not structural isomers, but what conformations are in three-dimensional space Those that do not overlap exactly even if they are removed (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are handled as different solvents.

  Furthermore, when it contains a solvent, it is preferable that it is a solvent which shows the following characteristics.

[Other components in the coating composition]
Moreover, it is preferable that the said coating composition contains a polymerization initiator, a hardening | curing agent, and a catalyst other than the above-mentioned antioxidant. A polymerization initiator and a catalyst are used to accelerate the curing of the resin film. As the polymerization initiator, those capable of initiating or accelerating polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization reaction or the like of components contained in the coating composition are preferable.

  Various polymerization initiators, curing agents and catalysts can be used. In addition, the polymerization initiator, the curing agent, and the catalyst may be used alone, or a plurality of 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 the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like. Examples of the crosslinking catalyst that promotes the urethane bond formation reaction include dibutyltin dilaurate and dibutyltin diethylhexoate.

  As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone type compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-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-phenylpropane-1-o , 1- [4- (2-Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and materials thereof And the like having a high molecular weight.

  Further, a leveling agent, a lubricant, an antistatic agent and the like may be added to the coating composition used for forming the resin film as long as the effects of the present invention are not impaired. Thereby, the resin film can contain a leveling agent, a lubricant, an antistatic agent, and the like.

  Examples of the leveling agent include acrylic copolymers, silicone-based and fluorine-based leveling agents. Examples of the antistatic agent include metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt and calcium salt.

[Manufacturing method of laminate]
Although the manufacturing method of the laminated body of this invention will not be specifically limited if a support base material can be peeled from a laminated body and a resin film can be obtained, the coating composition for resin films is apply | coated on a support base material, and as needed A method of providing a resin film by drying and curing is preferable.

  A coating method will not be specifically limited if the coating composition for resin films is apply | coated on a support base material and an in-plane uniform coating layer can be formed. The coating method on the film can be appropriately selected from a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method (US Pat. No. 2,681,294). Here, the coating layer refers to a “liquid layer” formed by a coating process.

  A drying method will not be specifically limited if a solvent can be removed from the application layer formed on the support base material. Examples of the drying method include heat transfer drying (adherence to a high-temperature object), convection heat transfer (hot air), radiant heat transfer (infrared ray), and others (microwave, induction heating). Among these, the present invention In this manufacturing method, a method using convective heat transfer or radiant heat transfer is preferable because it is necessary to make the drying speed uniform even in the width direction.

  In the curing method, after drying, the resin film is reacted by irradiating heat or energy rays to cure the coating film. When curing with heat in the curing step, the temperature is preferably from room temperature to 200 ° C, more preferably from 100 ° C to 200 ° C, and even more preferably from 130 ° C to 200 ° C, from the viewpoint of the activation energy of the curing reaction. Although it is the following, you may carry out continuously also combining with a drying process.

Moreover, when hardening with an energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When UV-curing using a high-pressure mercury lamp that is a discharge lamp method, the illuminance of UV is preferably from 100 to 3,000 (mW / cm ² ), more preferably from 200 to 2,000 (mW / cm ² ), and even more preferably. Is preferably irradiated with ultraviolet rays under the conditions of 300 to 1,500 (mW / cm ² ), and the cumulative amount of ultraviolet rays is preferably from 100 to 3,000 (mJ / cm ² ), more preferably from 200 to It is good to irradiate with ultraviolet rays under conditions of 2,000 (mJ / cm ² ), more preferably 300 to 1,500 (mJ / cm ² ). Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

[Production method of resin film]
Although the manufacturing method of the resin film of this invention is not specifically limited, The resin film of this invention can be obtained by peeling the support base material which can be peeled from the laminated body obtained by the above-mentioned manufacturing method.

[Application example]
The resin film of the laminate of the present invention can be suitably used for applications requiring particularly high flexibility and stretchability, taking advantage of excellent optical properties, flexibility, stretchability, and transportability.

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

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

[Synthesis of oligomer A]
The following 1 to 7 were mixed, held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene solution having a solid content concentration of oligomer A of 60% by mass.

