KR101989881B1 - Artificial marble having a themal storage and the manufacturing method thereof - Google Patents

Abstract

The present invention relates to (a) a phase transition microcapsule comprising a core containing a heat storage material and a shell comprising an acrylic polymer prepared from a monomer mixture comprising a methyl methacrylate monomer, an epoxy acrylate monomer and a polyfunctional acrylate monomer, (b) an acrylic resin composition comprising polymethyl methacrylate and methyl methacrylate monomer, and (c) a composition comprising an inorganic filler, and curing the composition, and a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an artificial marble having a heat storage function and a method of manufacturing the same,

TECHNICAL FIELD The present invention relates to artificial marble and a method for producing the same, and more particularly, to artificial marble comprising phase-transition microcapsules composed of a shell containing an acrylic polymer prepared with a core containing a heat storage material and an epoxy acrylate monomer, ≪ / RTI >

Energy conservation has become a global issue in recent years due to climate conventions to solve global warming problems. Energy conservation technology such as insulation of buildings using insulation has been widely used for heating and cooling, and has been contributing to energy conservation in many areas. At present, Korea consumes about 20% of the total national energy while the buildings are in use, and developed countries, such as the UK and Japan, which are more developed by heating and cooling, currently use about 26 ~ 28% ~ 40% of the energy is expected to be consumed. Also, in the United Kingdom and the like, development is being continued to improve thermal efficiency of walls and roofs using thermal mass.

In other words, research is needed to generate more thermal efficiency with the same amount of energy, and the use of heat storage material has the advantage of increasing the energy use efficiency by keeping the energy used for indoor heating and cooling for a long time at a constant temperature have. Especially, as the existing Ondol type building is replaced with concrete, the heat storage function of the building wall is lowered, resulting in a significant temperature difference between the floor and the wall, resulting in a decrease in energy efficiency. There is a growing demand for building materials having heat storage performance that can be maintained.

In the case of artificial marble, which is attached to the outer wall or inner wall of the building and has a beautiful appearance of the interior and exterior of the building, in order to maximize the energy efficiency of the building material, a heat insulating material is attached to the rear surface, In order to prevent them from being introduced into or discharged from the wall.

However, when the artificial marble is installed on the wall surface, the outside air easily flows into the room or the inside air is easily discharged to the outside of the room. Therefore, The energy consumption rate is increased. In addition, there has been a problem in that an additional heat insulating material is attached to the artificial marble to insulate it.

In addition, conventionally, artificial marble having a heat storage effect has been provided by a method in which a substance located inside a capsule of artificial marble flows out through pores to exert an effect or exhibits an effect when a capsule is broken by external pressure. However, The capsules were not robust in structure and thus were not suitable for use in artificial marble and the like.

In order to solve the above-mentioned problems, it is an object of the present invention to provide an artificial marble having enhanced durability and a method of manufacturing the same, with an excellent heat storage effect.

It is another object of the present invention to provide artificial marble having high latent heat and excellent energy efficiency.

It is also an object of the present invention to provide a composition comprising a spherical phase transition microcapsule having a smooth surface and excellent durability to an artificial marble comprising a surface layer.

As a result of research to achieve the above object, the artificial marble according to the present invention comprises (a) a core comprising a heat storage material and a monomer mixture comprising a methyl methacrylate monomer, an epoxy acrylate monomer and a polyfunctional acrylate monomer A phase transition microcapsule composed of a shell containing an acrylic polymer prepared from the above-

(b) an acrylic resin composition comprising polymethyl methacrylate and methyl methacrylate monomer, and

(c) an inorganic filler.

The composition according to an embodiment of the present invention may contain 10 to 40% by weight of phase transition microcapsules, 15 to 40% by weight of an acrylic resin composition and 30 to 65% by weight of an inorganic filler.

The monomer mixture of the phase transfer microcapsule according to an embodiment of the present invention comprises 75 to 85% by weight of methyl methacrylate monomer, 10 to 20% by weight of a polyfunctional acrylate monomer, and 1 to 10% by weight of an epoxy acrylate monomer can do.

The acrylic resin composition according to an embodiment of the present invention may include 10 to 30% by weight of polymethyl methacrylate and 70 to 90% by weight of methyl methacrylate.

The inorganic filler may be any one selected from aluminum hydroxide, calcium carbonate, silica, alumina, and magnesium hydroxide, or a mixture thereof.

