Method for producing a cured product and cured product obtained thereby

Abstract

The present invention provides a method for producing a cured product using an inactive redox initiator system and a cured product thereby. Specifically, the method for producing a cured product according to the present invention includes a step of bringing a layer of a curable composition containing a curable syrup and an initiator component into contact with an initiator component layer of a film containing an initiator component layer on a surface, wherein 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.

Description

Technical Field

[0001] The present invention relates to a method for producing a cured product and a cured product obtained thereby.

Background Art

[0002] Conventionally, in the method for producing a cured product, a solvent-based composition has been mainly used. However, the solvent-based composition requires high temperature or UV irradiation during the curing process such as the solvent evaporation step.

[0003] However, if necessary, after applying the composition required for forming the cured product 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, a problem may occur in that the physical properties of the device deteriorate. 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, the solvent-based composition induces 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 realize 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 producing a cured product using a non-active 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 Problems

[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 that the present invention includes all modifications, equivalents, and alternatives included in the spirit and technical scope of the present invention.

[0008] In this specification, the term "normal temperature" or "room temperature" means the natural temperature without artificial heating or cooling, and can indicate any one of the temperatures 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 "comprising" 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 should not be construed as precluding the presence or addition 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 construed to have a meaning consistent with the meaning in the context of the related art, and should not be construed 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 may relate to a method for producing a cured product. The method for producing a cured product according to the present invention is premised on an inactive redox initiator system. As used herein, the "redox initiator system" means a system in which radical polymerization is initiated by a redox initiator at room temperature. Specifically, it means a system in which free radicals generated by the redox reaction of the initiator initiate radical polymerization by an electron transfer reaction. Further, the present invention particularly utilizes an inactive redox initiator system. As used herein, the "inactive redox initiator system" means a redox initiator system that is composed such that redox is impossible with only a single initiator component.

[0012] In one example, the method for producing a cured product can include a step of bringing a layer of a curable composition containing a curable syrup and an initiator component into contact with an initiator component layer of a film containing an initiator component layer on a surface. The method of 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 is not greatly limited. As an example, the curable composition may be directly applied onto the film, or may be applied onto an arbitrary substrate and then laminated. Further, the step of bringing the initiator component layer of the film containing the initiator component layer on the surface into contact with the layer of the curable composition may be a step of bringing the initiator component layer of the film containing the initiator component layer on the surface into contact with one surface of the layer of the curable composition, or may include a step of bringing it into contact with both surfaces.

[0013] On the other hand, as used herein, the "curable syrup" means a unit that forms a polymer in the final cured product through curing or crosslinking, and can include an oligomer or a polymer component formed by polymerization of two or more monomers and a monomer component. As an example, the curable syrup can include a monomer, a (partial) polymer, and a crosslinking agent. However, when the monomer composition is partially polymerized according to the target composition, some monomers are polymerized to form an oligomer or a polymer, and the remaining monomers remain to constitute the curable syrup.

[0014] Therefore, the term "monomer unit" such as (meth)acrylate unit described later in this specification can mean a monomer that exists in a state of forming the oligomer or polymer in the curable syrup, or a monomer that is not polymerized and is contained in the curable syrup. Therefore, when calculating the content of the curable syrup in this specification, it means not only the components that do not participate in the polymerization and exist in the monomer state in the syrup component, but also all the components that participate in the polymerization.

[0015] Also, as described later, the oxidizing agent and the reducing agent, which are initiator components, are merely for generating radicals to initiate polymerization and are not added for the purpose of forming units of the polymer in the final cured product. Therefore, they are distinguished from the curable syrup. However, a part of the initiator components can also exist in combination with the polymer in the final cured product.

[0016] 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 the reducing agent mean components that participate in or assist in generating radicals that participate in or assist in inducing polymerization through an oxidation-reduction reaction under a redox initiator system.