1. Toluene: 50 parts by mass 2. Polytetramethylene glycol (PTMG 2000 manufactured by Mitsubishi Chemical Corporation): 330 parts by mass. Hexamethylene diisocyanate: 50 parts by mass 4. 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether: 0.02 parts by mass 7. 2-hydroxyethyl acrylate: 11 parts by mass.

[Synthesis of oligomer B]
The following 1 to 7 were mixed and then held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene solution having a solid content concentration of oligomer B of 60% by mass.

1. Toluene: 50 parts by mass 2. Polytetramethylene glycol (PTM1300 manufactured by Mitsubishi Chemical Corporation): 220 parts by mass Hexamethylene diisocyanate: 50 parts by mass 4. 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether 0.02 parts by mass 7. 2-hydroxyethyl acrylate: 11 parts by mass.

[Synthesis of Oligomer C]
The following 1 to 7 were mixed, held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene concentration solution of oligomer C having a solid content of 60% by mass.

1. Toluene: 50 parts by mass 2. Polyethylene glycol: (PEG # 2000, NOF Corporation): 330 parts by mass Hexamethylene diisocyanate: 50 parts by mass 4. 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether: 0.02 parts by mass 7. 2-hydroxyethyl acrylate: 11 parts by mass.

[Synthesis of oligomer D]
The following 1 to 7 were mixed, held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene solution having a solid content concentration of oligomer D of 60% by mass.

1. Toluene: 50 parts by mass Polytetramethylene glycol (PTM1300 manufactured by Mitsubishi Chemical Corporation): 220 parts by mass 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether: 0.02 parts by mass 7. 2-hydroxyethyl acrylate: 11 parts by mass.

[Synthesis of oligomer E]
The following 1 to 7 were mixed, held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene solution having a solid content concentration of oligomer E of 60% by mass.

1. Toluene: 50 parts by mass 2. Polytetramethylene glycol (PTM1300 manufactured by Mitsubishi Chemical Corporation): 220 parts by mass Hexamethylene diisocyanate: 50 parts by mass 4. 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether: 0.02 parts by mass 7.4-hydroxybutyl acrylate: 13 parts by mass.

[Synthesis of oligomer F]
The following 1 to 7 were mixed, held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene concentration solution of oligomer F having a solid content of 60% by mass.

1. Toluene: 50 parts by mass 2. Polytetramethylene glycol (PTM1000 manufactured by Mitsubishi Chemical Corporation): 165 parts by mass Hexamethylene diisocyanate: 50 parts by mass 4. 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether: 0.02 parts by mass 7.4-hydroxybutyl acrylate: 13 parts by mass.

[Synthesis of oligomer P]
The following 1 to 7 were mixed, held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene solution having a solid content concentration of oligomer P of 60% by mass.

1. Toluene: 50 parts by mass 2. Polycaprolactone diol (Placcel 220 manufactured by Daicel Corporation): 330 parts by mass. Hexamethylene diisocyanate: 50 parts by mass 4. 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether: 0.02 parts by mass 7. 2-hydroxyethyl acrylate: 11 parts by mass.

[Synthesis of oligomer Q]
The following 1 to 7 were mixed, held at 70 ° C. for 5 hours, and then diluted with toluene to obtain a toluene solution of oligomer Q having a solid content concentration of 60% by mass.

1. Toluene: 50 parts by mass 2. Polytetramethylene glycol (PTM650 manufactured by Mitsubishi Chemical Corporation): 110 parts by mass Hexamethylene diisocyanate: 50 parts by mass 4. 4. Hexamethylene diisocyanate isocyanurate modified type (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals, Inc.): 2 parts by mass Dibutyltin laurate: 0.02 parts by mass Hydroquinone monomethyl ether: 0.02 parts by mass 7.4-hydroxybutyl acrylate: 13 parts by mass.

[Preparation of coating composition for resin film formation]
[Coating composition 1 for resin film formation]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 1 having a solid concentration of 40% by mass.

・ Oligomer A toluene solution (solid content concentration 60 mass%): 100 mass parts ・ Hindered phenolic antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 ( BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition 2 for forming resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 2 having a solid content of 40% by mass.