The composition according to an embodiment of the present invention may further comprise a marble chip.

The artificial marble according to an aspect of the present invention may be a double composite panel in which an aluminum panel is attached to an artificial marble top.

The method of manufacturing artificial marble according to the present invention is a method of applying a composition containing phase transition microcapsules, an acrylic resin composition and an inorganic filler to cure by heat treatment,

The composition according to one aspect of the present invention comprises (a) a core comprising a heat storage material and

A phase transition microcapsule composed of a shell comprising an acrylic polymer prepared from a monomer mixture comprising a methyl methacrylate monomer, an epoxy acrylate monomer and a polyfunctional acrylate monomer,

(b) an acrylic resin composition comprising polymethyl methacrylate and methyl methacrylate monomer, and

(c) an inorganic filler.

An aluminum panel may be attached to the upper part of the artificial marble according to an embodiment of the present invention to produce a double composite panel.

The coating thickness according to an embodiment of the present invention may be 0.01 to 1 mm.

The heat treatment according to an embodiment of the present invention may be performed at 80 to 120 ° C.

The inorganic filler according to an embodiment of the present invention may be any one selected from aluminum hydroxide, calcium carbonate, silica, alumina, and magnesium hydroxide, or a mixture thereof.

The artificial marble according to the present invention has an advantage that the durability can be increased while having a heat storage effect.

Further, the artificial marble according to the present invention has an advantage that it can increase energy efficiency with high latent heat.

1 is a scanning electron microscope (SEM) image of phase-transition microcapsules according to one example of the present invention (a) and the comparative example (b).
2 is a SEM photograph of the surface (a) and the broken section (b) of artificial marble according to a comparative example of the present invention.
3 is a SEM photograph of a surface (a) and a broken section (b) of an artificial marble according to an embodiment of the present invention.

Hereinafter, artificial marble according to the present invention and a method for producing the same will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

As used herein, " acrylate " may include acrylate or methacrylate.

In the present specification, the term "polyfunctional" means a compound having two or more functional groups. For example, the polyfunctional acrylate-based monomer means an acrylate-based monomer having two or more functional groups.

As used herein, " microcapsules " may refer to spherical microcapsules containing one or more laminate coatings and a core that is chemically different from and surrounded by such coatings. The microcapsules can be distinguished from microspheres composed of a spherical homogeneous matrix.

In the case of architectural interiors that make up the inner walls of the building, they are pursuing beauty on the basis of their beauty. However, there are not many architectural interiors that have additional functionality other than an aesthetic point of view. Particularly, in the case of some insulation materials, attempts to minimize heat loss by blocking the heat transfer between the inside and outside of the building have been made in various directions, but they are not completely free from the space occupied by the walls,

The inventors of the present invention have conducted research to provide artificial marble capable of reducing the temperature change of the outside air by storing or releasing thermal energy through a phase change at a specific temperature range. Specifically, the present invention is to produce an environmentally friendly construction interior material having a heat storage function by applying phase transition microcapsules to artificial marble. The present invention also provides an economical effect because it is a wall having heat storage performance, excellent workability, and no need to install a separate heat insulating material and wall.

In order to achieve the above object, the present invention relates to artificial marble and a method of manufacturing the same.

Hereinafter, the present invention will be described in detail.

The artificial marble according to the present invention comprises (a) a core comprising a heat storage material and

A phase transition microcapsule composed of a shell comprising an acrylic polymer prepared from a monomer mixture comprising a methyl methacrylate monomer, an epoxy acrylate monomer and a polyfunctional acrylate monomer,

(b) an acrylic resin composition comprising polymethyl methacrylate and methyl methacrylate monomer, and

(c) a composition comprising an inorganic filler.

Since the artificial marble according to the present invention has a high latent heat, the energy efficiency can be remarkably improved.

The artificial marble according to an embodiment of the present invention can increase the durability while having a heat storage effect as the composition is included.

The phase transition microcapsules (a) included in the artificial marble according to the present invention are preferable because they extend the application range as phase change materials (PCM) and have excellent durability of microcapsules. More specifically, a core comprising a heat storage material; And a shell comprising an acrylic polymer prepared from a monomer mixture comprising a monomer mixture comprising a methyl methacrylate monomer, an epoxy acrylate monomer and a polyfunctional acrylate monomer, thereby increasing the durability of the microcapsule, It can be included in artificial marble to give excellent durability.