[0017] The curable composition in the present invention includes a monomer unit, a curable syrup containing a crosslinking agent and / or a (partial) polymer, a filler component, and an initiator which is a concept of combining a reducing agent and an oxidizing agent. It is necessary to design it to have excellent solubility, compatibility, dispersion rate, and reactivity among the components constituting the composition, but it is not limited thereto. However, this application can utilize the following composition.

[0018] In one example, the curable composition can contain a reducing agent in the range of 0.05 to 10 parts by weight based on 100 parts by weight of the curable syrup, and without being limited thereto, as an example, the lower limit of the reducing agent content can 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 can 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 ensure sufficient curability and obtain a cured product having the desired physical properties.

[0019] In one example, the reducing agent can contain 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 to induce or promote a redox reaction without separate heat or UV irradiation, and 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 preferred.

[0020] The metal compound can be contained in an effective amount in only one of the initiator component layer and the curable composition layer 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 initiator component layer and the curable composition layer, and may not be substantially contained in the other one. As an example, when the metal compound is contained in the initiator component layer of the film in an effective amount, the metal compound may not be substantially contained in the curable composition layer. Also, as another example, when the metal compound is contained in the curable composition layer in an effective amount, the metal compound may not be substantially contained in the initiator component layer of the film. Here, the meaning of not being substantially contained may be that it may be contained at 0% by weight, or even if the metal compound is contained in the curable composition layer, it may be contained in an amount of 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 in an effective amount capable of inducing a redox reaction.

[0021] Also, the layer in which the metal compound is contained in an effective amount among the initiator component layer and the curable composition layer of the film may not substantially contain an oxidizing agent. That is, in the present invention, it may not be assumed that 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 the initiator component layer of the film in an effective amount, the oxidizing agent is not contained in the initiator component layer of the film in an effective amount, but may be contained in the curable composition layer in an effective amount. As another example, when the metal compound is contained in the curable composition layer in an effective amount, the oxidizing agent is not contained in the curable composition layer in an effective amount, but may be contained in the initiator component layer of the film in an effective amount.

[0022] 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 thereof containing metal ions, and may contain one or more of them. 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, and the like. 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 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 copper ethylenediaminetetraacetate. In addition, examples of the metal compound include manganese naphthenate, nickel naphthenate, titanium acetylacetonate, copper sulfate, manganese sulfate, or nickel sulfate.

[0023] In particular, according to the method for producing a cured product according to the present application, by satisfying a combination of a specific composition of a curable syrup and an initiator component, the effects aimed at in the present application can be more excellently realized.

[0024] Also, the reducing agent can contain an organic compound, but the organic compound is not particularly limited as long as it induces or promotes 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.

[0025] The organic compound may be substantially contained 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 contained together in the layer containing the metal compound, but it can be selectively and substantially contained only in any one of the layer containing the oxidizing agent and the layer containing the metal compound.

[0026] As an example, the organic compound may be at least one or two or more of the group consisting of amines, pyridines, aldehyde-amine condensation compounds, thioureas, and their derivatives. Specifically, but 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. Preferably, a tertiary amine series of discarded compounds can be used. In particular, as the organic compound, a compound that is liquid and has a half-life within the range of 70 to 170 °C or within the range of 80 to 150 °C is preferable. By using an organic compound whose half-life temperature satisfies the above range, 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. In this specification, the half-life means the time until the remaining amount of the compound becomes half as an index indicating the decomposition rate of the compound.

[0027] In one example, when both the metal compound and the organic compound are included with a reducing agent, the organic compound can be included in the range of 100 to 700 parts by weight with respect to 100 parts by weight of the metal compound. As an example, the lower limit 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, or 300 parts by weight or more, and the upper limit may be 650 parts by weight or less, 600 parts by weight or less, 550 parts by weight or less, 500 parts by weight or less, 450 parts by weight or less, 400 parts by weight or less, 350 parts by weight or less, or 330 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.

