Method for producing cured product and cured product produced thereby

Abstract

Methods for producing cured products using an inert redox initiator system, and the cured products produced thereby, are provided. Specifically, the method for producing a cured product according to the present invention comprises a step of bringing a layer of a curable composition comprising a curable slurry and an initiator component into contact with a layer of the initiator component of a film comprising the layer of the initiator component on the surface, and characterized in that the initiator component is an inert redox initiator system comprising an oxidizing agent and a reducing agent, the reducing agent comprising a metal compound, and the metal compound being contained in an effective amount only in any one of the layer of the initiator component and the layer of the curable composition on the membrane.

Description

Technical Field

[0001] The present invention relates to a method for producing a cured product and the cured product produced thereby. Background Art

[0002] As an existing method for producing a cured product, a solvent-based composition is mainly used, wherein the solvent-based composition substantially requires high temperature or UV irradiation during a curing process (eg, a volatilization process of a solvent).

[0003] However, if necessary, the curing process may be performed after applying the composition required to form the cured product to a specific device, wherein the device to which the curable composition is applied is affected by high temperature or UV irradiation, thereby there may be a problem of reduced physical properties of the device. When forming a cured product in this way, there are cases where it is difficult to apply a high temperature or UV process.

[0004] Furthermore, solvent-based compositions cause pollution problems during the volatilization of the solvent and quality consequences due to gas generation.

[0005] In order to solve the above problems, a method of forming a cured product by minimizing the use of a solvent may also be considered, but it is a difficult task to achieve a cured product having physical properties similar to those of a solvent-based composition using a solventless composition. Summary of the invention

[0006] Technical issues

[0007] 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 by a method for producing a cured product using an inert redox initiator system. The technical problem of the present invention is not limited to the technical problem described above, and those skilled in the art will clearly understand other technical problems without any mention from the following description.

[0008] Technical Solution

[0009] The present invention can make multiple changes and can have multiple examples, thus specific examples will be shown in the drawings and described in detail. However, these are not intended to limit the present invention to specific embodiments, and should be understood to include all changes, equivalents and alternatives included in the spirit and technical scope of the present invention.

[0010] In the present specification, the term normal temperature or room temperature means a natural temperature without artificial heating or cooling, and may mean any temperature of about 10° C. to 30° C., preferably 23° C. to 27° C., depending on the season.

[0011] The terms used in this application are only used to describe specific examples, which are not intended to limit the present invention. Unless the context clearly stipulates otherwise, singular expressions include plural expressions. In this application, it must be understood that terms such as "including" or "having" are intended to indicate the presence of features, quantities, steps, operations, components, parts or combinations thereof described in the specification, but do not preclude the presence or possibility of adding one or more additional features, or quantities, steps, operations, components, parts or combinations thereof.

[0012] Unless otherwise defined, all terms (including technical or scientific terms) used herein have the same meaning as those generally understood by those skilled in the art to which the present invention belongs. Unless explicitly defined in this application, terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the relevant field, and they are not interpreted as ideal or overly formal meanings.

[0013] In a specific example according to the present invention, the present invention may relate to a method for producing a cured product. The method for producing a cured product of the present invention is based on an inert redox initiator system. In this specification, "redox initiator system" means initiating free radical polymerization by a redox initiator at room temperature, and specifically, means initiating free radical polymerization by an electron transfer reaction according to the free radicals generated by the redox reaction of the initiator. In addition, in particular, the present invention uses an inert redox initiator system, wherein in this specification, "inert redox initiator system" means a redox initiator system formulated so that redox is impossible only in the case of a single initiator component.

[0014] In one example, the method for producing a cured product may include a step of contacting a layer of a curable composition comprising a curable slurry and an initiator component with a layer of an initiator component of a film including a layer of an initiator component on the surface. The method of contacting a layer of a curable composition with a layer of an initiator component of a film including a layer of an initiator component on the surface is not greatly limited, but as an example, the curable composition may be applied directly to the film, or it may be applied to any substrate and then laminated. In addition, the step of contacting a layer of an initiator component of a film including a layer of an initiator component on the surface with a layer of a curable composition may also contact a layer of an initiator component of a film including a layer of an initiator component on the surface with one side of the layer of a curable composition, and may also include a step of contacting it with both sides.

[0015] Meanwhile, in this specification, "curable slurry" means a unit that forms a polymer in a final cured product by curing or crosslinking, which may include an oligomer formed by polymerizing two or more monomers, or a polymer component and a monomer component. As an example, the curable slurry may include a monomer, a (partial) polymer, and a crosslinking agent, wherein if the monomer component is partially polymerized according to the desired composition, some of the monomers are polymerized to form an oligomer or a polymer, and the remaining monomers remain, thereby constituting the curable slurry.