Since the phase transition microcapsule according to the present invention is produced in a spherical shape having a smooth surface according to the above composition, it has a narrow range of phase transition temperature range, thereby maximizing the heat storage function in a target temperature range. Can be manufactured.

The heat storage material of the phase change microcapsule according to an embodiment of the present invention may be any one or a mixture of two or more selected from C ₁₂ to C ₃₀ saturated hydrocarbons, C ₆ to C ₃₀ fatty acids and C ₆ to C ₃₀ fatty alcohols Lt; / RTI > And may be any one or a mixture of two or more selected from saturated hydrocarbons, preferably C ₁₄ to C ₃₀ fatty acids, C ₁₀ to C ₃₀ fatty acids and C ₁₀ to C ₃₀ fatty alcohols. The heat storage material can absorb or release latent heat while changing from a solid phase to a liquid phase or a liquid phase to a solid phase at a constant temperature range. Artificial marbles containing the phase transition microcapsules manufactured by this method can have excellent energy storage efficiency by storing high heat. In addition, it not only can reduce heat loss by blocking extreme overheating or cold heat, but also can keep the room temperature constant.

In addition, the heat storage material according to an embodiment of the present invention may have a melting point of 6 to 65 ° C. The phase change microcapsule according to an embodiment of the present invention can be prepared by heating at a temperature higher than the melting point of the heat storage material and encapsulating the phase change microcapsule. The heating temperature may be 30 to 80 占 폚. It is preferable to prevent evaporation or pyrolysis of the heat storage material at the heating temperature.

In general, microcapsules can improve the latent heat by increasing the content of the heat storage material, but they can not substantially increase the content, and the durability of the shell, which is a wall material of the microcapsule, is decreased.

In order to solve the above-mentioned disadvantages, the monomer mixture for forming the shell of the phase change microcapsule according to an embodiment of the present invention comprises a monomer mixture comprising a methyl methacrylate monomer, an epoxy acrylate monomer and a polyfunctional acrylate monomer And may include bonded acrylic polymers.

The monomer mixture of the phase transfer microcapsule according to an embodiment of the present invention may contain 50 to 90% by weight of methyl methacrylate monomer, 5 to 45% by weight of a polyfunctional acrylate monomer, and 1 to 10% by weight of an epoxy acrylate monomer have. Preferably, the monomer mixture of phase transfer microcapsules may comprise 75 to 85% by weight of methyl methacrylate monomer, 10 to 20% by weight of polyfunctional acrylate monomer and 1 to 10% by weight of epoxy acrylate monomer. In the above range, a shell having excellent durability that can prevent loss of heat storage material and damage to artificial marble can be manufactured, and thus it can be provided in artificial marble having excellent energy storage efficiency.

The epoxy acrylate monomer may be any one or more selected from bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, novolac-epoxy acrylate, cresol-novolak epoxy acrylate, and biphenol epoxy acrylate. When the epoxy acrylate monomer is mixed with the methyl methacrylate monomer and the polyfunctional acrylate monomer, a spherical microcapsule having a smooth surface can be formed. Since the sintered body has a spherical shape having a smooth surface as described above, it has a narrow phase transition temperature range, maximizing the heat storage function in a target temperature range, and thus can produce artificial marble having excellent energy efficiency.

The polyfunctional acrylate-based monomer may be an acrylate-based monomer having at least two functional groups. Preferably, the functional group may be a double bond, which is an unsaturated bond. Specific examples of the polyfunctional acrylate monomer include trimethylolpropane triacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, Ethylene glycol diacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, erythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol diacrylate, ethylene diacrylate, and the like. The multifunctional acrylate monomer is preferably mixed with the methyl methacrylate monomer and the epoxy acrylate monomer so that the surface of the shell can form a smooth spherical microcapsule. Since the shell is formed into a spherical shape having a smooth surface as described above, the artificial marble having a narrow range of the phase transition temperature range can maximize the heat storage function in a target temperature range and thus can be manufactured with energy efficiency.

