KR20200094125A - Solid dispersion for curing epoxy resin, epoxy resin composition comprising the dispersion and cured product thereof - Google Patents

Abstract

The present invention relates to a solid dispersion for curing an epoxy resin, an epoxy resin composition including the dispersion and a cured product thereof. Particularly, the solid dispersion for curing an epoxy resin uses an isotropic and/or anisotropic material derived from an inorganic or organic material as a dispersoid, and the dispersoid is dispersed in a curable dispersion medium which is a solid at room temperature. Therefore, the solid dispersion can be stored and used with ease, requires reduced transportation expenses, prevents or reduces aggregation and settling phenomena occurring during the storage of products to provide improved work efficiency and to reduce processing costs, and can provide improved strength as compared to the conventional curing agents.

Description

A solid dispersion for curing epoxy, an epoxy resin composition containing the dispersion, and a cured product thereof {Solid dispersion for curing epoxy resin, epoxy resin composition comprising the dispersion and cured product thereof}

The present invention relates to a solid dispersion for curing an epoxy, an epoxy resin composition comprising a dispersion, and a cured product thereof, and more specifically, using an isotropic and/or anisotropic material derived from an inorganic substance or an organic substance as a dispersing substance. By dispersing in a curable dispersion medium that is solid at room temperature, it is easy to store and use, reduces transportation costs, and prevents or improves agglomeration and sedimentation occurring during product storage, improving work efficiency and process The present invention relates to a solid dispersion for curing epoxy, an epoxy resin composition including the dispersion, and a cured product thereof, which can reduce costs and provide improved strength compared to conventional curing agents.

Isotropic and/or anisotropic materials derived from inorganic or organic materials include lightweight materials, hybrid materials, surface protectors, conductive pastes, conductive inks, sensors, precision analysis elements, optical memories, liquid crystal displays, nano magnets, thermoelectric media, fuel cells It is used as a main material in applications such as catalysts, organic solar cells, nano glass devices, abrasives, drug carriers, environmental catalysts, paints, printing inks, inkjet inks, color filter resists, writing tool inks, and the like. At this time, the isotropic material and/or the anisotropic material derived from the inorganic material or the organic material is prepared by using a dispersion as microparticles in an aqueous dispersion medium or a non-aqueous dispersion medium, thereby effectively improving processing properties, product properties, and material properties, It is used in industry as a material that contributes to stabilization of quality and improvement of yield during manufacturing.

However, it is difficult to stably disperse the dispersoid as the material of the dispersoid is changed, the size of the particle size is reduced, or the particle shape is controlled, so that the dispersoid causes aggregation or settling in a short time in the dispersion medium. The problem of agglomeration and sinking of the dispersoid not only leads to a decrease in productivity, a reduction in processing characteristics, a decrease in handling properties, and a decrease in product yield in the production of the dispersion, but also a decrease in properties, material properties and quality of the final product. In addition, it is known to cause undesirable phenomena such as a decrease in transparency, gloss and coloring power, and color stains and cracks. Dispersing agents are used to suppress aggregation and sinking of such dispersoids and to achieve dispersion stabilization.

Conventionally, as disclosed in Korean Patent Publication Nos. 10-2013-0023254, 10-2013-0096307 or 10-2013-0111313, a dispersion agent is used to suppress aggregation of the dispersion to obtain a stable dispersion composition. Although the examination is being conducted, the previously proposed dispersant is in view of diversification of the dispersion medium and dispersoid, micronization of the particle size of the dispersoid, diversification of the particle shape, high quality of the final product, improvement of productivity, and high demand for processing characteristics. Cannot fully meet the required characteristics.

The biggest problem of the existing dispersion composition is that when a dispersion composition using water as a dispersion medium is applied to a polyurethane resin and an epoxy resin, a process of preparing a master batch of water and polyol or a master batch of water and epoxy is additionally required. It is necessary, and there is a problem that a surfactant is needed to prevent aggregation of the dispersoid.

Accordingly, without the use of a separate dispersant or surfactant, there is a need to develop a dispersion composition capable of preventing or improving aggregation and sinking of the dispersoid and an epoxy resin composition using the same as a curing agent.

In order to solve the above problems, the present invention uses an isotropic and/or anisotropic material derived from an inorganic substance or an organic substance as a dispersing material and disperses it in a curable dispersion medium that is solid at room temperature, making it easy to store and use. The cost is reduced, and it is possible to prevent or improve the agglomeration and sinking phenomenon that occurs during product storage, thereby improving work efficiency, reducing process costs, and providing improved strength compared to conventional curing agents. It is an object to provide a solid dispersion for curing an epoxy, an epoxy resin composition containing the dispersion, and a cured product thereof.

In order to solve the above technical problem, the present invention is a room temperature solid dispersion for curing comprising a dispersion medium and a dispersion medium in which the dispersion material is dispersed, wherein the dispersion material is organic particles, inorganic particles or mixtures thereof, and the dispersion medium It provides a solid dispersion for curing, which is a non-aqueous dispersion medium in a solid state at room temperature.

According to another aspect of the invention, mixing the dispersoid and the dispersion medium; And melting the dispersion medium in the mixture, wherein the dispersion is organic particles, inorganic particles or mixtures thereof, and the dispersion medium is a non-aqueous dispersion medium in a solid state at room temperature. A method for producing a solid dispersion for a dragon is provided.

According to another aspect of the invention, the epoxy resin; And it provides an epoxy resin composition comprising the solid dispersion for curing.

According to another aspect of the present invention, there is provided a method for producing an epoxy resin composition comprising mixing an epoxy resin and the solid dispersion for curing.

According to another aspect of the present invention, a cured product obtained by curing the epoxy resin composition is provided.

According to another aspect of the present invention, a molded article comprising the cured product is provided.

The solid dispersion for curing in which an isotropic material and/or anisotropic material derived from an inorganic or organic material according to the present invention is dispersed can reduce or eliminate agglomeration when storing a product, and through this process when using a product (solid dispersion for curing) It is possible to shorten the input time, and it is possible to reduce or eliminate the additional additional process or time for redistributing the agglomerated products, and to improve work efficiency because there is little or no concern about worker's labor and safety during such additional work. . In addition, the solid dispersion for curing of the present invention is evenly dispersed in a large amount of dispersant, and when used as a curing agent for an epoxy resin, it is possible to provide an improved strength to the cured product of the epoxy resin compared to a conventional curing agent.

Hereinafter, the present invention will be described in detail.

The present invention is a room temperature solid dispersion for curing comprising a dispersion medium and a dispersion medium in which the dispersion material is dispersed, wherein the dispersion material is organic particles, inorganic particles or a mixture thereof, and the dispersion medium is a non-aqueous solid state at room temperature. A dispersion medium, which relates to a solid dispersion for curing.