・ Oligomer B Toluene solution (solid content concentration 60 mass%): 100 mass parts ・ Hindered phenol antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 ( BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition 3 for forming resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 3 having a solid content of 40% by mass.

・ Oligomer C toluene solution (solid content concentration 60 mass%): 100 mass parts ・ Hindered phenolic antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 ( BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition 4 for resin film formation]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 4 having a solid content of 40% by mass.

・ Oligomer D Toluene solution (solid content concentration 60 mass%) 100 mass parts ・ Hindered phenol antioxidant “IRGANOX” 1010 (BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 (BASF) (Japan Co., Ltd.): 1.5 parts by mass.

[Coating composition 5 for forming resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 5 having a solid content concentration of 40% by mass. Oligomer E toluene solution (solid content concentration 60% by mass): 100 parts by mass Hindered phenolic antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 parts by mass • Photopolymerization initiator “IRGACURE” 184 (manufactured by BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition 6 for forming resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 6 having a solid content concentration of 40% by mass. • Oligomer B toluene solution (solid content concentration 50% by mass): 100 parts by mass Phosphite antioxidant “IRGANOX” 1520 (manufactured by BASF Japan Ltd.): 5 parts by mass • Photopolymerization initiator “IRGACURE” 184 (manufactured by BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition 7 for forming resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 7 having a solid content of 40% by mass.

・ Oligomer B toluene solution (solid content concentration 60 mass%): 100 mass parts ・ Phosphorus antioxidant “IRGAFOS” 168 (manufactured by BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 (BASF Japan) Manufactured by): 1.5 parts by mass.

[Coating composition 8 for forming resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 8 having a solid content concentration of 40% by mass. • Oligomer B toluene solution (solid content concentration 60% by mass): 100 parts by mass Hindered amine-based antioxidant “TINUVIN PA144 (manufactured by BASF Japan Ltd.): 5 parts by mass • Photopolymerization initiator“ IRGACURE ”184 (manufactured by BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition for resin film formation 9]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 9 having a solid content of 40% by mass.

-Oligomer B toluene solution (solid content concentration 60 mass%): 100 mass parts-Photoinitiator "IRGACURE" 184 (made by BASF Japan Ltd.): 1.5 mass parts.

[Coating composition 10 for forming a resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 10 having a solid concentration of 40% by mass.

-Oligomer F toluene solution (solid content concentration 60 mass%): 100 mass parts-Photoinitiator "IRGACURE" 184 (made by BASF Japan Ltd.): 1.5 mass parts.

[Coating composition 11 for forming resin film]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 11 having a solid concentration of 40% by mass.

・ Oligomer B Toluene solution (solid content concentration 60 mass%): 100 mass parts ・ Carbodiimide-based hydrolysis inhibitor “Elastostab” H01 (BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 (BASF) (Japan Co., Ltd.): 1.5 parts by mass.

[Coating composition 12 for resin film formation]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 12 having a solid concentration of 40% by mass.

・ Oligomer B Toluene solution (solid content concentration: 60% by mass): 100 parts by mass • Hindered phenol antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 parts by mass • Carbodiimide hydrolysis inhibitor “Elastostab” H01 (manufactured by BASF Japan Ltd.): 5 parts by mass • Photopolymerization initiator “IRGACURE” 184 (manufactured by BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition for resin film formation 13]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 13 having a solid concentration of 40% by mass.

・ Oligomer P Toluene solution (solid content concentration: 60 mass%): 100 mass parts ・ Hindered phenol antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 ( BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition for resin film formation 14]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 14 having a solid concentration of 40% by mass.

・ Oligomer B Toluene solution (solid content concentration 60 mass%): 100 mass parts ・ Carbodiimide-based hydrolysis inhibitor “Elastostab” H01 (BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 (BASF) (Japan Co., Ltd.): 1.5 parts by mass.

[Coating composition 15 for resin film formation]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 15 having a solid content of 40% by mass.

-Oligomer P toluene solution (solid content concentration 60 mass%): 100 mass parts-Photoinitiator "IRGACURE" 184 (made by BASF Japan Ltd.): 1.5 mass parts.

[Coating composition 16 for resin film formation]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 16 having a solid concentration of 40% by mass.

