Laminated film and method for manufacturing the same

Abstract

This multilayer film has a resin substrate with a resin layer disposed on at least one surface thereof, the resin layer being located on at least one surface layer. With regard to the X ray absorption near edge structure (XANES) of the carbon K-edge of the resin layer surface, when the angle formed by the incident X-ray and the resin layer surface is θ, and the spectrum intensity at 293.5 eV obtained by the partial electron yield method is I (θ), the multilayered film satisfies I (15°) − I (90°) ≥ 0.1 .　Provided is a multilayer film which, as a release film for peeling after applying a coating solution containing a solvent and then drying and curing the same, has excellent coatability and peelability and does not exhibit surface layer separation after heating.

Description

[Technical Field]

[0001] The present invention relates to a laminated film having a resin layer on at least one side of a polyester film, and a method for producing the same. [Background technology]

[0002] Biaxially oriented polyester films are widely used as base films in many applications, such as magnetic recording materials and packaging materials, due to their excellent mechanical, electrical, dimensional stability, transparency, and chemical resistance. In recent years, there has been a growing demand for films with excellent release properties, particularly as protective films for adhesive layers in adhesive products and as carrier films in the processing of various industrial products. As films with excellent release properties, films with a layer containing a silicone compound as a release agent (hereinafter referred to as a resin layer) on the surface are the most commonly used, from the standpoint of industrial productivity and heat resistance (see, for example, Patent Document 1). However, when a silicone compound is included in the resin layer, the surface free energy of the resin layer becomes low, which can result in poor coating properties of the adherend.

[0003] In particular, when used as a process film in the manufacture of electronic components, the process involves applying a surface layer, such as a ceramic slurry, onto the resin layer of the polyester film, drying it, and then peeling the dried surface layer off the polyester film. At this time, if the resin layer contains a silicone compound, problems may arise when applying the surface layer to the resin layer, such as the silicone compound repelling or causing pinholes. Furthermore, even if no major problems occur during the coating process, when the surface layer is peeled off the polyester film, the silicone compound migrates to the surface layer and gradually vaporizes. This can then accumulate on the surface of electrical contacts due to arcs generated near the electrical contacts of electronic components, causing poor conductivity and negatively impacting their performance.

[0004] To address these challenges, studies are being conducted on using long-chain alkyl group-containing resins, olefin resins, fluorine compounds, and wax-based compounds, particularly long-chain alkyl group-containing resins, as release agents that do not contain silicone compounds (hereinafter referred to as non-silicone release agents) (see, for example, Patent Documents 2 to 6). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2010-155459 [Patent Document 2] Japanese Patent Publication No. 2017-170660 [Patent Document 3] Japanese Patent Publication No. 2010-144046 [Patent Document 4] Japanese Patent Publication No. 2004-351627 [Patent Document 5] International Publication No. 2018 / 037991 [Patent Document 6] Japanese Patent Publication No. 2020-152095 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, non-silicone release agents have the drawback of being more prone to excessive peeling compared to release agents containing silicone compounds. For example, when the present inventors verified the film described in Patent Document 2, they found that when the surface layer was applied to the resin layer, the surface layer components penetrated into the resin layer, resulting in excessive peeling of the surface layer.

[0007] Furthermore, it was confirmed that even when a long-chain alkyl group-containing resin is included, as in the films described in Patent Documents 3, 4, and 5, depending on the processing conditions, the orientation of the long-chain alkyl groups in the resin layer may not be sufficiently high, resulting in a problem where the peeling force to the surface layer becomes heavy peeling. On the other hand, in the method of using a long-chain alkyl acrylate resin and a melamine resin in combination, as in Patent Document 6, although it is possible to create a highly crosslinked resin layer, the surface free energy of the resin layer becomes too high, making it difficult to impart sufficient release properties and resulting in the problem of difficulty in peeling from the ceramic slurry. Moreover, since long-chain alkyl group-containing resins have strong hydrophobicity, and their aqueous dispersions are unstable and prone to aggregation, aggregates tend to be easily included in the resin layer. As a result, coarse protrusions caused by the aggregates are transferred to the layer provided by coating, which can result in increased surface roughness of the layer provided by coating.

[0008] Furthermore, even when a design with less peeling is achieved, it was found that when exposed to high temperatures during the drying process, thermal expansion of the resin layer can cause lifting of the slurry, which can interfere with subsequent processing. Here, lifting refers to the phenomenon where the applied ceramic slurry partially peels off.

[0009] Therefore, the present invention aims to overcome the above drawbacks and provide a laminated film that has excellent applicability for coating compositions that form layers, such as ceramic slurries, and excellent peelability of the coating-formed layer (surface layer), and in particular has few aggregates in the resin layer, as well as excellent transferability and smoothness. Another objective is to provide a laminated film that achieves both easy peelability of the surface layer and resin layer and suppression of lifting of the surface layer after exposure to high-temperature conditions. [Means for solving the problem]

[0010] To solve the above problems, the laminated film of the present invention has one of the following configurations: A laminated film having a resin layer on at least one side of a resin substrate, wherein the resin layer is on at least one surface, and for the X-ray absorption fine structure (XAFS) spectrum measured with respect to the resin layer surface by partial electron yield method, the X-ray absorption near-edge structure (XANES) spectrum of the carbon K absorption edge, where θ is the angle between the incident X-ray and the resin layer surface, and I(θ) is the spectral intensity of 293.5 eV, then I(15°)-I(90°)≧ 0.4 A laminated film that satisfies the following conditions (hereinafter sometimes referred to as the first embodiment), or A laminated film in which a resin layer is laminated on at least one side of a resin substrate, wherein the tape peeling force is 3.0 N / 19 mm or less, and the domain diameter observed in the elastic modulus image by AFM is 500 nm or less (hereinafter sometimes referred to as the second embodiment), That is the case.

[0011] The method for manufacturing the laminated film of the present invention consists of the following configuration. That is, The above-mentioned method for manufacturing a laminated film involves applying a coating composition containing a release agent (A) and at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, polyester resin, acrylic resin, and urethane resin to at least one surface of a resin substrate, then stretching it in at least one axial direction, and then heating it to 150°C or higher to form a resin layer.

[0012] In the present invention, it is preferable that the surface modulus of the resin layer, as measured by atomic force microscopy (AFM), is 1 GPa or higher.

[0013] The laminated film of the present invention is a laminated film in which a resin layer is laminated on at least one side of a resin substrate, preferably having a tape peeling force of 3.0 N / 19 mm or less, and a domain diameter of 500 nm or less as observed in the elastic modulus image by atomic force microscopy (AFM).

[0014] In the laminated film of the present invention, it is preferable that the water contact angle of the resin layer is 85° or more and 110° or less.

[0015] For the laminated film of the present invention, regarding the X-ray absorption near-edge structure (XANES) spectrum at the K absorption edge of carbon among the X-ray absorption fine structure (XAFS) spectra measured by the partial electron yield method with respect to the resin layer surface, when the angle formed by the incident X-ray and the resin layer surface is θ and the spectral intensity at 293.5 eV is I(θ), it is preferable to satisfy [I(15°) - 0.1] / I(90°) > 1.

[0016] When the surface of the resin layer of the laminated film of the present invention is analyzed by time-of-flight secondary ion mass spectrometry, the ratio (P / K) of the peak intensity (P) of the fragment derived from polydimethylsiloxane to the peak intensity (K) of the fragment detected at the maximum intensity is preferably less than 0.01.

[0017] The laminated film of the present invention contains a long-chain alkyl-based resin as the release agent (A) in the resin layer, and when the long-chain alkyl-based resin is heated from 25°C to 200°C at 20°C / min using a differential scanning calorimeter (DSC) and then cooled from 200°C to -50°C at 20°C / min, the exothermic peak temperature (Tc) in the cooling process is preferably 30°C or higher.

[0018] The laminated film of the present invention is preferably formed from a coating composition in which the resin layer contains at least one resin or compound (B) selected from an epoxy resin, an oxazoline compound, a carbodiimide compound, a polyester resin, an acrylic resin, and a urethane resin, in addition to the release agent (A).

[0019] The laminated film of the present invention preferably has a film thickness of the resin layer greater than 10 nm and less than 200 nm.

[0020] The resin base material of the laminated film of the present invention is preferably a polyester film.

[0021] The laminated film of the present invention is preferably used in applications where a ceramic slurry is applied to the surface of the resin layer, solidified, and then peeled off. [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a laminated film that exhibits excellent applicability of coating compositions, such as ceramic slurries, which form layers on a resin layer by application, as well as excellent peelability of the layers formed by application, fewer aggregates in the resin layer, and excellent transferability and smoothness. Furthermore, it is possible to provide a laminated film that achieves both easy peelability between the surface layer and the resin layer, and suppression of lifting of the surface layer after exposure to high-temperature conditions. [Modes for carrying out the invention]

[0023] A first aspect of the laminated film of the present invention is a laminated film having a resin layer on at least one side of a resin substrate, wherein the resin layer is on at least one surface layer, and for the XANES spectrum of the carbon K absorption edge of the resin layer surface, when the angle between the incident X-ray and the resin layer surface is θ, and the spectral intensity of 293.5 eV obtained by the partial electron yield method is I(θ), then the relationship between I(15°) and I(90°) at θ = 15° and 90° is I(15°) - I(90°) ≥ 0.4 This is a laminated film that satisfies the following conditions. First, we will explain the meaning of these physical properties and provide examples of control methods.

[0024] In this invention, the XANES spectrum refers to the X-ray absorption fine structure (XAFS) spectrum obtained by irradiating the resin layer surface of the laminated film of the present invention with X-rays and measuring the amount of absorption, specifically the X-ray absorption edge-near structure spectrum of carbon's K absorption edge. The measurement conditions for the XAFS spectrum will be described later.

[0025] An XAFS spectrum is obtained by measuring the amount of X-ray absorption of a sample while changing the energy of the irradiated X-rays. Since the absorption energy of each element differs depending on the element, this measurement provides information such as the bonding state (valence) and coordination environment (interatomic distance, coordination number) of the elements. In this invention, the K absorption edge of carbon around 284.2 eV, specifically the σ of the CC bond, is targeted. * We focus on the 293.5 eV peak attributed to the transition.