[0016] Therefore, in this specification, the term of the monomer unit such as the (meth)acrylate unit described below may mean a monomer present in the curable syrup in a state of forming an oligomer or a polymer, or a monomer that is not polymerized but contained in the curable syrup. Therefore, when the content of the curable syrup is calculated in this specification, it means that the syrup components include not only components that are in a monomer state and do not participate in polymerization, but also components that participate in polymerization.

[0017] In addition, as described below, the oxidizing agent and the reducing agent as initiator components are only used to initiate polymerization by generating free radicals, and are not introduced into the final cured product for the purpose of forming units of the polymer, thereby distinguishing from the curable syrup, but some of the initiator components may also be present in the final cured product by bonding to the polymer.

[0018] In addition, in the present specification, the initiator component means a redox initiator, which may include an oxidant and a reductant. In the present specification, the oxidant and the reductant mean components that participate in or assist in generating free radicals that initiate polymerization by participating in or assisting in oxidation-reduction reactions under a redox initiator system.

[0019] The curable composition of the present invention comprises: a curable slurry containing a monomer unit, a crosslinking agent and / or (partial) polymer, a filler component, and an initiator, wherein the initiator is a concept covering a reducing agent and an oxidizing agent, and needs to be designed to have excellent solubility, compatibility, dispersion rate and reactivity between the components constituting the composition, but is not limited thereto, but the following composition can be used in this application.

[0020] In one example, the curable composition may include a reducing agent in a range of 0.05 to 10 parts by weight relative to 100 parts by weight of the curable slurry, which is not limited thereto, but as an example, the lower limit of the reducing agent content may be 0.07 parts by weight or more, 0.1 parts by weight or more, 0.13 parts by weight or more, 0.15 parts by weight or more, 0.17 parts by weight or more, 0.2 parts by weight or more, 0.25 parts by weight or more, 0.3 parts by weight or more, 0.35 parts by weight or more, 0.4 parts by weight or more, 0.45 parts by weight or more, 0.5 parts by weight or more, 0.55 parts by weight or more, 0.6 parts by weight or more, 0.65 parts by weight or more, 0.7 parts by weight or more, 0.75 parts by weight or more, or 0.8 parts by weight or more, and the upper limit thereof may be 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, or 2 parts by weight or less. By containing the reducing agent in the above content, the present invention can obtain a cured product that ensures sufficient curability to have desired physical properties.

[0021] In one example, the reducing agent may include a metal compound. According to the present invention, the metal compound is not significantly limited as long as the layer of the curable composition and the layer of the initiator component are in direct contact with each other to initiate or promote the redox reaction without separate heat or UV irradiation, and the composition containing the reducing agent can be stably stored, and it is particularly preferred to have excellent solubility, compatibility, dispersion rate and reactivity with the curable slurry.

[0022] The metal compound may be included in any one of the layers of the initiator component and the curable composition in the film in an effective amount. Here, the effective amount means the amount that can cause a significant redox reaction to produce a cured product. That is, the metal compound may be included in any one of the layers of the initiator component and the curable composition in an effective amount, and may not be substantially included in another layer. As an example, when the metal compound is included in the layer of the initiator component in an effective amount, the metal compound may not be substantially included in the layer of the curable composition. In addition, as another example, when the metal compound is included in the layer of the curable composition in an effective amount, the metal compound may not be substantially included in the layer of the initiator component. Here, the meaning of its being substantially not included may be the meaning of being included in 0 wt %, and even if the metal compound is included in the layer of the curable composition, it is also included in 1 wt % or less, 0.5 wt % or less, or 0.1 wt % or less, so that it can be included in one of the effective amounts rather than being able to cause an oxidation-reduction reaction in a trace amount.

[0023] In addition, in the layer of the initiator component in the film and the layer of the curable composition, the layer containing the metal compound in an effective amount may not substantially contain an oxidant. That is, in the present invention, the situation in which the oxidant and the metal compound are substantially contained in the same layer at the same time before the cured product is formed may not be adopted. In other words, when the metal compound is contained in the layer of the initiator component in the film in an effective amount, the oxidant may not be contained in the layer of the initiator component in 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 oxidant may not be 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.