The solid dispersion for curing of the present invention may be solid at room temperature. The normal temperature in the present specification is a range of 20±5°C as a normal temperature, and may be, for example, 25°C.

The solid dispersion for curing of the present invention contains a dispersoid dispersed in a dispersion medium. When the dispersion contained in the solid dispersion for curing is applied to curing of the epoxy resin, it may serve to improve the electrical properties, thermal properties, and/or mechanical properties of the cured epoxy resin according to the type of dispersion. , But is not limited to this.

The dispersoid particles dispersed in the dispersion medium of the present invention may be selected from inorganic particles, organic particles, or mixtures thereof.

For example, as inorganic particles, iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver (for example, silver particles, silver nanowires, silver nanorods, etc.) ), gold (e.g., gold particles, gold nanowires, gold nanorods, etc.), platinum, alloys of two or more of these metals, or mixtures of two or more of these can be used. At that time, in order to stably extract the above-mentioned inorganic particles from the medium, alkanoic acids, fatty acids, hydroxycarboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, alkenyl succinic anhydrides, thiols, phenol induction They may be coated with protective agents such as retention, amines, amphiphilic polymers, polymer surfactants, and low molecular surfactants.

In addition, kaolin, clay, talc, mica, bentonite, dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate, zirconium oxide , Magnesium oxide, aluminum oxide, titanium oxide, iron oxide, zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black, graphite, rock wool, glass wool, glass fiber , Graphene, graphite, carbon fibers, carbon nanofibers or carbon nanotubes (single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes) and the like can be used as inorganic particles, but are not limited thereto.

In addition, as the organic particles, azo-based compounds, diazo-based compounds, condensed azo-based compounds, thioindigo-based compounds, indanthrone-based compounds, quinacridone-based compounds, anthraquinone-based compounds, benzimidazolones-based compounds, perylene-based compounds, Organic pigments such as phthalocyanine compounds, anthrapyridine compounds or dioxazine compounds; Polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, acrylic resin, vinylon resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, acetate fiber, cellulose (for example, nanocellulose) Fibril, nanocellulose crystal, etc.), hemicellulose, lignin, chitin, chitosan, starch, polyacetal, aramid resin, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone, polybutylene terephthalate, polyethylene na Polymer resins such as phthalate, polybutylene naphthalate, polysulfone, polyphenylene sulfide or polyimide; Or a mixture of these may be used, but is not limited thereto.

The dispersoid particles dispersed in the dispersion medium of the present invention may be crystalline or amorphous. In addition, the dispersoid particles dispersed in the dispersion medium of the present invention may be isotropic particles, anisotropic particles, or fibrous.

The dispersoid particles dispersed in the dispersion medium of the present invention are preferably nanocellulose fibrils, nanocellulose crystals, graphene, graphite, carbon nanotubes, carbon nanofibers, silver particles, silver nanowires, silver nanorods, gold It may be one or more selected from the group consisting of particles, gold nanowires, gold nanorods, or a combination thereof, but is not limited thereto.

In the present invention, as the dispersoid particles, those obtained by a known method can be used. As a method for preparing dispersoid fine particles, a top-down method of mechanically crushing and coarsening the coarse particles, and a number of unit particles are generated, and the bottom-up of the particles is formed through the aggregated cluster state. There are two types of (bottom-up) methods, but those prepared by any method can be preferably used. Moreover, as a method for preparing fine particles, any of the wet method and the dry method may be used. Further, there are physical methods and chemical methods in the bottom-up method, but any method may be used.

In order to describe the bottom-up method in more detail, a method for preparing metal nanoparticles among the dispersoid particles is illustrated. Among the bottom-up methods, a representative example of a physical method is an evaporation method in a gas in which bulk metal is evaporated in an inert gas, cooled and condensed by collision with the gas to generate nanoparticles. Further, the chemical method includes a liquid phase reduction method in which metal ions are reduced in the presence of a protective agent in a liquid phase, and the resulting zero-valent metal is stabilized to a nano size, or a thermal decomposition method of a metal complex. As the liquid phase reduction method, a chemical reduction method, an electrochemical reduction method, a photoreduction method, or a combination of a chemical reduction method and a light irradiation method can be used.

In addition, the dispersoid particles which can be preferably used in the present invention may be obtained by any of the top-down method and bottom-up method, as described above, and they are prepared under any of an aqueous liquid phase, a non-aqueous liquid phase and a gas phase. It may be done.

The solid dispersion for curing of the present invention includes a dispersion medium for dispersing the dispersoid. When the dispersion medium contained in the solid dispersion for curing is applied to curing of the epoxy resin, it may serve to cure the epoxy resin.

The dispersion medium that can be used in the present invention is a solid phase at room temperature, but a non-aqueous dispersion medium that can be changed into a liquid phase when heated to a melting point exceeding room temperature may be used. By using such a non-aqueous dispersion medium, upon storage of a product (solid dispersion for curing) at room temperature, dispersion stabilization can be achieved by preventing or improving the dispersoid from flocculating or fading.

The non-aqueous dispersion medium is preferably capable of curing the epoxy resin, for example, one selected from amine-based compounds, phenol-based compounds, imidazole-based compounds, acid anhydride-based compounds, or anhydrosugar alcohols, or It may be a mixture of two or more, but particularly preferably, one or a mixture of two or more selected from anhydrosugar alcohols such as mono-sugar alcohol and di-sugar alcohol may be used, but is not limited thereto.

However, if chemical dispersion medium is used, environmental problems may be an issue. For example, when using a phenol-based compound, there is a problem that a small amount of free phenol is detected after curing, and when using an amine-based compound, there is a limitation in operation due to odor.

According to one embodiment, it may be desirable to use anhydrosugar alcohol as the non-aqueous dispersion medium of the present invention. In this case, there is no problem such as limitation of work due to odor and elution of chemical substances after curing.

The type of the amine-based compound is not particularly limited, and can be used without limitation as long as it is solid at room temperature and is converted to a liquid when heated to a melting point above room temperature. For example, poly(ethylene glycol)diamine [Poly(ethylene glycol) )diamine], (R)-(+)-1,1′-binaphthyl-2,2'-diamine[(R)-(+)-1,1′-Binaphthyl-2,2′-diamine] , (S)-(-)-1,1'-binaphthyl-2,2'-diamine[(S)-(-)-1,1'-Binaphthyl-2,2'-diamine], 1, 1′-binaphthyl-2,2′-diamine[1,1′-Binaphthyl-2,2′-diamine], 4-ethoxybenzene-1,2-diamine[4-ethoxybenzene-1,2-diamine ], Diamido-dPEG ^® -diamine, (1R,2R)-N,N'-dimethyl-1,2-diphenylethane-1,2-diamine[(1R,2R)-N,N'-dimethyl-1 ,2-diphenylethane-1,2-diamine], N,N-bis(4-butylphenyl)benzene-1,4-diamine[N,N-Bis(4-butylphenyl)benzene-1,4-diamine] or Any one selected from the group consisting of mixtures of these can be used.