[0026] X-rays are linearly polarized, and the electric field vector is perpendicular to the X-ray and occurs in the horizontal plane. Here, the X-ray absorption intensity of the sample being measured depends on the direction of the electric field vector and the coupling axis. Therefore, by performing angle-resolved measurements on the 293.5 eV peak originating from the CC coupling, it is possible to evaluate the orientation of the CC coupling. In this invention, the angle between the incident X-ray and the surface of the sample being measured is θ, and the X-ray absorption spectral intensity at 293.5 eV is denoted as I(θ).

[0027] When θ = 15°, the X-ray electric field vector is approximately perpendicular to the resin surface, and when θ = 90°, the X-ray electric field vector is approximately parallel to the resin surface. In other words, a larger value of I(15°)-I(90°) means that the degree of orientation of CC bonds is higher in the direction perpendicular to the resin surface, and this can serve as an indicator of the vertical orientation of long-chain alkyl groups in a resin layer containing long-chain alkyl resins, for example.

[0028] While the transmission method, which measures the intensity before and after irradiating a sample with X-rays, is a common method for detecting absorption spectra, the K absorption edge of carbon in this invention is in an energy region called soft X-rays, and since most of the X-ray energy is absorbed within the material, detection methods such as electron yield, fluorescence yield, and ion yield can be used. In this invention, the electron yield method, particularly the partial electron yield method which provides information near the surface, is used.

[0029] The total electron yield method involves irradiating a material with soft X-rays that have an energy higher than the binding energy of its core orbitals. Due to the photoelectric effect, electrons from the core orbitals are emitted as photoelectrons from the material surface. This method detects all electrons without energy selection. A method that selectively detects electrons with a kinetic energy above a certain level is called the partial electron yield method. In the partial electron yield method, the energy of electrons emitted from the surface is selected using an electron spectrometer, and electrons with low kinetic energy and long mean free paths in the material are not detected. This makes it a more surface-sensitive method than the total electron yield method, enabling analysis of sample surfaces down to a few nanometers.

[0030] A first aspect of the laminated film of the present invention is I(15°)-I(90°)≧ 0.4 By satisfying these conditions, it is possible to achieve both good applicability of the coating composition for forming a layer on the resin layer by coating or the like (hereinafter, the layer formed on the surface of the resin layer of the laminated film of the present invention by coating or the like may be called the surface layer), and good peelability between the resin layer and the surface layer.

[0031] As mentioned above, laminated films having a resin layer are sometimes used as carrier films in the processing of various industrial products. In this process, a surface layer containing a solvent is applied to the resin layer of the laminated film, dried, and then peeled off from the laminated film. When a coating solution that forms the surface layer is applied to the resin layer of the laminated film, the components of the surface layer may penetrate into the resin layer.

[0032] If the vertical orientation of long-chain alkyl groups on the surface of the resin layer of the laminated film is insufficient, the penetration of components of the surface layer cannot be suppressed at the surface of the resin layer, and the peeling force of the surface layer becomes severe due to the anchoring effect between the surface layer and the resin layer. The resin layer of the first embodiment of the laminated film of the present invention has I(15°)-I(90°)≧ 0.4 This means that the degree of vertical orientation of the long-chain alkyl groups in the resin layer is high, which makes it difficult for components of the surface layer to penetrate into the resin layer, and thus makes it possible to achieve good peelability of the surface layer. The range (15°)-I(90°) is preferably I(15°)-I(90°)≧ 0.6More preferably, I(15°)-I(90°)≧ 0.8 Therefore, if I(15°)-I(90°)<0.1, the long-chain alkyl groups in the resin layer are not oriented vertically. As a result, when a surface layer is applied on top of the resin layer, the components of the surface layer penetrate into the resin layer, creating an anchoring effect between the resin layer and the surface layer, leading to poor peelability of the surface layer. There is no particular upper limit to I(15°)-I(90°), but it is approximately 1.0.

[0033] The resin layer of the laminated film of the present invention is I(15°)-I(90°)≧ 0.4 Methods for controlling this include, for example, the components constituting the resin layer, the paint composition, and the manufacturing method, which will be described later. The preferred ranges for each will be described later.

[0034] A second aspect of the laminated film of the present invention is a laminated film having a resin layer on at least one side of a resin substrate, wherein the tape peeling force is 3.0 N / 19 mm or less, and the domain diameter observed in the elastic modulus image by atomic force microscopy (AFM) is 500 nm or less. The meaning of these characteristics and examples of control methods will be explained.

[0035] To suppress the occurrence of surface layer delamination even after exposure to high-temperature conditions, a second aspect of the laminated film of the present invention requires that the tape peeling force is 3.0 N / 19 mm or less, and the domain diameter observed in the elastic modulus image by AFM is 500 nm or less. This makes it possible to achieve both easy peelability of the surface layer and resin layer and suppression of delamination at high temperatures when a surface layer is provided, and to prevent the surface layer from breaking during the peeling process.

[0036] In the second embodiment of the laminated film of the present invention, the tape peeling force is preferably 2.5 N / 19 mm or less, and more preferably 2.0 N / 19 mm or less. The lower limit of the tape peeling force is not particularly limited, but it is preferably 0.01 N / 19 mm from the viewpoint of suppressing peeling of the surface layer provided on the resin layer during the roll transport process. The tape peeling force represents the interaction between the resin layer and the surface layer, and reducing the interaction between the resin layer and the surface layer makes it possible to lower the peeling force from the surface layer. If the tape peeling force exceeds 3.0 N / 19 mm, the surface layer may not peel off from the resin layer during the process of peeling the surface layer, causing it to break and reducing the yield.

[0037] In this invention, tape peeling force is defined as follows. First, an acrylic polyester adhesive tape (Nitto Denko Corporation, Nitto 31B tape, 19 mm wide) is bonded onto the resin layer of the laminated film of the present invention, and a 2 kgf roller is passed over it once. After that, the laminated film with the bonded tape is left to stand for 24 hours in an environment of 25°C, 65% RH, and the peeling load obtained when peeling the tape using a Shimadzu Corporation universal testing machine "Autograph AG-1S" at a peeling angle of 180° and a tensile speed of 300 mm / min is defined as the tape peeling force. The specific method for measuring the tape peeling force will be described later.

[0038] To control the tape peeling force within the above preferred range, one method is to include a release agent in the resin layer to reduce the surface free energy. Details of preferred release agents will be described later, but it is particularly preferable to use a long-chain alkyl resin in which methyl groups with low surface free energy are exposed on the surface by orientation and crystallization perpendicular to the surface.

[0039] The laminated film of the present invention, when the domain diameter observed in the elastic modulus image by AFM is 500 nm or less, can be obtained that achieves both easy peelability of the surface layer and resin layer and suppression of delamination at high temperatures. The reason for this is thought to be as follows.

[0040] When a resin layer is composed of a release agent (e.g., a long-chain alkyl resin) and a resin other than the release agent (e.g., epoxy resin, oxazoline compound, carbodiimide compound, melamine resin, polyester resin, acrylic resin, urethane resin, etc.), the release agent may be locally unevenly distributed on the surface of the resin layer, forming domains. In these domains, the amount of release agent is relatively high, while in areas outside the domains, the amount of release agent is low. Therefore, when a surface layer is applied on top of the resin layer, delamination between the resin layer and the surface layer may occur as a double delamination. Furthermore, in these domains, thermal expansion may occur in high-temperature environments, causing film peeling or lifting of the resin layer.

[0041] The domain diameter is preferably 250 nm or less, more preferably 100 nm or less. If the domain diameter is greater than 500 nm, the amount of crosslinking agent in the domains becomes relatively small, which can cause the components of the surface layer to penetrate into the resin layer, resulting in an anchoring effect and severe delamination, or film peeling or lifting may occur due to thermal expansion in high-temperature environments. There is no particular lower limit to the domain diameter, but it should be around 10 nm.

[0042] Methods for controlling the tape peeling force of the laminated film of the present invention to 3.0 N / 19 mm or less and the domain diameter observed in the AFM elastic modulus image to 500 nm or less include, for example, the components constituting the resin layer, the paint composition, and the manufacturing method, which will be described later. The preferred ranges for each will be described later.

[0043] The laminated film of the present invention will be described in detail below. <Resin substrate> The resin substrate in the laminated film of the present invention will be described in detail. The resin substrate is not particularly limited, and the resin type constituting the resin substrate may be either a thermoplastic resin or a thermosetting resin, and may be a homopolymer, copolymer, or a blend of two or more types. From the viewpoint of good moldability, a thermoplastic resin is preferred.

[0044] While not particularly limited, thermoplastic resins such as polyethylene, polypropylene, polystyrene, polymethylpentene, polyolefins, alicyclic polyolefins, nylon 6, nylon 66, polyamides, aramids, polyimides, polyesters, polycarbonates, polyarylates, polyacetals, polyphenylene sulfide, tetrafluoroethylene, trifluoroethylene, trifluoroethylene chloride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride, fluorine, acrylics, methacrylics, polyacetals, polyglycolic acid, and polylactic acid can be used. Examples of thermosetting resins include phenolic resins, epoxy resins, urea resins, melamine resins, unsaturated polyesters, polyurethanes, polyimides, and silicone resins. From the viewpoint of mechanical properties and moldability, polyester is particularly preferred.

[0045] Polyester is a general term for polymers whose main chain is an ester bond, and examples include ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate, and ethylene-α,β-bis(2-chlorophenoxy)ethane-4,4-dicarboxylate. The resin substrate can preferably be one in which at least one of these resins is the main component. In particular, polyethylene terephthalate is preferred, and if the resin substrate is subjected to heat or shrinkage stress, polyethylene-2,6-naphthalate, which has excellent heat resistance and rigidity, is more preferable.

[0046] In addition to the above-mentioned resin types, various additives, such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic particles, fillers, antistatic agents, and nucleating agents, may be added to an extent that does not impair their properties.

[0047] From the viewpoint of mechanical and thermal properties, the resin substrate is preferably composed mainly of polyester (hereinafter, a resin substrate composed mainly of polyester may be referred to as a polyester film). Here, "main component" means that it is the most abundant component among the components that make up the resin substrate.