[0024] As an example, the metal contained in the metal compound can be a transition metal, and the metal compound can be a salt or chelate containing metal ions or a hydrate thereof, and can include one type or more. Here, the metal ion can be selected from one or more of cobalt, iron, vanadium, copper, manganese, nickel, titanium, aluminum, tin, chromium, zinc, zirconium, indium, manganese and mixtures thereof. In detail, the metal compound can be a cobalt-containing component, wherein in the cobalt-containing component, cobalt can have an oxidation state of +2 valence or +3 valence. Available cobalt-containing components can include cobalt naphthenate, cobalt sulfide, etc., but are not limited thereto. As another example, the metal compound can be an iron-containing component, wherein in the iron-containing component, iron can have an oxidation state of +2 valence or +3 valence. Available iron-containing components can include iron sulfate (III), iron sulfate (II), iron chloride (III), iron chloride (II), iron carboxylate, iron naphthenate, iron (III), iron (II)), or iron acetylacetonate, but are not limited thereto. As another example, the metal compound can be a vanadium-containing component, wherein in the vanadium-containing component, vanadium can have an oxidation state of +4 or +5 valences. Available vanadium-containing components can include vanadium acetylacetonate, vanadium stearate, vanadium naphthenate, vanadium benzoyl acetonate, vanadium oxalate, triisopropoxide vanadium (V), ammonium metavanadate (V), sodium metavanadate, vanadium pentoxide (V) or vanadium sulfate (V), but are not limited thereto. As another example, the metal compound can be a copper-containing component, wherein in the copper-containing component, copper can have an oxidation state of +1 or +2 valences. Available copper-containing components can include a complex of copper acetate, copper chloride, copper benzoate, copper acetone, copper naphthenate, copper carboxylate, copper salicylate, copper and thiourea or ethylenediaminetetraacetic acid, but are not limited thereto. In addition, the metal compound can be exemplified by manganese naphthenate, nickel naphthenate, titanium acetylacetonate, copper sulfate, manganese sulfate or nickel sulfate, etc.

[0025] In particular, according to the method for producing a cured product according to the present application, by satisfying a combination of specific compositions having a curable syrup and an initiator component, the desired effects in the present application can be more excellently achieved.

[0026] Furthermore, the reducing agent may include an organic compound, wherein the organic compound is not significantly limited as long as it initiates or promotes an oxidation-reduction reaction by directly contacting a layer of the curable composition with a layer of the initiator component without separate heat or UV irradiation.

[0027] The organic compound may also be substantially contained together in the layer containing the oxidant in the layer of the initiator component and the layer of the curable composition in the film, and may also be substantially contained together in the layer containing the metal compound, but may be selectively and substantially contained only in the layer containing the oxidant or the layer containing the metal compound.

[0028] As an example, the organic compound may be at least one of the group consisting of amine, pyridine, aldehyde amine condensation compound, thiourea and derivatives thereof, and may also be two or more. In detail, examples of organic compounds may include N, N-dimethyl-p-toluidine, N, N-dimethylformamide, triethylamine, N, N-diisopropyl alcohol p-chloroaniline, N, N-diisopropyl alcohol p-bromoaniline, N, N-diisopropyl alcohol 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., but are not limited thereto, and preferably, tertiary amine-based organic compounds may be used. In particular, the organic compound is preferably a compound in a liquid phase and having a half-life in the range of 70°C to 170°C or in the range of 80°C to 150°C. By using an organic compound whose half-life temperature satisfies the above range, the present invention can suppress self-reaction in a 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 showing the decomposition rate of a compound, which means the time until the remaining amount of the compound is halved.

[0029] In an example, when comprising both metallic compound and organic compound as reducing agent, relative to the metallic compound of 100 weight parts, organic compound can be included in the scope of 100 weight parts to 700 weight parts, and as an example, its lower limit can be 130 weight parts or more, 150 weight parts or more, 170 weight parts or more, 200 weight parts or more, 230 weight parts or more, 250 weight parts or more, 270 weight parts or more or 300 weight parts or more, and its upper limit can be 650 weight parts or less, 600 weight parts or less, 550 weight parts or less, 500 weight parts or less, 450 weight parts or less, 400 weight parts or less, 350 weight parts or less or 330 weight parts or less.By comprising metallic compound and organic compound via enough curing rate with above-mentioned weight ratio, the present invention can provide the cured product with excellent curing physical property.

[0030] In addition, in one example, the curable composition may include an oxidant, wherein the oxidant is not significantly limited as long as it participates in an oxidation-reduction reaction to generate free radicals that initiate polymerization, and in particular, it is preferred that it has excellent compatibility with the curable slurry. As an example, the oxidant may include peroxides, peroxyesters, diacyl peroxides, or persulfates, but is not limited thereto, and specifically, as the oxidant, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxydecanoate, 1,5-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, ethyl acetoacetate peroxide, benzoyl peroxide, hydrogen peroxide, or a combination thereof may be used.

[0031] In one example, the oxidizing agent may be included in the range of 100 parts by weight to 2,000 parts by weight relative to 100 parts by weight of the reducing agent, and as an example, the lower limit thereof may be 130 parts by weight or more, 150 parts by weight or more, 170 parts by weight or more, 200 parts by weight or more, 230 parts by weight or more, 250 parts by weight or more, 270 parts by weight or more, 300 parts by weight or more, 400 parts by weight or more, 500 parts by weight or more, 600 parts by weight or more, parts by weight or less, 700 parts by weight or more, 800 parts by weight or more, or 900 parts by weight or more, and the upper limit thereof may be 1,900 parts by weight or less, 1,800 parts by weight or less, 1,700 parts by weight or less, 1,600 parts by weight or less, 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, or 1,000 parts by weight or less.