・ Oligomer P Toluene solution (solid content concentration: 60 mass%): 100 mass parts ・ Hindered phenol antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 mass parts ・ Carbodiimide hydrolysis inhibitor “Elastostab” H01 (manufactured by BASF Japan Ltd.): 5 parts by mass • Photopolymerization initiator “IRGACURE” 184 (manufactured by BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition 17 for resin film formation]
While stirring 200 parts by mass of toluene cooled to 10 ° C., the following materials were added little by little, and the mixture was heated to 80 ° C. with the stirring state maintained and dissolved, and after dissolution, diluted with toluene, the solid content A coating composition 17 for forming a resin film having a concentration of 40% by mass was obtained.

Polyether-based thermoplastic urethane elastomer “Elastollan” 1180A (manufactured by BASF Japan): 100 parts by mass Hindered phenolic antioxidant “IRGANOX” 1010 (manufactured by BASF Japan): 5 parts by mass.

[Coating composition 18 for resin film formation]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin film-forming coating composition 18 having a solid concentration of 40% by mass.

・ Oligomer Q toluene solution (solid content concentration 60 mass%): 100 mass parts ・ Hindered phenolic antioxidant “IRGANOX” 1010 (manufactured by BASF Japan Ltd.): 5 mass parts ・ Photopolymerization initiator “IRGACURE” 184 ( BASF Japan Ltd.): 1.5 parts by mass.

[Coating composition for release layer]
The following materials were mixed and diluted with a methyl ethyl ketone / isopropyl alcohol mixed solvent (mass mixing ratio 50/50) to obtain a release layer coating composition having a solid content concentration of 5 mass%.
Side chain type carbinol-modified reactive silicone oil (X-22-4015 Shin-Etsu Chemical Co., Ltd., solid content concentration: 100% by mass): 5 parts by mass Double-end polyether modified reactive type silicone oil (X-22) -4952 Shin-Etsu Chemical Co., Ltd. Solid content concentration: 100% by mass): 5 parts by mass Acrylic modified alkyd resin solution (Hariftar KV-905 Harima Chemicals Co., Ltd. solid content concentration 53% by mass): 100 parts by mass modified with isobutyl alcohol Melamine resin solution (Melan 2650L Hitachi Chemical Co., Ltd. solid content concentration 60% by mass): 20 parts by mass / paratoluenesulfonic acid: 5 parts by mass.

[Production method of laminate and resin film]
[Formation of support substrate]
Using a coating apparatus having a small-diameter gravure coater, the release layer coating composition described in Table 1 is applied to a polyester film (trade name “Lumirror” (registered trademark) R75X, manufactured by Toray Industries, Inc.) having a thickness of 50 μm. Adjust the number of gravure lines, peripheral speed, and solid content so that the thickness is adjusted, and then hold it at a hot air temperature of 140 ° C. for 30 seconds to dry and harden the support substrate with a release layer. Obtained.

[Formation of laminate A]
Using the above-mentioned support substrate with a release layer as a support substrate, using the continuous coating device by a slot die coater, the above-mentioned coating composition for forming a resin film is placed on the release layer of the above-mentioned support substrate. The resin film after curing was applied by adjusting the discharge flow rate so that the thickness of the resin film became a specified film thickness. The conditions of the drying wind that hits the liquid film from application to drying and curing are as follows.

[Drying process]
Ventilation temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the substrate surface, anti-application Surface side: perpendicular to the surface of the substrate Residence time: 2 minutes [curing step]
Irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1% by volume.

[Formation of laminate B]
Using the above-mentioned support substrate with a release layer as a support substrate, using the continuous coating device by a slot die coater, the above-mentioned coating composition for forming a resin film is placed on the release layer of the above-mentioned support substrate. The resin film after curing was applied by adjusting the discharge flow rate so that the thickness of the resin film became a specified film thickness. The conditions of the drying wind that hits the liquid film from application to drying and curing are as follows.

[Drying process]
Ventilation temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the substrate surface, anti-application Surface side: perpendicular to the surface of the base material Residence time: 2 minutes The laminates and resin films of Examples 1 to 11 and Comparative Examples 1 to 8 were prepared by the method described above. The resin film-forming coating composition corresponding to each example and comparative example, the method of forming the laminate, and the thickness of each resin film are shown in Table 1 described later.