The composition may further contain 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, of a C ₈ to C ₂₀ alkyl acrylate monomer based on 100 parts by weight of the monomer mixture according to an embodiment of the present invention. The C ₈ to C ₂₀ alkyl acrylate, if further comprise a monomer artificial marble factory or the core in the microcapsule interior by the high-temperature heat flows out through the pores of the shell, it is possible to prevent the shape microcapsules break. Specifically, the C ₈ to C ₂₀ alkyl acrylate-based monomer may exist in a swollen form due to the long chain at the interface between the core and the shell. In addition, the storage material can be selectively absorbed by the lipophilic property, thereby enhancing the stability of the microcapsule. Therefore, the C ₈ -C ₂₀ alkyl acrylate monomer absorbs or protects the interface between the core and the shell so as to prevent the heat storage material from flowing out, thereby preventing the microcapsules from breaking or popping due to expansion of the heat storage material due to high temperature and high pressure Artificial marble with improved durability can be provided.

Specific examples of the C ₈ -C ₂₀ alkyl acrylate monomer include dodecyl acrylate, isodecyl acrylate, n-undecyl acrylate, tridecyl acrylate, n-octyl acrylate, n-octyl methacrylate Acrylate, isobutyl acrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate And a mixture of two or more selected from the group consisting of methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate,

The phase change microcapsule according to an embodiment of the present invention may have 60 to 90% by weight of the core and 10 to 40% by weight of the shell. Preferably, the core may be 65 to 85 wt% and the shell may be 15 to 35 wt%, but is not limited thereto. In the above range, it is possible to maximize the content of the core including the heat accumulating material even though it has a thin shell, and it can be included in the artificial marble to further improve the latent heat characteristic of the artificial marble to realize high energy efficiency.

For example, the phase-transition microcapsule may have an average particle diameter of 1 to 20 mu m, preferably 5 to 15 mu m, although it is not limited according to one embodiment of the present invention. When the average particle size is within the above range, the dispersibility and miscibility between the surface layer compositions are excellent, which is preferable, but not limited thereto.

The phase change microcapsule according to an embodiment of the present invention may contain 10 to 40% by weight, preferably 10 to 30% by weight, more preferably 10 to 20% by weight based on the total weight of artificial marble %. When it is included in the above-mentioned range, the artificial marble has an excellent heat storage effect and durability can be increased.

The acrylic resin composition (b) contained in the artificial marble according to an embodiment of the present invention may include polymethyl methacrylate and methyl methacrylate monomers.

By including the polymethylmethacrylate resin as described above, transparency of the artificial marble and reactivity between the monomers can be improved, which is preferable. Further, by including the methyl methacrylate monomer, the composition can be uniformly mixed easily, and the processability can be remarkably improved.

The acrylic resin composition according to an embodiment of the present invention may include 10 to 30% by weight of polymethyl methacrylate and 70 to 90% by weight of methyl methacrylate. Preferably 15 to 30% by weight of polymethyl methacrylate and 70 to 85% by weight of methyl methacrylate. When it is included in the above-mentioned range, the viscosity can be easily formed when applying the artificial marble composition, and the workability can be further improved.

The acrylic resin composition may contain 15 to 40% by weight, preferably 20 to 35% by weight, based on the total weight of the artificial marble. When included in the above range, the phase transition microcapsule and the inorganic filler can be combined with the mechanical strength and elasticity of the artificial marble as well as the latent heat characteristics.

The inorganic filler according to an embodiment of the present invention may be any one selected from aluminum hydroxide, calcium carbonate, silica, alumina, and magnesium hydroxide, or a mixture thereof. Preferably, it may be aluminum hydroxide, but is not limited thereto. The inorganic filler can provide an artificial marble with a transparent and beautiful appearance close to natural stone.

The inorganic filler may have an average particle diameter of 1 to 50 mu m, and preferably 5 to 30 mu m according to an embodiment, but the present invention is not limited thereto. When the average particle diameter is set, the viscosity can be adjusted according to a wide specific surface area, and it is possible to provide a natural stone-like appearance. In addition, the phase transition microcapsule and the acrylic resin composition are mixed with each other to provide a uniform heat storage effect over the entire surface of artificial marble, and excellent durability can be provided.

The inorganic filler may contain 30 to 65% by weight, preferably 40 to 60% by weight, based on the total weight of the artificial marble. If the inorganic filler is included in the range as described above, It is possible to provide a close appearance.

The artificial marble according to an embodiment of the present invention may include 10 to 40% by weight of phase transition microcapsules, 15 to 40% by weight of an acrylic resin composition and 40 to 60% by weight of an inorganic filler based on the total weight of artificial marble. Preferably 20 to 40% by weight of phase transition microcapsules, 15 to 40% by weight of an acrylic resin composition and 40 to 60% by weight of an inorganic filler.