[0032] As described above, the curable syrup may be a polymer component. In one example, the curable syrup may include an alkyl (meth)acrylate unit, a monomer unit containing a polar functional group, and a crosslinking agent.

[0033] In one example, the (meth) alkyl acrylate unit can be an (meth) alkyl acrylate having an alkyl group containing 4 to 20 carbon atoms, wherein the carbon number of the alkyl group can be, for example, 16 or less, 12 or less, or 8 or less. Such an alkyl (meth) acrylate can be included in the curable slurry at a ratio of about 30% by weight to 70% by weight. In another example, the ratio can be 33% by weight or more, 35% by weight or more, 37% by weight or more, 40% by weight or more, 43% by weight or more, 45% by weight or more, 47% by weight or more, or 48% by weight or more, or can also be 77% by weight or less, 75% by weight or less, 73% by weight or less, 70% by weight or less, 67% by weight or less, 65% by weight or less, 63% by weight or less, 60% by weight or less, 57% by weight or less, 55% by weight or less, 53% by weight or less, or about 50% by weight or less.

[0034] In addition, the alkyl group in the (meth)acrylic acid alkyl ester unit may be a linear or branched aliphatic alkyl group, and may be in a substituted or unsubstituted state. As the linear or branched aliphatic (meth)acrylic acid alkyl ester, for example, any one or two or more selected from the following groups may be used: n-butyl (meth)acrylate, tert-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.

[0035] The curable syrup may include a polar functional group-containing monomer unit as an additional component. The curable syrup may include a hydroxyl 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, but is not limited thereto.

[0036] As the monomer having a polar functional group, 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 carbon number of the alkyl group may be 1 to 20, 1 to 16, 1 to 12, 1 to 8 or 1 to 4, and the alkyl group may be linear or branched, or may be substituted or unsubstituted); or hydroxypolyalkylene glycol (meth)acrylates such as 2-hydroxypolyethylene glycol (meth)acrylate or 2-hydroxypolypropylene glycol (meth)acrylate; epoxy-containing (meth)acrylates such as glycidyl (meth)acrylate; or acrylic acid, etc., but are not limited thereto.

[0037] In one embodiment of the present application, the monomer unit having a polar functional group can be included in the polymer component in the range of 3 to 60 parts by weight relative to 100 parts by weight of the (meth) alkyl ester unit. In another example, the ratio can be 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, or 13 parts by weight or more, or can also be 55 parts by weight or less, 50 parts by weight or less, 48 ​​parts by weight or less, 46 parts by weight or less, 44 parts by weight or less, 42 parts by weight or less, 40 parts by weight or less, 37 parts by weight or less, 35 parts by weight or less, 33 parts by weight or less, 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, or about 15 parts by weight or less.

[0038] The curable syrup may further include units of a monomer represented by Formula 1 below.

[0039] [Formula 1]

[0040]

[0041] In Formula 1, R is hydrogen or an alkyl group, and P is a monovalent substituent having a non-aromatic ring structure of 3 to 20 carbon atoms. Since the (meth)acrylic acid alkyl ester unit is a linear or branched aliphatic unit, it is different from Formula 1 in that it does not have a ring structure.

[0042] Here, the alkyl group can be exemplified by a linear, branched or cyclic substituted or unsubstituted alkyl group 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.

[0043] Meanwhile, P has a total carbon number of 3 to 20, and is a monovalent substituent with a non-aromatic ring structure, and for example, it can be a monovalent substituent derived from an aliphatic saturated or unsaturated hydrocarbon ring compound. The ring structure can be monocyclic, or it can also have a polycyclic structure, such as a condensed type or a spirocyclic type, and in another example, the number of carbon atoms forming the ring structure can be 5 or more, 6 or more, or 7 or more, or it can be 18 or less, 16 or less, 14 or less, or 12 or less. Such a substituent can be suitable for example isobornyl, cyclohexyl, norbornyl, norbornenyl, dicyclopentadienyl, ethynylcyclohexyl, ethynylcyclohexenyl or ethynyldecalinyl, but is not limited thereto. In addition, the ring structure can be unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms.

[0044] The monomer unit of Formula 1 may be included in the polymer component in a range of about 10 parts by weight to 80 parts by weight relative to 100 parts by weight of the alkyl (meth)acrylate unit. In another example, the ratio can be 10 parts by weight or more, 13 parts by weight or more, 17 parts by weight or more, 21 parts by weight or more, 25 parts by weight or more, 29 parts by weight or more, 33 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, 57 parts by weight or more, or 58 parts by weight or more, or can also be 80 parts by weight or less, 78 parts by weight or less, 76 parts by weight or less, 74 parts by weight or less, 72 parts by weight or less, 70 parts by weight or less, 68 parts by weight or less, 66 parts by weight or less, 64 parts by weight or less, 62 parts by weight or less, 60 parts by weight or less, 55 parts by weight or less, 50 parts by weight or less, 47 parts by weight or less, 45 parts by weight or less, or 40 parts by weight or less. Furthermore, the curable syrup of the present invention may further contain monomer units other than the foregoing, if necessary.

