Method for producing film and cured product using the same

Abstract

The present invention relates to a film and a method for producing a cured product using the same, and more specifically, to a film and a method for producing a cured product that can be used in an inert redox initiator system. Specifically, the film according to the present invention includes a base material and an activation layer containing an initiator component on the surface of the base material, and a layer of a curable composition containing a curable syrup, a filler component, and an initiator component is brought into contact with the initiator component of the film to perform a curing reaction. The initiator component is an inert redox initiator system containing an oxidizing agent and a reducing agent, the reducing agent contains a metal compound, and the metal compound is contained in an effective amount in either the activation layer of the film or the layer of the curable composition.

Description

Technical Field

[0001] The present invention relates to a film and a method for producing a cured product using the same, and more particularly, to a film and a method for producing a cured product that can be used in an inert redox initiator system.

Background Art

[0002] Conventionally, solvent-based compositions have been mainly used as methods for producing cured products. However, solvent-based compositions essentially require high temperature or UV irradiation during the curing process such as the solvent evaporation step.

[0003] However, if necessary, the curing process can be performed after the composition required for the formation of the cured product is applied to a specific device. At this time, however, the device to which the curable composition is applied may be affected by high temperature or UV irradiation, resulting in a problem that the physical properties of the device deteriorate. Thus, there are cases where it is difficult to apply a high temperature or UV process when forming a cured product.

[0004] In addition, solvent-based compositions cause contamination problems during the solvent evaporation process and quality issues due to gas generation.

[0005] To solve the above problems, it is also possible to consider a method of forming a cured product by minimizing the use of solvents. However, it is a difficult task to implement a cured product having physical properties similar to those of a solvent-based composition using a solvent-free composition.

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, the problem to be solved by the present invention is to provide a cured product that can be produced without applying a separate high temperature or UV process through a film that can be used in an inert redox initiator system and a method for producing a cured product using the same. The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Means for Solving the Problem

[0007] The present invention can be subjected to various modifications and may have various embodiments. Specific embodiments are illustrated in the drawings and described in detail below. However, this is not intended to limit the present invention to the specific embodiments, and it should be understood to include all modifications, equivalents, or alternatives included in the spirit and technical scope of the present invention.

[0008] In this specification, normal temperature or room temperature means the natural temperature without artificial heating or cooling, and can represent any temperature of about 10 to 30°C, preferably 23 to 27°C, depending on the season.

[0009] The terms used in this application are merely used to describe specific embodiments and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly has a different meaning. In this application, terms such as "including" or "having" are intended to specify the presence of the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and it should not be understood to preclude the presence or addition possibility of one or more other features, numbers, steps, operations, components, parts, or combinations thereof in advance.

[0010] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs. Terms defined as in commonly used dictionaries should be interpreted to have a meaning consistent with the meaning in the context of the related art, and should not be interpreted as an ideal or overly formal meaning unless clearly defined in this application.

[0011] In one specific example according to the present invention, the present invention relates to a film. More specifically, the film of the present invention relates to an inert redox system that forms a kit together with a layer of a curable composition, and the inert redox system is premised on an inert redox initiator system. As used herein, the "redox initiator system" is one in which radical polymerization is initiated by a redox initiator at room temperature. Specifically, it means that free radicals generated by the redox reaction of the initiator initiate radical polymerization by an electron transfer reaction. In particular, the present invention uses an inert redox initiator system. As used herein, the "inert redox initiator system" means a redox initiator system that is composed such that redox is impossible with only a single initiator component.

[0012] In one example, the film according to the present application may include a substrate and an activation layer containing an initiator component on the surface of the substrate.

[0013] The substrate may be used without limitation as long as the activation layer can be applied to the surface. As an example, it may include a polymer, plastic, metal, wood, leather, or concrete. The polymer substrate is not limited thereto, and examples include cellulose acylate polymers, cycloolefin polymers, polycarbonate polymers, acrylate polymers, polyester polymers, and polyimide polymers. The plastic substrate is not limited thereto, and examples include polyethylene terephthalate (PET), polyethersulfone (PES), polycarbonate (PC), polyarylate (Par), and cyclic olefin copolymer (COC). The metal substrate is not limited thereto, and may include aluminum, copper, silver, iron, zinc, nickel, titanium, and gold.

[0014] The film may perform a curing reaction by bringing a layer of a curable composition containing a curable syrup, a filler component, and an initiator component into contact with the initiator component of the activation layer within the film. Thus, the film according to the present invention has excellent storage stability. By simply bringing the layer of the curable composition into contact with the film, while performing the curing reaction, not only the surface of the film in contact with the curable composition is partially cured, but also there is almost no difference in the degree of curing in the thickness direction of the film, and a cured product that can be uniformly cured throughout can be provided.

[0015] Also, in this specification, the "curable syrup" means a unit that forms a polymer in the final cured product through curing or crosslinking, and may include an oligomer or polymer component formed by polymerization of two or more monomers and a monomer component. As an example, the curable syrup may include a monomer, a (partial) polymer, and a crosslinking agent. However, when the monomer composition is partially polymerized to the (partial) polymer according to the desired composition, some monomers are polymerized to form an oligomer or polymer, and the remaining monomers may remain to constitute the curable syrup.

[0016] Therefore, in this specification, the term of monomer unit such as (meth)acrylate unit described later means a monomer that exists in a state of forming the oligomer or polymer within the curable syrup or a monomer that is included in the curable syrup without being polymerized. Therefore, when calculating the content of the curable syrup in this specification, it means including not only the component that does not participate in the polymerization and is in a monomer state in the syrup component, but also all the components that participate in the polymerization.

[0017] On the other hand, as will be described later, the oxidizing agent and the reducing agent, which are the initiator components, are simply for generating radicals to initiate polymerization, and are not added for the purpose of forming units that form polymers in the final cured product. Therefore, they are distinguished from the curable syrup. However, a part of the initiator component may exist in combination with the polymer in the final cured product.

[0018] In addition, in this specification, the initiator component means a redox initiator and may include an oxidizing agent and a reducing agent. In this specification, the oxidizing agent and the reducing agent mean components that participate or assist in generating radicals that participate or assist in the redox reaction under the redox initiator system to induce polymerization.

[0019] The curable composition in the present invention contains a curable syrup containing monomer units, a crosslinking agent and / or a (partial) polymer, a filler component, and an initiator which is a concept combining a reducing agent and an oxidizing agent, and it is necessary to design it to have excellent solubility, compatibility, dispersion rate, and reactivity among the components constituting the composition, but it is not limited thereto. The present application can use the following compositions.

[0020] In one specific example, the curable composition contains a filler component. The term "filler component" means a component composed of a filler, that is, a component containing only a filler.

[0021] In one example, the filler component may include two or more fillers having different average particle sizes from each other. In one example, the filler component may include three or more fillers having different average particle sizes from each other, or may be composed of three to six, three to five, three to four, or three fillers having different average particle sizes from each other. That is, in one example, the filler component may contain only three to six, three to five, three to four, or three fillers having different average particle sizes from each other.