[0028] Also, in one example, the curable composition can contain an oxidizing agent. The oxidizing agent is not greatly limited as long as it participates in a redox reaction to generate radicals that induce polymerization, and those having particularly excellent compatibility with the curable syrup are preferred. As an example, but not limited thereto, the oxidizing agent can contain peroxides, peroxy esters, diacyl peroxides, or persulfates. Specifically, methyl ethyl ketone peroxide, t-butyl hydroxy peroxide, 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 as the oxidizing agent.

[0029] In one example, the oxidizing agent can be contained in the range of 100 to 2,000 parts by weight based on 100 parts by weight of the reducing agent. As an example, the lower limit can 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, 700 parts by weight or more, 800 parts by weight or more, or 900 parts by weight or more, and the upper limit can 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.

[0030] The curable syrup may be a polymer component as described above. In one example, the curable syrup can contain alkyl (meth)acrylate units, polar functional group-containing monomer units, and a crosslinking agent.

[0031] In one example, the alkyl (meth)acrylate unit may be an alkyl (meth)acrylate having an alkyl group with 4 to 20 carbon atoms, and the number of carbon atoms of the alkyl group may be, for example, 16 or less, 12 or less, or 8 or less. Such an alkyl (meth)acrylate may be contained in the curable syrup at a ratio of about 30 to 70% by weight. In other examples, the ratio is 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 may be about 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 50% by weight or less.

[0032] 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.

[0033] The curable syrup can contain a polar functional group-containing monomer unit as an additional component. The curable syrup can contain, but is not limited to, a hydroxy group-containing monomer unit, a carboxyl group-containing monomer unit, or an epoxy group-containing monomer unit as the polar functional group-containing monomer unit. 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.

[0034] 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 carbon number of the alkyl group above 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, substituted or unsubstituted); or hydroxy polyalkylene glycol (meth) acrylates such as 2-hydroxy polyethylene glycol (meth) acrylate or 2-hydroxy polypyropylene glycol (meth) acrylate, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, acrylic acid, etc. may be used, but are not limited thereto.

[0035] In one embodiment of the present application, the monomer unit having a polar functional group may be included in the polymer component in the range of 3 to 60 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate unit. In other examples, the ratio may 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 may be about 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 15 parts by weight or less.

[0036] In addition, the curable syrup can further contain a unit of the monomer represented by the following Chemical Formula 1.

[0037]

Chemical formula

[0038] In Chemical Formula 1, R is hydrogen or an alkyl group, and P is a monovalent substituent having a non-aromatic ring structure with 3 to 20 carbon atoms. Since the alkyl (meth)acrylate unit is linear or branched aliphatic, it is distinguished from Chemical Formula 1 in that it does not have a ring structure.

[0039] Examples of the alkyl group may 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.

[0040] On the other hand, P has a total of 3 to 20 carbon atoms and is a monovalent substituent having a non-aromatic ring structure, and may be, for example, a monovalent substituent derived from an aliphatic saturated or unsaturated hydrocarbon cyclic compound. The ring structure may be monocyclic or may have a polycyclic structure such as a condensed type or a spiro type, and the number of carbon atoms forming the ring structure may be 5 or more, 6 or more or 7 or more in other examples, or may be 18 or less, 16 or less, 14 or less or 12 or less. Examples of such substituents include, but are not limited to, an isobornyl group, a cyclohexyl group, a norbornanyl group, a norbornenyl group, a dicyclopentadienyl group, an ethynylcyclohexane group, an ethynylcyclohexene group or an ethynyldecahydronaphthalene group. Further, the ring structure may be substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms.

[0041] The unit of the monomer of the above Chemical Formula 1 can be included in the polymer component within the range of 10 to 80 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate unit. In other examples, 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 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. Further, the curable syrup of the present invention can additionally contain units of monomers other than those described above, if necessary.