[0045] For example, the curable slurry may further include nitrogen-containing reactive monomer units. Such nitrogen-containing reactive monomers may be exemplified by one or two or more of the following: (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, but are not limited thereto. Suitable monomers may be exemplified by, for example, (meth)acrylamide, N-alkyl(meth)acrylamide and / or N,N-dialkyl(meth)acrylamide, etc. Here, the alkyl group can be exemplified by a linear, branched or cyclic substituted or unsubstituted alkyl group 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.

[0046] Such nitrogen-containing reactive monomer units may be included in the polymer component in an amount ranging from about 1 to 20 parts by weight relative to 100 parts by weight of the (meth) alkyl ester units. In another example, the ratio may be 3 parts by weight or more, 5 parts by weight or more, 7 parts by weight or more, or 9 parts by weight or more, or may also be about 17 parts by weight or less, 15 parts by weight or less, 13 parts by weight or less, or 10 parts by weight or less.

[0047] The curable syrup may further include a monomer unit of Formula 2 below.

[0048] [Formula 2]

[0049]

[0050] In Formula 2, Q is hydrogen or an alkyl group, U is an alkylene group having 1 to 4 carbon atoms, m is a number in the range of 1 to 5, and Z is hydrogen or an alkyl group. Unlike the above Formula 2, the (meth)acrylic acid alkyl ester unit is composed of an alkyl group containing only carbon and hydrogen at the terminal, but Formula 2 differs therefrom in that the -UO- unit is repeated in the residue, thus containing at least one oxygen.

[0051] In Formula 2 above, the alkyl group may be exemplified by a linear, branched or cyclic substituted or unsubstituted alkyl group 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.

[0052] Furthermore, the alkylene group can be exemplified by a linear or branched substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, wherein examples thereof can be exemplified by a propylene group or an ethylene group.

[0053] Furthermore, in Formula 2, m may be 4 or less, 3 or less, or 2 or less, or may also be 2 or more.

[0054] The monomer unit of the above formula 2 may be included in the polymer component in a range of about 10 to 50 parts by weight relative to 100 parts by weight of the (meth) alkyl ester unit. In another example, the ratio may be about 13 parts by weight or more, 15 parts by weight or more, 17 parts by weight or more, 19 parts by weight or more, 21 parts by weight or more, 23 parts by weight or more, 25 parts by weight or more, or 27 parts by weight or more, or may be about 45 parts by weight or less, 40 parts by weight or less, 37 parts by weight or less, 35 parts by weight or less, 33 parts by weight or less, or about 30 parts by weight or less.

[0055] If necessary, the curable composition according to one example of the present application may further include a crosslinking agent, which may form a cured product having appropriate adhesion and hardness by realizing a crosslinking structure with the components included in the curable syrup.

[0056] As a crosslinking agent, for example, an acrylate crosslinking agent based on carbamate, an aliphatic isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent and a metal chelate crosslinking agent can be used, but it is not limited thereto. In addition, as a crosslinking agent, one, or two or more types can be used. The acrylate crosslinking agent based on carbamate is a compound having a plurality of carbamate bonds (-NHCOO-) in its molecular chain and having an acrylic group capable of reacting with ultraviolet rays at the end of the molecule, and commercial PU330 (Miwon Commercial), PU256 (Miwon Commercial), PU610 (Miwon Commercial) and PU340 (Miwon Commercial) etc. can be used. The aliphatic isocyanate crosslinking agent is, for example, an isocyanate compound, such as isophorone diisocyanate, methylene dicyclohexyl diisocyanate or cyclohexane diisocyanate, but derivatives thereof, such as dimers or trimers, can also be used. As the epoxy crosslinking agent, for example, ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N,N,N',N'-tetraglycidylethylenediamine, or glycerol diglycidyl ether, etc. can be used. As the aziridine crosslinking agent, for example, N,N'-toluene-2,4-bis(1-aziridinecarboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), triethylene melamine, bisisoprotaloyl-1-(2-methylaziridine), or tri-1-aziridinylphosphine oxide, etc. can 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, etc. can be used.

[0057] The method of preparing the curable syrup containing such units is not particularly limited. For example, in order to achieve the above-mentioned syrup composition, the curable syrup can be formed by mixing monomers at a desired ratio and then appropriately partially polymerizing the mixture.

[0058] According to the method for producing a cured product according to the present invention, a cured product with the desired physical properties of the present invention can be produced only by contacting a layer of a curable composition with a layer of an initiator component in a film including a layer of an initiator component on the surface as described above. That is, the present application can provide a cured product with desired hardness and physical properties without the need for separate heat or UV irradiation, because the curing reaction starts at room temperature and proceeds at room temperature. However, it is also possible to add an irradiation step of heat or UV as needed, but this is not necessary in the present invention. In other words, curing can 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, without the need for any separate thermal initiator or photoinitiator.