The type of the phenolic compound is not particularly limited, and may be used without limitation as long as it is solid at room temperature and is converted to a liquid phase when heated to a melting point above room temperature. For example, 2,3-xyrenol [2,3- Xylenol], 2,4-Xylenol[2,4-Xylenol], 2,5-Xylenol[2,5-Xylenol], 2,6-Xylenol[2,6-Xylenol], 3,4-Zyre From the group consisting of nol [3,4-Xylenol], 3,5-xylenol [3,5-Xylenol], 2.5-dimethylphenol [2.5-Dimethylphenol], 2.3-dimethylphenol [2.3-Dimethylphenol], or mixtures thereof. You can use what you choose.

The type of the imidazole-based compound is not particularly limited, and can be used without limitation as long as it is a solid at room temperature and is converted to a liquid when heated to a melting point above room temperature. For example, imidazole [Imidazole], 1-(2 -Hydroxyethyl)imidazole [1-(2-hydroxyethyl)imidazole], imidazole trifluoromethanesulfonate, imidazole-2-carboxylic acid, 4- Bromo-1H-imidazole [4-bromo-1H-imidazole], N-benzyl-2-nitro-1H-imidazole-1-acetamide [N-Benzyl-2-nitro-1H-imidazole-1-acetamide ], 2-Chloro-1H-imidazole [2-Chloro-1H-imidazole], imidazole-d[Imidazole-d], imidazole-N[Imidazole-N], imidazole-2-C,N[Imidazole -2-C,N] or mixtures thereof.

The type of the acid anhydride-based compound is not particularly limited, and may be used without limitation as long as it is solid at room temperature and is converted to a liquid phase when heated to a melting point above room temperature, for example, (2-dodecene-1-yl) Succinic anhydride[(2-Dodecen-1-yl)succinic anhydride], Maleic anhydride, Succinic anhydride, Phthalic anhydride, Glutaric anhydride, 3 ,4,5,6-tetrahydrophthalic anhydride [3,4,5,6-Tetrahydrophthalic anhydride], diglycolic anhydride, Itaconic anhydride, trans-1,2-cyclohexanedica Leic acid anhydride[trans-1,2-Cyclohexanedicarboxylic anhydride], 2,3-dimethylmaleic anhydride[2,3-Dimethylmaleic anhydride], 3,3-tetramethyleneglutaric anhydride[3,3-Tetramethyleneglutaric anhydride] , Stearic anhydride, cis-aconitic anhydride, Trimellitic anhydride chloride, Phenylsuccinic anhydride, 3,3-dimethylglutaric acid An anhydride [3,3-Dimethylglutaric anhydride], methyl succinic anhydride [Methylsuccinic anhydride], or a mixture selected from the group consisting of these may be used.

The type of the mono-sugar alcohol is not particularly limited, and may be used without limitation as long as it is solid at room temperature and is converted to a liquid when heated to a melting point above room temperature. For example, Tetritan, Pentitanium, Hexytan, Heptane Titanium or a mixture of these and the like can be used, and preferably, hexitan, such as sorbitan, mannitane, iditan, galactan, or a mixture thereof can be used.

The type of the dianhydrosugar alcohol is not particularly limited, and may be used without limitation as long as it is solid at room temperature and is converted to a liquid when heated to a melting point above room temperature. For example, dianhydrosugar hexitol, specifically isosorbide, Any one selected from the group consisting of isomannide, isoidide, or mixtures thereof can be used.

In the solid dispersion for curing of the present invention, the content of the dispersoid may vary depending on the type of dispersoid used, but based on 100 parts by weight of the dispersion medium, 0.0001 parts by weight or more, 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight Parts, 0.5 parts by weight or more, 1 part by weight or more, 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less or 50 parts by weight or less, for example, 0.0001 The weight may be 95 parts by weight, preferably 0.05 parts by weight to 80 parts by weight, but is not limited thereto. When the content of the dispersoid is too small, physical and electrical properties due to the dispersoid effect in the cured epoxy resin to which a solid dispersion for curing is applied may be weak, and when the content of the dispersoid is too large, for curing It does not exist in a dispersed state in the solid dispersion, but may exist in a state in which dispersoids are entangled with each other.

According to another aspect of the invention, mixing the dispersoid and the dispersion medium; And melting the dispersion medium in the mixture, wherein the dispersion is organic particles, inorganic particles or mixtures thereof, and the dispersion medium is a non-aqueous dispersion medium in a solid state at room temperature. A method for producing a solid dispersion for a dragon is provided.

Although not particularly limited, in the step of melting the dispersion medium in the mixture, the mixture may be melted while removing moisture by applying a vacuum at a temperature above the melting point of the dispersion medium. In addition, the molten mixture may then be cooled to room temperature to obtain a solid dispersion for curing that is solid at room temperature.

In this specification, each component described in the method for preparing the dispersion composition is the same as the components of the dispersion composition described above.

According to another aspect of the invention, the epoxy resin; And it provides an epoxy resin composition comprising the solid dispersion for curing.

In one embodiment, as the epoxy resin, bisphenol A-epichlorohydrin resin, epoxy novolak resin, alicyclic epoxy resin, aliphatic epoxy resin, bicyclic epoxy resin, glycidyl ester type epoxy resin, brominated epoxy resin, Bio-derived epoxy resin, epoxidized soybean oil (epoxidized soybean oil) or those selected from the group consisting of a combination thereof, but are not limited thereto.

In another specific example, the epoxy resin includes: novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; Bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; Aromatic glycidylamine type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, and aminophenol type glycidylamine; Hydroquinone type epoxy resins; Biphenyl-type epoxy resins; Stilbene type epoxy resin; Triphenolmethane type epoxy resin; Triphenol propane type epoxy resin; Alkyl-modified triphenolmethane type epoxy resins; Triazine core containing epoxy resin; Dicyclopentadiene modified phenol type epoxy resin; Naphthol-type epoxy resins; Naphthalene type epoxy resins; Aralkyl-type epoxy resins such as a phenolaralkyl-type epoxy resin having a phenylene and/or biphenylene skeleton, and a naphthol-aralkyl-type epoxy resin having a phenylene and/or biphenylene skeleton; Vinyl cyclohexene dioxide, dicyclopentadiene oxide, alicyclic diepoxy- adipate, such as alicyclic epoxy, such as aliphatic epoxy resin, or a combination of these may be mentioned, but is not limited thereto.