[0022] In another example, the filler component can exhibit at least two peaks in the volume curve of the particle size distribution measured using the laser diffraction method. In one example, the filler component can exhibit three or more peaks in the volume curve of the particle size distribution, or can exhibit three to six, three to five, three to four, or three peaks. For example, in the range of filler components exhibiting three peaks, filler components exhibiting one, two, or four or more peaks are not included.

[0023] The average particle size of the filler in this application means the particle size at which the volume accumulation is 50% in the volume curve of the particle size distribution measured by the laser diffraction method, which may also be referred to as the median diameter. That is, in this application, the particle size distribution is determined on a volume basis through the laser diffraction method, and the particle size at the point where the cumulative value is 50% in the cumulative curve with the total volume as 100% is defined as the average particle size. Such an average particle size may be referred to as the median diameter or D 50 particle size in other examples.

[0024] Therefore, the two types of fillers having different average particle sizes as described above mean fillers with different particle sizes at the point where the cumulative value is 50% in the volume curve of the particle size distribution.

[0025] Generally, when mixing two or more types of fillers with different average particle sizes to form a filler component, in the volume curve of the particle size distribution measured using the laser diffraction method for the filler component, peaks corresponding only to the types of fillers mixed appear. Therefore, for example, when three types of fillers with different average particle sizes are mixed to form a filler component, the volume curve of the particle size distribution measured using the laser diffraction method for the filler component shows three peaks.

[0026] The filler component may be a thermally conductive filler component. The term thermally conductive filler component means a filler component that functions such that the curable composition can exhibit the thermal conductivity described later after curing.

[0027] As an example, the curable composition of the present application may contain 200 parts by weight or more of a filler component with respect to 100 parts by weight of the curable syrup. In other examples, the filler component may be 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, 550 parts by weight or more, 600 parts by weight or more, 650 parts by weight or more, 670 parts by weight or more, 700 parts by weight or more, or 730 parts by weight or more with respect to 100 parts by weight of the curable syrup. The upper limit is not greatly restricted, but it may be 1,500 parts by weight or less, 1,400 parts by weight or less, 1,300 parts by weight or less, 1,200 parts by weight or less, 1,100 parts by weight or less, 1,000 parts by weight or less, 900 parts by weight or less, or 800 parts by weight or less.

[0028] That is, according to the present application, even when the curable composition contains an excessive amount of the filler component relatively, the packaging density is increased through adjustment of the particle size and / or ratio of the filler contained in the filler component, showing excellent thermal conductivity. Also, it can be cured by a redox initiator at room temperature without a separate energy source such as UV or heat, and can provide a cured product with desired physical properties.

[0029] The filler component contained in the curable composition of the present application can satisfy the following general formula 1.

[0030] [General formula 1] 5 ≤ D 50A / D 50C ≤ 100

[0031] In general formula 1, D 50A is the maximum average particle size of the filler component, and D 50C is the minimum average particle size of the filler component.

[0032] In the above, the maximum average particle size (D 50A ) of the filler component means the average particle size of the filler with the largest average particle size among the fillers contained in the filler component when the filler component contains two or more kinds of fillers with different average particle sizes from each other. Or in other examples, the maximum average particle size (D 50AIt means the particle size of the peak that appears at the largest particle size among the peaks that appear in the volume curve of the particle size distribution measured using the laser diffraction method for the filler component.

[0033] In the above, the minimum average particle size (D 50C ) of the filler component means the average particle size of the filler with the smallest average particle size among the fillers included in the filler component when the filler component contains two or more fillers with different average particle sizes from each other. Or in another example, the minimum average particle size (D 50C ) of the filler component means the particle size of the peak that appears at the smallest particle size among the peaks that appear in the volume curve of the particle size distribution measured using the laser diffraction method for the filler component.

[0034] The D 50A / D 50C value may be further adjusted within the range of 5 or more, 7 or more, 10 or more, 13 or more, 15 or more, 17 or more, 20 or more, 23 or more, 25 or more, 27 or more, 30 or more, 32 or more, 34 or more, 36 or more, 38 or more, 40 or more, or 42 or more and / or within the range of 100 or less, 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 58 or less, 56 or less, 54 or less, 52 or less, 50 or less, 48 or less, 46 or less, or 44 or less in other examples.

[0035] As an example, the filler component of the curable composition of the present application may include fillers having at least three different average particle sizes. Such a filler component can exhibit at least three peaks in the volume curve of the particle size distribution measured using the laser diffraction method. In general, an excessive amount of filler needs to be applied in order for the curable composition to cure and exhibit a thermal conductivity above a certain level. However, according to the present application, it is very effective in exhibiting the desired hardness and thermal conductivity even when applied to a curable composition containing an excessive amount of filler. However, when an excessive amount of filler is contained, there may be a problem that the viscosity of the curable composition containing the filler increases significantly. The filler component of the present application can maintain the viscosity of the curable composition at an appropriate level even when an excessive amount of filler is applied to the curable composition by applying fillers having different average particle sizes so as to satisfy the general formula 1.

[0036] In one specific example, the filler component may include a first filler having an average particle size exceeding 40 μm and not exceeding 200 μm, a second filler having an average particle size exceeding 5 μm and not exceeding 40 μm, and a third filler having an average particle size of 0.2 μm to 5 μm. The filler component may include the three types of fillers or only the three types of fillers. Further, when the three types of fillers are included, the first filler may be the filler having the largest average particle size among the fillers contained in the filler component, and the third filler may be the filler having the smallest average particle size among the fillers contained in the filler component. Therefore, in this case, the average particle size of the first filler may be the maximum average particle size (D 50A ) of the general formula 1, and the average particle size of the third filler may be the minimum average particle size (D 50C ) of the general formula 1.

[0037] In other specific examples, the volume curve of the particle size distribution measured using the laser diffraction method for the filler component may exhibit a first peak appearing at a particle size exceeding 40 μm and not exceeding 200 μm, a second peak appearing within a range of exceeding 5 μm and not exceeding 40 μm, and a third peak appearing within a range of 0.2 μm to 5 μm. The volume curve of the particle size distribution can include at least the three types of peaks or represent only the three types of peaks. Further, when including at least the three types of peaks, the first peak may be the peak appearing at the largest particle size among the peaks shown by the volume curve, and the third peak may be the peak appearing at the lowest particle size among the peaks shown by the volume curve. Therefore, in this case, the particle size at which the first peak appears is the maximum average particle size (D 50A ) of the general formula 1, and the particle size at which the third peak appears can be the minimum average particle size (D 50C ) of the general formula 1.

[0038] The average particle size of the first filler or the particle size at which the first peak appears may be further adjusted in other examples within a range of 190 μm or less, 180 μm or less, 170 μm or less, 160 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 120 μm or less, 115 μm or less, 110 μm or less, 105 μm or less, 100 μm or less, 95 μm or less, 90 μm or less, 85 μm or less, 80 μm or less, or about 75 μm or less and / or within a range of 61 μm or more, 62 μm or more, 63 μm or more, 64 μm or more, 65 μm or more, 66 μm or more, 67 μm or more, 68 μm or more, 69 μm or more, or 70 μm or more.

