Method for producing a film and a cured product using the same

Abstract

The present invention relates to a film and a method for manufacturing a cured product using the film. Specifically, it relates to a film that can be used in a non-active redox initiator system and a method for manufacturing a cured product using the same. As a specific example, the film according to the present invention includes an auxiliary substrate having magnetism and an activation layer containing an initiator component on the surface of the auxiliary substrate. When 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, a curing reaction is carried out. The initiator component is a non-active redox initiator system containing an oxidizing agent and a reducing agent. The reducing agent contains a metal compound, and the metal compound can be contained in an effective amount in only one of the activation layer of the film and the layer of the curable composition.

Description

Technical Field

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

Background Art

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

[0003] However, depending on the need, after the composition required for the formation of the cured product is applied to a specific device, the curing process may be performed. At this time, since the device to which the curable composition is applied is affected by high temperature or UV irradiation, problems such as a decrease in the physical properties of the device may occur. Thus, in the process of forming a cured product, there may be cases where it is difficult to apply a high temperature or UV process.

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

[0005] In order to solve the above problems, it is also possible to consider a method of forming a cured product by minimizing the use of a solvent. However, it is a difficult task to embody 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 manufactured without applying a separate high temperature or UV process through a method for manufacturing a film and a cured product using the same that can be used in an inactive redox initiator system. The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned should 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 can 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 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] As used herein, the term "normal temperature" or "room temperature" means the natural temperature without artificial heating or cooling, and can indicate any one 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 otherwise clearly stated in the context. Terms such as "including" or "having" in this application are intended to specify the presence of the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and it should be understood that they do not preclude the presence or addition possibility of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

[0010] Unless otherwise defined, all terms used herein, including technical and 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 that are the same as those defined 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 in an ideal or overly formal sense 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 inactive redox system that forms a kit together with a layer of a curable composition, and the inactive redox system is premised on an inactive 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 utilizes an inactive redox initiator system. As used herein, the "inactive redox initiator system" is 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 can include an auxiliary substrate having magnetism and an activation layer containing an initiator component on the surface of the substrate. Here, the auxiliary substrate is a magnetic layer containing magnetic particles, and the present application enables a process by magnetic force by including the magnetic layer. Specifically, with sufficient magnetic force, the film according to the present application can be fixed, and further, by additionally arranging a magnet on one side of the film, the initiator components in the activation layer and the layer of the curable composition can be sufficiently diffused, and not only the surface in contact with the activation layer and the curable composition is partially cured, but the entire opposite surface that is not in contact can also be uniformly cured throughout.

[0013] As long as the auxiliary substrate contains magnetic particles, its material is not particularly limited. As an example, it can include one or more selected from the group consisting of iron, nickel, chromium, aluminum, zinc, silicone, and combinations thereof.

[0014] In one example, the film may additionally include a base material. If the base material is included, it may have a structure in which the base material, the auxiliary base material, and the activation layer are laminated in this order. The base material, unlike the auxiliary base material, may not contain magnetic particles and can be used without limitation as long as an activation layer containing an initiator component can be disposed on the surface of the auxiliary base material. As an example, it can include polymers, plastics, metals, wood, leather, or concrete, etc. Examples of the polymer base material include, but are not limited to, cellulose acylate-based polymers, cycloolefin polymers, polycarbonate-based polymers, acrylate-based polymers, polyester-based polymers, polyimide-based polymers, etc. Examples of the plastic base material include, but are not limited to, polyethylene terephthalate (PET), polyethersulfone (PES), polycarbonate (PC), polyarylate (Par), cyclic olefin copolymer (COC), etc. Examples of the metal base material include, but are not limited to, aluminum, copper, silver, iron, zinc, nickel, titanium, and gold, etc.

[0015] When the film brings 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 in the film, a curing reaction can be carried out. Thus, the film according to the present invention has excellent storage stability. Just by bringing the film into contact with a layer of the curable composition, a curing reaction is carried out, and it is not the case that only the surface of the film in contact with the curable composition is partially cured. Since there is almost no difference in the degree of curing in the thickness direction of the film, a cured product that can be uniformly cured throughout can be provided.

[0016] On the one hand, in this specification, the "curable syrup" means units that form polymers in the final cured product through curing or crosslinking, and can include oligomers or polymer components formed by the polymerization of two or more monomers and monomer components. As an example, the curable syrup can include monomers, (partial) polymers, and crosslinking agents. However, depending on the intended composition, when the monomer composition is partially polymerized to the (partial) polymer, some monomers can be polymerized to form oligomers or polymers, and the remaining monomers can remain and constitute the curable syrup components.