[Evaluation of Laminate, Resin Film, Resin Film]
The laminated body and the resin film were subjected to the following performance evaluation, and the obtained results are shown in Table 2. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

  In addition, about the resin film, it considered that it was equivalent to a laminated body, and performed the same evaluation.

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

[5% strain stress, 100% strain stress]
After the laminate was cut into a 10 mm wide × 150 mm long rectangle, the resin film was peeled off from the support base material to obtain a test piece. In addition, each 150 mm length direction was match | combined with the longitudinal direction of the laminated body. Using a tensile tester (Orientec Tensilon UCT-100), the distance between the initial tensile chucks was set to 50 mm, the tensile speed was set to 300 mm / min, and a tensile test was performed at a measurement temperature of 23 ° C.

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

  Of the data obtained above, the stress at 5% strain was taken as 5% strain stress and the stress at 100% strain was taken as 100% strain stress.

[Measurement of elastic recovery rate]
The resin film was cut into a 10 mm wide × 150 mm long rectangle to obtain a test piece. In addition, each 150 mm length direction was match | combined with the longitudinal direction of the laminated body. Using a tensile tester (Orientec Tensilon UCT-100), the initial tensile chuck distance was set to 50 mm, the tensile speed was set to 50 mm / min, and the tensile test was performed at a measurement temperature of 23 ° C. At that time, after the sample was stretched to a strain amount of 10 mm (= 20%), the tensile load on the sample was released. This test method is a tensile test method with a deformation of 20%.

The elastic recovery rate z% was calculated from the following equation by measuring the distance marked as the initial test length before measurement as Lmm.
Elastic recovery rate: z = (1− (L−50) / 20) × 100 (%).

[Measurement of dimensional change rate]
After the laminate was cut into a 10 mm wide rectangle, the support substrate was peeled from the resin film to obtain a test piece.

Based on the tensile vibration-non-resonance method of JIS K7244 (1998) (this is referred to as a dynamic viscoelastic method), the storage elastic modulus of the resin film using a dynamic viscoelasticity measuring device “DMS6100” manufactured by Seiko Instruments Inc. And the loss modulus was obtained.
Measurement mode: Distance between tension chucks: 20 mm
Specimen width: 10mm
Frequency: 1Hz
Strain amplitude: 10 μm
Minimum tension: 20mN
Initial value of force amplitude: 40mN
Measurement temperature: -100 ° C. to 200 ° C. Rate of temperature increase: 5 ° C./min At this time, a dL value (LVDT (Linear Variable Differential Transformer) output value) is obtained simultaneously with the measurement of storage elastic modulus and loss elastic modulus, This represents a value corresponding to the dimension of the test piece at the time of measurement. The dL value at 30 ° C. was set to a30 (μm), the dL value at 150 ° C. was set to a150 (μm), and the dimensional change rate was obtained by the following formula.
(Dimensional change rate) = ((a150−a30) / 20,000) × 100
Furthermore, the absolute value of the dimensional change rate obtained by the above formula was calculated.

[Measurement of infrared absorption spectra of resin films by FT-IR]
The FT-IR spectrum was measured by the ATR method on the surface of the resin film. Measuring devices and measuring conditions are as follows.

Measuring apparatus: FT-IR Varian-670 manufactured by Varian
Measurement conditions: Light source Special ceramics
Detector DTGS
Resolution 4cm ^-1
Accumulation count 128 times
Measurement wave number range: 4,000 to 680 cm ⁻¹ .

From the obtained spectrum, among the peaks derived from the carbodiimide group of 2,100 to 2,200 cm ⁻¹ and the peaks derived from the isocyanate group of 2,240 to 2,270 cm ⁻¹ , the intensity P1 having the highest peak intensity And peak intensity P2 resulting from NH stretching vibration of a urethane group of 3,000 cm ^{−1 to} 3,500 cm ⁻¹ was determined, and P1 / P2 was calculated. There are cases where multiple peaks appear within this range due to the hydrogen bond with the carbonyl group that serves as the acceptor, the ether bond of the polyol residue, and the ester bond. Is selected as P2 having the highest peak intensity.