[0039] Also, the average particle size of the second filler or the particle size at which the second peak appears may, in other examples, be further adjusted within a range exceeding about 6 μm, exceeding 7 μm, exceeding 8 μm, exceeding 9 μm, exceeding 10 μm, exceeding 11 μm, exceeding 12 μm, exceeding 13 μm, exceeding about 14 μm, exceeding 15 μm, exceeding 16 μm, exceeding 17 μm, exceeding 18 μm, or exceeding 19 μm and / or within a range of 39 μm or less, 38 μm or less, 37 μm or less, 36 μm or less, 35 μm or less, 34 μm or less, 33 μm or less, 32 μm or less, 31 μm or less, 30 μm or less, 29 μm or less, 28 μm or less, about 27 μm or less, 26 μm or less, 25 μm or less, 24 μm or less, 23 μm or less, 22 μm or less, 21 μm or less, or 20 μm or less.

[0040] Also, the average particle size of the third filler or the particle size at which the third peak appears may, in other examples, be further adjusted within a range of about 0.3 μm or more, 0.4 μm or more, or about 0.5 μm or more and / or within a range of about 5 μm or less, 4.5 μm or less, about 4 μm or less, about 3.5 μm or less, about 3.3 μm or less, about 3 μm or less, about 2.7 μm or less, about 2.5 μm or less, about 2 μm or less, or about 1.7 μm or less.

[0041] When the filler component contains three kinds of fillers as described above, the ratio (D1 / D2) of the average particle size (D1) of the first filler to the average particle size (D2) of the second filler may be within a range of about 3 to 20. In other examples, the ratio (D1 / D2) may be 3.1 or more, 3.2 or more, 3.3 or more, 3.4 or more, or 3.5 or more, or about 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less.

[0042] When the second filler and the third filler having sizes within the above range are included together with the first filler and their relationship satisfies the general formula 1 or the like, it is possible to effectively satisfy a high thermal conductivity while maintaining the viscosity of the resin composition at an appropriate level.

[0043] In one example, the curable composition may contain 200 parts by weight or more of a filler component with respect to 100 parts by weight of the curable syrup. In other examples, the filler component may be contained in an amount of 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, 550 parts by weight or more, 600 parts by weight or more, 650 parts by weight or more, or 700 parts by weight or more with respect to 100 parts by weight of the curable syrup. There is no significant upper limit for the filler component, but it may be 2,000 parts by weight or less, 1,500 parts by weight or less, 1,000 parts by weight or less, or 900 parts by weight or less with respect to 100 parts by weight of the curable syrup.

[0044] On the other hand, when the first to third fillers are contained in the filler component, it may contain about 10 to 90 parts by weight of the second filler and about 60 to 140 parts by weight of the third filler with respect to 100 parts by weight of the first filler. In other examples, with respect to 100 parts by weight of the first filler, the proportion of the second filler may be about 15 parts by weight or more, about 20 parts by weight or more, about 25 parts by weight or more, about 30 parts by weight or more, about 35 parts by weight or more, about 40 parts by weight or more, about 45 parts by weight or more, or about 47 parts by weight or more, or about 85 parts by weight or less, about 80 parts by weight or less, about 75 parts by weight or less, about 70 parts by weight or less, about 65 parts by weight or less, about 60 parts by weight or less, about 55 parts by weight or less, or about 53 parts by weight or less. The proportion of the third filler may be about 65 parts by weight or more, about 70 parts by weight or more, about 75 parts by weight or more, about 80 parts by weight or more, about 85 parts by weight or more, about 90 parts by weight or more, or about 95 parts by weight or more, or about 135 parts by weight or less, about 130 parts by weight or less, about 125 parts by weight or less, about 120 parts by weight or less, about 115 parts by weight or less, about 110 parts by weight or less, or about 105 parts by weight or less in other examples.

[0045] As an example, the content of the first filler may be about 10 parts by weight to about 60 parts by weight with respect to 100 parts by weight of the total filler component, the content of the second filler may be about 1 part by weight to about 40 parts by weight with respect to 100 parts by weight of the total filler component, and the content of the third filler may be about 10 parts by weight to about 60 parts by weight with respect to 100 parts by weight of the total filler.

[0046] In one example, the filler component may contain 30% by weight or more of spherical fillers. Generally, if the shape of the filler is spherical, it is not advantageous for achieving higher thermal conductivity. That is, it is advantageous to use non-spherical fillers in terms of thermal conductivity. However, since it is not advantageous in terms of the hardness of the solid when the filler is non-spherical, by including spherical fillers at a certain level or more in the filler component, an advantageous effect can be exerted in terms of the hardness of the solid. Also, according to the composition of the present application, a high thermal conductivity can be achieved even under the content of the spherical filler as described above. In other examples, the content of the spherical filler in the filler component may be 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, or 57% by weight or more. The upper limit of the content of the spherical filler in the filler component may be adjusted within a range of 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, or 65% by weight or less, considering the thermal conductivity and the hardness characteristics of the solid.

[0047] For example, when non-spherical fillers are present in the filler component, it is advantageous to select fillers with a small average particle size as the non-spherical fillers. For example, when the filler component contains the first to third fillers, a non-spherical filler may be selected as the third filler.

[0048] The term "spherical filler" refers to a filler with a sphericity of 0.9 or more. In other examples, the sphericity of the spherical filler may be 0.95 or more. Therefore, a filler with a sphericity of less than 0.9 is a non-spherical filler.

[0049] The sphericity can be confirmed through particle shape analysis. In one specific example, the sphericity of the filler can be defined as the ratio (S' / S) of the surface area (S) of the particle to the surface area (S') of a sphere having the same volume as the particle. Generally, circularity is used for actual particles. The circularity is obtained by finding a two-dimensional image of the actual particle and representing it as the ratio of the boundary of a circle having the same area A as the image to the boundary of the image, and is obtained by the following mathematical formula.

[0050] <Circularity mathematical formula> Circularity = 4πA / P 2

[0051] The circularity appears as a value from 0 to 1. A perfect circle has a value of 1, and the more irregularly shaped the particles are, the lower the value is than 1.

[0052] As an example, the filler component may be a thermally conductive filler component. As described above, the term thermally conductive filler refers to a filler component that functions such that the curable composition exhibits a thermal conductivity of about 3.0 W / mK or more when cured. Such a filler component may include a filler made of a material having a thermal conductivity of about 1 W / mK or more, 5 W / mK or more, 10 W / mK or more, or about 15 W / mK or more. In other examples, the thermal conductivity of the material may be about 400 W / mK or less, 350 W / mK or less, or about 300 W / mK or less. The types of such materials are not particularly limited, and examples include ceramic materials such as aluminum oxide (alumina: Al2O3), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si3N4), silicon carbide (SiC), beryllium oxide (BeO), zinc oxide (ZnO), magnesium oxide (MgO), or boehmite.