[0017] Therefore, the term "monomer unit" such as (meth)acrylate unit described later in this specification can mean monomers existing in a state of forming the oligomers or polymers in the curable syrup or monomers that are not polymerized and are contained in the curable syrup. Therefore, when calculating the content of the curable syrup in this specification, it means not only the components existing in the monomer state without participating in the polymerization in the syrup components, but also all the components participating in the polymerization.

[0018] Also, as described later, the oxidizing agent and reducing agent, which are initiator components, are merely for generating radicals to initiate polymerization and are not introduced for the purpose of forming units of polymers in the final cured product. Therefore, they are distinguished from the curable syrup. However, a part of the initiator components may exist in combination with the polymers in the final cured product.

[0019] Also, in this specification, the initiator component means a redox initiator and can include an oxidizing agent and a reducing agent. In this specification, the oxidizing agent and reducing agent mean components that participate in or assist in generating radicals that participate in or assist in the oxidation-reduction reaction to induce polymerization under the redox initiator system.

[0020] The curable composition in the present invention includes a curable syrup containing monomer units, a crosslinking agent and / or a (partial) polymer, a filler component, and an initiator including 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. Although not limited thereto, the present application can utilize the following compositions.

[0021] 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 the filler.

[0022] In one exemplary case, the filler component can include two or more fillers having different average particle sizes from each other. In one exemplary case, the filler component may include three or more fillers having different average particle sizes from each other, and may consist 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 exemplary case, the filler component may include only three to six, three to five, three to four, or three fillers having different average particle sizes from each other.

[0023] In another exemplary case, 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 exemplary case, the filler component may exhibit three or more peaks in the volume curve of the particle size distribution, and may exhibit three to six, three to five, three to four, or three peaks. For example, in the range of filler components showing three peaks, filler components showing one, two, or four or more peaks are not included.

[0024] The average particle size of the filler of this application means the particle diameter at which the volume cumulative value is 50% in the volume curve of the particle size distribution measured by the laser diffraction method, which may also be called 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 diameter at the point where the cumulative value is 50% in the cumulative curve with the total volume being 100% is taken as the average particle size. Such an average particle size can, in other examples, be called the median particle size or D 50 particle diameter.

[0025] Therefore, the two fillers having different average particle sizes as described above can be meant to be fillers with different particle diameters at the point where the cumulative value is 50% in the volume curve of the particle size distribution.

[0026] Generally, when mixing two or more 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 only for the types of fillers mixed appear. Therefore, for example, when three 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.

[0027] The filler component may be a thermally conductive filler component. The term "thermally conductive filler component" means a filler component that functions to exhibit the thermal conductivity described later when the curable composition is cured.

[0028] As an example, the curable composition of the present application can contain a filler component in an amount of 200 parts by weight or more based on 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 based on 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.

[0029] That is, according to the present application, the curable composition contains a relatively excessive amount of the filler component, and by adjusting the particle size and / or ratio of the filler contained in the filler component, the packaging density is increased to exhibit 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 a cured product with the desired physical properties can be provided.

[0030] The filler component contained in the curable composition of the present application can satisfy the following general formula 1.

[0031] [General formula 1]

[0032] 5 ≤ D 50A / D 50C ≤ 100

[0033] 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.

[0034] As described above, the maximum average particle size (D 50A) can mean the average particle size of the filler with the largest 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 maximum average particle size (D 50A ) of the filler component can mean the particle size of the peak represented by the largest particle size among the peaks appearing in the volume curve of the particle size distribution measured using the laser diffraction method for the filler component.

[0035] In the above, the minimum average particle size (D 50C ) of the filler component can mean 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 flat particle sizes from each other. Or, in another example, the minimum average particle size (D 50C ) of the filler component can mean the particle size of the peak represented by the smallest particle size among the peaks appearing in the volume curve of the particle size distribution measured using the laser diffraction method for the filler component.

[0036] The D 50A / D 50C value in the general formula 1 may be additionally 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 about 44 or less in another example.

[0037] As an example, the filler component of the curable composition of the present application can 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 be cured and exhibit a thermal conductivity above a certain level. However, according to the present application, it is very effective in achieving 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 included, a problem may occur in 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.