[0042] For example, the curable syrup can additionally contain a nitrogen-containing reactive monomer unit. Examples of such nitrogen-containing reactive monomers include one or more of (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, diacetone(meth)acrylamide, N-vinylacetamide, N,N'-methylenebis(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, or (meth)acryloylmorpholine, but are not limited thereto. Examples of suitable monomers include, for example, (meth)acrylamide, N-alkyl(meth)acrylamide, and / or N,N-dialkyl(meth)acrylamide. Examples of the alkyl group described above 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.

[0043] Units of such nitrogen-containing reactive monomers can be included in the polymer component in the range of 1 to 20 parts by weight based on 100 parts by weight of the alkyl (meth)acrylate units. In other examples, 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 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.

[0044] The curable syrup may additionally contain units of the monomer of Chemical Formula 2 below.

[0045]

Chemical Formula

[0046] In Chemical 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. The alkyl (meth)acrylate units are composed of an alkyl group containing only carbon and hydrogen at the terminal, which is different from Chemical Formula 2. Chemical Formula 2 is distinguished in that the -U-O- unit is repeated in the residue and contains one or more oxygen atoms.

[0047] In Chemical Formula 2, examples of the alkyl group may 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.

[0048] Examples of the alkylene group may include linear or branched substituted or unsubstituted alkylene groups having 1 to 4 carbon atoms, and examples thereof may include a propylene group or an ethylene group.

[0049] In Chemical Formula 2, m may be 4 or less, 3 or less, or 2 or less, or may be 2 or more.

[0050] The unit of the monomer of the chemical formula 2 can be included in the polymer component within the range of about 10 to 50 parts by weight based on 100 parts by weight of the alkyl (meth) acrylate unit. In other examples, the ratio can 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 can 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, about 33 parts by weight or less, or about 30 parts by weight or less.

[0051] The curable composition according to an example of the present application can optionally further contain a crosslinking agent. The crosslinking agent can form a cured product having appropriate adhesive strength and hardness by embodying the composition and crosslinking structure contained in the curable syrup. The crosslinking agent includes a polyfunctional acrylate compound, a polyfunctional isocyanate compound, or a urethane acrylate compound.

[0052] 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, etc., and 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. Commercially available products such as PU330 (Miyakoshi Shoten), PU256 (Miyakoshi Shoten), PU610 (Miyakoshi Shoten), and PU340 (Miyakoshi Shoten) can be used. The aliphatic isocyanate crosslinking agent can use, for example, isocyanate compounds such as isophorone diisocyanate or methylene dicyclohexyl diisocyanate or cyclohexane diisocyanate, and derivatives such as its dimer or trimer. The epoxy crosslinking agent can use, 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 use, for example, N,N'-toluene-2,4-bis(1-aziridine carboxamide), N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxamide), triethylenemelamine, bisisoprothalloyl-1-(2-methylaziridine), or tri-1-aziridinylphosphine oxide. The metal chelate crosslinking agent can use, 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.

[0053] The method for producing 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 a target ratio, this can be appropriately partially polymerized to form the curable syrup.

[0054] According to the method for producing a cured product of the present invention, the curable composition can be cured only by contacting the layer of the curable composition with the initiator component layer of the film containing the initiator component layer on the surface as described above, to produce a cured product having the physical properties targeted in the present invention. That is, in this 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 can also be added, but this is not essentially required in the present invention. In other words, 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 even without a separate thermal initiator or photoinitiator.

[0055] The cured product of the present invention can be produced by layers having different components contacting each other and the metal compound diffusing into the contacting layer to induce a redox reaction. At this time, if the curing reaction proceeds too fast, the metal compound etc. may not diffuse sufficiently and the crosslinking reaction between the curable syrups may not easily 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 production method at an appropriate level by having the composition as described above.

[0056] The curable composition of the present invention may be a solventless composition. Here, the solventless composition is a composition that substantially does not contain solvents (aqueous solvents and organic solvents). Therefore, the content of the aqueous and organic solvents in the curable composition may be 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less, or may be substantially 0% by weight. That is, by being embodied to have the composition as described above, the curable composition of the present invention is solventless while having physical properties equivalent to or better than those of a solvent-based composition, and at the same time can be compatible with a non-active redox system.