[0048] The polyester film is preferably biaxially oriented. A biaxially oriented polyester film is generally made by stretching an unstretched polyester film by approximately 2.5 to 5 times in both the longitudinal direction and the width direction perpendicular to the longitudinal direction, and then subjecting it to heat treatment to complete the crystal orientation, resulting in a film that exhibits a biaxial orientation pattern when measured by wide-angle X-ray diffraction. Biaxially oriented polyester films are preferred in terms of the thermal stability of the laminated film, particularly in terms of dimensional stability, mechanical strength, and flatness.

[0049] Furthermore, the polyester film may be a laminated structure of two or more layers. Examples of laminated structures include a composite film having three or more layers, wherein the inner layer substantially does not contain particles and the surface layer contains particles, and the inner layer and the surface layer may be made of chemically different polymers or the same polymer.

[0050] The thickness of the polyester film is not particularly limited and is selected appropriately depending on the application and type, but from the viewpoint of mechanical strength and handling properties, it is usually preferably 10 to 500 μm, more preferably 23 to 125 μm, and most preferably 38 to 75 μm. The polyester film may also be a composite film produced by co-extrusion, or a film obtained by laminating the resulting films by various methods. In this specification, "~" indicating a range of values ​​means "greater than or equal to, and less than or equal to" including the lower limit and upper limit.

[0051] <Resin layer> The resin layer in the laminated film of the present invention is provided on at least one side of the aforementioned resin substrate. The resin layer is necessary for easily peeling off the adhesive tape or the surface layer formed from the ceramic slurry, which will be described later, from the laminated film.

[0052] In the laminated film of the present invention, it is preferable that the surface modulus of the resin layer, as measured by atomic force microscopy (AFM), is 1 GPa or higher. More preferably, the surface modulus is 1.5 GPa or higher, and even more preferably 2.0 GPa or higher. When the surface modulus is within the above preferred range, it means that the resin layer is sufficiently crosslinked, which suppresses the penetration of components of the surface layer into the resin layer, making it possible to reduce the peeling force of the surface layer and tape peeling force. There is no particular upper limit, but from the viewpoint of preventing the resin layer from cracking when the laminated film is bent, the upper limit is set at 10 GPa.

[0053] Here, AFM measurement of elastic modulus is a compression test using a probe on an extremely small area, and since it measures the degree of deformation due to the pressing force, the surface elastic modulus of the resin layer and its spatial distribution can be measured using a cantilever with a known spring constant. Details will be described in the Examples section, but using the atomic force microscope shown below, the probe at the tip of the cantilever can be brought into contact with the resin layer and the force curve can be measured. At this time, information in the depth direction of the coating film can be obtained depending on the indentation depth, but generally, the material present at a depth of about 5 to 10 times the set indentation depth affects the measurement. Therefore, by setting the indentation depth to 1 / 10 of the thickness of the resin layer, the properties of the resin layer become dominant over the influence of the underlying resin substrate. Furthermore, the spatial resolution in the planar direction depends on the scan range and number of scan lines of the atomic force microscope, but under realistic measurement conditions, the lower limit of spatial resolution in the planar direction is approximately 50 nm. Details and measurement methods will be described later.

[0054] In the laminated film of the present invention, the resin layer preferably has a water contact angle of 85° or more and 110° or less. In the laminated film of the present invention, by setting the water contact angle of the resin layer to 85° or more, good release properties can be provided to the laminated film. Furthermore, in the laminated film of the present invention, by setting the water contact angle of the resin layer to 110° or less, it is possible to achieve both easy peeling of the surface layer and tape and good applicability of ceramic slurry, and it is also possible to prevent the ceramic slurry from naturally peeling off from the resin layer. More preferably, it is 92° or more and 108° or less, and even more preferably 96° or more and 106° or less.

[0055] In this invention, the water contact angle is determined by the static droplet method described in JIS R 3257:1999. It is a value that can be determined by the following formula when a water droplet is placed on a solid surface and equilibrium is reached in that atmosphere, and is generally used as an indicator to judge the wettability of the solid surface. That is, the smaller the value of the water contact angle, the better the wettability of the solid surface, and the larger the value, the worse the wettability.

[0056] γS = γLcosθ + γSL (In the above formula, γS is the surface tension of the solid, γL is the surface tension of the liquid, γSL is the interfacial tension between the solid and liquid, and θ is the contact angle.)

[0057] The above equation is called "Young's equation," and it defines the angle between a liquid surface and a solid surface as the "contact angle." The water contact angle can be measured using commercially available devices, such as a Contact Angle Meter (manufactured by Kyowa Interface Science Co., Ltd.). The specific numerical range and measurement method for the water contact angle will be described later.

[0058] In the resin layer of the laminated film of the present invention, it is preferable that, for the X-ray absorption near-edge structure (XANES) spectrum of the carbon K absorption edge among the XAFS spectra measured by the partial electron yield method, when θ is the angle between the incident X-ray and the resin layer surface and I(θ) is the spectral intensity at 293.5 eV, [I(15°)-0.1] / I(90°)>1 is satisfied. More preferably, [I(15°)-0.1] / I(90°)>1.2, and even more preferably, [I(15°)-0.1] / I(90°)>1.4. By setting [I(15°)-0.1] / I(90°) within the above preferred range, it is possible to achieve good tape peeling force and surface layer peeling force.

[0059] In the laminated film of the present invention, it is preferable that the ratio (P / K)[-] of the peak intensity of the fragment derived from polydimethylsiloxane to the peak intensity (K) of the fragment detected at maximum intensity in time-of-flight secondary ion mass spectrometry (GCIB-TOF-SIMS) is less than 0.01. When the peak intensity ratio is less than 0.01, the resin layer contains less polydimethylsiloxane-derived components, so when the laminated film of the present invention is used as a process film for the manufacture of electronic components, there is no migration of silicone compounds (especially polydimethylsiloxane) to the product, thus preventing problems such as poor conductivity. The ratio (P / K)[-] of the peak intensity of the fragment derived from polydimethylsiloxane to the peak intensity (K) of the fragment detected at maximum intensity in time-of-flight secondary ion mass spectrometry can be determined by the measurement method described in the Examples section.

[0060] The resin layer of the laminated film of the present invention preferably contains a long-chain alkyl group-containing resin as a release agent (A), and more preferably the exothermic peak temperature (Tc) of the long-chain alkyl group-containing resin during the cooling process, when the temperature is raised from 25°C to 200°C at 20°C / min and then cooled from 200°C to -50°C at 20°C / min using a differential scanning calorimeter (DSC), is 30°C or higher, even more preferably 35°C or higher, and most preferably 45°C or higher. A high exothermic peak temperature Tc of 30°C or higher facilitates the vertical orientation of the long-chain alkyl group of the release agent (A), allowing it to be adjusted to I(15°)-I(90°)≧0.1.

[0061] The resin layer of the laminated film of the present invention may contain, in addition to the release agent (A), at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, polyester resin, acrylic resin, and urethane resin, to the extent that it does not impair the coatability and release properties. Further details are described in the section on paint composition.

[0062] The resin layer of the laminated film of the present invention preferably has a film thickness greater than 10 nm and less than 200 nm. By setting the film thickness of the resin layer to greater than 10 nm and less than 200 nm, it becomes easier to provide a resin layer with uniform coating properties and release properties on the base resin. If the film thickness of the resin layer is less than 200 nm, manufacturing costs can be reduced, and the occurrence of unevenness and streaks during coating of the resin layer can be suppressed, thereby maintaining the quality of the laminated film. Furthermore, by increasing the film thickness of the resin layer to more than 10 nm, the decrease in release properties can be suppressed.

[0063] <Surface layer> The laminated film of the present invention is preferably used with a surface layer formed on top of a resin layer. Here, the surface layer refers to a layered molded body containing resin, metal, ceramic, etc., formed on the surface of the laminated film having a resin layer. The method for creating the surface layer is not particularly limited, but it can be formed on the surface of the resin layer by methods such as coating, vapor deposition, or lamination. In this specification, when a coating liquid containing a solvent component is used to create the surface layer, or when the surface layer is a cured layer formed by the reaction of reactive active sites, the term "surface layer" may include both the undried and uncured states. In a particularly preferred application of the present invention, the surface layer is a ceramic sheet formed by a process of coating with a ceramic slurry.

[0064] <Paint composition> This document describes preferred coating compositions for forming the resin layer of the laminated film of the present invention. The resin layer of the laminated film of the present invention is preferably formed from a coating composition containing a release agent (A) and at least one resin or compound (B) selected from epoxy resins, oxazoline compounds, carbodiimide compounds, melamine resins, polyester resins, acrylic resins, and urethane resins. With this configuration, for the X-ray absorption near-edge structure (XANES) spectrum of the carbon K absorption edge of the resin layer surface, when θ is the angle between the incident X-ray and the resin layer surface, and Iθ is the spectral intensity of 293.5 eV obtained by the partial electron yield method, I(15°)-I(90°)≧ 0.4 This makes it easier to form a resin layer that exhibits the following characteristics. Furthermore, this configuration makes it easier to form a resin layer in which the tape peeling force is 3.0 N / 19 mm or less and the domain diameter observed in the elastic modulus image by AFM is 500 nm or less.

[0065] <Release agent (A)> In this invention, the release agent (A) refers to a compound that, when included in a paint composition, imparts release properties (i.e., properties that reduce the surface free energy of the resin or reduce the peeling force of the resin layer) to the surface of the coated layer. Examples of release agents (A) that can be used in this invention include long-chain alkyl group-containing resins, olefin resins, fluorine compounds, and wax-based compounds. Among these, long-chain alkyl group-containing resins are preferred because they can impart good peelability. When a long-chain alkyl resin is used, the long-chain alkyl, which has a low surface free energy, segregates on the surface of the resin layer and orients and crystallizes perpendicular to the surface, exposing the terminal methyl groups to the surface and reducing the surface free energy, resulting in easy peelability.