[0038] In one specific example, the filler component can 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 can 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 can be the filler having the largest average particle size among the fillers included in the filler component, and the third filler can be the filler having the smallest average particle size among the fillers included in the filler component. Therefore, in this case, the average particle size of the first filler can be the maximum average particle size (D 50A ) of the general formula 1, and the average particle size of the third filler can be the minimum average particle size (D 50C ) of the general formula 1.

[0039] In another specific example, the volume curve of the particle size distribution measured using the laser diffraction method for the filler component shows a first peak where the particle size exceeds 40 μm and appears within 200 μm or less, a second peak where the particle size exceeds 5 μm and appears within the range of 40 μm or less, and a third peak where the particle size is within the 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 can show only the three types of peaks. Further, when including at least the three types of peaks, the first peak is the peak that appears at the largest particle size among the peaks shown by the volume curve, and the third peak may be the peak that appears at the lowest particle size among the peaks shown by the volume curve. Therefore, in this case, the particle size indicated by the first peak is the maximum average particle size (D 50A ) of the general formula 1, and the particle size indicated by the third peak can be the minimum average particle size (D 50C ) of the general formula 1.

[0040] The average particle size of the first filler or the particle size indicated by the first peak can be additionally adjusted in another example within the 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 the 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.

[0041] Further, in other examples, the average particle size of the second filler or the particle size indicated by the second peak can be additionally 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.

[0042] Further, in other examples, the average particle size of the third filler or the particle size indicated by the third peak can be additionally 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 2.4 μm or less, about 2.5 μm or less, about 2 μm or less or about 1.7 μm or less.

[0043] When the filler component contains three types 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 in the 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, and may be 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.

[0044] 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.

[0045] In one example, the curable composition can contain a filler component in an amount of 200 parts by weight or more per 100 parts by weight of the curable syrup. In other examples, the filler component can 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 per 100 parts by weight of the curable syrup. The upper limit of the filler component is not greatly restricted, 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 per 100 parts by weight of the curable syrup.

[0046] On the other hand, when the first to third fillers are contained in the filler component, about 10 to 90 parts by weight of the second filler and about 60 to 140 parts by weight of the third filler can be contained per 100 parts by weight of the first filler. In other examples, the ratio of the second filler to 100 parts by weight of the first 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, and may be 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. In other examples, the ratio 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, and may be 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.

[0047] As an example, the content of the first filler may be about 10 to about 60 parts by weight per 100 parts by weight of the total filler component, the content of the second filler may be about 1 to about 40 parts by weight per 100 parts by weight of the total filler component, and the content of the third filler may be about 10 to about 60 parts by weight per 100 parts by weight of the total filler.

[0048] In one example, the filler component can contain 30 wt% or more of spherical fillers. Generally, when the form of the filler is spherical, it is disadvantageous for achieving a higher thermal conductivity. That is, in terms of thermal conductivity, it is advantageous to use non-spherical fillers. However, when the filler is non-spherical, it is disadvantageous in terms of the hardness of the solid. Therefore, by including spherical fillers at a certain level or above 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 with the content of spherical fillers as described above. In other examples, the content of spherical fillers in the filler component may be 35 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 55 wt% or more, or 57 wt% or more. The upper limit of the content of the spherical fillers in the filler component can be adjusted within the range of 95 wt% or less, 90 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, or 65 wt% or less, considering the thermal conductivity and the hardness characteristics of the solid.

[0049] For example, when there are non-spherical fillers 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 can be selected as the third filler.

[0050] 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.

[0051] 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 shown as the ratio of the boundary of a circle having the same area (A) as the boundary (P) of the image obtained from the two-dimensional image of the actual particle, and is obtained by the following formula.

[0052] <Circularity formula>

[0053] Circularity = 4πA / P 2

[0054] The circularity is indicated by a value from 0 to 1. A perfect circle has a value of 1, and the more irregular the particle shape, the lower the value will be compared to 1.

[0055] As an example, the filler component may be a heat-conductive filler component. As described above, the term "heat-conductive filler" is 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 can 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 exemplary cases, 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 type of such material is not particularly limited, and examples can 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.

[0056] In addition to the heat conductive filler as described above, the filler component can include various types of fillers when 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) can be applied.

[0057] In one example, the moisture content (water content) of the filler component may be about 1,000 ppm or less. The moisture content can be measured with a Karl Fischer titrator (KR831) under the conditions of a relative humidity of 10% and a drift of 5.0 or less. At this time, the moisture content may be the average moisture content with respect to the total filler component 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 moisture content range by a method such as drying the filler component to be used in an oven at a temperature of about 200°C. In 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.