[0057] Also, the curable composition of the present invention may have a viscosity measured at a temperature of 25°C and a shear rate of 50 rpm in the range of 1,000 cps to 5,000 cps. The viscosity can be measured at room temperature using a Brookfield HB type viscometer.

[0058] In another embodiment, the present invention can provide a cured product produced by the curing method. The cured product is a cured product of the curable composition mentioned in the production method, and the initiator component in the curable composition may or may not additionally contain a reducing agent. When the initiator component additionally contains a reducing agent, the reducing agent does not have to contain a metal compound in an effective amount.

Advantages of the Invention

[0059] According to an embodiment of the present invention, instead of using a two-component curing method in which the main agent and the curing agent are separately mixed and then applied, a one-component curing method is used to provide a method for producing a cured product that has excellent storage stability and can be cured under room temperature and dark reaction conditions without separate UV or heat.

Modes for Carrying Out the Invention

[0060] Hereinafter, preferred experimental examples (examples) are presented to assist in understanding the present invention. However, the following experimental examples are only for assisting in understanding the present invention, and the present invention is not limited by the following experimental examples.

[0061] Production Example 1: Production of Hardening Syrup 2-Ethylhexyl acrylate (2-EHA), isobornyl acrylate (IBA), dimethyl acrylamide, di(ethylene glycol)ethyl acrylate, and 4-hydroxybutyl acrylate (HBA) were added to a flask equipped with a mechanical stirrer at a weight ratio of 50:20:5:15:10. After nitrogen purging, the temperature was raised to 60°C.

[0062] Subsequently, an initiator (2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)) was additionally added to the flask at about 0.002% by weight based on the total weight of the compounds added to the flask, and then thoroughly stirred to obtain a curable syrup (solid content: 16.36%).

[0063] The viscosity of the curable syrup, measured with a Brookfield DV-3 at a temperature of 25°C, a torque of 90%, and a shear rate of 50 rpm, was approximately 3,250 cps, and the weight-average molecular weight (Mw) was approximately 1,050,000 g / mol.

[0064] Production Example 2: Production of Hardening Syrup 2-Ethylhexyl acrylate (2-EHA), isobornyl acrylate (IBA), and 2-hydroxyethyl acrylate (HEA) were added to a flask equipped with a mechanical stirrer at a weight ratio of 50:30:20. After nitrogen purging, the temperature was raised to 60°C.

[0065] After that, an initiator (2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)) of about 0.001% by weight based on the total weight of the compounds added to the flask was additionally added to the flask, and then sufficiently stirred to obtain a curable syrup (solid content: 25.6%).

[0066] The viscosity of the curable syrup, measured with a Brookfield DV-3 at a temperature of 25°C, a torque of 90%, and a shear rate of 40 rpm, was about 2,540 cps, and the weight average molecular weight (Mw) was about 371,000 g / mol.

[0067] Example 1 To 100 parts by weight of the curable syrup according to Production Example 1, 2 parts by weight of methyl ethyl ketone peroxide (MEKP, an oxidizing agent) and 0.6 parts by weight of N,N-dimethyl-p-toluidine (an organic compound (reducing agent)) were mixed to produce a curable composition. The viscosity of the curable composition thus produced, measured with a Brookfield DV-3 at a temperature of 25°C, a torque of 90%, and a shear rate of 50 rpm immediately after blending, was about 3,300 cps.

[0068] On the other hand, cobalt naphthenate, a metal compound (reducing agent), was applied to PET at 0.2 parts by weight per 100 parts by weight of the curable syrup.

[0069] Thereafter, a curable composition in which the curable syrup, the oxidizing agent, and the organic compound were mixed was applied onto the PET coated with the metal compound, and left at room temperature for about 90 minutes to produce a cured product.