[0053] In addition to the heat conductive fillers as described above, the filler component may contain various types of fillers as necessary. For example, carbon fillers such as graphite, fumed silica, clay, aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), or fillers such as calcium carbonate (CaCO3) may also be applied.

[0054] In one example, the moisture content (water content) of the filler component may be about 1,000 ppm or less. The moisture content may be measured with a Karl Fischer titrator (KR831) under the conditions of 10% relative humidity and a drift of 5.0 or less. At this time, the moisture content may be the average moisture content with respect to all filler components used in the resin composition. In the present application, a filler component that satisfies the above conditions may be selectively used, or the moisture content of the filler may be adjusted to satisfy the above range of the moisture content by a method such as drying the filler component to be used in an oven at a temperature of about 200°C. In still another example, the upper limit of the moisture content of the filler component may be about 800 ppm or less, 600 ppm or less, or about 400 ppm or less, and the lower limit may be about 100 ppm or more or about 200 ppm or more.

[0055] In one example, the curable composition may contain a reducing agent in the range of 0.05 to 6 parts by weight with respect to 100 parts by weight of the curable syrup, but is not limited thereto. As an example, the lower limit of the reducing agent content may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.7 part by weight or more, 1 part by weight or more, 1.3 part by weight or more, 1.5 part by weight or more, 1.7 part by weight or more, 2 part by weight or more, 2.3 part by weight or more, 2.5 part by weight or more, 2.7 part by weight or more, 3 part by weight or more, or 3.2 part by weight or more, and the upper limit may be 6 part by weight or less, 5.5 part by weight or less, 5 part by weight or less, 4.5 part by weight or less, 4 part by weight or less, or 3.5 part by weight or less. By containing the reducing agent in the above content, the present invention can ensure sufficient curability and obtain a cured product having desired physical properties.

[0056] Also, in one example, the reducing agent may contain a metal compound. According to the present invention, the metal compound can induce or promote a redox reaction when the layer of the curable composition and the layer of the initiator component are in direct contact without separate heat or UV irradiation, and there is no particular limitation as long as the composition containing the reducing agent can be stably stored. In particular, it preferably has excellent solubility, compatibility, dispersion rate, and reactivity with the curable syrup.

[0057] The metal compound may be contained in an effective amount in either the layer of the initiator component of the film or the layer of the curable composition. Here, the effective amount means an amount capable of inducing a meaningful redox reaction for producing a cured product. That is, the metal compound is contained in an effective amount in either the layer of the initiator component or the layer of the curable composition, and may not be substantially contained in the remaining one. As an example, when the metal compound is contained in the layer of the initiator component in an effective amount, the metal compound may not be substantially contained in the layer of the curable composition. Also, as another example, when the metal compound is contained in the layer of the curable composition in an effective amount, the metal compound may not be substantially contained in the layer of the initiator component. Here, the meaning of not being substantially contained may be that it may be contained in 0% by weight, and even if the metal compound is contained in the layer of the curable composition, it may be contained in 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less and is not an effective amount capable of inducing a redox reaction, and may be contained in a trace amount.

[0058] Also, in either the layer of the initiator component of the film or the layer of the curable composition, the layer containing the metal compound in an effective amount may not substantially contain an oxidizing agent. That is, in the present invention, it is not necessary to assume the case where the oxidizing agent and the metal compound are substantially contained together in the same layer before forming the cured product. That is, when the metal compound is contained in the layer of the initiator component of the film in an effective amount, the oxidizing agent is not contained in the layer of the initiator component of the film in an effective amount, but may be contained in the layer of the curable composition in an effective amount. As another example, when the metal compound is contained in the layer of the curable composition in an effective amount, the oxidizing agent is not contained in the layer of the curable composition in an effective amount, but may be contained in the layer of the initiator component of the film in an effective amount.

[0059] As an example, the metal contained in the metal compound may be a transition metal, and the metal compound may be a salt, chelate or hydrate containing metal ions, and may contain one or more of them. Here, the metal ions may be at least one selected from cobalt, iron, vanadium, copper, manganese, nickel, titanium, aluminum, tin, chromium, zinc, zirconium, indium, manganese and mixtures thereof. Specifically, the metal compound may be a cobalt-containing component, and in the cobalt-containing component, cobalt may have an oxidation state of +2 or +3. Examples of cobalt-containing components that can be used include, but are not limited to, cobalt naphthenate, cobalt sulfide, etc. As another example, the metal compound may be an iron-containing component, and in the iron-containing component, iron may have an oxidation state of +2 or +3. Examples of iron-containing components that can be used include, but are not limited to, iron(III) sulfate, iron(II) sulfate, iron(III) chloride, iron(II) chloride, iron carboxylate, iron naphthenate, iron(III), iron(II) or iron(III) acetylacetonate. As yet another example, the metal compound may be a vanadium-containing component, and in the vanadium-containing component, vanadium may have an oxidation state of +4 or +5. Examples of vanadium-containing components that can be used include, but are not limited to, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadyl oxalate, vanadium(V) oxytris(isopropoxide), ammonium metavanadate(V), sodium metavanadate, vanadium pentoxide(V) or vanadyl sulfate(V). As yet another example, the metal compound may be a copper-containing component, and in the copper-containing component, copper may have an oxidation state of +1 or +2. Examples of copper-containing components that can be used include, but are not limited to, copper acetate, copper chloride, copper benzoate, copper acetylacetonate, copper naphthenate, copper carboxylate, copper salicylate, a complex of copper and thiourea or ethylenediaminetetraacetic acid. Other examples of metal compounds include manganese naphthenate, nickel naphthenate, titanium acetylacetonate, copper sulfate, manganese sulfate or nickel sulfate, etc.Further, the reducing agent may contain an organic compound, but there are no major restrictions on the organic compound as long as it can induce or promote a redox reaction by direct contact between the layer of the curable composition and the layer of the initiator component without separate heat or UV irradiation.

[0060] The organic compound may be substantially contained together in the layer containing the oxidizing agent among the layer of the initiator component of the film and the layer of the curable composition, or may be substantially contained together in the layer containing the metal compound, but may be selectively and substantially contained in either the layer containing the oxidizing agent or the layer containing the metal compound.

[0061] As an example, the organic compound may be at least one selected from the group consisting of amines, pyridines, aldehyde-amine condensation compounds, thioureas, and their derivatives, or may be two or more. Specifically, although not limited thereto, examples of the organic compound include N,N-dimethyl-p-toluidine, N,N-dimethylformamide, triethylamine, N,N-diisopropanol-p-chloroaniline, N,N-diisopropanol-p-bromoaniline, N,N-diisopropanol-p-bromo-o-methylaniline, N,N-dimethyl-p-chloroaniline, N,N-dimethyl-p-bromoaniline, N,N-diethyl-p-chloroaniline, N,N-diethyl-p-bromoaniline, 3,5-diethyl-1,2-dihydro-1-phenyl-2-propylpyridine, N-benzoylthiourea, or tetramethylthiourea, etc. Preferably, a tertiary amine-based organic compound may be used. In particular, as the organic compound, a compound that is in a liquid phase and has a half-life within the range of 70 to 170 °C or within the range of 80 to 150 °C together with this is preferable. By using an organic compound whose half-life temperature satisfies the above range, the present invention can suppress self-reaction in the storage state and can maintain the viscosity of the composition containing the organic compound at a desired level in the present invention. In this specification, the half-life is an index indicating the decomposition rate of a compound and means the time until the remaining amount of the compound becomes half.