[0058] Also, in a specific example of the present invention, the curable composition can contain a reducing agent in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the curable syrup. Although not limited thereto, as an example, the lower limit of the reducing agent content may be 0.1 part by weight or more, 0.5 part by weight or more, 1 part by weight or more, 1.5 part by weight or more, 2 part by weight or more, 2.5 part by weight or more, 3 part by weight or more, 3.5 part by weight or more, 4 part by weight or more, 4.5 part by weight or more, 5 part by weight or more, 5.5 part by weight or more, or 6.2 part by weight or more, and the upper limit may be 9.5 part by weight or less, 9 part by weight or less, 8.5 part by weight or less, 8 part by weight or less, 7.5 part by weight or less, 7 part by weight or less, 6.7 part by weight or less, 6.5 part by weight or less, or 6.3 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 the desired physical properties.

[0059] In one example, the reducing agent can include a metal compound. According to the present invention, the metal compound is not greatly limited as long as the layer of the curable composition and the layer of the initiator component directly contact each other without separate heat or UV irradiation to induce or promote a redox reaction so that the composition containing the reducing agent can be stably stored. In particular, those having excellent solubility, compatibility, dispersion rate, and reactivity with the curable syrup are preferable.

[0060] The metal compound can be contained in an effective amount in only one of the layer of the initiator component and the layer of the curable composition of the film. 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 only one of the layer of the initiator component and the layer of the curable composition, and may not be substantially contained in the other one. As an example, when the metal compound is contained in an effective amount in the layer of the initiator component, 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 an effective amount in the layer of the curable composition, 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 at 0% by weight, and even if it is said that the metal compound is contained in the layer of the curable composition, it may be contained at 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less, and is contained in a trace amount rather than an effective amount capable of inducing a redox reaction.

[0061] Further, in the layer containing the metal compound in an effective amount among the layer of the initiator component of the film and the layer of the curable composition, the layer 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. In other words, when the metal compound is contained in an effective amount in the layer of the initiator component of the film, the oxidizing agent is not contained in an effective amount in the layer of the initiator component of the film, but may be contained in an effective amount in the layer of the curable composition. As another example, when the metal compound is contained in an effective amount in the layer of the curable composition, the oxidizing agent is not contained in an effective amount in the layer of the curable composition, but may be contained in an effective amount in the layer of the initiator component of the film.

[0062] 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 one or more of them can be included. Here, the metal ions may be one or more 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 can 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 can 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 still another example, the metal compound may be a vanadium-containing component, and in the vanadium-containing component, vanadium can 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(V) pentoxide or vanadyl sulfate(V). As still another example, the metal compound may be a copper-containing component, and in the copper-containing component, copper can 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. In addition, examples of the metal compound include manganese naphthenate, nickel naphthenate, titanium acetylacetonate, copper sulfate, manganese sulfate or nickel sulfate.

[0063] Further, the reducing agent can contain an organic compound, but the organic compound is not greatly limited as long as it can induce or promote a redox reaction by directly contacting the layer of the curable composition and the layer of the initiator component without separate heat or UV irradiation.

[0064] The organic compound may be substantially included together in the layer containing the oxidizing agent among the layer of the initiator component and the layer of the curable composition of the film, or may be substantially included together in the layer containing the metal compound, but can be selectively and substantially included only in any one of the layer containing the oxidizing agent and the layer containing the metal compound.

[0065] As an example, the organic compound may be at least one of the group consisting of amines, pyridine, aldehyde amine condensation compounds, thiourea, and their derivatives, or may be two or more. Specifically, although not limited thereto, as an example of the organic compound, 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. may be mentioned, and preferably, a tertiary amine series organic compound can be used. In particular, as the organic compound, a compound that is liquid and at the same time has a half-life within the range of 70 to 170 °C or within the range of 80 to 150 °C is preferable. The present invention can suppress the self-reaction in the storage state and maintain the viscosity of the composition containing the organic compound at the level targeted in the present invention by using an organic compound whose half-life temperature satisfies the above range. In this specification, the half-life is an index indicating the decomposition rate of the compound and means the time until the remaining amount of the compound becomes half.