[0059] When layers having different components are in contact with each other and the metal compound diffuses into the contact layer, thereby initiating an oxidation-reduction reaction, a cured product of the present invention can be produced, wherein if the curing reaction proceeds too quickly, the metal compound, etc. cannot be sufficiently diffused, and thus a cross-linking reaction is difficult to occur between the curable slurries, so that the cured product may not have uniform physical properties. Therefore, by having such a composition, the present invention can control the curing reaction rate of the curable composition to a suitable level according to the above production method.

[0060] The curable composition of the present invention can be a solvent-free composition. Here, the solvent-free composition is a composition substantially free of solvents (aqueous solvents and organic solvents). Therefore, the content of the aqueous solvent and the organic solvent in the curable composition can be 1 wt % or less, 0.5 wt % or less, 0.1 wt % or less, or can be substantially 0 wt %. That is, the curable composition of the present invention is realized to have such a composition that it can achieve physical properties equal to or better than the physical properties of the solvent-based while being solvent-free, and can be applicable to inert redox systems at the same time.

[0061] In addition, the curable composition of the present invention may have a viscosity in the range of 1,000 to 5,000 cps measured at a temperature of 25° C. and a shear rate of 50 rpm. The viscosity may be measured using a Brookfield HB type viscometer at room temperature.

[0062] In another example, the present invention can provide a cured product produced according to the curing method. The cured product can be a cured product of the curable composition mentioned in the production method, and the initiator component in the curable composition may also contain a reducing agent or not, but if the initiator component also contains a reducing agent, the metal compound may not be included in an effective amount as a reducing agent.

[0063] Beneficial Effects

[0064] According to one example of the present invention, by using a one-component curing method rather than a two-component curing method in which a main agent and a curing agent are separated and mixed and then applied, a method for producing a cured product is provided, wherein the cured product has excellent storage characteristics and can be cured even under reaction conditions of room temperature and darkness without separate UV or heat. DETAILED DESCRIPTION

[0065] Hereinafter, preferred experimental examples are presented to help understand the present invention. However, the following experimental examples are only intended to help understand the present invention, and the present invention is not limited to the following experimental examples.

[0066] Preparation Example 1: Preparation of curable slurry

[0067] To a flask equipped with a mechanical stirrer, 2-ethylhexyl acrylate (2-EHA), isobornyl acrylate (IBA), dimethylacrylamide, diethylene glycol ethyl ether acrylate, and 4-hydroxybutyl acrylate (HBA) were added in a weight ratio of 50:20:5:15:10, and after nitrogen purging, the temperature was raised to 60°C.

[0068] Then, an initiator (2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile)) was further added to the flask in an amount of about 0.002 wt % relative to the total weight of the compounds added to the flask, followed by sufficient stirring to obtain a curable slurry (solid content: 16.36%).

[0069] The curable syrup had a viscosity of about 3,250 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 50 rpm, and a weight average molecular weight (Mw) of about 1,050,000 g / mol.

[0070] Preparation Example 2: Preparation of curable slurry

[0071] To a flask equipped with a mechanical stirrer, 2-ethylhexyl acrylate (2-EHA), isobornyl acrylate (IBA) and 2-hydroxyethyl acrylate (HEA) were added in a weight ratio of 50:30:20, and after nitrogen purging, the temperature was raised to 60°C.

[0072] Then, an initiator (2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile)) was further added to the flask in an amount of about 0.001 wt % relative to the total weight of the compounds added to the flask, followed by sufficient stirring to obtain a curable slurry (solid content: 25.6%).

[0073] The curable syrup had a viscosity of about 2,540 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 40 rpm, and a weight average molecular weight (Mw) of about 371,000 g / mol.

[0074] Example 1

[0075] A curable composition was prepared by mixing 2 parts by weight of methyl ethyl ketone peroxide (MEKP) as an oxidizing agent and 0.6 parts by weight of N,N-dimethyl-p-toluidine as an organic compound (reducing agent) relative to 100 parts by weight of the curable syrup according to the above Preparation Example 1. Immediately after formulation, the curable composition thus prepared had a viscosity of about 3,300 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 50 rpm.

[0076] Meanwhile, cobalt naphthenate as a metal compound (reducing agent) was applied to PET in an amount of 0.2 parts by weight relative to 100 parts by weight of the curable syrup.

[0077] Then, a curable composition in which the curable syrup, the oxidizing agent, and the organic compound are mixed is applied to the PET to which the metal compound is applied, and is left at room temperature for about 90 minutes to produce a cured product.

[0078] Example 2

[0079] A curable composition was prepared by mixing 2 parts by weight of methyl ethyl ketone peroxide (MEKP) as an oxidizing agent relative to 100 parts by weight of the curable syrup according to the above Preparation Example 1. Immediately after formulation, the curable composition thus prepared had a viscosity of about 3,300 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 50 rpm.