[Changes in stress before and after storage of laminate in wet heat]
The laminate was cut into a 10 mm wide × 150 mm long rectangle and placed in a constant temperature and humidity layer at 85 ° C. to 85% and stored for 500 hours. After 500 hours, 100% strain stress (F3) of the taken-out laminated body and the laminated body (F1) not put in the constant temperature and humidity layer were determined for 100% strain stress by the above-described method, and F3 / F1 was calculated. Calculated.

[Stress change before and after storage of resin film in wet heat]
In a state where the resin film was cut into a rectangle of 10 mm width × 150 mm length, it was placed in a constant temperature and humidity layer at 85 ° C. to 85% and stored for 500 hours. After 500 hours, the 100% strain stress (F5) of the taken out resin film and the resin film (F4) that was not put in the constant temperature and humidity layer were determined for the 100% strain stress by the method described above, and F5 / F4 was calculated. Calculated.

[Evaluation of flexibility]
About the resin film which peeled the support base material from the laminated body, light force was applied to the pulling direction by hand, and the determination was performed according to the following criteria. Judgment was made by three people, the results were averaged, and the first decimal place was rounded off.
10 points: Can be deformed with very light force.
7 points: Can be deformed if light force is applied.
4 points: Can be deformed by applying a slightly stronger force.
1 point: Other (A strong force is required to deform, etc.).

[Evaluation of restoreability]
About the resin film which peeled the support base material from the laminated body, light force was applied to the pulling direction by hand, and the determination was performed according to the following criteria. Judgment was made by three people, the results were averaged, and the first decimal place was rounded off.
10 points: Restore the original shape by removing the load after deformation.
7 points: Mostly restored to its original shape when the load is removed after deformation.
4 points: If the load is removed after deformation, it will be restored to its original shape.
1 point: Others (not restored at all).

[Evaluation of heat resistance]
The laminate was cut into a width of 150 mm and a length of 250 mm, and this sample was placed in a hot air oven adjusted to 180 ° C. and allowed to stand for 1 minute. Then, the sample was taken out from the hot air oven, the state of wrinkles and irregularities generated in the laminate was visually observed, and a determination was made according to the following criteria. Judgment was made by three people, the results were averaged, and the first decimal place was rounded off.
10 points: No wrinkles, unevenness or curling.
7 points: Slight wrinkles, unevenness and curling occur.
4 points: Small wrinkles, irregularities and curls occur.
1 point: Other (large wrinkles, irregularities, curls, etc.).

[Evaluation of heat and humidity resistance]
The laminate was cut into a width of 150 mm and a length of 250 mm, this sample was stored at 85 ° C.-85% for 500 hours, and then compared with a sample stored at room temperature. Judgment was made by three people, the results were averaged, and the first decimal place was rounded off.
10 points: No change in appearance with respect to room temperature storage products, and can be extended with the same force.
7 points: There is no change in appearance compared to room temperature storage products, but the restoration speed is slightly slow when pulled at high speed.
4 points: No change in appearance compared to room temperature storage products, but can be pulled with low force.
1 point: There is a clear change in appearance with respect to a room temperature storage product, and the restorability is remarkably inferior.

[Evaluation of post-processing suitability]
A release film (Toray Film Processing Co., Ltd., thickness 38 μm “Celapeel” (registered trademark) MDA) was used as a support base, and an acrylic adhesive (Toyochem) was used on the release surface using a wire bar (No. 40). Co., Ltd., Olivevine BPS-8170) was applied, and the adhesive was dried in an oven at 150 ° C. for 2 minutes to prepare an adhesive film.

  Next, the above-mentioned pressure-sensitive adhesive film was bonded to the resin film surface side of the laminate of the present invention while being pressure-bonded with a 5 kg roller. Similarly, a polyester film (thickness 125 μm “Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) was bonded in the same manner as Sample 2.