[0066] In one example, when both a metal compound and an organic compound are included as reducing agents, the organic compound can be included in the range of 1 to 30 parts by weight with respect to 100 parts by weight of the metal compound. As an example, the lower limit thereof may be 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more, 5 parts by weight or more, 5.5 parts by weight or more, 6 parts by weight or more, 6.5 parts by weight or more, 7 parts by weight or more, 7.5 parts by weight or more, 8 parts by weight or more, 8.5 parts by weight or more, 9 parts by weight or more, 9.5 parts by weight or more, or 10 parts by weight or more, and the upper limit thereof may be 30 parts by weight or less, 27 parts by weight or less, 25 parts by weight or less, 23 parts by weight or less, 20 parts by weight or less, 17 parts by weight or less, 15 parts by weight or less, 13 parts by weight or less, or 12 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.

[0067] Also, in one example, the curable composition can include an oxidizing agent. The oxidizing agent is not greatly limited as long as it participates in an oxidation-reduction reaction and generates radicals that induce polymerization. In particular, those having excellent compatibility with the curable syrup are preferred. As an example, although not limited thereto, the oxidizing agent can include peroxides, peroxy esters, diacyl peroxides, or persulfates. Specifically, as the oxidizing agent, 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 can be used.

[0068] In one example, the oxidizing agent can be included in the range of 5 to 70 parts by weight with respect to 100 parts by weight of the reducing agent. As an example, the lower limit thereof can be 7 parts by weight or more, 10 parts by weight or more, 13 parts by weight or more, 15 parts by weight or more, 17 parts by weight or more, 20 parts by weight or more, 23 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more, and the upper limit thereof can be 65 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, 53 parts by weight or less, 50 parts by weight or less, 47 parts by weight or less, 45 parts by weight or less, 43 parts by weight or less, 40 parts by weight or less, 37 parts by weight or less, or 35 parts by weight or less.

[0069] 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 can contain a curable syrup together with a large amount of filler components. Therefore, as described later, the present application can utilize a curable syrup of a specific component in combination with a large amount of filler components, and thus can have excellent properties not only in terms of compatibility but also in terms of blendability between the large amount of filler components and the curable syrup.

[0070] The curable composition can contain the curable syrup in an amount of 3 to 20% by weight, although it is not limited thereto. As an example, the lower limit of the curable syrup can be 4% by weight or more, 5% by weight or more, 6% by weight or more, 7% by weight or more, 8% by weight or more, 9% by weight or more, or 10% by weight or more, and the upper limit thereof can 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.

[0071] In one example, the curable syrup can contain alkyl (meth)acrylate units, polar functional group-containing monomer units, 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 can be contained in the curable syrup at about 1 to 12% by weight. The upper limit of the ratio may, in other examples, be 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, 5.2% by weight or more, 5.5% by weight or more, or 5.7% by weight or more, and the lower limit thereof 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.

[0072] 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.

[0073] The curable syrup can contain, as an additional component, polar functional group-containing monomer units. The curable syrup can contain, as polar functional group-containing monomer units, but is not limited to, hydroxy group-containing monomer units, carboxyl group-containing monomer units, or epoxy group-containing monomer units.

[0074] Examples of the monomer 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 (wherein the alkyl group may have 1 to 20, 1 to 16, 1 to 12, 1 to 8 or 1 to 4 carbon atoms, 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, etc. may be used, but are not limited thereto.

[0075] In one specific example 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 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, or 1,400 parts by weight or more, and the upper limit may be 3,000 parts by weight or less, 2,500 parts by weight or less, 2,000 parts by weight or less, 1,700 parts by weight or less, 1,650 parts by weight or less, 1,600 parts by weight or less, 1,550 parts by weight or less, or 1,500 parts by weight or less.

[0076] In addition, the curable syrup of the present invention may optionally contain additional monomer units other than those described above.

[0077] For example, the curable syrup can additionally contain nitrogen-containing reactive monomer units. Examples of such nitrogen-containing reactive monomers include, but are not limited to, 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. Suitable monomers can include, for example, (meth)acrylamide, N-alkyl(meth)acrylamide, and / or N,N-dialkyl(meth)acrylamide. Examples of the alkyl group described above can 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.

[0078] The curable composition according to an example of the present application can additionally contain a crosslinking agent as needed. The crosslinking agent can form a cured product having appropriate adhesive strength and hardness by embodying a structure and a crosslinked structure contained in the curable syrup.