[0070] Example 2 To 100 parts by weight of the curable syrup according to Production Example 1, 2 parts by weight of methyl ethyl ketone peroxide (MEKP), which is an oxidizing agent, was mixed to produce a curable composition. The curable composition produced as described above had a viscosity of about 3,300 cps as measured with a Brookfield DV-3 at a temperature of 25°C, a torque of 90%, and a shear rate of 50 rpm immediately after compounding.

[0071] On the other hand, cobalt naphthenate, which is a metal compound (reducing agent), was applied to PET at 0.2 parts by weight per 100 parts by weight of the curable syrup.

[0072] Thereafter, the curable composition in which the curable syrup and the oxidizing agent were mixed was applied onto the PET onto which the metal compound had been applied, and left at room temperature for about 90 minutes to produce a cured product.

[0073] Example 3 To 100 parts by weight of the curable syrup according to Production Example 2, 2 parts by weight of methyl ethyl ketone peroxide (MEKP), which is an oxidizing agent, and 0.6 parts by weight of N,N-dimethyl-p-toluidine, which is an organic compound (reducing agent), were mixed to produce a curable composition. The curable composition produced as described above had a viscosity of about 2,540 cps as measured with a Brookfield DV-3 at a temperature of 25°C, a torque of 90%, and a shear rate of 40 rpm immediately after compounding.

[0074] On the other hand, cobalt naphthenate, which is a metal compound (reducing agent), was applied to PET at 0.2 parts by weight per 100 parts by weight of the curable syrup.

[0075] Thereafter, the curable composition in which the curable syrup, the oxidizing agent, and the organic compound were mixed was applied onto the PET onto which the metal compound had been applied, and left at room temperature for about 90 minutes to produce a cured product.

[0076] Comparative Example 1 To 100 parts by weight of the curable syrup according to Production Example 1, 2 parts by weight of methyl ethyl ketone peroxide (MEKP), which is an oxidizing agent, and 0.6 parts by weight of N,N-dimethyl-p-toluidine, which is an organic compound (reducing agent), were mixed to produce a curable composition. The curable composition produced as described above had a viscosity of about 3,280 cps as measured by DV-3 of Brookfield at a temperature of 25°C, a torque of 90%, and a shear rate of 50 rpm immediately after compounding.

[0077] On the other hand, the curable composition in which the curable syrup, the oxidizing agent, and the organic compound were mixed was applied onto the prepared PET, and left at room temperature for about 90 minutes to produce a cured product.

[0078] Comparative Example 2 To 100 parts by weight of the curable syrup according to Production Example 1, 2 parts by weight of methyl ethyl ketone peroxide (MEKP), which is an oxidizing agent, 0.6 parts by weight of N,N-dimethyl-p-toluidine, which is an organic compound (reducing agent), and 0.2 parts by weight of cobalt naphthenate, which is a metal compound (reducing agent), were mixed to produce a curable composition. The curable composition produced as described above had a viscosity of about 3,300 cps as measured by DV-3 of Brookfield at a temperature of 25°C, a torque of 90%, and a shear rate of 50 rpm immediately after compounding.

[0079] On the other hand, the curable composition in which the curable syrup, the oxidizing agent, the organic compound, and the metal compound were mixed was applied onto the prepared PET, and left at room temperature for about 90 minutes.

[0080] Comparative Example 3 To 100 parts by weight of the curable syrup according to Production Example 1, 0.3 part by weight of a photoinitiator (Irgacure 651) was added and mixed to produce a curable composition. Thereafter, the curable composition was joined between PETs and then irradiated with UV to obtain a cured product.

[0081] Comparative Example 4 To 100 parts by weight of the curable syrup according to Production Example 2, 2 parts by weight of methyl ethyl ketone peroxide (MEKP, an oxidizing agent) and 0.6 part by weight of N,N-dimethyl-p-toluidine (an organic compound (reducing agent)) were mixed to produce a curable composition. The curable composition produced as described above had a viscosity of about 2,540 cps as measured with a Brookfield DV-3 at a temperature of 25°C, a torque of 90%, and a shear rate of 40 rpm immediately after blending.