The artificial marble according to an embodiment of the present invention further includes any one or a mixture of two or more selected from the group consisting of (a) phase transition microcapsule, (b) acrylic resin composition and (c) inorganic filler, .

The type of the initiator is not limited as long as it is a conventional radical initiator for carrying out the polymerization of the (a) phase transition microcapsule, (b) the acrylic resin composition and (c) the inorganic filler and the crosslinking agent. Specific examples of the initiator include peroxyketals; Dialkyl peroxides; Diacyl peroxide; Peroxyesters; And hydroperoxides; And the like.

The peroxyketals may be selected from the group consisting of 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate and 2,2- have.

The dialkyl peroxide may be selected from the group consisting of di-t-butyl peroxide, duckcumperoxide, t-butylcumylperoxide, a, a-bis (t- butylperoxy- 2,5-bis (t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3.

The above-mentioned diacyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m -Toluylperoxide, and the like, or a mixture of two or more thereof.

The peroxy ester is selected from the group consisting of t-butyl peroxyacetate, t-butyl peroxyisobutylate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, Di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t- butylperoxyisopropylcarbonate, Tartrate and the like, or a mixture of two or more thereof.

The hydroperoxide is selected from the group consisting of t-butyl hydroperoxide, diisopropylbenzene, hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutylhydroxide Peroxide, and the like, or a mixture of two or more thereof.

In addition, the illustrated radical initiators may be used alone or in combination. But is not limited thereto. In addition, the illustrated radical initiators may be used alone or in combination.

The initiator may be added in an amount of 0.1 to 10 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of the composition. When included in the above range, the hardening speed of the artificial marble can be kept constant, and as a result, the workability can be improved.

The crosslinking agent may be a monomer having an unsaturated group capable of copolymerizing in the molecule and capable of forming a polymer cross-linking with the monomer by polymerization with the monomer. The crosslinking agent used in the present invention is not particularly limited according to an embodiment, but it is possible to use a multifunctional monomer capable of crosslinking with (a) phase transition microcapsules and (b) an acrylic resin composition, desirable.

Specific examples of the crosslinking agent include ethylene glycol dimethacrylate, ethylene glycol trimethacrylate, trimethylolpropane trimethacrylate, triaryl cyanate, diaryl phthalate, aryl methacrylate, and triethylene glycol dimethacrylate Lt; RTI ID = 0.0 > and / or < / RTI >

The crosslinking agent may be added in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the composition. When included in the above range, solvent resistance, heat resistance, mechanical properties and the like can be improved. In addition, phase separation in the artificial marble can be prevented to provide a beautiful appearance, stretchability and durability can be improved, and workability can be improved.

The coupling agent refers to a material having both a hydrophobic functional group capable of binding with a resin in a molecule and a hydrophilic functional group capable of binding with an inorganic filler at the same time.

Specific examples of the coupling agent include beta-3,4-epoxycyclohexylethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-amino Propyltrimethoxysilane, hydroxyethyl methacrylate excipient phosphate, hydroxymethyl methacrylate excipient phosphate, 3- (trimethoxycaryl) propyl methacrylate, vinyltrimethoxysilane, vinyltriethoxysilane and Hydroxyethyl methacrylate acid phosphate, hydroxyethyl methacrylate acid phosphate, and the like, but is not limited thereto.

The coupling agent may be added in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the composition. Within the above range, the bonding force between (a) the phase transition microcapsule, (b) the acrylic resin composition and (c) the inorganic filler can be further improved.

The artificial marble according to an embodiment of the present invention may further include a marble chip. If the marble chips are further included, marble patterns can be provided to the artificial marble.

According to one embodiment of the present invention, the artificial marble may further include any one or two or more additives selected from antibacterial agents, pigments, dyes, ultraviolet absorbers, flame retardants, fluidizers, polymerization inhibitors, antioxidants, chain transfer agents and antifoaming agents , But is not limited thereto.

The artificial marble according to an aspect of the present invention may be a double composite panel in which an aluminum panel is attached to an artificial marble top.

In the present invention, the aluminum panel may be made of aluminum alone, or may further include any one or a mixture of two or more selected from aluminum, synthetic resin, wood, metal, and the like in addition to aluminum.

The inorganic material may include, for example, any one or two or more selected from cement, concrete, calcium silicate, magnesium, vermiculite, gypsum, porcelain and porcelain.