[0066] Commercially available long-chain alkyl group compounds may be used. Specifically, the "Ashiorezin" (registered trademark) series of long-chain alkyl compounds manufactured by Ashio Industries Co., Ltd., the "Piroyl" (registered trademark) series of long-chain alkyl compounds manufactured by Lion Specialty Chemicals Co., Ltd., and the Rezem series of aqueous dispersions of long-chain alkyl compounds manufactured by Chukyo Oil & Fat Co., Ltd. can be used.

[0067] The mold release agent (A) is preferably a resin having an alkyl group with 12 or more carbon atoms, and more preferably a resin having an alkyl group with 16 or more carbon atoms. By increasing the number of carbon atoms in the alkyl group to 12 or more, the hydrophobicity is enhanced, promoting the orientation of the alkyl chain on the surface and enabling sufficient mold release performance. There is no particular upper limit to the number of carbon atoms in the alkyl group, but it is preferable to have 25 or less because it is easier to manufacture.

[0068] Furthermore, the distance between the Hansen solubility parameter (HSP value) of the mold release agent (A) and the HSP value of at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, polyester resin, acrylic resin, and urethane resin is set to 14 MPa. 1 / 2 The following is preferable. More preferably 12 MPa 1 / 2 More preferably, 10 MPa1 / 2 The following applies: By setting the HSP distance to the preferred range described above, the compatibility between the release agent (A) and at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, melamine resin, polyester resin, acrylic resin, and urethane resin is increased, and the release agent (A) can be uniformly dispersed in the resin layer. To control the HSP distance to the preferred range described above, for example, one can control the copolymerization composition ratio of the release agent (A), or one can use a release agent (A) having a molecular structure compatible with at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, melamine resin, polyester resin, acrylic resin, and urethane resin.

[0069] The mold release agent (A) is more preferably a block copolymer consisting of units having alkyl groups. The mold release agent being a block copolymer consisting of units having alkyl groups facilitates the orientation of the alkyl groups. As for the method of producing the block copolymer, there are no particular restrictions as long as it is a living radical polymerization method other than the atom transfer radical polymerization method (ATRP method). Various polymerization methods such as reversible addition-cleavage chain transfer polymerization (RAFT method), polymerization using organic tellurium compounds (TERP method), polymerization using organic antimony compounds (SBRP method), polymerization using organic bismuth compounds (BIRP method), and exchange chain mechanism living radical polymerization methods such as iodine transfer polymerization, as well as the nitroxy radical method (NMP method), can be employed. Among these, the RAFT method and the NMP method are preferred from the viewpoint of polymerization controllability and ease of implementation.

[0070] The ratio of alkyl group-containing monomers to alkyl group-free monomers in the mold release agent (A) is preferably 50 to 99% in molar ratio, more preferably 60 to 97%, and even more preferably 70 to 95%. By setting the alkyl group-containing monomer to the above ratio, the compatibility of the mold release agent (A) with at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, melamine resin, polyester resin, acrylic resin, and urethane resin is increased, allowing the mold release agent (A) to be uniformly dispersed in the resin layer and obtaining an easily peelable resin layer.

[0071] When using a resin having an alkyl group in the mold release agent (A), it may also contain molecular structures other than alkyl groups. In particular, from the viewpoint of increasing reactivity with the crosslinking agent, improving compatibility with at least one resin or compound (B) selected from epoxy resins, oxazoline compounds, carbodiimide compounds, melamine resins, polyester resins, acrylic resins, and urethane resins, and obtaining a uniform resin layer, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxytriethylene glycol acrylate, polyethylene glycol methyl ester acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, methoxytriethylene glycol methacrylate, polyethylene glycol methyl ester methacrylate, etc., can be preferably used. <Resin or compound (B)> The resin layer of the laminated film of the present invention may be formed from a coating composition containing a release agent and a resin or compound. Examples of resins or compounds include at least one resin or compound selected from epoxy resins, oxazoline compounds, carbodiimide compounds, melamine resins, polyester resins, acrylic resins, and urethane resins. Among these, polyester resins, acrylic resins, melamine resins, and oxazoline compounds are particularly preferred from the viewpoint of promoting crosslinking of the coating film and increasing the surface modulus of elasticity by AFM.

[0072] As epoxy resins, for example, sorbitol polyglycidyl ether-based crosslinking agents, polyglycerol polyglycidyl ether-based crosslinking agents, diglycerol polyglycidyl ether-based crosslinking agents, and polyethylene glycol diglycidyl ether-based crosslinking agents can be used. Commercially available epoxy resins may also be used, for example, epoxy compounds "Denacol" (registered trademark) EX-611, EX-614, EX-614B, EX-512, EX-521, EX-421, EX-313, EX-810, EX-830, EX-850 etc. manufactured by Nagase Chemtec Corporation, diepoxy / polyepoxy compounds (SR-EG, SR-8EG, SR-GLG etc.) manufactured by Sakamoto Pharmaceutical Co., Ltd., epoxy crosslinking agents "EPICLON" (registered trademark) EM-85-75W or CR-5L manufactured by Dainippon Ink & Industries, Ltd. can be suitably used, and among these, those with water solubility are preferred.

[0073] The oxazoline compound is preferably one that has an oxazoline group as a functional group in the compound, and is composed of an oxazoline group-containing copolymer obtained by copolymerizing at least one monomer containing an oxazoline group with at least one other monomer.

[0074] Examples of monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. One or more of these can be used as a mixture. Among these, 2-isopropenyl-2-oxazoline is preferred because it is readily available industrially.

[0075] In oxazoline compounds, at least one other monomer used with a monomer containing an oxazoline group is a monomer copolymerizable with the monomer containing an oxazoline group, such as acrylic acid esters or methacrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; acrylonitrile, methacrylonitrile, etc. Unsaturated nitriles, unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, olefins such as ethylene and propylene, halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride, and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene can be used, and one or more of these can be used as a mixture.

[0076] Carbodiimide compounds are compounds that have one or more carbodiimide groups or cyanamide groups in a tautomer relationship as functional groups within their molecule. Specific examples of such carbodiimide compounds include dicyclohexylmethanecarbodiimide, dicyclohexylcarbodiimide, tetramethylxylylenecarbodiimide, and urea-modified carbodiimide, and these can be used individually or as a mixture of two or more.

[0077] As the melamine resin, for example, melamine, methylolated melamine derivatives obtained by condensing melamine with formaldehyde, compounds partially or completely etherified by reacting methylolated melamine with a lower alcohol, and mixtures thereof can be used. The melamine resin may be a monomer or a condensate consisting of two or more polymers, or a mixture thereof. As the lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol can be used. As the functional group, it may have an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule, and may be an imino-type methylated melamine resin, a methylol-type melamine resin, a methylol-type methylated melamine resin, or a fully alkyl-type methylated melamine resin. Among these, methylolated melamine resin is most preferably used.

[0078] The polyester resin is preferably one having ester bonds in the main chain or side chains, and obtained by polycondensation of a dicarboxylic acid and a diol.

[0079] Aromatic, aliphatic, and alicyclic dicarboxylic acids can be used as raw materials for polyester resins. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bisphenoxyethane-p,p'-dicarboxylic acid, and phenylindanedicarboxylic acid. Examples of aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedionic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and their ester-forming derivatives.

[0080] Diol components used as raw materials for polyester resins include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl- 1,6-Hexanediol, 1,2-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol, 4,4'-Thiodiphenol, Bisphenol A, 4,4'-Methylenediphenol, 4,4'-(2-Norbornylidene)diphenol, 4,4'-Dihydroxybiphenol, o-, m-, and p-Dihydroxybenzene, 4,4'-Isopropylidenephenol, 4,4'-Isopropylidenebinediol, Cyclopentane-1,2-Diol, Cyclohexane-1,2'-Diol, Cyclohexane-1,2-Diol, Cyclohexane-1,4-Diol, etc. can be used.

[0081] Furthermore, modified polyester copolymers, such as block copolymers or graft copolymers modified with acrylic, urethane, epoxy, etc., can also be used as the polyester resin.

[0082] While there are no particular limitations on the acrylic resin, those composed of alkyl methacrylate and / or alkyl acrylate are preferred.

[0083] Preferably, alkyl methacrylates and / or alkyl acrylates include methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, maleic acid, itaconic acid, acrylamide, N-methylolacrylamide, and diacetoneacrylamide. One or more of these can be used.

[0084] The urethane resin is preferably a resin obtained by reacting a polyhydroxy compound and a polyisocyanate compound using known polymerization methods for urethane resins, such as emulsion polymerization or suspension polymerization.

[0085] Examples of polyhydroxy compounds include polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaptolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, polycarbonate diol, and glycerin.

[0086] Examples of polyisocyanate compounds that can be used include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, adducts of tolylene diisocyanate and trimethylenepropane, and adducts of hexamethylene diisocyanate and trimethylolethane.

[0087] Furthermore, the resin layer of the laminated film of the present invention may contain an isocyanate compound as the resin or compound. Examples of isocyanate compounds include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, metaxylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, adducts of tolylene diisocyanate and hexanetriol, adducts of tolylene diisocyanate and trimethylolpropane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-vitrylene-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, and metaphenylene diisocyanate.

[0088] Furthermore, since isocyanate groups readily react with water, in terms of the pot life of the coating agent, blocked isocyanate compounds, in which the isocyanate groups are masked with a blocking agent, can be suitably used. In this case, when heat is applied during the drying process after coating the polyester film with the coating composition, the blocking agent dissociates, exposing the isocyanate groups, and as a result, the crosslinking reaction proceeds.

[0089] The coating composition for forming the resin layer of the laminated film of the present invention preferably has a mass ratio of release agent to resin or compound of 10 / 90 to 100 / 0, more preferably in the range of 20 / 80 to 70 / 30, and even more preferably in the range of 30 / 70 to 60 / 40. By setting the ratio within this range, a sufficient amount of release agent is present in the resin layer, resulting in good tape peeling strength and surface layer peeling strength. At the same time, a sufficient amount of resin or compound that is susceptible to changes due to heating is also present, thereby suppressing lifting of the surface layer during heating.