[0079] The crosslinking agent can be, 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, but is not limited thereto. Also, one or more crosslinking agents can be used. The urethane acrylate crosslinking agent is a compound having a large number of urethane bonds (-NHCOO-) in the branched chain and an acrylic group capable of reacting with ultraviolet rays at the molecular terminal, and commercially available products such as PU330 (Miyakoshi Shoji), PU256 (Miyakoshi Shoji), PU610 (Miyakoshi Shoji), and PU340 (Miyakoshi Shoji) can be used. The aliphatic isocyanate crosslinking agent can be, for example, an isocyanate compound such as isophorone diisocyanate or methylene dicyclohexyl diisocyanate or cyclohexane diisocyanate, or derivatives such as its dimer or trimer. The epoxy crosslinking agent can be, for example, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidyl ethylenediamine, or glycerin diglycidyl ether. The aziridine crosslinking agent can be, for example, N,N-toluene-2,4-bis(1-aziridine carboxylate), N,N-diphenylmethane-4,4'-bis(1-aziridine carboxylate), triethylenemelamine, bisisopropyltaloyl-1-(2-methylaziridine), or tri-1-aziridinylphosphine oxide. The metal chelate crosslinking agent can be, 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 to acetylacetone or ethyl acetoacetate, etc.

[0080] The method for manufacturing the curable syrup containing the units as described above is not particularly limited. For example, for the embodiment of the syrup component described above, after mixing the monomers at the target ratio, this can be appropriately partially polymerized to form the curable syrup.

[0081] According to the present invention, by simply 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, the curable composition can be cured to produce a cured product having the physical properties targeted 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 the targeted hardness and physical properties can be provided without separately irradiating heat or UV. However, if necessary, a step of additionally irradiating heat or UV may be added. 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.

[0082] The cured product of the present invention can be produced by layers having different components coming into contact and the metal compound diffusing into the layer where the metal compound comes into contact to induce a redox reaction. At this time, if the curing reaction proceeds too fast, the metal compound and the like may not diffuse sufficiently and the crosslinking reaction between the curable syrups may hardly occur, so 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 manufacturing method to an appropriate level by having the composition as described above.

[0083] The curable composition in the present invention may be a solvent-free composition. Here, the solvent-free 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 wt% or less, 0.5 wt% or less, or 0.1 wt% or less, and may substantially be 0 wt%. That is, the curable composition of the present invention is embodied to have the composition as described above, so that it is solvent-free and has physical properties equivalent to or better than those of the solvent type, and at the same time can be compatible with the non-active redox system.

[0084] In addition, the curable composition of the present invention 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 with a Brookfield HB type viscometer.

[0085] The cured product according to this application may be thermally conductive. Specifically, the cured product may have a thermal conductivity of 0.1 W / mk or more. Without being 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, according to the ASTM D5470 standard or the ISO 22007-2 standard. By exhibiting the above thermal conductivity, the cured product according to this application is useful in various applications and can be particularly effective in releasing heat generated inside the battery module to the outside.

[0086] Also, in another specific example of this application, a method for manufacturing a cured product can be provided. The method for manufacturing the cured product may include providing a film containing a layer of an initiator component on the surface of an auxiliary substrate having magnetism; and contacting a layer of a curable composition containing a curable syrup, a filler component, and an initiator component with the layer of the initiator component of the film having the layer of the initiator component on its surface.

[0087] For each configuration, the same applies as described above. The initiator component is an inactive redox initiator system containing an oxidizing agent and a reducing agent, the reducing agent contains a metal compound, and the metal compound can be contained in an effective amount in only one of the layer of the initiator component on the film and the layer of the curable composition.

[0088] The method of bringing the layer of the curable composition into contact with the layer of the initiator component of the film including the layer of the initiator component on the surface is not greatly restricted. As an example, the curable composition may be directly applied on the film, or may be laminated after being applied on an arbitrary substrate. Further, when bringing the layer of the initiator component of the film including 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 including 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.

Advantages of the Invention

[0089] According to an embodiment of the present invention, a one-component curing method is used instead of a two-component curing method in which the main agent and the curing agent are separately mixed and then applied. By using the one-component curing method, a film used for producing a cured product having excellent storage stability and capable of curing even under room temperature and dark reaction conditions without separate UV or heat, and a method for producing a cured product using the film are provided.

Modes for Carrying Out the Invention

[0090] Hereinafter, preferred experimental examples (examples) are presented to assist in the understanding of the present invention. However, the following experimental examples are only for assisting in the understanding of the present invention, and the present invention is not limited by the following experimental examples.

[0091] Production of Radical Polymer (P)

[0092] 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). After adding a solution obtained by diluting Irgacure 184, which is a photoinitiator, and ethyl acetate (EAC) at a ratio of 1:1 at about 0.1% by weight based on the total weight of the compounds added to the flask, nitrogen gas was introduced under normal pressure conditions and the temperature was raised to about 60°C. While stirring, a metal halide lamp was irradiated, and at the moment when the temperature reached 68°C, the introduction of nitrogen gas and the irradiation of the lamp were interrupted to obtain a radical polymer (P) (solid content: about 12%).