[0062] In one example, when both a metal compound and an organic compound are included as reducing agents, the organic compound may be included in the range of 5 to 50 parts by weight with respect to 100 parts by weight of the metal compound. As an example, the lower limit thereof may be 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, 15 parts by weight or more, 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, 20 parts by weight or more, or 21 parts by weight or more, and the upper limit thereof may be 45 parts by weight or less, 43 parts by weight or less, 40 parts by weight or less, 37 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, 27 parts by weight or less, 25 parts by weight or less, or 23 parts by weight or less. By including the metal compound and the organic compound in the above weight ratio, the present invention can provide a cured product having excellent cured physical properties through a sufficient curing rate.

[0063] Also, in one example, the curable composition may contain an oxidizing agent. There is no major limitation as long as the oxidizing agent participates in an oxidation-reduction reaction and generates radicals that induce polymerization, and it is particularly preferable that the oxidizing agent has excellent compatibility with the curable syrup. As an example, but not limited thereto, the oxidizing agent may contain a peroxide, a peroxyester, a diacyl peroxide, or a persulfate. Specifically, methyl ethyl ketone peroxide, t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, t-butyl peroxy laurate, t-butyl peroxy benzoate, t-butyl peroxy decanoate, 1,5-di-t-butyl peroxy-3,3,5-trimethylcyclohexane, ethyl acetoacetate peroxide, benzoyl peroxide, hydrogen peroxide, or a combination thereof may be used as the oxidizing agent.

[0064] In one example, the oxidizing agent may be contained in the range of 30 to 100 parts by weight with respect to 100 parts by weight of the reducing agent. As an example, the lower limit thereof may be 35 parts by weight or more, 37 parts by weight or more, 40 parts by weight or more, 43 parts by weight or more, 45 parts by weight or more, 47 parts by weight or more, 50 parts by weight or more, 53 parts by weight or more, 55 parts by weight or more, or 57 parts by weight or more, and the upper limit thereof may be 95 parts by weight or less, 93 parts by weight or less, 90 parts by weight or less, 87 parts by weight or less, 85 parts by weight or less, 83 parts by weight or less, 80 parts by weight or less, 77 parts by weight or less, 75 parts by weight or less, 73 parts by weight or less, 70 parts by weight or less, 67 parts by weight or less, 65 parts by weight or less, or 63 parts by weight or less.

[0065] In one specific example, the curable syrup may be a polymer component as described above. In particular, the layer of the curable composition of the present application may contain a curable syrup together with a large amount of filler components. Therefore, as described later, the present application may have excellent properties not only in compatibility but also in blendability between a large amount of filler components and a curable syrup by using a curable syrup of a specific component in combination with a large amount of filler components.

[0066] The curable composition may contain the curable syrup at 6 to 20% by weight, and although not limited thereto, as an example, the lower limit of the curable syrup may be 6% by weight or more, 6.5% by weight or more, 7% by weight or more, 7.5% by weight or more, 8% by weight or more, 8.5% by weight or more, 9% by weight or more, 9.5% by weight or more, or 10% by weight or more, and the upper limit thereof may be 19% by weight or less, 18% by weight or less, 17% by weight or less, 16% by weight or less, 15% by weight or less, 14% by weight or less, 13% by weight or less, or 12% by weight or less.

[0067] In one example, the curable syrup may contain an alkyl (meth)acrylate unit, a polar functional group-containing monomer unit, and a crosslinking agent. As an example, the alkyl (meth)acrylate unit may be an alkyl (meth)acrylate having an alkyl group with 4 to 20 carbon atoms, and the number of carbon atoms of the alkyl group may be, for example, 16 or less, 12 or less, or 8 or less. Such an alkyl (meth)acrylate may be contained in the curable syrup at about 1 to 12% by weight. The upper limit of the ratio may be, in other examples, 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 3% by weight or more, 3.5% by weight or more, 4% by weight or more, 4.5% by weight or more, 5.5% by weight or more, or 5.7% by weight or more, and the lower limit may be 11.5% by weight or less, 11% by weight or less, 10.5% by weight or less, 10% by weight or less, 9.5% by weight or less, 9% by weight or less, 8.5% by weight or less, 8% by weight or less, 7.5% by weight or less, 7% by weight or less, or 6.5% by weight or less.

[0068] Also, the alkyl group in the alkyl (meth)acrylate unit may be a linear or branched aliphatic alkyl group, and may be in a substituted or unsubstituted state. The linear or branched aliphatic alkyl (meth)acrylate may be, for example, any one or two or more selected from the group consisting of n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, and tetradecyl (meth)acrylate.

[0069] The curable syrup may contain a polar functional group-containing monomer unit as an additional component. The curable syrup may contain, but is not limited to, a hydroxy group-containing monomer unit, a carboxyl group-containing monomer unit, or an epoxy group-containing monomer unit as the polar functional group-containing monomer unit.

[0070] Examples of monomers having a polar functional group include, for example, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and / or 8-hydroxyoctyl (meth) acrylate (in the above, the number of carbon atoms of the alkyl group may be 1 to 20, 1 to 16, 1 to 12, 1 to 8 or 1 to 4, the alkyl group may be linear or branched, and may be substituted or unsubstituted.), or hydroxy polyalkylene glycol (meth) acrylates such as 2-hydroxy polyethylene glycol (meth) acrylate, or 2-hydroxy polypropylene glycol (meth) acrylate, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate or acrylic acid may be used, but are not limited thereto. The polar functional group includes a hydroxy group, an epoxy group, an isocyanate group, a glycidyl group, an alkenyloxycarbonyl group, a (meth) acryloyl group or an alkenyloxyalkyl group.

[0071] In one embodiment of the present application, the monomer unit having the polar functional group may be contained in an amount of 500 parts by weight or more based on 100 parts by weight of the alkyl (meth) acrylate unit. In other examples, the lower limit thereof may be 600 parts by weight or more, 700 parts by weight or more, 800 parts by weight or more, 900 parts by weight or more, 1,000 parts by weight or more, 1,100 parts by weight or more, 1,200 parts by weight or more, 1,300 parts by weight or more, 1,350 parts by weight or more, 1,400 parts by weight or more or 1,450 parts by weight or more, and the upper limit thereof may be 3,000 parts by weight or less, 2,500 parts by weight or less, 2,000 parts by weight or less, or 1,700 parts by weight or less.