Examples of the synthetic resin material include polyvinyl chloride, polyethylene, polypropylene, polyester, unsaturated polyester, polyamide, polystyrene, polyurethane, polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS) And polylactic acid may be included.

It is also possible to use, as the wood, one or more selected from the group consisting of a lumber material, a floor board material, sawdust, a medium density fiberboard (MDF) material, a high density fiberboard (HDF) You can include ...

The metal material may include one or more selected from among Fe, Cu, Sn, and the like.

The aluminum panel may have a general board shape or a honeycomb shape.

In the present invention, the aluminum panel may have a thickness of 0.1 to 30 mm, preferably 0.5 to 3.0 mm, which is advantageous from the viewpoints of handleability, light weight, workability and other physical properties while maximizing the effect of the composite panel , But the present invention is not limited thereto.

Another aspect of the present invention is to provide the artificial marble composition as a surface layer on a conventional artificial marble.

According to an aspect of the present invention, when the artificial marble is provided as a surface layer, the heat inside or outside the building can be directly discharged or absorbed, thereby further improving the latent heat characteristic. At this time, conventional artificial marble means a marble which does not contain phase transition microcapsules or which is commercialized.

Describing another embodiment of the present invention in detail,

The method of manufacturing artificial marble according to the present invention is a method of applying a composition containing phase transition microcapsules, an acrylic resin composition and an inorganic filler to cure by heat treatment,

The composition comprises (a) a core comprising a heat storage material and

A phase transition microcapsule composed of a shell comprising an acrylic polymer prepared from a monomer mixture comprising a methyl methacrylate monomer, an epoxy acrylate monomer and a polyfunctional acrylate monomer,

(b) an acrylic resin composition comprising polymethyl methacrylate and methyl methacrylate monomer, and

(c) an inorganic filler.

 The types of the phase-transition microcapsule, the acrylic resin composition and the inorganic filler are as described above, and thus will not be described.

According to one embodiment, the method for producing artificial marble according to the present invention can be produced by mixing the composition in a reactor. At this time, the reactor is not limited to the type as long as it is commonly used in the art, and it is more preferable that the reactor is provided with a stirrer, a thermometer, a vacuum deaerator, and the like.

(B) an acrylic resin composition; (c) an inorganic filler; an initiator; a crosslinking agent; a coupling agent; and other additives are introduced into a reactor, and the mixture is stirred for 20 minutes Or more and can be vacuum degassed.

The surface layer composition is then cast into a mold or equipment and cured. At this time, the surface layer composition can be applied to the surface of the PVA film by preparing a polyvinyl alcohol (PVA) film on the bottom of the mold or equipment.

In this case, the PVA film is used to prevent the composition from adhering to the mold or equipment according to an embodiment, and is preferably 30 to 50 탆 in thickness.

The coating thickness of the surface layer composition according to an embodiment of the present invention may be 0.01 to 1 mm, preferably 0.01 to 0.5 mm. Although the specific gravity of the artificial marble is reduced during application in the above-mentioned range, the energy efficiency can be improved by providing an excellent heat storage effect.

The application of the surface layer composition may be carried out by various methods such as batch or continuous casting, but it is preferable to select the continuous casting method from the viewpoints of high productivity and reduced production cost. The continuous casting method will be described in detail as follows. The surface layer composition can be uniformly applied to the forming mold on which the PVA film is laid by using a metering pump. At this time, the speed of the metering pump may be 800 to 1,000 rpm.

An aluminum panel may be attached to the upper part of the artificial marble according to an embodiment of the present invention to produce a double composite panel.

The heat treatment according to an embodiment of the present invention may be performed at 80 to 120 ° C. Although the curing time is not limited at the above-mentioned heat treatment temperature, it is preferable that curing is carried out within about 1 hour. After curing, artificial marble can be visually inspected and mechanical performance checked after demoulding in molding mold.

The artificial marble according to the present invention has excellent storage and latent heat effects, thereby maximizing the energy storage efficiency and excellent durability, thus being excellent in use as artificial marble.

Hereinafter, artificial marble according to the present invention and a method for producing the same will be described in more detail with reference to the following examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the unit of the additives not specifically described in the specification may be% by weight.

[Measurement of physical properties]

1. Latent heat measurement

The latent heat of a microcapsule according to one embodiment was measured with a differential scanning calorimeter (DSC, TA company Q1000).