[0082] On the other hand, iron acetylacetonate (a metal compound (reducing agent)) was applied to PET at 0.2 part by weight per 100 parts by weight of the curable syrup.

[0083] Thereafter, the curable composition in which the curable syrup, the oxidizing agent, and the organic compound were mixed was applied onto the PET onto which the metal compound had been applied, and left at room temperature for about 90 minutes to produce a cured product.

[0084] 1. Evaluation of total mass loss (TML) TML was evaluated by the following method. The cured products having a thickness of 100 μm produced in the above Experimental Examples and Comparative Examples were cut into samples having a horizontal × vertical size of 30 mm × 30 mm, and the weight (A, unit: g) of the samples was measured. Thereafter, the weight (B, unit: g) of the samples was measured immediately after leaving the samples at 150°C for 45 minutes, and TML was calculated by the following general formula. [General formula] TML (%) = 100 × (1 - B / A)

[0085] 2. Evaluation of Gel Time The Gel Time was evaluated by the following method. The initial viscosity immediately after compounding the curable compositions in the above Examples and Comparative Examples was measured, and after storing at 50°C for 24 hours, the viscosity was measured. When the change was 10% or less with respect to the initial viscosity, it was indicated by O, and when the change exceeded 10%, it was indicated by X. Table 1 below summarizes the results of the above evaluation.

[0086] [Table 1]

[0087] Although the present invention has been described with reference to the Examples, those skilled in the relevant technical field will 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. including the step of bringing a layer of a curable composition containing a curable syrup and an initiator component into contact with a layer of an initiator component of a film containing a layer of an initiator component 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 layer of the initiator component on the film and the layer of the curable composition, A method for producing a cured product, characterized in that.

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

3. The curable composition contains 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, A method for producing a cured product according to claim 1, characterized in that.

4. The metal compound is a salt, chelate or hydrate 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. A method for producing a cured product according to claim 1, characterized in that.

5. 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, A method for producing a cured product according to claim 1, characterized in that.

6. The organic compound is contained in the range of 100 to 700 parts by weight with respect to 100 parts by weight of the metal compound, A method for producing a cured product according to claim 5, characterized in that.

7. The oxidizing agent contains a peroxide, a peroxyester, a diacyl peroxide or a persulfate, A method for producing a cured product according to claim 1, characterized in that.

8. The method for producing a cured product according to claim 1, wherein the oxidizing agent is contained in the range of 100 to 2,000 parts by weight based on 100 parts by weight of the reducing agent.

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

10. The method for producing a cured product according to claim 9, wherein the polar functional group contains a hydroxy 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 contains an alkyl (meth) acrylate unit in an amount of 30 to 70% by weight.

12. The method for producing a cured product according to claim 9, wherein the curable syrup contains a polar functional group-containing monomer unit in the range of 3 to 60 parts by weight based on 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 contains a hydroxy 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 crosslinking agent contains a polyfunctional acrylate compound, a polyfunctional isocyanate compound, or a urethane acrylate compound.

15. The method for producing a cured product according to claim 1, which is cured at room temperature.

16. The method for producing a cured product according to claim 15, wherein the curing is carried out by a redox polymerization reaction between an initiator component of the curable composition and an initiator component present on the surface of the film.

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

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

19. A cured product of a curable composition containing a curable syrup and an initiator component, wherein the initiator component is an inactive redox initiation control system containing an oxidizing agent, and when the initiator component additionally contains a reducing agent, the reducing agent does not contain a metal compound in an effective amount.

20. When the initiator component additionally contains a reducing agent, The cured product according to claim 19, wherein the curable composition contains a reducing agent in the range of 0.05 to 10 parts by weight based on 100 parts by weight of the curable syrup.

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

22. The cured product according to claim 21, wherein the polar functional group contains a hydroxy 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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