[0090] <Ceramic slurry> As a particularly preferred use of the laminated film of the present invention, there is a process film for the process of applying a ceramic slurry to the surface of a resin layer and peeling off a surface layer in which the ceramic slurry is solidified. Here, the ceramic slurry is composed of a ceramic, a binder resin, and a solvent.

[0091] The raw material of the ceramic constituting the ceramic slurry is not particularly limited, and various dielectric materials can be used. For example, oxides composed of metals such as titanium, aluminum, barium, lead, zirconium, silicon, yttrium, etc., barium titanate, Pb(Mg 1 / 3 ,Nb 2 / 3 )O3, Pb(Sm 1 / 2 ,Nb 1 / 2 )O3, Pb(Zn 1 / 3 ,Nb 2 / 3 )O3, PbThO3, PbZrO3, etc. can be used. These may be used alone or in combination of two or more.

[0092] As the binder resin constituting the ceramic slurry, polymers such as polyurethane resin, urea resin, melamine resin, epoxy resin, vinyl acetate resin, acrylic resin, polyvinyl alcohol, polyvinyl butyral, etc. can be used. These may be used alone or in combination of two or more.

[0093] The solvent of the ceramic slurry may be water or an organic solvent. In the case of an organic solvent, toluene, ethanol, methyl ethyl ketone, isopropyl alcohol, γ-butyrolactone, etc. can be used. These may be used alone or in combination of two or more. Further, a plasticizer, a dispersant, an antistatic agent, a surfactant, etc. may be added to the ceramic slurry as necessary.

[0094] <Manufacturing method of laminated film> The manufacturing method of the laminated film of the present invention will be described. Here, a polyester film will be described as an example of the resin base material, but it is not limited thereto.

[0095] The method for providing a resin layer on at least one side of a polyester film can be either an in-line coating method or an off-line coating method. The in-line coating method is a method of applying a coating composition at any stage in the polyester film manufacturing process, specifically, from the melt extrusion of the polyester resin to the biaxial stretching, heat treatment, and winding. Typically, the coating is applied to one of the following films: a substantially amorphous unstretched (unoriented) polyester film (film A) obtained by thoroughly vacuum-drying polyethylene terephthalate pellets, feeding them into an extruder, melt-extruding them into a sheet, and allowing them to cool and solidify; a uniaxially stretched (uniaxially oriented) polyester film (film B) which is then stretched in the longitudinal direction; or a biaxially stretched (biaxially oriented) polyester film (film C) before heat treatment, which is further stretched in the width direction. For example, a coating composition prepared to a predetermined concentration can be applied to one side of a uniaxially oriented polyester film (corresponding to film B) obtained by stretching an unoriented polyester film (corresponding to film A) 2.5 to 5.0 times in the longitudinal direction on a roll heated to 80 to 120°C.

[0096] The offline coating method is a method of applying a coating composition to a polyester film in a process separate from the polyester film manufacturing process. In this case, the polyester film to be coated may be an unstretched polyester film, a uniaxially oriented polyester film, or a biaxially oriented polyester film.

[0097] In this invention, it is preferable to manufacture the laminated film by an in-line coating method. By manufacturing by an in-line coating method, it is possible to manufacture the laminated film at a lower cost than by an offline coating method, and by applying high-temperature heat treatment of 200°C or higher, which is substantially impossible with the offline coating method, the orientation of the resin layer is promoted, resulting in I(15°)-I(90°)≧ 0.4 It can be adjusted accordingly. In addition, the cross-linking reaction of the coating film is also promoted, which can increase the surface modulus measured by AFM.

[0098] In particular, it is preferable to manufacture the polyester film by a manufacturing method in which a coating composition containing a mold release agent is applied to at least one side of the polyester film before crystal orientation is completed, the film is stretched in at least one axial direction, and then heat-treated to complete the crystal orientation of the polyester film. By applying the coating composition to the polyester film before crystal orientation is completed, a very small amount of the coating composition penetrates into the polyester film, thereby providing adhesion between the resin layer and the thermoplastic resin film. As a result, excellent peeling strength can be maintained. When a resin layer is provided on a polyester film using a conventional off-coat method, the highly hydrophobic resin layer has poor adhesion to the film, which can lead to problems such as the resin layer being scraped off when the film roll is rewound, resulting in a deterioration of the peeling strength.

[0099] At this point, a surface treatment such as corona discharge treatment may be performed on the polyester film surface before coating. By performing a surface treatment such as corona discharge treatment, the wettability of the coating composition to the polyester film can be improved, the coating composition can be prevented from repelling, and a uniform coating thickness can be achieved.

[0100] Any known coating method can be used to apply the coating composition to the polyester film, such as the bar coating method, reverse coating method, gravure coating method, die coating method, blade coating method, etc.

[0101] Next, it is preferable to form a resin layer by drying the paint composition. If the paint composition contains a solvent, it is preferable to use an aqueous solvent. Using an aqueous solvent suppresses the rapid evaporation of the solvent during the drying process, which not only allows for the formation of a uniform resin layer but also has advantages in terms of environmental impact.

[0102] Here, an aqueous solvent refers to a mixture of water or an organic solvent that is soluble in water, such as water and alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol), ketones (e.g., acetone, methyl ethyl ketone), or glycols (e.g., ethylene glycol, diethylene glycol, propylene glycol), in any ratio.

[0103] The solid content concentration of the paint composition is preferably 40% by mass or less. By setting the solid content concentration to 40% by mass or less, good coatability can be imparted to the paint composition, and a laminated film having a uniform resin layer can be manufactured. Here, the solid content concentration represents the ratio of the mass of the paint composition to the mass of the paint composition, excluding the mass of the solvent (i.e., [solid content concentration] = [(mass of paint composition) - (mass of solvent)] / [mass of paint composition]).

[0104] Drying can be carried out at a temperature range of 80 to 130°C to complete the removal of the solvent from the paint composition. By setting the drying temperature higher than the melting point of the release agent, the release agent is stretched in a molten state, resulting in good dispersibility of the release agent within the resin layer and the formation of a uniform resin layer without thickness variations.

[0105] After solvent drying, the film may be stretched 1.1 to 5.0 times in the width direction, and then a heat treatment is performed at a temperature range of 150 to 250°C for 1 to 30 seconds to thermally cure the paint composition and complete the crystal orientation of the polyester film. In the subsequent cooling step, the molten release agent can be solidified by holding it at 40 to 100°C for 1 to 30 seconds. This cooling step enhances the crystallinity and orientation of the release agent, resulting in I(15°)-I(90°)≧ 0.4 From the viewpoint of adjusting the temperature, it is more preferable to perform the treatment at a temperature of ±10°C of the crystallization temperature of the release agent for at least 10 seconds, and even more preferable to perform the treatment at a temperature of ±5°C. In addition, a relaxation treatment of 3 to 15% in the width direction or longitudinal direction may be performed during the heat treatment as needed.

[0106] Among these methods, the method of applying the coating composition to a film (B film) that has been uniaxially stretched in the longitudinal direction, then stretching it in the width direction and heat-treating it, is superior. This is because, compared to the method of applying the coating to an unstretched film and then biaxially stretching it, there is one less stretching step, which reduces the likelihood of defects and cracks in the resin layer caused by stretching, and allows for the formation of a resin layer with excellent smoothness.

[0107] <Methods for measuring characteristics and evaluating effects> The method for measuring the properties and evaluating the effects in this invention is as follows.

[0108] (1) X-ray absorption near-edge structure (XANES) spectrum The laminated film was polished on the side opposite the resin layer to adjust its thickness to 10 μm. A sample measuring 12 mm in the longitudinal direction and 6 mm in the width direction was cut from the polished laminated film to be used as the measurement sample. Next, the resin layer surface of the measurement sample was irradiated with X-rays, and the amount of absorption was measured to determine the X-ray absorption fine structure (XAFS) spectrum. The measurement and analysis conditions were as follows.

[0109] Experimental facility: Ritsumeikan University SR Center Experiment Station: BL11 Spectrometer: Diffraction grating spectrometer Absorption edge: K (284.2 eV) absorption edge of carbon E0: 287.319eV Pre-edge range: -20~10eV Normalization range: 15~70eV Detection method: Partial electron yield method using multi-channel plate measurement. Horizontal axis correction: Pi of highly oriented pyrolysis graphite * Corrected to peak value of 255.5 eV In the above XAFS spectrum, for the X-ray absorption edge-near-end structure (XANES) spectrum of the K-edge absorption of carbon, the angle between the incident X-ray and the longitudinal vector of the resin layer surface of the laminated film was defined as θ, and the spectral intensity of 293.5 eV obtained by the partial electron yield method was defined as I(θ). The value obtained by subtracting the spectral intensity I(90°) at θ = 90° from the spectral intensity I(15°) at θ = 15° was defined as I(15°) - I(90°).

[0110] (2) Domain diameter and surface modulus determined by AFM Using a BRUKER AFM (Atomic Force Microscope) "Dimension Icon ScanAsyst," absolute calibration (measurement of warpage sensitivity, calibration of spring constant, and measurement of probe tip curvature (ScanAsyst NoiseThreshold: 1.0 nm)) was performed, and then the resin layer side surface of the laminated film was measured, and the elastic modulus was determined from the obtained surface information. <Measurement conditions> Software: "NanoScope Analysis" Measurement probe: RTESPA-300 Measurement mode: Peak Force QNM in Air Measurement range: 3 μm × 3 μm Number of measurement lines: 512 Measurement speed: 0.977Hz Response sensitivity: 25 Indentation depth: The depth should be 1 / 10 of the thickness of the resin layer. Poisson's ratio: 0.3 Specifically, after measurement, "Roughness" was selected in "DMTModulus," and the image displayed on that screen was binarized using "ScionImage" (maximum value: 10 GPa, minimum value: 0 GPa, threshold 180). Areas with high elastic modulus were represented in white (non-domain), and areas with low elastic modulus were represented in black (domain). Next, the longest axis length was measured for all domains in the image, and the average of the top 5 largest sizes was measured. Furthermore, a measurement range was arbitrarily selected and measured 10 times, and the average of the total of 8 measurements excluding the maximum and minimum values ​​was taken as the domain diameter.