Samples 1 and 2 described above were allowed to stand for 1 hour in an atmosphere of room temperature 23 ° C. and humidity 65% RH. After leaving, sample 1 and sample 2 are cut, a double-sided tape is pasted on a stainless steel plate with a thickness of 0.5 mm, sample 1 is peeled off the release film on the laminate side, and sample 2 is a polyester film. Bonding directly, the test piece was created. And about the sample 1 and the sample 2, the stress when the release film of an adhesive film peeled 180 degrees at a speed | rate of 300 mm / min was measured using the tension tester, respectively. From this result, the following R was obtained, and R was determined to be 0.5 or more and 1.5 or less.
R = F1 / F2
F1: Release film peeling force of sample 2 (mN / 50mm)
F2: Release film peeling force of sample 2 (mN / 50 mm).

  Table 2 contains the segments of the chemical formulas 1 to 3 of the resin film and the presence / absence of the antioxidant, Table 3 shows the evaluation results of the conditions 1 to 5 described above, and Table 4 shows the flexibility and resilience of the resin film. The evaluation results of heat resistance and post-processing suitability are summarized.

1, 4, 8, 12, 17, 21, 26, 32: Laminate 2, 5, 9, 13, 18, 22, 27, 33: Resin films 6, 10, 14, 15, 23, 28, 30, 34: Release layer 3, 7, 11, 16, 19, 24, 29, 35: Support base material 20, 25, 31, 37: Protective material 36: Adhesive layer

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

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

Claims (4)

A resin film comprising a polyether segment, a (meth) acrylic segment, and a urethane segment,
A resin film characterized by satisfying all of the following conditions 1 to 4 and condition 6.
Condition 1 The 5% strain stress of the resin film is 10 MPa or less.
Condition 2 The elastic recovery rate is 70% or more in the tensile test method when the deformation amount of the resin film is 20%.
Condition 3 The absolute value of the dimensional change rate at 150 ° C. based on the size at 30 ° C. of the resin film is 10% or less.
Condition 4 Among the peaks derived from the carbodiimide group of 2,100 to 2,200 cm ^{−1 and} the isocyanate group of 2,240 to 2,270 cm ⁻¹ in the FT-IR spectrum of the resin film, the intensity P1 of the one having the highest peak intensity And the ratio of the peak intensity P2 due to the NH stretching vibration of the urethane group of 3,000 cm ^{−1 to} 3,450 cm ⁻¹ , P1 / P2 is 0.01 or less.
Condition 6: Stress F4 when the resin film at 23 ° C. is stretched to 100% strain and stress F5 when the resin film at 23 ° C. is stretched to 100% strain after 500 hours at 85 ° C.-85%. Ratio, F5 / F4 is 0.4 or more.   2. The resin film according to claim 1, wherein the resin film contains at least one antioxidant selected from the group consisting of hindered phenolic, semi-hindered phenolic, phosphite, and thioethers. . A laminate having a resin film comprising a polyether segment, a (meth) acrylic segment, and a urethane segment, and a support substrate that can be peeled on at least one surface of the resin film,
The said resin film satisfy | fills all the following conditions 1-5, The laminated body characterized by the above-mentioned.
Condition 1 The 5% strain stress of the resin film is 10 MPa or less.
Condition 2 The elastic recovery rate is 70% or more in the tensile test method when the deformation amount of the resin film is 20%.
Condition 3 The absolute value of the dimensional change rate at 150 ° C. based on the size at 30 ° C. of the resin film is 10% or less.
Condition 4 Among the peaks derived from the carbodiimide group of 2,100 to 2,200 cm ^{−1 and} the isocyanate group of 2,240 to 2,270 cm ⁻¹ in the FT-IR spectrum of the resin film, the intensity P1 of the one having the highest peak intensity And the ratio of the peak intensity P2 due to the NH stretching vibration of the urethane group of 3,000 cm ^{−1 to} 3,450 cm ⁻¹ , P1 / P2 is 0.01 or less.
Condition 5 Stress F1 when the resin film at 23 ° C. is stretched to 100% strain, and after lapse of 500 hours at 85 ° C.-85% in the state of the laminate, the resin film at 23 ° C. is stretched to 100% strain. The ratio with the stress F3 when F3 / F1 is 0.5 or more.   The laminate according to claim 3, wherein the resin film contains at least one antioxidant selected from the group consisting of hindered phenols, semi-hindered phenols, phosphites, and thioethers. .

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