[0093] At this time, the viscosity of the produced radical polymer (P) measured with Brookfield's DV-3 using a No. 63 spindle at a temperature of 25°C and a torque of 31.6% was about 11,110 cps, the weight average molecular weight (Mw) was about 2,192,000 g / mol, and the polydispersity index (PDI) was about 3.08.

[0094] Production Example 1: Production of a curable composition

[0095] As a curable syrup, the radical polymer (P) produced above, 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), the polyfunctional aliphatic urethane acrylate (SUO-1020 of SHIN-A T&C Co., Ltd.) which is a crosslinking agent (H), the phosphorus-based flame retardant (FR-119L of CHEMPIA Co., Ltd.) which is a flame retardant (N), the modified polyester dispersant (Disperbyk-111 of BYK Co., Ltd.) which is a dispersant (D), the filler component (F), methyl ethyl ketone peroxide (MEKP, Methyl ethyl ketone peroxide) which is an oxidizing agent (O), and N,N-dimethyl p-toluidine (DMPT, Dimethyl p-toluidine) which is an organic compound (A) were used and added to a paste mixer at a weight ratio of about 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) and stirred well. A curable composition having a viscosity of about 200,000 cps measured with a DV-3 of Brookfield at a temperature of 25 °C and a shear rate of 1 rpm at room temperature was produced.

[0096] The filler composition (F) used was a mixture of spherical alumina (BAK-70 of Bestrytech Co., Ltd. with an average particle size of about 70 μm and a sphericity of 0.95 or more), aluminum hydroxide (DH-50P of Korea Alumina Co., Ltd. with an average particle size of about 20 μm and a sphericity of 0.95 or more), and angular alumina (KLS-51 of Korea Alumina Co., Ltd. with an average particle size of about 1.6 μm and a sphericity of less than 0.9) at a weight ratio of about 34.42:17.21:34.42.

[0097] Production Example 2: Production of Curable Composition

[0098] As a curable syrup, the radical polymer (P) produced above, 2-hydroxyethyl acrylate (HEA), glycidyl methacrylate (GMA), and a polyfunctional aliphatic urethane acrylate (SUO-1020 of SHIN-A T&C) as a crosslinking agent (H) were used, a phosphorus-based flame retardant (FR-119L of CHEMPIA) as a flame retardant (N), a modified polyester dispersant (Disperbyk-111 of 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) were used, and they were added to a paste mixer at a weight ratio of about 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.

[0099] The filler composition (F) used was a mixture of spherical alumina (BAK-70 of Bestrytech, average particle size of about 70 μm, sphericity of 0.95 or more), aluminum hydroxide (DH-50P of Korea Alumina Co., average particle size of about 20 μm, sphericity of 0.95 or more), and angular alumina (KLS-51 of Korea Alumina Co., average particle size of about 1.6 μm, sphericity of less than 0.9) at a weight ratio of about 36.82:18.41:36.82.

[0100] Example 1

[0101] A metal compound solution was prepared by diluting iron(III) acetylacetonate as a metal compound (M) in toluene so that it was 15% by weight.

[0102] Thereafter, using the curable composition according to Production Example 1, the metal compound solution was applied onto an iron mesh so that the weight ratio of the oxidizing agent, organic compound, and metal compound was about 0.23:0.07:0.64 (O:A:M). After drying at about 25°C for 5 minutes, it was further dried on a hot plate at 100°C for 5 minutes. Thereafter, the iron mesh coated with the metal compound was placed on an aluminum foil.

[0103] The curable composition produced as described above was applied so as to be in contact with the iron mesh having the metal compound applied to its surface and placed on the aluminum foil. At this time, the curable composition was applied to have a thickness of 2T. Thereafter, a PET film was placed on the surface of the curable composition that was not in contact with the aluminum foil.

[0104] Example 2

[0105] A magnet was additionally placed on the PET film, and the iron mesh was moved in the direction of the magnet.

[0106] Comparative Example 1

[0107] A metal compound solution was prepared by diluting toluene with iron(III) acetylacetonate, which is a metal compound (M), to a concentration of 15% by weight. The metal compound solution was mixed with the curable composition produced as described above so that the weight ratio of the oxidizing agent, organic compound, and metal compound was about 0.23:0.07:0.64 (O:A:M), and the mixture was stirred well.