[0111] The surface modulus was calculated using the in-plane average value from the modulus image obtained under the above measurement conditions. Ten measurements were taken at an arbitrary location, and the average of the eight measurements (excluding the maximum and minimum values) was adopted as the surface modulus.

[0112] (3) Water contact angle First, the laminated film was left in an atmosphere at room temperature (23°C) and relative humidity (65%) for 24 hours. Then, under the same atmosphere, the contact angle of pure water with respect to the surface side of the resin layer of the laminated film was measured at five points using a CA-D type contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The average of the three measurements obtained by excluding the maximum and minimum values ​​from the five measurements was defined as the water contact angle.

[0113] (4) Method for analyzing the composition of the resin layer surface The surface composition of the resin layer of a laminated film was analyzed using GCIB-TOF-SIMS (GCIB: gas cluster ion beam, TOF-SIMS: time-of-flight secondary ion mass spectrometry). The measurement conditions were as follows. <Sputtering conditions> Ion source: Argon gas cluster ion beam <Detection conditions> Primary ion: Bi 3++ (25keV) Secondary ionic polarity: Negative Mass range: m / z 0~1,000 Measurement range: 200 × 200 μm 2 The peak intensity of the fragment detected at maximum intensity was defined as K, and the peak intensity of the fragment derived from polydimethylsiloxane (SiCH3+ fragment ion (M / Z=43)) was defined as P. The ratio P / K was then calculated. If P / K < 0.01, it was determined that the resin layer substantially did not contain any silicone compounds.

[0114] (5) Exothermic peak temperature (Tc) during the DSC cooling process A 10g aqueous dispersion of the mold release agent prepared in the reference example was placed in a 5cm diameter aluminum cup and dried in a hot air oven at 80°C for 24 hours to create a solid sample of the dried mold release agent. A 3mg sample of the prepared solid mold release agent was taken and measured using a differential scanning calorimeter DSC6220 (manufactured by Hitachi High-Tech Science Corporation). First, the temperature was increased from 25°C to 200°C at a rate of 20°C / min in a nitrogen atmosphere and held at 200°C for 5 minutes. Then, the temperature was decreased to -50°C at a rate of 20°C / min, and the peak temperature of the curve obtained during this cooling was measured. The average value of three such measurements was defined as Tc. In this case, there may be cases where two or more melting peak temperatures are observed within the aforementioned temperature range, or where the peak temperature is observable on a multi-stage DSC chart called a shoulder (observable in the case of a chart where two or more peaks overlap). However, in this invention, Tc is defined as the peak temperature with the largest absolute value of the heat quantity (unit: mW) on the vertical axis of the DSC chart.

[0115] (6) Thickness of the resin layer The laminated film was stained with RuO4 and / or OsO4. Next, the laminated film was frozen and cut in the film thickness direction to obtain 10 ultrathin section samples for observation of the resin layer cross-section. Each sample cross-section was observed at 10,000 to 1,000,000x magnification using a TEM (transmission electron microscope: Hitachi H7100FA), and cross-sectional images were obtained. The measured resin layer thickness of the 10 samples was averaged to determine the resin layer thickness of the laminated film.

[0116] (7) HSP distance 50 mg of the sample was placed in a 6 mL glass screw-top vial, and 1 mL of each solvent was added to immerse the entire sample in the test solvent. After standing at the treatment temperature for 6 hours, the dissolution state of the sample was visually observed and evaluated according to the following criteria [I] and [II], and the HSP value was calculated using HSP calculation software. [I]: It is neither swollen nor dissolved. [II]: Swelled or dissolved.

[0117] The HSP value of each sample is calculated by dissolving or dispersing the sample in a solvent with a known HSP value and evaluating its solubility or dispersibility in that specific solvent. Solubility and dispersibility are evaluated by visually determining whether the target composition has dissolved or dispersed in the solvent, based on the above criteria. This is done for multiple solvents. Next, the obtained solubility or dispersibility evaluation results are plotted in a three-dimensional space (HSP space) consisting of the HSP dispersion term δd, polarity term δp, and hydrogen bonding term δh. A sphere (Hansen sphere) is created in which the solvent in which the target composition dissolves or disperses is contained on the inside, the solvent in which the target composition does not dissolve or disperse is on the outside, and the radius is minimized. The center coordinates (δd, δp, δh) of the obtained Hansen sphere are taken as the HSP value of the target composition. For example, if the HSP value of component 1 is (δd1, δp1, δh1) and the HSP value of component 2 is (δd2, δp2, δh2), the HSP distance between component 1 and component 2 can be calculated by the following formula. The solubility of each component can be evaluated using the HSP distance. HSP distance = [4(δd1-δd2) 2 +(δp1-δp2) 2 +(δh1-δH2) 2 ] 1 / 2 <Measurement conditions> Test solvents: n-Hexane, cyclohexane, methyl isobutyl ketone, n-butyl acetate, toluene, tetrahydrofuran, methyl ethyl ketone, chloroform, methyl acetate, acetone, 1,4-dioxane, pyridine, N-methylpyrrolidone, hexafluoroisopropanol, 1-butanol, acetonitrile, diethylene glycol, N,N-dimethylformamide, γ-butyllactone, ethanol, dimethyl sulfoxide, methanol, 2-aminoethanol, cyclohexane, d-limonene, p-xylene, diiodomethane, anisole, heptane Processing temperature: 40℃ Calculation software: HSPiP (Hansen Solubility Parameter in Practice) ver. 5.2.05 (8) PVB applicability The coating property of polyvinyl butyral (PVB) was evaluated as an index for the workability of the surface layer. The PVB solution mixed with the following composition was applied onto the resin layer of the laminated film obtained in the examples using an applicator so that the thickness of the PVB layer after drying would be 3 μm, 1 μm, and 300 nm, respectively. After that, it was dried in a hot air oven at 100 °C for 3 minutes, and the presence or absence of PVB peeling was evaluated by visual observation according to the following criteria. Those with an evaluation of A or above were considered to have good slurry coating properties, and B was considered to be at a level with no practical problems. Generally, the smaller the coating thickness of the PVB solution, the more likely peeling is to occur.

[0118] S: No peeling is observed at any coating thickness.

[0119] A: No peeling is observed at coating thicknesses of 3 μm and 1 μm, but peeling is observed at 300 nm.

[0120] B: No peeling is observed at a coating thickness of 3 μm, but peeling is observed at 1 μm and 300 nm.

[0121] C: Peeling is observed at all coating thicknesses. <Composition of PVB solution> · 100 parts by mass of polyvinyl butyral (“Esrec (registered trademark)” BM-2 manufactured by Sekisui Chemical Co., Ltd.) · 150 parts by mass of toluene · 150 parts by mass of ethanol (9) PVB peel strength (PVB peel strength under room temperature atmosphere) For PVB peel strength, the PVB solution prepared in "(8) PVB Applicability" was applied to the resin layer of the laminated film obtained in the example using an applicator, so that the thickness of the PVB layer after drying was 3 μm. The PVB layer was then dried in a hot air oven at 100°C for 3 minutes to form the PVB layer. The PVB layer was subjected to a 180° peel test at a peel speed of 300 mm / min using a Shimadzu Corporation universal testing machine "Autograph AG-1S" and a 50N load cell. The average value of the peel strength at 5 to 10 seconds was calculated from the graph of peel strength (N) - test time (sec) obtained from the measurement. This measurement was performed 5 times, and the average of the 3 measurements excluding the maximum and minimum values ​​was taken as the peel strength of the laminated film and evaluated according to the following criteria. An evaluation of A or higher was considered good, and B was considered a level that does not pose a practical problem.

[0122] S: 16mN / less than 20mm A: 16mN / 20mm or more, 31mN / less than 20mm B: 31mN / 20mm or more, 61mN / less than 20mm C:61mN / 20mm or more (10) PVB adhesion at high temperatures (PVB peel strength in a high-temperature atmosphere) To evaluate the lifting after heat treatment, a PVB layer was prepared using the same method as in "(9) PVB peel strength," and a 180° peel test was performed at a peel speed of 300 mm / min using a Shimadzu Corporation universal testing machine "Autograph AG-1S" and a 50N load cell in a 120°C atmosphere. The average value of the peel strength at 5-10 seconds was calculated from the graph of peel strength (N)-test time (sec) obtained from the measurement. This measurement was performed 5 times, and the average of the 3 measurements excluding the maximum and minimum values ​​was taken as the peel strength of the laminated film, and evaluated according to the following criteria. An evaluation of A or higher was considered good, and B was considered a level that does not pose a practical problem.

[0123] S:50mN / 20mm or more A: 40mN / 20mm or more, 50mN / less than 20mm B: 30mN / 20mm or more, 40mN / less than 20mm C: 30mN / less than 20mm [Examples]

[0124] The laminated film of the present invention will be described in detail below based on specific examples, but the present invention is not limited to these examples.

[0125] (Reference example 1) A long-chain alkyl group-containing resin a1 was obtained through the following steps (I) and (II). Process (I): A 25 mL pressure-resistant glass polymerization ampoule was filled with methyl methacrylate (MMA) (manufactured by Kanto Chemical Co., Ltd.), α,α'-azobisisobutyronitrile (AIBN) (manufactured by Kanto Chemical Co., Ltd.) as a polymerization initiator, cumyl dithiobenzoate (CDB) as a RAFT agent, and toluene as a solvent, in a weight (g) ratio of MMA / CDB / AIBN / toluene = 2.92 / 0.03 / 0.007 / 2.27. Next, the mixed solution in the ampoule was degassed twice by freeze-degassing, the ampoule was sealed, and heated in an oil bath at 100°C for 18 hours to obtain a reaction solution containing polymer (I-1). Process (II): To the reaction solution in the ampoule, docosyl acrylate, AIBN as a polymerization initiator, and toluene as a solvent were added in a ratio of docosyl acrylate / AIBN / toluene of 1.37 / 0.003 / 1.3 by weight (g). After two freeze-degassing cycles, the ampoule was sealed and heated at 100°C for 48 hours. Subsequently, the polymerization solution was added dropwise to 20 times its mass of hexane and stirred to precipitate a solid. The obtained solid was filtered and vacuum-dried overnight at 40°C to obtain a long-chain alkyl group-containing resin (a block copolymer having an alkyl group with 22 carbon atoms (referred to as long-chain alkyl group-containing resin a1)).