In another embodiment, as the epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin, naphthalene skeleton Type epoxy resin, tetraphenylolethane type epoxy resin, diphenyl phosphate (DPP) type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, bisphenol Aethylene oxide adduct diglycidyl Glycidyl ether having one epoxy group such as diglycidyl ether of bisphenol A propylene oxide adduct, diglycidyl ether of bisphenol A, phenyl glycidyl ether, cresyl glycidyl ether, and these epoxy What is selected from the group consisting of a nucleated hydrogenated epoxy resin or a combination of these, but is not limited thereto.

In the epoxy resin composition of the present invention, the content ratio of the epoxy resin and the solid dispersion for curing is the equivalent ratio of the solid dispersion for curing to the epoxy resin (equivalent to the curing dispersion/equivalent of the epoxy resin), for example , It may be to be in the range of 0.25 to 1.75, more specifically to be such that the equivalent ratio is in the range of 0.75 to 1.25, and more specifically to be in the range of 0.95 to 1.05 in the equivalent ratio. have. If the equivalent amount of the solid dispersion for curing relative to the equivalent of the epoxy resin is too small, there may be a problem that the mechanical strength is lowered and the physical properties are deteriorated in terms of thermal and adhesive strength. Conversely, the solid dispersion for curing relative to the equivalent of the epoxy resin Even if the equivalent is too large, there may be a problem in that physical properties are deteriorated in terms of mechanical strength, thermal and adhesive strength.

For the effect of promoting curing, the epoxy resin composition of the present invention may further include a curing catalyst.

The curing catalyst usable in the present invention includes, for example, amine compounds such as benzyldimethylamine, tris(dimethylaminomethyl)phenol, and dimethylcyclohexylamine (eg, tertiary amine); Imidazole compounds such as 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole; Organophosphorus compounds such as triphenylphosphine and triphenylphosphite; Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; Diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate or aluminum acetylacetone complex; Quaternary ammonium salts such as tetraethylammonium bromide and tetrabutylammonium bromide; Boron compounds such as boron trifluoride and triphenyl borate; Metal halides such as zinc chloride and stannous chloride; Latent curing catalyst (e.g., a high melting point dispersion type latent amine adduct containing dicyandiamide and amine added to an epoxy resin, etc.; microcapsule type latent catalyst coated with a polymer on the surface of an imidazole, phosphorus, or phosphine accelerator) ; Amine salt-type latent catalysts; high-temperature dissociation-type thermocationic polymerization-type latent catalysts such as Lewis acid salt and Bronsted acid salt), or combinations thereof, but are not limited thereto.

In one embodiment, the curing catalyst may be selected from the group consisting of amine compounds, imidazole compounds, organophosphorus compounds, or combinations thereof.

When a curing catalyst is included in the epoxy resin composition of the present invention, the amount used may be 0.01 parts by weight to 1.0 parts by weight, more specifically 0.05 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the solid dispersion for curing. It may be from 0.5 to 0.5 parts by weight, more specifically from 0.08 parts by weight to 0.2 parts by weight, but is not limited thereto. If the amount of the curing catalyst used is too small, the curing reaction of the epoxy resin may not proceed sufficiently, resulting in a problem of deterioration of mechanical properties and thermal properties. Conversely, if the amount of the curing catalyst is used too much, the curing reaction is carried out even during storage of the epoxy resin composition. Since it progresses slowly, there may be a problem that the viscosity increases.

If necessary, the epoxy resin composition of the present invention may further include one or more additive components commonly used in the epoxy resin composition.

Such additive components include, for example, antioxidants, UV absorbers, fillers, resin modifiers, silane coupling agents, diluents, colorants, defoamers, defoamers, dispersants, viscosity modifiers, gloss modifiers, wetting agents, conductivity imparting agents or combinations thereof. Any one selected from the group consisting of can be used.

The antioxidant may be used to further improve the heat stability of the resulting cured product, and is not particularly limited, for example, phenol-based antioxidants (such as dibutylhydroxytoluene), sulfur-based antioxidants (mercaptopropionic acid derivatives, etc.) , Phosphorus-based antioxidants (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.) or combinations thereof can be used. The content of the antioxidant in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the epoxy resin and the solid dispersion for curing.

Although it does not specifically limit as said UV absorber, For example, benzotriazole type UV absorber represented by TINUBIN P or TINUVIN 234 manufactured by BASF Japan Ltd.; Triazine-based UV absorbers such as TINUVIN 1577ED; Hindered amine UV absorbers such as CHIMASSOLV 2020FDL or combinations thereof may be used. The content of the UV absorber in the composition may be 0.01 to 10 parts by weight, or 0.05 to 5 parts by weight, or 0.1 to 3 parts by weight based on 100 parts by weight of the epoxy resin and the solid dispersion for curing.

The filler is used for the main purpose of improving the mechanical properties of the cured product by blending it with an epoxy resin or a curing agent. Examples of the inorganic filler include bulking agents such as talc, sand, silica, talc, and calcium carbonate; Reinforcing fillers such as mica, quartz, and glass fibers; Some have special uses such as quartz powder, graphite, alumina, and aerosil (for the purpose of imparting thixotropy), and metal materials contribute to thermal expansion coefficients such as aluminum, aluminum oxide, iron, iron oxide, copper, abrasion resistance, thermal conductivity, and adhesion Or anti-oxidant (SB ₂ O ₃ ), flame retardant properties, barium titanate, and organic materials include lightweight plastic fillers (phenolic resins, urea resins, etc.) and lightweight fillers. In addition, various glass fibers or chemical fiber cloths as reinforcing fillers can be handled as fillers in a broad sense in the manufacture of laminates. Thixotropic (thixotropic or thixotropic) refers to the properties of liquid phase and solid state when suspended in a flow so that the resin attached or impregnated in the lamination material does not flow or lose during curing. In order to impart), fine particles having a large unit surface area are used. For example, colloidal silica (Aerosil) or bentonite-based clay is used.

In one embodiment, the filler is not particularly limited, and for example, one selected from the group consisting of glass fiber, carbon fiber, titanium oxide, alumina, talc, mica, aluminum hydroxide, or a combination thereof can be used. The content of the filler in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin and the solid dispersion for curing.

The resin modifier is not particularly limited, and examples thereof include flexible additives such as polypropylene glycidyl ether, polymerized fatty acid polyglycidyl ether, polypropylene glycol, and urethane prepolymer. The content of the resin modifier in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin and the solid dispersion for curing.