[0108] The mixture was applied onto the aluminum foil to have a thickness of 2T, and a PET film was placed on top.

[0109] Comparative Example 2

[0110] It was produced in the same manner as in Example 1, except that the curable composition according to Production Example 2 was used.

[0111] In this case, the compatibility between the curable syrup and the filler component decreased, resulting in a phenomenon where they were not properly blended and the mixture crumbled.

[0112] Experimental Example 1: Hardness

[0113] The PET film attached to the cured products manufactured through the examples and comparative examples was removed, and a durometer shore A hardness meter was used to measure the surface of the cured product from which the PET film had been removed at a temperature of approximately 25°C. The hardness value indicated the average value after 3-point measurement.

[0114] Experimental Example 2: Total Mass Loss (TML)

[0115] The total mass loss was evaluated in the following manner. The PET film attached to the cured products manufactured through the examples and comparative examples was removed, and samples with a thickness of approximately 2T were prepared by cutting to fit an aluminum dish with a diameter of approximately 5 cm, and the weight of the samples (A, unit: g) was measured. Subsequently, immediately after leaving the samples at 150°C for 45 minutes, the weight of the samples (B, unit: g) was measured, and the TML was calculated according to the following General Formula 2. Here, C is the weight of aluminum attached to the cured product (unit: g).

[0116] [General Formula 2]

[0117] Total Mass Loss (TML, unit: %) = (A - B) / (A - C) × 100

[0118] Table 1 below summarizes the results of the above experimental examples.

[0119] In particular, the required time in Table 1 indicates the time required to reach the corresponding hardness.

[0120]

Table 1

[0121] Although the invention has been described with reference to the embodiments, those skilled in the art should understand that the present invention can be variously modified and changed without departing from the spirit and scope of the present invention described in the following claims.

Claims

1. A film comprising an auxiliary substrate having magnetism and an activation layer containing an initiator component on the surface of the auxiliary substrate, wherein when 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, a curing reaction is carried out, the initiator component is a non-active 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 only one of the activation layer of the film and the layer of the curable composition.

2. The film according to claim 1, further comprising a substrate, wherein the substrate comprises 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 contains two or more kinds of fillers having different average particle diameters and satisfies the following general formula 1: 【General formula 1】

5. 5 ≤ D ５０Ａ / D ５０Ｃ ≤ 100 In the general formula 1, D ５０Ａ is the maximum average particle diameter of the filler in the filler component, and D ５０Ｃ is the minimum average particle diameter of the filler in the filler component. The film according to claim 1, wherein the filler component contains three kinds of fillers having different average particle diameters from each other.

6. The film according to claim 1, wherein the filler component comprises a first filler having an average particle diameter in the range of 60 μm to 200 μm; a second filler having an average particle diameter exceeding 5 μm and being 40 μm or less; and a third filler having an average particle diameter in the range of 0.2 μm to 5 μm.

7.

8. The filler component includes, as a filler, 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. The film according to claim 1 The film according to claim 1, wherein the curable composition contains the reducing agent in the range of 0.05 to 10 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 additionally contains 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 1 to 30 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 5 to 70 parts by weight based on 100 parts by weight of the reducing agent.

14. The film according to claim 1, wherein the curable composition includes the curable syrup in an amount of 3 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 an alkyl (meth)acrylate unit in an amount of 1 to 12% by weight.

18. The film according to claim 15, wherein the curable syrup includes a polar functional group-containing monomer unit in an amount of 500 parts by weight or more based on 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 units.

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 curing reaction is carried out at room temperature.

22. The film according to claim 21, wherein the curing reaction is carried out by a redox polymerization reaction of an initiator component in the curable composition and an initiator component present in the activation layer of the film.

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

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

25. The film according to claim 1, wherein the cured product obtained by the curing reaction has thermal conductivity.

26. Providing a film according to any one of claims 1 to 25, comprising a layer of an initiator component on the surface of an auxiliary substrate having magnetism; and A step of bringing a layer of a curable composition containing a curable syrup, a filler component, and an initiator component into contact with an initiator component layer of a film containing an initiator component layer on a surface, The initiator component is an inactive 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 only in one of the initiator component layer on the film and the curable composition layer. A method for producing a cured product.

27. The method for producing a cured product according to claim 26, including a step of bringing the initiator component layer of the film containing the initiator component layer on the surface into contact with both surfaces of the curable composition layer.

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