[0072] Although not limited thereto, in one embodiment of the present application, it is possible to assume a case where the curable syrup contains a hydroxy group-containing monomer unit and an epoxy group-containing monomer unit as a polar functional group-containing monomer unit, and the hydroxy-containing monomer unit (M OH ) and the epoxy group-containing monomer unit (ME ) ratio (M OH / M E ) may be in the range of 0.1 to 10, and the upper limit thereof may be 0.3 or more, 0.5 or more, 0.7 or more, 1 or more, 1.3 or more, 1.5 or more, 1.7 or more, 2 or more, 2.3 or more, 2.5 or more, 2.7 or more, or 3 or more, and the lower limit thereof may be 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.7 or less, 3.5 or less, or 3.3 or less.

[0073] Further, the curable syrup of the present invention may further contain monomer units in addition to the above, if necessary.

[0074] For example, the curable syrup may further contain a nitrogen-containing reactive monomer unit. Examples of such nitrogen-containing reactive monomers include one or more of (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, diacetone(meth)acrylamide, N-vinylacetamide, N,N'-methylenebis(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, or (meth)acryloylmorpholine, etc., but are not limited thereto. Suitable monomers include, for example, (meth)acrylamide, N-alkyl(meth)acrylamide and / or N,N-dialkyl(meth)acrylamide, etc. In the above, examples of the alkyl group include linear, branched or cyclic substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.

[0075] The curable composition according to an example of the present application may further contain a crosslinking agent, if necessary. The crosslinking agent can form a cured product having appropriate adhesiveness and hardness by embodying the structure and crosslinked structure contained in the curable syrup.

[0076] As the crosslinking agent, for example, a urethane acrylate crosslinking agent, an aliphatic isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent may be used, but are not limited thereto. Also, one or more crosslinking agents may be used. The urethane acrylate crosslinking agent is a compound having a large number of urethane bonds (-NHCOO-) in the molecular chain and an acrylic group capable of reacting with ultraviolet rays at the molecular terminal. Commercially, PU330 (Mihara Shoji), PU256 (Mihara Shoji), PU610 (Mihara Shoji), PU340 (Mihara Shoji), etc. may be used. As the aliphatic isocyanate crosslinking agent, for example, isocyanate compounds such as isophorone diisocyanate, methylene dicyclohexyl diisocyanate, or cyclohexane diisocyanate, and derivatives such as its dimer or trimer may be used. As the epoxy crosslinking agent, for example, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidyl ethylenediamine, or glycerin diglycidyl ether may be used. As the aziridine crosslinking agent, for example, N,N'-toluene-2,4-bis(1-aziridine carboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxamide), triethylenemelamine, bisisoprothalloyl-1-(2-methylaziridine), or tri-1-aziridinylphosphine oxide may be used. As the metal chelate crosslinking agent, for example, a metal chelate component which is a compound in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium is coordinated with acetylacetone or ethyl acetoacetate may be used.

[0077] The method for producing the curable syrup containing the units as described above is not particularly limited. For example, after mixing monomers at a desired ratio for the embodiment of the syrup components described above, it may be appropriately partially polymerized to form a curable syrup.

[0078] According to the present invention, the curable composition can be cured only by bringing the layer of the curable composition into contact with the initiator component layer of the film containing the initiator component layer on the surface as described above, and a cured product having desired physical properties can be produced in the present invention. That is, in the present application, the curing reaction starts at room temperature and proceeds at room temperature, and a cured product having desired hardness and physical properties can be provided without separate heat or UV irradiation. However, a step of further irradiating heat or UV may be added as necessary. The curing may be carried out by a redox polymerization reaction between the initiator component of the curable composition and the initiator component present on the surface of the film.

[0079] The cured product of the present invention can be produced by layers having different components contacting each other and the metal compound diffusing into the contacting layer to induce a redox reaction. At this time, if the curing reaction is too fast, the metal compound and the like do not diffuse sufficiently, the crosslinking reaction between the curable syrups hardly occurs, and the cured product may not have uniform physical properties. Therefore, the present invention can control the curing reaction rate of the curable composition by the production method to an appropriate level by having the composition as described above.

[0080] In the present invention, the curable composition may be a solventless composition. Here, the solventless composition is a composition that substantially does not contain a solvent (aqueous solvent and organic solvent). Therefore, the content of the aqueous and organic solvents in the curable composition may be 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less, and may be substantially 0% by weight. That is, the curable composition of the present invention is embodied to have the composition as described above, so that it has physical properties equivalent to or better than those of a solvent-based composition while being solventless, and at the same time is suitable for an inert redox system.

[0081] In addition, in the present invention, the curable composition may have a viscosity measured at a temperature of 25°C and a shear rate of 1 rpm within the range of 10,000 cps to 30,000 cps, 15,000 cps to 25,000 cps, 17,000 cps to 23,000 cps, or 18,000 cps to 22,000 cps. The viscosity can be measured at room temperature using a No. 63 spindle in a Brookfield HB type viscometer.

[0082] The cured product according to the present application may be thermally conductive. Specifically, the cured product may have a thermal conductivity of 0.1 W / mK or more. Although not limited thereto, as an example, the cured product may have a thermal conductivity of about 50 W / mK or less, 45 W / mk or less, 40 W / mk or less, 35 W / mk or less, 30 W / mk or less, 25 W / mk or less, 20 W / mk or less, 15 W / mk or less, about 10 W / mK or less, 9 W / mK or less, 8 W / mK or less, 7 W / mK or less, 6 W / mK or less, 5 W / mK or less, or about 4 W / mK or less. The thermal conductivity of the cured product can be measured, for example, in accordance with ASTM D5470 standard or ISO 22007-2 standard.

[0083] In one example, the cured product according to the present application may be used as a battery module case or a battery cell by exhibiting the thermal conductivity, and is effective in releasing the heat generated in the battery module to the outside. The battery cell may be housed in the module case, there may be at least one in the module case, or a plurality of battery cells may be housed in the module case. The type of the battery cell housed in the module case is not particularly limited, and various known battery cells may all be applicable. In one example, the battery cell may be a pouch type. FIGS. 1 and 2 are schematic views of a module case 10 in which a battery cell 20 is housed, observed from above. The exemplary module case 10 may be box-shaped including one lower plate 10a and a plurality of side walls 10b, and may further include an upper plate 10c that seals the internal space. The film 30 may be in the form of a relatively thin layer (see FIG. 2), or may be in the form of filling the internal space of the case 10. Further, as shown in FIG. 2, a guide portion 10d capable of guiding the housed battery cell 20 may be present on at least one surface inside the module case 10, for example, the surface 10a in contact with the film 30.

[0084] In another specific example according to the present invention, the present invention relates to a method for manufacturing a cured product. The method for manufacturing a cured product may include a step of bringing a layer of a curable composition containing a curable syrup component, a filler component, and an initiator component into contact with the layer of the initiator component of the film described above containing the layer of the initiator component on the surface.