The silane coupling agent is not particularly limited, and examples thereof include chloropropyl trimethoxysilane, vinyl trichlorosilane, γ-methacryloxypropyl trimethoxysilane, and γ-aminopropyl triethoxysilane. Can. The content of the silane coupling agent in the composition may be 0.01 to 20 parts by weight, or 0.05 to 10 parts by weight, or 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy resin and the solid dispersion for curing.

The diluent is used for the main purpose of reducing the viscosity by adding to an epoxy resin or a curing agent, and serves to effectively add flowability, defoaming property, improvement in penetration to component details, or filler when used. . Diluents do not volatilize, unlike solvents, and remain in the cured product upon curing of the resin, and are divided into reactive and non-reactive diluents. Here, the reactive diluent has one or more epoxy groups, participates in the reaction, enters the crosslinked structure into the cured product, and the non-reactive diluent is only physically mixed and dispersed in the cured product. Commonly used reactive diluents include Butyl Glycidyl Ether (BGE), Phenyl Glycidyl Ether (PGE), and Aliphatic Glycidyl Ether (C12-C14). , Modified t-carboxyl glycidyl ester (Modified-tert-Carboxylic Glycidyl Ester). Dibutyl phthalate (DiButylPhthalate, DBP), dioctyl phthalate (DOP), Nonyl-Phenol, Hysol, etc. are generally used.

In one embodiment, the diluent is not particularly limited, for example, n-butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, vinyl cyclohexene dioxide, diglycidyl aniline, Any one selected from the group consisting of glycerin triglycidyl ether or a combination thereof can be used. The content of the diluent in the composition may be 0.01 to 80 parts by weight, or 0.01 to 50 parts by weight, or 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy resin and the solid dispersion for curing.

Pigments or dyes are used as colorants for coloring the resin. As a commonly used pigment, colorants such as titanium dioxide, cadmium red, shiny green, carbon black, chrome green, chrome yellow, navy blue, and shiny blue are used.

In addition, antifoaming agents and defoaming agents used for the purpose of removing air bubbles in the resin, dispersing agents for increasing the dispersion effect between the resin and the pigment, wetting agents for improving adhesion between the epoxy resin and the material, viscosity modifier Various additives can be used, such as a gloss modifier for adjusting the gloss of the resin, an additive for improving the adhesion, an additive for imparting electrical properties, and the like.

The curing method of the epoxy resin composition of the present invention is not particularly limited, and, for example, a conventionally known curing apparatus such as a sealed curing furnace or a tunnel furnace capable of continuous curing can be used. Although the heating method used for this hardening is not specifically limited, For example, it can be performed by a conventionally well-known method, such as hot air circulation, infrared heating, and high frequency heating.

Curing temperature and curing time may be in the range of 30 seconds to 10 hours at 80 ℃ ~ 250 ℃. In one embodiment, after 80 °C ~ 120 °C, 0.5 hours ~ 5 hours of the conditions of the foreground, after 120 °C ~ 180 °C, 0.1 hours ~ 5 hours can be cured. In one embodiment, it can be cured under the conditions of 150 ℃ ~ 250 ℃, 30 seconds ~ 30 minutes for a short time curing.

According to another aspect of the present invention, there is provided a method for producing an epoxy resin composition comprising mixing an epoxy resin and the solid dispersion for curing.

According to another aspect of the present invention, a cured product obtained by curing the epoxy resin composition is provided.

According to another aspect of the present invention, a molded article comprising the cured product is provided.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[Example]

<Preparation of solid dispersion for curing>

Example A1: Solid dispersion for curing comprising nanocellulose fibrils and anhydrosugar alcohol

To the rotary evaporator, 100 g of isosorbide (Samyang Co.), a dispersion medium, and 100 g of an aqueous solution in which nanocellulose fibrils were dispersed at 1% by weight (KB101, Asia Nanocellulose Co., Ltd.) were mixed uniformly. Thereafter, under the temperature condition of 80° C. above the melting point of isosorbide, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare isosorbide (a solid dispersion for curing) in which nanocellulose fibrils were dispersed.

Example A2: Solid dispersion for curing comprising graphene and anhydrosugar alcohol

The dispersion medium was added with 100 g of isosorbide (Samyang Co.), a dispersion medium, and 100 g of an aqueous solution in which graphene was dispersed at 1.5 mg/mL (WDG, MexFlorer Co., Ltd.), and uniformly mixed. Thereafter, under the temperature condition of 80° C. above the melting point of isosorbide, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare isosorbide (hardened dispersion for curing) in which graphene is dispersed.

Example A3: Solid dispersion for curing comprising nanocellulose fibrils and amine compounds

Dispersing medium (1R,2R)-N,N'-dimethyl-1,2-diphenylethane-1,2-diamine 10g (Sigma Aldrich) in a rotary concentrator and 10g aqueous solution in which nanocellulose fibrils are dispersed at 1% by weight (KB101, Asia Nanocellulose Co., Ltd.) was added and mixed uniformly. Thereafter, under the temperature conditions of 80° C., which is higher than the melting point of (1R,2R)-N,N′-dimethyl-1,2-diphenylethane-1,2-diamine, the mixture is melted while vacuum is removed to remove moisture. Ordered. Subsequently, the molten mixture was cooled to room temperature, and (1R,2R)-N,N'-dimethyl-1,2-diphenylethane-1,2-diamine in which nanocellulose fibrils were dispersed (solid dispersion for curing) ) Was prepared.

Example A4: Solid dispersion for curing comprising graphene and amine compound

Dispersing medium (1R,2R)-N,N'-dimethyl-1,2-diphenylethane-1,2-diamine 10g (Sigma Aldrich) in a rotary concentrator and 10g aqueous solution in which graphene is dispersed at 1.5mg/mL ( WDG, MexFlorer Co., Ltd.) and mixed uniformly. Thereafter, under the temperature conditions of 80° C., which is higher than the melting point of (1R,2R)-N,N′-dimethyl-1,2-diphenylethane-1,2-diamine, the mixture is melted while vacuum is removed to remove moisture. Ordered. Subsequently, the molten mixture was cooled to room temperature, so that (1R,2R)-N,N'-dimethyl-1,2-diphenylethane-1,2-diamine in which graphene was dispersed (solid dispersion for curing) was obtained. It was prepared.

Example A5: Solid dispersion for curing comprising nanocellulose fibrils and phenolic compounds

A dispersion medium of 2,3-xyrenol 10g (Sigma Aldrich) and a nanocellulose fibril in an amount of 1% by weight of 10g (KB101, Asia Nanocellulose Co., Ltd.) were added to the rotary concentrator and uniformly mixed. Thereafter, under the temperature condition of 80° C. above the melting point of 2,3-xyrenol, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare 2,3-xylenol (hardened solid dispersion for dispersion) of nanocellulose fibrils.