[0126] The obtained long-chain alkyl group-containing resin a1 was emulsified as follows to obtain an aqueous resin emulsion. 375g of water was placed in a 1L homomixer, and 45g of polyoxyethylene nonylphenyl ether, 30g of polyoxyethylene polyoxypropylene glycol, 200g of long-chain alkyl group-containing resin a1, and 150g of toluene were added sequentially. The mixture was heated to 70°C and stirred uniformly. This mixture was transferred to a pressurized homogenizer for emulsification, and then the toluene was removed by distillation under reduced pressure and heating.

[0127] (Reference example 2) 200 parts xylene and 600 parts octadecyl isocyanate were added to a four-necked flask and heated with stirring. From the moment the xylene began to reflux, 100 parts of polyvinyl alcohol with an average degree of polymerization of 500 and a degree of saponification of 88 mol% were added in small amounts at 10-minute intervals over approximately 2 hours. After the addition of polyvinyl alcohol was completed, reflux was continued for another 2 hours to terminate the reaction. The reaction mixture was cooled to approximately 80°C and then added to methanol. The reaction product precipitated as a white precipitate, which was filtered off. 140 parts xylene was added and heated to completely dissolve it. This process of adding methanol again to precipitate was repeated several times, and the precipitate was washed with methanol and dried and ground to obtain a long-chain alkyl group-containing resin (polymethylene as the main chain with C18 alkyl groups in the side chains (referred to as long-chain alkyl group-containing resin a2)). This was diluted with water to a concentration of 20% by mass.

[0128] (Reference example 3) A long-chain alkyl group-containing resin a3 was obtained as follows. Methyl methacrylate (α), hydroxyethyl methacrylate (β), and octadecyl methacrylate (γ) were charged into a stainless steel reaction vessel in a mass ratio of (α) / (β) / (γ) = 94 / 1 / 5. Sodium dodecylbenzenesulfonate was added as an emulsifier, 2 parts by mass per 100 parts by mass of the total of (α) to (γ), and the mixture was stirred to prepare Mixture 1. Next, a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was prepared. 60 parts by mass of the above Mixture 1, 200 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate as a polymerization initiator were charged into the reaction apparatus and heated to 60°C to prepare Mixture 2. Mixture 2 was kept at 60°C for 20 minutes. Mixture 3 was prepared consisting of 40 parts by mass of Mixture 1, 50 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate. Next, using a dropping funnel, mixture 3 was added dropwise to mixture 2 over 2 hours to prepare mixture 4. Then, mixture 4 was kept heated to 60°C for 2 hours, and after being cooled to below 50°C, it was transferred to a container equipped with a stirrer and vacuum equipment. 60 parts by mass of 25% aqueous ammonia and 900 parts by mass of pure water were added, and isopropyl alcohol and unreacted monomers were recovered under reduced pressure while heating to 60°C to obtain a long-chain alkyl group-containing resin dispersed in pure water (methacrylate as the main chain with C18 alkyl groups in the side chains (referred to as long-chain alkyl group-containing resin a3)).

[0129] (Reference example 4) Except for using octadecyl acrylate instead of docosyl acrylate, the resin was synthesized using the same method as in Reference Example 1 to obtain a long-chain alkyl group-containing resin (a block copolymer having an alkyl group with 18 carbon atoms (referred to as long-chain alkyl group-containing resin a4)), which was then converted into an aqueous resin emulsion in the same manner as in Reference Example 1.

[0130] (Reference example 5) Except for using eicosyl isocyanate instead of octadecyl isocyanate, the resin was synthesized using the same method as in Reference Example 2 to obtain a long-chain alkyl group-containing resin (polymethylene as the main chain with a C20 alkyl group in the side chain (referred to as long-chain alkyl group-containing resin a5)).

[0131] (Reference Example 6) A long-chain alkyl group-containing resin (having a polymethylene main chain and an alkyl group with 12 carbon atoms in the side chain (referred to as long-chain alkyl group-containing resin a6)) was obtained by synthesizing in the same production method as in Reference Example 2, except that dodecyl isocyanate was used instead of octadecyl isocyanate.

[0132] (Reference Example 7) A long-chain alkyl group-containing resin (having a polymethylene main chain and an alkyl group with 8 carbon atoms in the side chain (referred to as long-chain alkyl group-containing resin a7)) was obtained by synthesizing in the same production method as in Reference Example 2, except that octyl isocyanate was used instead of octadecyl isocyanate.

[0133] (Reference Example 8) The long-chain alkyl group-containing resin a8 was obtained through the following steps (I) and (II). Step (I): Into a 25 mL pressure-resistant glass polymerization ampoule, 2-hydroxyethyl acrylate (HEA) (manufactured by Kanto Chemical Co., Inc.), α,α'-azobisisobutyronitrile (AIBN) (manufactured by Kanto Chemical Co., Inc.) as a polymerization initiator, cumyl dithiobenzoate (CDB) as a RAFT agent, and toluene as a solvent were charged at a weight (g) ratio of HEA / CDB / AIBN / toluene = 0.35 / 0.03 / 0.007 / 2.27. Next, the mixed solution in the ampoule was degassed twice by the freeze-degas method, and then the ampoule was sealed and heated in an oil bath at 100 °C for 18 hours to obtain a reaction solution containing polymer (I-8). Step (II): To the reaction solution in the ampoule, docosyl acrylate, AIBN as a polymerization initiator, and toluene as a solvent were added in a ratio of docosyl acrylate / AIBN / toluene = 4.65 / 0.003 / 1.3 by weight (g). After two freeze-degassing cycles, the ampoule was sealed and heated at 100°C for 48 hours. Subsequently, the polymerization solution was added dropwise to 20 times its mass of hexane and stirred to precipitate a solid. The obtained solid was filtered and vacuum-dried overnight at 40°C to obtain a long-chain alkyl group-containing resin (a block copolymer having an alkyl group with 22 carbon atoms (referred to as long-chain alkyl group-containing resin a8)). The obtained long-chain alkyl group-containing resin a8 was emulsified in the same manner as in Reference Example 1 to obtain an aqueous resin emulsion.

[0134] (Reference example 9) A long-chain alkyl group-containing resin a9 was obtained in the same manner as in Reference Example 1, except that 4-hydroxybutyl acrylate (HBA) (manufactured by Kanto Chemical Co., Ltd.) was used instead of HEA as the monomer in step I. The obtained long-chain alkyl group-containing resin a9 was emulsified using the same method as in Reference Example 1 to obtain an aqueous resin emulsion.

[0135] (Reference example 10) A long-chain alkyl group-containing resin a10 was obtained in the same manner as in Reference Example 1, except that methoxytriethylene glycol methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of HEA as the monomer in step I. The obtained long-chain alkyl group-containing resin a10 was emulsified using the same method as in Reference Example 1 to obtain an aqueous resin emulsion.

[0136] (Reference example 11) Except for using octadecyl acrylate instead of docosyl acrylate, the resin was synthesized in the same manner as in Reference Example 8 to obtain a long-chain alkyl group-containing resin (a block copolymer having an alkyl group with 18 carbon atoms (referred to as long-chain alkyl group-containing resin a11)), which was then converted into an aqueous resin emulsion in the same manner as in Reference Example 1.

[0137] (Reference example 12) Except for using 0.16g of HEA and 4.84g of docosyl acrylate as the starting weight, the resin was synthesized using the same method as in Reference Example 1 to obtain long-chain alkyl group-containing resin a12, which was then prepared as an aqueous resin emulsion in the same manner as in Reference Example 1.

[0138] (Reference example 13) Acrylic resin was obtained as follows. Methyl methacrylate (α), hydroxyethyl methacrylate (β), and urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., Art Resin® UN-3320HA, with 6 acryloyl groups) (γ) were charged into a stainless steel reaction vessel in a mass ratio of (α) / (β) / (γ) = 94 / 1 / 5. Sodium dodecylbenzenesulfonate was added as an emulsifier at a ratio of 2 parts by mass to 100 parts by mass of the total of (α) to (γ), and the mixture was stirred to prepare mixed solution 5. Next, a reaction apparatus equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was prepared. 60 parts by mass of the above mixed solution 5, 200 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate as a polymerization initiator were charged into the reaction apparatus and heated to 60°C to prepare mixed solution 6. Mixed solution 6 was maintained at 60°C for 20 minutes. Mixture 7 was prepared, consisting of 40 parts by mass of mixture 5, 50 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate. Subsequently, mixture 7 was added dropwise to mixture 2 over 2 hours using a dropping funnel to prepare mixture 8. Then, mixture 8 was heated to 60°C and held for 2 hours, then cooled to below 50°C, and transferred to a container equipped with a stirrer and vacuum equipment. 60 parts by mass of 25% aqueous ammonia and 900 parts by mass of pure water were added, and the isopropyl alcohol and unreacted monomers were recovered under reduced pressure while heating to 60°C to obtain acrylic resin dispersed in pure water.

[0139] (Reference example 14) A polyester resin consisting of the following copolymer composition was prepared as an aqueous dispersion. <Copolymerization component> (Dicarboxylic acid component) 2,6-Dimethyl naphthalenedicarboxylate: 88 mol% Dimethyl sodium 5-sulfoisophthalate: 12 mol% (Diol component) Compound obtained by adding 2 moles of ethylene oxide to 1 mole of bisphenol S: 86 mole% 1,3-Propanediol: 14 mol% (Reference example 15) As a silicone resin, a mixture of KM-3951, X-52-6015, and CAT-PM-10A manufactured by Shin-Etsu Chemical Co., Ltd. was prepared in a mass ratio of 85:15:5.

[0140] (Reference example 16) Except for using 2-perfluorohexylethyl acrylate (synthesized from 2-perfluorohexylethanol using a known method and purified by simple distillation) instead of docosyl acrylate, the fluorine-based resin f1 was synthesized using the same method as in Reference Example 1.

[0141] (Reference example 17) Except for using 2-perfluorodecylethyl acrylate (synthesized from 2-perfluorodecylethanol using a known method and purified by simple distillation) instead of docosyl acrylate, the fluorine-based resin f2 was synthesized using the same method as in Reference Example 1.