[0080] Meanwhile, cobalt naphthenate as a metal compound (reducing agent) was applied to PET in an amount of 0.2 parts by weight relative to 100 parts by weight of the curable syrup.

[0081] Then, the curable composition mixed with the curable syrup and the oxidizing agent was applied to the PET applied with the metal compound, and left at room temperature for about 90 minutes to produce a cured product.

[0082] Example 3

[0083] A curable composition was prepared by mixing 2 parts by weight of methyl ethyl ketone peroxide (MEKP) as an oxidizing agent and 0.6 parts by weight of N,N-dimethyl-p-toluidine as an organic compound (reducing agent) relative to 100 parts by weight of the curable syrup according to the above Preparation Example 2. Immediately after formulation, the curable composition thus prepared had a viscosity of about 2,540 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 40 rpm.

[0084] Meanwhile, cobalt naphthenate as a metal compound (reducing agent) was applied to PET in an amount of 0.2 parts by weight relative to 100 parts by weight of the curable syrup.

[0085] Then, a curable composition in which the curable syrup, the oxidizing agent, and the organic compound are mixed is applied to the PET to which the metal compound is applied, and is left at room temperature for about 90 minutes to produce a cured product.

[0086] Comparative Example 1

[0087] A curable composition was prepared by mixing 2 parts by weight of methyl ethyl ketone peroxide (MEKP) as an oxidizing agent and 0.6 parts by weight of N,N-dimethyl-p-toluidine as an organic compound (reducing agent) relative to 100 parts by weight of the curable syrup according to the above Preparation Example 1. Immediately after formulation, the curable composition thus prepared had a viscosity of about 3,280 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 50 rpm.

[0088] Meanwhile, a curable composition mixed with a curable syrup, an oxidizing agent and an organic compound was applied to the prepared PET and left at room temperature for about 90 minutes to produce a cured product.

[0089] Comparative Example 2

[0090] A curable composition was prepared by mixing 2 parts by weight of methyl ethyl ketone peroxide (MEKP) as an oxidizing agent, 0.6 parts by weight of N,N-dimethyl-p-toluidine as an organic compound (reducing agent), and 0.2 parts by weight of cobalt naphthenate as a metal compound (reducing agent) relative to 100 parts by weight of the curable syrup according to the above Preparation Example 1. Immediately after formulation, the curable composition thus prepared had a viscosity of about 3,300 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 50 rpm.

[0091] Meanwhile, a curable composition mixed with a curable syrup, an oxidizing agent, an organic compound, and a metal compound was applied to the prepared PET and left at room temperature for about 90 minutes.

[0092] Comparative Example 3

[0093] A curable composition was prepared by adding 0.3 parts by weight of a photoinitiator (irgacure 651) relative to 100 parts by weight of the curable syrup according to the above Preparation Example 1 and mixing them. Then, the curable composition was bonded between PET and then irradiated with UV to obtain a cured product.

[0094] Comparative Example 4

[0095] A curable composition was prepared by mixing 2 parts by weight of methyl ethyl ketone peroxide (MEKP) as an oxidizing agent and 0.6 parts by weight of N,N-dimethyl-p-toluidine as an organic compound (reducing agent) relative to 100 parts by weight of the curable syrup according to the above Preparation Example 2. Immediately after formulation, the curable composition thus prepared had a viscosity of about 2,540 cps measured by Brookfield's DV-3 at a temperature of 25° C., a torque of 90%, and a shear rate of 40 rpm.

[0096] Meanwhile, iron acetylacetonate as a metal compound (reducing agent) was applied to PET in an amount of 0.2 parts by weight relative to 100 parts by weight of the curable syrup.

[0097] Then, a curable composition in which the curable syrup, the oxidizing agent, and the organic compound are mixed is applied to the PET to which the metal compound is applied, and is left at room temperature for about 90 minutes to produce a cured product.

[0098] 1. Total mass loss (TML) assessment

[0099] TML was evaluated in the following manner.

[0100] The cured products with a thickness of 100 μm produced according to the above examples and comparative examples were each cut into a width of 30 mm × 30 mm × length to prepare a sample, and the weight (A, unit: g) of the sample was measured. Thereafter, immediately after the sample was placed at 150° C. for 45 minutes, the weight (B, unit: g) of the sample was measured, and TML was calculated according to the following general formula.

[0101] [General]

[0102] TML (%) = 100 x (1-B / A)

[0103] 2. Gel Time Evaluation

[0104] The gel time was evaluated in the following manner. Immediately after formulating each of the curable compositions in the above Examples and Comparative Examples, the initial viscosity was measured, and the viscosity was measured after storage at 50° C. for 24 hours, wherein if it changed by 10% or less compared with the initial viscosity, it was marked as O, and if it changed by more than 10%, it was marked as X.

[0105] The results of the evaluation are summarized in Table 1 below.