Example A6: Curing solid dispersion comprising graphene and phenolic compound

A dispersion medium of 2,3-xyrenol 10g (Sigma Aldrich) and 10 g of an aqueous solution in which graphene is dispersed at 1.5 mg/mL (WDG, Mex Flora) were added to the rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 80° C. above the melting point of 2,3-xyrenol, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare 2,3-xyrenol (hardened dispersion for curing) in which graphene is dispersed.

Example A7: Solid dispersion for curing comprising nanocellulose fibrils and imidazole compounds

A dispersion medium of imidazole 10g (Sigma Aldrich) and nanocellulose fibrils in an amount of 1% by weight of an aqueous dispersion (KB101, Asia Nanocellulose Co., Ltd.) were added to the rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 100° C. above the melting point of the imidazole, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare imidazole (a solid dispersion for curing) in which nanocellulose fibrils were dispersed.

Example A8: Solid dispersion for curing comprising graphene and imidazole-based compound

A dispersion medium of imidazole 10g (Sigma Aldrich) and graphene was added with an aqueous solution of 100g (WDG, MexFlorer) dispersed in 1.5mg/mL, and mixed uniformly. Thereafter, under the temperature condition of 100° C. above the melting point of the imidazole, the mixture was melted while vacuum was removed to remove moisture. Subsequently, the molten mixture was cooled to room temperature, thereby preparing imidazole (a solid dispersion for curing) in which graphene was dispersed.

Example A9: Solid dispersion for curing comprising nanocellulose fibrils and acid anhydride compounds

100 g of maleic anhydride (Sigma Aldrich), a dispersion medium, and 100 g of an aqueous solution in which nanocellulose fibrils were dispersed at 1% by weight (KB101, Asia Nanocellulose Co., Ltd.) were added to a rotary concentrator and mixed uniformly. Thereafter, under the temperature condition of 80° C., which is higher than the melting point of maleic anhydride, the mixture was melted while removing vacuum to remove moisture. Subsequently, the molten mixture was cooled to room temperature to prepare maleic anhydride (a solid dispersion for curing) in which nanocellulose fibrils were dispersed.

Example A10: Solid dispersion for curing comprising graphene and acid anhydride-based compound

A dispersion medium of 100 g of maleic anhydride (Sigma Aldrich) as a dispersion medium and 100 g of an aqueous solution in which graphene was dispersed at 1.5 mg/mL (WDG, Mex Flora) were added and mixed uniformly. Thereafter, under the temperature condition of 80° C., which is higher than the melting point of maleic anhydride, the mixture was melted while removing vacuum to remove moisture. Subsequently, the molten mixture was cooled to room temperature, thereby preparing maleic anhydride (hardened solid dispersion for dispersion) in which graphene was dispersed.

Comparative Example A1: Curing agent comprising nanocellulose fibrils and polypropylene glycol

100 g of liquid polypropylene glycol (PPG-3000, Kumho Petrochemical) and nanocellulose fibrils dispersed at 1% by weight were added to a rotary concentrator at room temperature (KB101, Asia Nanocellulose Co., Ltd.) and uniformly mixed. . Thereafter, vacuum was applied to remove moisture to prepare polypropylene glycol (liquid curing agent) in which nanocellulose fibrils were dispersed.

Comparative Example A2: Curing agent comprising graphene and polypropylene glycol

The rotary concentrator was charged with 100 g of liquid polypropylene glycol (PPG-3000, Kumho Petrochemical) at room temperature and 100 g of aqueous solution in which graphene was dispersed at 1.5 mg/mL (WDG, MexFlorer Co., Ltd.) and mixed uniformly. Then, vacuum was applied to remove moisture to prepare polypropylene glycol (liquid curing agent) in which graphene is dispersed.

<Preparation of epoxy resin composition>

Example B1: Preparation of epoxy resin composition using solid dispersion for curing containing nanocellulose fibrils and anhydrosugar alcohol

Diglycidyl ether of bisphenol A (Diglycidyl ether of bisphenol A, DGEBA)-based bifunctional epoxy resin (YD-128, Kukdo Chemical, Epoxy equivalent weight (EEW): 187 g/eq, 1 equivalent) And isosorbide (Samyang Corporation, hydroxyl equivalent weight, HEW: 73 g/eq, 1 equivalent) in which nanocellulose fibrils prepared in Example A1 are dispersed, are mixed, and based on 100 parts by weight of the mixture. , As a catalyst, 0.1 parts by weight of N,N-dimethylbutylamine (N,N-dimethylbutylamine, DMBA, Sigma aldrich) was added to prepare an epoxy resin composition.

Subsequently, the epoxy resin composition was placed in a mold coated with a Teflon film, and cured stepwise at 100°C for 1 hour, at 120°C for 1 hour, at 150°C for 3 hours, and at 180°C for 1 hour.

Example B2: Preparation of epoxy resin composition using solid dispersion for curing containing graphene and anhydrosugar alcohol

As a curing agent, instead of isosorbide in which the nanocellulose fibril prepared in Example A1 was dispersed, graphene prepared in Example A2 was dispersed in isosorbide (Samyang Corporation, hydroxy equivalent weight, HEW: 73 g/eq, 1 equivalent), except that the epoxy resin composition was prepared in the same manner as in Example B1, and then cured.

Example B3: Preparation of epoxy resin composition using solid dispersion for curing containing nanocellulose fibrils and amine compounds

(1R,2R)-N,N'-dimethyl-1 in which nanocellulose fibrils prepared in Example A3 were dispersed instead of isosorbide in which nanocellulose fibrils prepared in Example A1 were dispersed as a curing agent. An epoxy resin composition was prepared in the same manner as in Example B1, except that 2-diphenylethane-1,2-diamine was used, and then cured.

Example B4: Preparation of epoxy resin composition using solid dispersion for curing containing graphene and amine compound

(1R,2R)-N,N'-dimethyl-1,2- in which graphene prepared in Example A4 was dispersed instead of isosorbide in which nanocellulose fibrils prepared in Example A1 was dispersed as a curing agent. An epoxy resin composition was prepared in the same manner as in Example B1, except that diphenylethane-1,2-diamine was used, and then cured.

Example B5: Preparation of epoxy resin composition using solid dispersion for curing containing nanocellulose fibrils and phenolic compounds

Example, except that the nanocellulose fibril prepared in Example A5 was dispersed in 2,3-xyrenol instead of isosorbide in which nanocellulose fibril prepared in Example A1 was dispersed as a curing agent. After preparing the epoxy resin composition in the same manner as B1, it was cured.