[0085] The method of bringing the layer of the curable composition into contact with the layer of the initiator component of the film containing the layer of the initiator component on the surface is not greatly limited. As an example, the curable composition may be directly applied onto the film, or may be laminated after being applied onto an arbitrary substrate. Further, when bringing the layer of the initiator component of the film containing the layer of the initiator component on the surface into contact with the layer of the curable composition, the layer of the initiator component of the film containing the layer of the initiator component on the surface may be brought into contact with one surface of the layer of the curable composition, or may be brought into contact with both surfaces.

[0086] Each configuration is applied identically as described above.

Advantages of the Invention

[0087] According to an embodiment of the present invention, by using a one-component curing method instead of a two-component curing method in which the main agent and the curing agent are separately mixed and then applied, a film with excellent storage stability and curable at room temperature and under dark reaction conditions without separate UV or heat is provided.

Brief Description of the Drawings

[0088]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0089] Hereinafter, preferred experimental examples (example) are presented to assist in the understanding of the present invention. However, the following experimental examples are for assisting in the understanding of the present invention, and the present invention is not limited by the following experimental examples.

[0090] Production of Radical Polymer (P) 2-Ethylhexyl acrylate (2-EHA) and 2-hydroxyethyl acrylate (HEA) were added to a flask equipped with a mechanical stirrer at a weight ratio of 60:40 (2-EHA:HEA). A solution in which Irgacure 184, a photoinitiator, and ethyl acetate (EAC) were diluted at a ratio of 1:1 was further added at about 0.1% by weight based on the total weight of the compounds added to the flask. Then, nitrogen gas was introduced under normal pressure conditions, and the temperature was raised to about 60 °C. While stirring, it was irradiated with a metal halide lamp. At the moment when the temperature reached 68 °C, the introduction of nitrogen gas and the lamp irradiation were interrupted, and a radical polymer (P) (solid content: about 12%) was obtained.

[0091] At this time, the viscosity of the produced radical polymer (P) measured with a Brookfield DV-3 using a No. 63 spindle at a temperature of 25 °C and a torque of 31.6% was about 26,830 cps, the weight average molecular weight (Mw) was about 2,192,000 g / mol, and the polydispersity index (PDI) was about 3.08.

[0092] Production Example 1: Production of a curable composition Using the radical polymer (P) produced as described above with a sclerosing syrup, 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), and a polyfunctional aliphatic urethane acrylate (SUO-1020 from SHIN-A T&C) as a crosslinking agent (H), a phosphorus-based flame retardant (FR-119L from Kanpia) as a flame retardant (N), a modified polyester dispersant (Disperbyk-111 from BYK) as a dispersant (D), a filler component (F), methyl ethyl ketone peroxide (MEKP) as an oxidizing agent (O), and N,N-dimethyl p-toluidine (DMPT) as an organic compound (A), they were added to a paste mixer at a weight ratio of approximately 1.17:7.48:2.49:0.59:1.76:0.1:86.05:0.23:0.07 (P:2-HEA:GMA:H:N:D:F:O:A), stirred well, and a curable composition having a viscosity of approximately 200,000 cps measured with a DV-3 from Brookfield at a temperature of 25 °C and a shear rate of 1 rpm at room temperature was produced.

[0093] The filler composition (F) used was a mixture of spherical alumina with an average particle size of approximately 70 μm (BAK-70 from Bestrytech, sphericity of 0.95 or more), aluminum hydroxide with an average particle size of approximately 20 μm (DH-50P from Korea Alumina, sphericity of 0.95 or more), and angular alumina with an average particle size of approximately 1.6 μm (KLS-51 from Korea Alumina, sphericity of less than 0.9) at a weight ratio of approximately 34.42:17.21:34.42.

[0094] Production Example 2: Production of Curable Composition The radical polymer (P) produced as described above with a hardening syrup, 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), and a crosslinking agent (H), a polyfunctional aliphatic urethane acrylate (SUO-1020 from SHIN-A T&C Co., Ltd.), were used, along with a phosphorus-based flame retardant (FR-119L from Campia Co., Ltd.) as the flame retardant (N), a modified polyester dispersant (Disperbyk-111 from BYK Co., Ltd.) as the dispersant (D), a filler component (F), methyl ethyl ketone peroxide (MEKP) as the oxidizing agent (O), and N,N-dimethyl p-toluidine (DMPT) as the organic compound (A). They were added to a paste mixer at a weight ratio of approximately 0.5:3.7:1.2:0.48:1.71:0.1:92.05:0.2:0.06 (P:2-HEA:GMA:H:N:D:F:O:A) and stirred well.

[0095] The filler composition (F) used was a mixture of spherical alumina with an average particle size of approximately 70 μm (BAK-70 from Bestrytech Co., Ltd., sphericity of 0.95 or more), aluminum hydroxide with an average particle size of approximately 20 μm (DH-50P from Korea Alumina Co., Ltd., sphericity of 0.95 or more), and angular alumina with an average particle size of approximately 1.6 μm (KLS-51 from Korea Alumina Co., Ltd., sphericity of less than 0.9) mixed at a weight ratio of approximately 36.82:18.41:36.82.

[0096] Example 1 A metal compound solution was prepared by diluting iron(III) acetylacetonate, which is a metal compound (M), in toluene so that it was 15% by weight.

[0097] Next, in the curable composition according to Production Example 1, the metal compound solution was applied onto aluminum foil so that the weight ratio of the oxidizing agent, the organic compound, and the metal compound was about 0.23:0.07:0.32 (O:A:M). After that, it was dried at about 25°C for 5 minutes and then dried on a hot plate at 100°C for 5 minutes to produce a film containing an activation layer.

[0098] The curable composition produced above was applied so as to be in contact with the metal compound of the activation layer to produce a cured product. At this time, the curable composition was applied to a thickness of 1T.

[0099] Example 2 Iron(III) acetylacetonate, which is a metal compound (M), was diluted to 15% by weight in toluene to produce a metal compound solution.

[0100] Next, in the curable composition according to Production Example 1, the metal compound solution was applied onto a PET film so that the weight ratio of the oxidizing agent, the organic compound, and the metal compound was about 0.23:0.07:0.32 (O:A:M). After that, it was dried at about 25°C for 5 minutes and then dried on a hot plate at 100°C for 5 minutes to produce a film containing an activation layer.

[0101] The curable composition produced above was applied so as to be in contact with the metal compound of the activation layer to produce a cured product. At this time, the curable composition was applied to a thickness of 1T.

[0102] Comparative Example 1 Iron(III) acetylacetonate, which is a metal compound (M), was diluted to 15% by weight in toluene to produce a metal compound solution.

[0103] Next, in the curable composition according to Production Example 1, the metal compound solution was mixed with the curable composition produced above so that the weight ratio of the oxidizing agent, the organic compound, and the metal compound was about 0.23:0.07:0.64 (O:A:M), and stirred well.

[0104] The mixture was applied onto the aluminum foil to a thickness of 2T, and a PET film was placed on top.