[0106] [Table 1]

[0107] TML (unit: %) Gel time evaluation Example 1 1.98 O Example 2 2.11 O Example 3 1.74 O Comparative Example 1 2.5 O Comparative Example 2 Unable to measure X Comparative Example 3 5.2 O Comparative Example 4 74.4 O

[0108] While described with reference to the above embodiments, those skilled in the relevant art will appreciate that various modifications and changes may be made to the present invention without departing from the spirit and scope of the invention as described in the appended claims.

Claims

1. A method for producing a cured product, comprising: a step of contacting a layer of a curable composition comprising a curable syrup and an initiator component with a layer of an initiator component of a film including a layer of an initiator component on a surface thereof, wherein The initiator component is an inert redox initiator system comprising an oxidizing agent and a reducing agent, wherein the reducing agent comprises a metal compound, and the metal compound is contained in an effective amount only in any one of the layer of the initiator component and the layer of the curable composition on the film.

2. The method for producing a cured product according to claim 1, comprising: A step of bringing the layer of the initiator component of the film including the layer of the initiator component on the surface into contact with both sides of the layer of the curable composition.

3. The method for producing a cured product according to claim 1, wherein The curable composition includes the reducing agent in an amount of 0.05 parts by weight to 10 parts by weight relative to 100 parts by weight of the curable syrup.

4. The method for producing a cured product according to claim 1, wherein The metal compound is a salt or chelate containing a metal ion, or a hydrate thereof, and the metal ion is selected from the group consisting of cobalt, iron, vanadium, copper, manganese, nickel, titanium, aluminum, tin, chromium, zinc, zirconium, indium, manganese and a mixture thereof.

5. The method for producing a cured product according to claim 1, wherein The reducing agent further comprises at least one organic compound selected from amines, pyridine, aldehyde-amine condensation compounds, thiourea and derivatives thereof.

6. The method for producing a cured product according to claim 5, wherein The organic compound is included in an amount of 100 parts by weight to 700 parts by weight relative to 100 parts by weight of the metal compound.

7. The method for producing a cured product according to claim 1, wherein The oxidizing agent includes peroxides, peroxyesters, diacyl peroxides or persulfates.

8. The method for producing a cured product according to claim 1, wherein The oxidizing agent is included in an amount of 100 parts by weight to 2,000 parts by weight relative to 100 parts by weight of the reducing agent.

9. The method for producing a cured product according to claim 1, wherein The curable syrup comprises an alkyl (meth)acrylate unit, a monomer unit containing a polar functional group, and a cross-linking agent.

10. The method for producing a cured product according to claim 9, wherein The polar functional group includes a hydroxyl group, an epoxy group, an isocyanate group, a glycidyl group, an alkenyloxycarbonyl group, a (meth)acryloyl group or an alkenyloxyalkyl group.

11. The method for producing a cured product according to claim 9, wherein The curable syrup includes the alkyl (meth)acrylate unit in an amount of 30 wt % to 70 wt %.

12. The method for producing a cured product according to claim 9, wherein The curable syrup includes the polar functional group-containing monomer unit in an amount of 3 parts by weight to 60 parts by weight relative to 100 parts by weight of the alkyl (meth)acrylate unit.

13. The method for producing a cured product according to claim 9, wherein The curable syrup includes a hydroxyl group-containing monomer unit or an epoxy group-containing monomer unit as the polar functional group-containing monomer unit.

14. The method for producing a cured product according to claim 9, wherein The cross-linking agent includes a multifunctional acrylate compound, a multifunctional isocyanate compound or a urethane acrylate compound.

15. The method for producing a cured product according to claim 1, wherein Curing takes place at room temperature.

16. The method for producing a cured product according to claim 15, wherein The curing is performed by a redox polymerization reaction of the initiator component of the curable composition with the initiator component present in the surface of the film.

17. The method for producing a cured product according to claim 1, wherein The curable composition is solvent-free.

18. The method for producing a cured product according to claim 1, wherein The curable composition has a viscosity ranging from 1,000 cps to 5,000 cps measured at a temperature of 25° C. and a shear rate of 50 rpm.

19. A cured product, the cured product being a cured product of a curable composition comprising a curable syrup and an initiator component, wherein The initiator component is an inert redox initiator system comprising an oxidizing agent, and when the initiator component further comprises a reducing agent, a metal compound is not contained in an effective amount as the reducing agent.

20. The cured product according to claim 19, wherein When the initiator component further comprises the reducing agent, The curable composition includes the reducing agent in an amount of 0.05 parts by weight to 10 parts by weight relative to 100 parts by weight of the curable syrup.

21. The cured product according to claim 19, wherein The curable syrup comprises an alkyl (meth)acrylate unit, a monomer unit containing a polar functional group, and a cross-linking agent.

22. The cured product according to claim 21, wherein The polar functional group includes a hydroxyl group, an epoxy group, an isocyanate group, a glycidyl group, an alkenyloxycarbonyl group, a (meth)acryloyl group or an alkenyloxyalkyl group.

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