Example B6: Preparation of epoxy resin composition using solid dispersion for curing containing graphene and phenolic compound

Example B1, except that the graphene prepared in Example A6 was dispersed in place of the isosorbide in which the nanocellulose fibrils prepared in Example A1 was dispersed, as a curing agent, After the epoxy resin composition was prepared in the same manner, it was cured.

Example B7: Preparation of epoxy resin composition using solid dispersion for curing containing nanocellulose fibrils and imidazole compounds

The same method as in Example B1, except that the nanocellulose fibrill prepared in Example A7 was used instead of the imidazole dispersed in nanocellulose fibril prepared in Example A1 as a curing agent. After preparing an epoxy resin composition, it was cured.

Example B8: Preparation of epoxy resin composition using solid dispersion for curing containing graphene and imidazole-based compound

Epoxy in the same manner as in Example B1, except that the graphene prepared in Example A8 was used instead of the isosorbide in which the nanocellulose fibril prepared in Example A1 was dispersed as a curing agent. After preparing the resin composition, it was cured.

Example B9: Preparation of epoxy resin composition using solid dispersion for curing containing nanocellulose fibrils and acid anhydride compounds

Same as Example B1, except that the nanocellulose fibril-dispersed maleic anhydride prepared in Example A9 was used instead of the isosorbide dispersed nano-cellulose fibrils prepared in Example A1 as a curing agent. After the epoxy resin composition was prepared by the method, it was cured.

Example B8: Preparation of epoxy resin composition using solid dispersion for curing comprising graphene and acid anhydride-based compound

In the same manner as in Example B1, except that the maleic anhydride in which the graphene prepared in Example A10 was dispersed was used instead of the isosorbide in which the nanocellulose fibril prepared in Example A1 was dispersed as a curing agent. After preparing the epoxy resin composition, it was cured.

Comparative Example B1: Preparation of epoxy resin composition using anhydrosugar alcohol as a curing agent

Except for using isosorbide (Samyang Corporation, hydroxyl equivalent weight, HEW: 73 g/eq, 1 equivalent) instead of isosorbide in which nanocellulose fibrils prepared in Example A1 were dispersed as a curing agent Then, the epoxy resin composition was prepared in the same manner as in Example B1, and then cured.

Comparative Example B2: Preparation of an epoxy resin composition using anhydrosugar alcohol as a curing agent and adding a separate nanocellulose fibril

Diglycidyl ether of bisphenol A (Diglycidyl ether of bisphenol A, DGEBA)-based bifunctional epoxy resin (YD-128, Kukdo Chemical, Epoxy equivalent weight (EEW): 187 g/eq, 1 equivalent) , Isosorbide (Samyang Corporation, hydroxy equivalent weight (HEW: 73 g/eq, 1 equivalent) and nanocellulose fibril 0.73 g, and, based on 100 parts by weight of the mixture, N,N- as a catalyst Epoxy resin composition was prepared by adding 0.1 parts by weight of dimethylbutylamine (N,N-dimethylbutylamine, DMBA, Sigma aldrich).

Subsequently, the epoxy resin composition was placed in a mold coated with a Teflon film, and cured stepwise at 100°C for 1 hour, at 120°C for 1 hour, at 150°C for 3 hours, and at 180°C for 1 hour.

Comparative Example B3: Preparation of an epoxy resin composition using anhydrosugar alcohol as a curing agent and adding a separate graphene

An epoxy resin composition was prepared in the same manner as in Comparative Example B2, except that 0.73 g of graphene was added instead of 0.73 g of nanocellulose fibrils, followed by curing.

Comparative Example B4: Preparation of an epoxy resin composition using a curing agent comprising nanocellulose fibrils and polypropylene glycol

As a curing agent, except for using the curing agent prepared in Comparative Example A1 (polypropylene glycol in which nanocellulose fibrils are dispersed) instead of the curing agent prepared in Example A1 (isosorbide in which nanocellulose fibrils are dispersed). After preparing an epoxy resin composition in the same manner as in Example B1, it was cured.

Comparative Example B5: Preparation of an epoxy resin composition using a curing agent containing graphene and polypropylene glycol

As a curing agent, except that the curing agent prepared in Comparative Example A2 (polypropylene glycol in which graphene is dispersed) was used instead of the curing agent prepared in Example A1 (isosorbide in which nanocellulose fibrils are dispersed). An epoxy resin composition was prepared in the same manner as in Example B1, and then cured.

<Method for measuring physical properties>

[Method for evaluating redispersibility]

After the solid dispersion for curing prepared in Examples A1 to A10 and Comparative Examples A1 to A2 was stored at room temperature for 24 hours, 10 g of the solid dispersion for curing was placed in a vial containing 15 ml of water, and a magnetic bar was added. The sample was prepared by stirring for 1 hour. Subsequently, the degree of dispersion of the dispersion in the prepared sample was observed with the naked eye, and the results are shown in Table 1 below.

○○: The dispersion state of the dispersoid is the same as that of the solid dispersion for curing immediately after preparation.

○: The dispersion state of the dispersoid is a small lump floating compared to immediately after the preparation of the solid dispersion for curing.

X: The dispersion state of the dispersoid is a state in which a large lump floats compared to immediately after the preparation of the solid dispersion for curing.

××: dispersoid is insoluble in water

[How to evaluate storage stability]

Samples were prepared in the same manner as described in the redispersibility evaluation method above. Subsequently, each of the prepared samples was stored at room temperature for 1 hour, and then the degree of aggregation and subsidence of the dispersoid was visually observed, and the results are shown in Table 1 below.

○○: dispersoid is not aggregated and does not sink

(Circle): Dispersion|aggregation is a little aggregated and sinks.

×: Most of the dispersoid aggregated and subsided

[Evaluation method of tensile stress]

Tensile stress was measured using a universal tensile tester according to ASTM D412 for the cured specimens of the epoxy resin compositions prepared in Examples B1 to B10 and Comparative Examples B1 to B5, and five times for each specimen. The tensile stress was measured and the average value of the five times is shown in Table 2 below.

As described in Table 1, in the case of Examples A1 to A10 according to the present invention, the solid dispersion for curing was present in a solid state at room temperature, and thus, storage stability was excellent, which facilitates long-term storage and redispersibility. Excellent was confirmed.

However, in the case of a liquid dispersion in which the dispersion medium is present in a liquid state at room temperature (Comparative Examples A1 and A2), the dispersoids are entangled with each other, resulting in agglomeration in the form of small lumps, which results in poor redispersibility and also at room temperature. It was confirmed that storage stability was poor due to aggregation and sinking during long-term storage.