[0105] Comparative Example 2 The procedure was the same as in Example 1, except that the metal compound solution was not applied onto the aluminum foil, and the curable composition produced therefrom was applied to a thickness of 1T.

[0106] Comparative Example 3 The metal compound solution was not applied onto the aluminum foil. In the curable composition according to Production Example 1, the metal compound solution and the curable composition produced therefrom were mixed so that the weight ratio of the oxidizing agent, organic compound, and metal compound was about 0.23:0.07:0.32 (O:A:M), and then applied onto the aluminum foil to a thickness of about 1T. After drying at about 25°C for 5 minutes, it was further dried on a hot plate at 100°C for 5 minutes to produce a film containing an activation layer.

[0107] Comparative Example 4 The production was carried out in the same manner as in Example 1, except that the curable composition according to Production Example 2 was used.

[0108] In this case, the phenomenon that the compatibility between the curable syrup and the filler component decreased and it crumbled without being compounded occurred.

[0109] Experimental Example 1: Hardness The PET film adhered to the cured products produced through the Examples and Comparative Examples was removed, and the surface from which the PET film was removed on the cured product was measured using a durometer shore A hardness tester at a temperature of about 25°C. The hardness value represents the average value after 3-point measurement.

[0110] Experimental Example 2: Total Mass Loss (TML) The total mass loss was evaluated in the following manner. The PET film attached to the cured products produced through the Examples and Comparative Examples was removed, cut to fit an aluminum dish with a diameter of about 5 cm to produce a sample with a thickness of about 2T, and the weight (A, unit: g) of the sample was measured. Then, the weight (B, unit: g) of the sample immediately after leaving the sample at 150 °C for 45 minutes was measured, and the TML was calculated by the following General Formula 2. Hereinafter, C is the weight (unit: g) of aluminum attached to the cured product.

[0111] [General Formula 2] Total mass loss (TML, unit: %) = (A - B) / (A - C) × 100

[0112] Table 1 below summarizes the results of the said experimental examples.

[0113]

Table 1

Claims

1. A film comprising a substrate and an activation layer containing an initiator component on the surface of the substrate, contacting a layer of a curable composition containing a curable syrup, a filler component, and an initiator component with the initiator component of the film to carry out a curing reaction, wherein the initiator component is an inert redox initiator system containing an oxidizing agent and a reducing agent, the reducing agent contains a metal compound, and the metal compound is contained in an effective amount in either the activation layer of the film or the layer of the curable composition.

2. The film according to claim 1, wherein the substrate includes a polymer, plastic, metal, wood, leather, or concrete.

3. The film according to claim 1, wherein the curable composition contains the filler component in an amount of 200 parts by weight or more based on 100 parts by weight of the curable syrup.

4. The film according to claim 1, wherein the filler component includes two or more fillers having different average particle sizes and satisfies the following general formula 1. [General formula 1] 5 ≤ D ５０Ａ / D ５０Ｃ ≤ 100 In the general formula 1, D ５０Ａ is the maximum average particle size in the filler component, and D ５０Ｃ is the minimum average particle size in the filler component.

5. The film according to claim 1, wherein the filler component includes three fillers having different average particle sizes from each other.

6. The film according to claim 1, wherein the filler component includes a first filler having an average particle size exceeding 40 μm and not exceeding 200 μm, a second filler having an average particle size exceeding 5 μm and not exceeding 40 μm, and a third filler having an average particle size in the range of 0.2 μm to 5 μm.

7. The filler component, as a filler, is fumed silica, clay, calcium carbonate (CaCO ３ ), aluminum oxide (Al ２ O ３ ), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ３ N ４ ), silicon carbide (SiC), beryllium oxide (BeO), zinc oxide (ZnO), aluminum hydroxide (Al(OH) ３ ), boehmite, magnesium oxide (MgO), magnesium hydroxide (Mg(OH) ２ ), or a carbon filler, and the film according to claim 1.

8. The film according to claim 1, wherein the curable composition contains the reducing agent in the range of 0.05 to 6 parts by weight based on 100 parts by weight of the curable syrup.

9. The film according to claim 1, wherein the metal compound is a salt, chelate, or hydrate thereof containing metal ions, and the metal ions are selected from cobalt, iron, vanadium, copper, manganese, nickel, titanium, aluminum, tin, chromium, zinc, zirconium, indium, manganese, and mixtures thereof.

10. The film according to claim 1, wherein the reducing agent further includes at least one organic compound selected from the group consisting of amines, pyridines, aldehyde-amine condensation compounds, thioureas, and derivatives thereof.

11. The film according to claim 10, wherein the organic compound is contained in the range of 5 to 50 parts by weight based on 100 parts by weight of the metal compound.

12. The film according to claim 1, wherein the oxidizing agent includes a peroxide, a peroxyester, a diacyl peroxide, or a persulfate.

13. The film according to claim 1, wherein the oxidizing agent is included in a range of 30 to 100 parts by weight with respect to 100 parts by weight of the reducing agent.

14. The film according to claim 1, wherein the curable composition includes the curable syrup at 6 to 20% by weight.

15. The film according to claim 1, wherein the curable syrup includes an alkyl (meth) acrylate unit, a polar functional group-containing monomer unit, and a crosslinking agent.

16. The film according to claim 15, wherein the polar functional group includes a hydroxy group, an epoxy group, an isocyanate group, a glycidyl group, an alkenyloxycarbonyl group, a (meth) acryloyl group, or an alkenyloxyalkyl group.

17. The film according to claim 15, wherein the curable syrup includes the alkyl (meth) acrylate unit at 1 to 12% by weight.

18. The film according to claim 15, wherein the curable syrup includes the polar functional group-containing monomer unit in an amount of 500 parts by weight or more with respect to 100 parts by weight of the alkyl (meth) acrylate unit.

19. The film according to claim 15, wherein the curable syrup includes a hydroxy group-containing monomer unit and an epoxy group-containing monomer unit as the polar functional group-containing monomer unit.

20. The film according to claim 15, wherein the crosslinking agent includes a polyfunctional acrylate compound, a polyfunctional isocyanate compound, or a urethane acrylate compound.

21. The film according to claim 1, wherein the curable composition is solvent-free.

22. The film according to claim 1, wherein the curable composition has a viscosity in the range of 10,000 cps to 30,000 cps as measured at a temperature of 25°C and a shear rate of 1 rpm.

23. A method for producing a cured product, comprising the step of bringing a layer of the curable composition including the curable syrup, the filler component, and the initiator component into contact with a layer of the initiator component of the film according to any one of claims 1 to 22.

24. The method for producing a cured product according to claim 23, comprising the step of bringing the layer of the initiator component of the film including the layer of the initiator component into contact with both sides of the layer of the curable composition.

25. The method for producing a cured product according to claim 23, wherein a curing reaction is carried out at room temperature through the step of bringing them into contact.

26. The method for producing a cured product according to claim 25, wherein the curing reaction is carried out by a redox polymerization reaction between the initiator component of the curable composition and the initiator component present in the activation layer of the film.

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