[0142] (Example 1) ·Paint composition: A coating composition was obtained by adding 0.1 parts by mass of a fluorine-based surfactant ("Pluscoat" RY-2, manufactured by Go-O Chemical Industry Co., Ltd.) to 100 parts by mass of a long-chain alkyl group-containing resin a1. The fluorine-based surfactant was added to improve the applicability to polyester film. • Polyester film: PET pellets (intrinsic viscosity 0.64 dl / g) containing 4 mass% silica particles (primary particle size 0.3 μm) and 2 mass% calcium carbonate particles (primary particle size 0.8 μm) were thoroughly vacuum-dried. Next, the PET pellets were fed into an extruder and melted at 280°C, extruded into a sheet through a T-shaped die, and the unstretched film was wrapped around a mirror-finish casting drum with a surface temperature of 25°C using an electrostatic casting method and cooled and solidified. The unstretched film was heated to 90°C and stretched 3.1 times in the longitudinal direction to obtain a uniaxially oriented film (film B). • Laminated film: The obtained uniaxially oriented film was subjected to corona discharge treatment in air, and then the coating composition shown in Table 1 was applied using a bar coat to a coating thickness of approximately 6 μm. Subsequently, both ends of the uniaxially oriented film coated with the coating composition were grasped in the width direction with clips and guided to a preheating zone. The ambient temperature of the preheating zone was set to 90-100°C to dry the solvent of the coating composition. Subsequently, the film was continuously stretched 3.6 times in the width direction in a stretching zone at 100°C, and then heat-treated for 20 seconds in a heat treatment zone at 230-240°C to form a resin layer. Furthermore, while performing a 5% relaxation treatment in the width direction at the same temperature, it was cooled at 55°C for 30 seconds to obtain a laminated film in which the crystal orientation of the polyester film was completed. In the obtained laminated film, the thickness of the polyester film was 50 μm and the thickness of the resin layer was 30 nm. The properties of the laminated film obtained in the example are shown in Tables 3-6.

[0143] (Example 2~ 34. References 1-31 ) Laminated films were obtained in the same manner as in Example 1, except that the paint compositions shown in Tables 1 and 2 and the temperature conditions shown in Tables 3 and 4 were used. The long-chain alkyl group-containing resins a1 to a12 shown in Tables 1 and 2 were those obtained in Reference Examples 1 to 12, the acrylic resin in Reference Example 13, and the polyester resin in Reference Example 14. In addition, the melamine resin used was "Nikarac" (registered trademark) MW-035 (solids concentration 70% by mass, solvent: water) manufactured by Sanwa Chemical Co., Ltd., and the oxazoline compound used was "Epocross" (registered trademark) WS-500 (solids concentration 40% by mass, solvent: water) manufactured by Nippon Shokubai Co., Ltd. The solids mass ratio represents the ratio to the total mass of the resins and compounds listed in the table. , reference exampleIn this case, both the PVB coating properties and peelability were good.

[0144] (Comparative Example 1) A laminated film was obtained in the same manner as in Example 1, except that the coating composition substantially did not contain long-chain alkyl group-containing resins, contained an olefin resin (Mitsui Chemicals, Inc.'s "Chemipearl" (registered trademark) XEP800H) and the acrylic resin obtained in Reference Example 13, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. The properties of the obtained laminated film are shown in Tables 4 and 6. Although the PVB coating properties and PVB adhesion at high temperatures were good, the PVB peelability was poor.

[0145] (Comparative Example 2) A laminated film was obtained in the same manner as in Example 1, except that the coating composition substantially contained no long-chain alkyl group-containing resin, and included the silicone resin prepared in Reference Example 15 and Sanwa Chemical Co., Ltd.'s "Nikarac" (registered trademark) MW-035 (solids content 70% by mass, solvent: water) as the melamine resin, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. Although the PVB peelability was good, the PVB coating properties and PVB adhesion at high temperatures were poor.

[0146] (Comparative Example 3) A laminated film was obtained in the same manner as in Example 1, except that the coating composition substantially did not contain a long-chain alkyl group-containing resin, contained the fluororesin f1 obtained in Reference Example 16 and the acrylic resin obtained in Reference Example 13, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. Although the PVB coating properties and PVB adhesion at high temperatures were good, the PVB peelability was poor.

[0147] (Comparative Example 4) A laminated film was obtained in the same manner as in Example 1, except that the long-chain alkyl group-containing resin a1 was replaced with long-chain alkyl group-containing resin a7, the coating composition contained the acrylic resin obtained in Reference Example 13, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. Although the PVB coating properties and PVB adhesion at high temperatures were good, the PVB peelability was poor.

[0148] (Comparative Example 5) A laminated film was obtained in the same manner as in Example 1, except that the coating composition substantially contained no long-chain alkyl group-containing resin, and included the acrylic resin obtained in Reference Example 13 and Sanwa Chemical Co., Ltd.'s "Nikarac" (registered trademark) MW-035 (solids content 70% by mass, solvent: water) as the melamine resin, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. Although the PVB coating properties and PVB adhesion at high temperatures were good, the PVB peelability was poor.

[0149] (Comparative Example 6) A laminated film was obtained in the same manner as in Example 1, except that the coating composition substantially did not contain long-chain alkyl group-containing resins, contained an olefin resin (Mitsui Chemicals, Inc.'s "Chemipearl" (registered trademark) XEP800H) and the acrylic resin obtained in Reference Example 13, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. Although the PVB coating properties and PVB adhesion at high temperatures were good, the PVB peelability was poor.

[0150] (Comparative Example 7) A laminated film was obtained in the same manner as in Example 1, except that the coating composition substantially did not contain long-chain alkyl group-containing resins, and contained the silicone resin prepared in Reference Example 15 and Sanwa Chemical Co., Ltd.'s "Nikarac" (registered trademark) MW-035 (solids content 70% by mass, solvent: water) as the melamine resin, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. Although the PVB peelability was good, the PVB coating properties and PVB adhesion at high temperatures were poor.

[0151] (Comparative Example 8) A laminated film was obtained in the same manner as in Example 1, except that the coating composition substantially did not contain a long-chain alkyl group-containing resin, contained the fluororesin f1 obtained in Reference Example 17 and the acrylic resin obtained in Reference Example 13, and the coating composition and temperature conditions were as shown in Table 2 and Table 4, respectively. Although the PVB coating properties and PVB adhesion at high temperatures were good, the PVB peelability was poor.

[0152] [Table 1]

[0153] [Table 2]

[0154] [Table 3]

[0155] [Table 4]

[0156] [Table 5]

[0157] [Table 6] [Industrial applicability]

[0158] The laminated film of the present invention exhibits excellent coatability and peelability of surface layers, such as ceramic slurries, as well as superior adhesion at high temperatures, making it suitable for use as a process film in the manufacturing process of electronic components.

Claims

1. A laminated film having a resin layer on at least one side of a resin substrate made of polyethylene terephthalate film, the resin layer being a release agent (A) containing a long-chain alkyl group having 16 or more carbon atoms, wherein the resin layer is on at least one surface layer, and with respect to the resin layer surface, the laminated film satisfies I(15°) - I(90°) ≥ 0.4, where θ is the angle between the incident X-ray and the resin layer surface, and I(θ) is the spectral intensity at 293.5 eV, in the XAFS spectrum measured by partial electron yield method, for the X-ray absorption edge structure (XANES) spectrum of the K absorption edge of carbon, the angle between the incident X-ray and the resin layer surface is θ, and I(θ) is the spectral intensity at 293.5 eV.

2. The laminated film according to claim 1, wherein the surface modulus of the resin layer, as measured by AFM, is 1 GPa or more.

3. The laminated film according to claim 1 or claim 2, wherein a resin layer is laminated on at least one side of the resin substrate, the tape peeling force is 3.0 N / 19 mm or less, and the domain diameter observed in the elastic modulus image by AFM is 500 nm or less.

4. The laminated film according to any one of claims 1 to 3, wherein the water contact angle of the resin layer is 85° or more and 110° or less.

5. A laminated film according to any one of claims 1 to 4, wherein, with respect to the resin layer surface, the XAFS spectrum measured by the partial electron yield method, specifically the X-ray absorption edge-near structure (XANES) spectrum of the carbon K absorption edge, is such that when the angle between the incident X-ray and the resin layer surface is θ and the spectral intensity at 293.5 eV is I(θ), then [I(15°) - 0.1] / I(90°) > 1.

6. The laminated film according to any one of claims 1 to 5, wherein, when the surface of the resin layer is analyzed by time-of-flight secondary ion mass spectrometry, the ratio (P / K) [-] of the peak intensity (P) of the fragment derived from polydimethylsiloxane to the peak intensity (K) of the fragment detected at maximum intensity is less than 0.

01.

7. The laminated film according to any one of claims 1 to 6, wherein the release agent (A) is heated from 25°C to 200°C at a rate of 20°C / min using a differential scanning calorimeter (DSC), and then cooled from 200°C to -50°C at a rate of 20°C / min, the exothermic peak temperature (Tc) during the cooling process is 30°C or higher.

8. The laminated film according to any one of claims 1 to 7, wherein the resin layer is formed from a coating composition containing a release agent (A) and at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, polyester resin, acrylic resin, and urethane resin.

9. The laminated film according to any one of claims 1 to 8, wherein the thickness of the resin layer is greater than 10 nm and less than 200 nm.

10. The laminated film according to any one of claims 1 to 9, wherein the number of carbon atoms in the long-chain alkyl group-containing resin is 25 or less.

11. A method for manufacturing a laminated film according to any one of claims 1 to 10, comprising: applying a coating composition containing a release agent (A) and at least one resin or compound (B) selected from epoxy resin, oxazoline compound, carbodiimide compound, polyester resin, acrylic resin, and urethane resin to at least one surface of a resin substrate; then stretching in at least one axial direction; and then heating to 150°C or higher to form a resin layer.

12. A laminated film according to any one of claims 1 to 10, used for the purpose of applying a ceramic slurry to the surface of the resin layer, allowing it to solidify, and then peeling it off.

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