In addition, as described in Table 2, in the case of Examples B1 to B10 according to the present invention, as the dispersoid (nanocellulose fibril or graphene) is used evenly dispersed solid dispersion for curing, epoxy resin It can be seen that the tensile stress of the cured product of the composition was significantly improved to 68 Mpa or more.

However, in the case of Comparative Example B1, in which a dispersion medium (anhydrosugar alcohol) was used alone as a curing agent, tensile stress was poor compared to the example, and while using a dispersion medium (anhydrosugar alcohol) alone as a curing agent, additives (nanocellulose fibrils) Alternatively, in the case of Comparative Examples B2 and B3 in which graphene) was mixed without prior dispersion, the additives were not evenly dispersed, and in the case of the cured product of the epoxy resin composition to which it was applied, aggregation occurred, so that the tensile stress itself could not be measured.

In addition, in the case of Comparative Examples B4 and B5 in which the dispersoid is dispersed, but the liquid dispersion is present in the liquid phase at room temperature, the dispersoids are entangled with each other, causing agglomeration and sinking in small lumps. During the measurement of the tensile stress twice, the measurement was impossible due to agglomeration, and the average value of the tensile stress 5 times was significantly inferior to the example. In this case, there was a hassle of performing an additional process of stirring before using the curing agent. When stored for a long period of time, there was a problem that the dispersoid aggregated and was not well dispersed even by stirring.

Claims (12)

A room temperature solid dispersion for curing comprising a dispersion medium and a dispersion medium in which the dispersion material is dispersed,
The dispersoid is an organic particle, an inorganic particle, or a mixture thereof,
The dispersion medium is a non-aqueous dispersion medium in a solid state at room temperature,
Solid dispersion for hardening. The method according to claim 1, wherein the inorganic particles are iron, aluminum, chromium, nickel, cobalt, zinc, tungsten, indium, tin, palladium, zirconium, titanium, copper, silver, gold, platinum, kaolin, clay, talc, mica, bentonite , Dolomite, calcium silicate, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, aluminum sulfate, aluminum hydroxide, iron hydroxide, aluminum silicate, zirconium oxide, magnesium oxide, aluminum oxide, titanium oxide, iron oxide , Zinc oxide, antimony trioxide, indium oxide, indium tin oxide, silicon carbide, silicon nitride, boron nitride, barium titanate, diatomaceous earth, carbon black, graphite, rock wool, glass wool, glass fiber, graphene, graphite, carbon fiber, carbon nano Solid dispersion for curing, which is selected from the group consisting of fibers, carbon nanotubes, alloys of two or more of them, or mixtures of two or more of them. The method of claim 1, wherein the organic particles are azo-based compounds, diazo-based compounds, condensed azo-based compounds, thioindigo-based compounds, indanthrone-based compounds, quinacridone-based compounds, anthraquinone-based compounds, benzimidazolone-based compounds, feryl Ren compound, phthalocyanine compound, anthrapyridine compound, dioxazine compound, polyethylene resin, polypropylene resin, polyester resin, nylon resin, polyamide resin, aramid resin, acrylic resin, vinylon resin, urethane resin, melamine resin, polystyrene Resin, polylactic acid, acetate fiber, cellulose, hemicellulose, lignin, chitin, chitosan, starch, polyacetal, aramid resin, polycarbonate, polyphenylene ether, polyether ether ketone, polyether ketone, polybutylene terephthalate, polyethylene Solid dispersion for curing, which is selected from the group consisting of naphthalate, polybutylene naphthalate, polysulfone, polyphenylene sulfide, polyimide or mixtures thereof. The solid dispersion for curing according to claim 1, wherein the dispersion medium is at least one selected from the group consisting of amine compounds, phenol compounds, imidazole compounds, acid anhydride compounds, anhydrosugar alcohols, or combinations thereof. The dispersion medium according to claim 4, wherein the dispersion medium is poly(ethylene glycol)diamine, (R)-(+)-1,1'-binaphthyl-2,2'-diamine, (S)-(-)-1,1 ′-Binaphthyl-2,2′-diamine, 1,1′-binaphthyl-2,2′-diamine, 4-ethoxybenzene-1,2-diamine, (1R,2R)-N,N '-Dimethyl-1,2-diphenylethane-1,2-diamine, N,N-bis(4-butylphenyl)benzene-1,4-diamine, 2,3-xyrenol, 2,4-xyrenol , 2,5-xyrenol, 2,6-xyrenol, 3,4-xyrenol, 3,5-xyrenol, 2.5-dimethylphenol, 2.3-dimethylphenol, imidazole, 1-(2-hydroxyethyl )Imidazole, imidazole trifluoromethanesulfonate, imidazole-2-carboxylic acid, 4-bromo-1H-imidazole, N-benzyl-2-nitro-1H-imidazole-1-acetamide, 2-chloro-1H-imidazole, imidazole-d, imidazole-N, imidazole-2-C,N, (2-dodecene-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, Phthalic anhydride, glutaric anhydride, 3,4,5,6-tetrahydrophthalic anhydride, diglycolic anhydride, itaconic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride, 2,3-dimethylmale Acid anhydride, 3,3-tetramethyleneglutaric anhydride, stearic anhydride, cis-aconitic anhydride, trimellitic anhydride chloride, phenylsuccinic anhydride, 3,3-dimethylglutaric anhydride, methyl succinic anhydride Solid dispersion for curing, at least one selected from the group consisting of, Tetritan, Pentitanium, Heptitanium, Sorbitan, Mannitanium, Iditan, Galactitanium, Isosorbide, Isomanide, Isoided, or combinations thereof. sieve. According to claim 1, The content of the dispersant is based on 100 parts by weight of the dispersion medium, 0.0001 parts by weight to 95 parts by weight, solid dispersion for curing. Mixing a dispersoid and a dispersion medium; And
A method for producing a solid dispersion for curing comprising the step of melting the dispersion medium in the mixture,
The dispersoid is an organic particle, an inorganic particle, or a mixture thereof,
The dispersion medium is a non-aqueous dispersion medium in a solid state at room temperature,
Method for producing solid dispersion for curing. The method of claim 7, wherein the step of melting the dispersion medium in the mixture melts the mixture while removing moisture by applying vacuum at a temperature equal to or higher than the melting point of the dispersion medium. Epoxy resins; And epoxy resin composition comprising a solid dispersion for curing any one of claims 1 to 6. A method for producing an epoxy resin composition comprising the step of mixing the epoxy resin and the solid dispersion for curing according to any one of claims 1 to 6. A cured product obtained by curing the epoxy resin composition of claim 9. A molded article comprising the cured product of claim 11.