Measurement conditions: a temperature of 60 DEG C in a nitrogen atmosphere at a heating rate of 5 DEG C / min

2. Observation of morphology.

The FE-SEM (JSM 7610F, JEOL) was measured to observe the morphology of the phase transition microcapsule and artificial marble according to one embodiment and is shown in FIG. 1 to FIG. FE-SEM was prepared by diluting the microcapsule slurry with a 100-mL vial using 10 times distilled water, applying a thin film on the cover glass, and drying at room temperature. Subsequently, the sample was placed into a chamber using a SC7620 Sputter Coater to perform platinum coating on the sample, and the platinum coating was performed twice at a current of about 10 to 15 mA when the vacuum gauge reached 8 × 10 ^-2 mbar or less. After the coating was finished, the vacuum of the chamber was released, and the particle morphology and surface morphology of the capsules were observed at 1 kV using a high resolution developmental scanning electron microscope. In the case of artificial marble panels, after crushing with liquid nitrogen, the section was measured in the same manner as above.

[Production Example 1]

(Initiator Vazo 52G (ADVN, Dupont) 0.36 g) was added to 3.6 g of methyl methacrylate (MMA, LG-MMA), 3.6 g of trimethylolpropane triacrylate (TMPTA, KPX) and 1.2 g of epoxy acrylate (Miramer PE210, Miwon specialty Chemical) g, and then sufficiently melted to prepare a shell mixture. The shell mixture was added to 53.2 g of n-octadecane (RT28HC, RUBITHERM) heated to 40 DEG C and melted and 2.8 g of stearyl alcohol (Aecochem) to prepare a dispersed phase. Then, 79.64 ml of a 10 wt% aqueous solution of polyvinyl alcohol (PVA217, KURARAY POVAL) maintained at 40 DEG C was continuously added to the dispersion phase at 2,500 rpm using a homomixer for 2 minutes and emulsified for 10 minutes to obtain a stable o / w emulsion was prepared. Thereafter, the stirring speed was set to 300 rpm, the pH was adjusted to 4 with a 1 wt% aqueous phosphoric acid solution, and suspension polymerization was carried out at 60 캜 for 4 hours to prepare water in suspension. After cooling the suspension polymer to room temperature, the suspension polymer was pulverized using a spray dryer (FSD-1.5R) at a feeding rate of 100 ml / min, an atomizer speed of 13,000 rpm, In let temp. 180 캜, Out let temp. Spray-drying was carried out under the condition of 80 캜 to prepare phase change microcapsules.

As a result of measuring the particle size of the final product, a microcapsule having an average particle size of 10.4 탆, a latent heat capacity of 179.4 J / g, and a smooth surface and a complete spherical shape was obtained.

 [Production Example 2]

12.8 g of methyl methacrylate (MMA), 2.4 g of trimethylolpropane triacrylate (TMPTA) and 0.8 g of epoxy acrylate (Miramer PE 210, Miwon specialty Chemical) and initiator Vazo 52G (ADVN, Dupont ) Was used as the starting material.

The particle size of the final product was measured. As a result, microcapsules having an average particle size of 4.3 μm, a latent heat capacity of 202.0 J / g, and a smooth surface and complete spherical shape were obtained. .

 [Production Example 3]

In Preparation Example 1, 10.0 g of methyl methacrylate (MMA), 4.4 g of trimethylolpropane triacrylate (TMPTA), 1.8 g of epoxy acrylate (Miramer PE 210, Miwon specialty Chemical) and initiator Vazo 52G (ADVN, Dupont ) Was used as the starting material.

As a result of measuring the particle size of the final product, it was found that the average particle size was 6.6 탆, the latent heat capacity was 185.1 J / g, and the surface was smooth, spherical, and partially irregular or cracked.

 [Production Example 4]

 Except that n-nonadecane (RT31, RUBITHERM) was used instead of n-octadecane in Preparation Example 1 above.

As a result of measuring the particle size with respect to the final product, microcapsules having an average particle size of 9.2 mu m, a latent heat capacity of 100.2 J / g, and a smooth surface and complete spherical shape were obtained.

[Production Example 5]

Except that the epoxy acrylate was used in place of Miramer PE210 in the above Production Example 1, using Miramer PE250.

As a result of measuring the particle size with respect to the final product, a microcapsule having an average particle size of 9.5 mu m, a latent heat capacity of 170.7 J / g, and a smooth surface was obtained.

[Production Example 6]

Except that 1 part by weight of n-octyl acrylate was further added to 100 parts by weight of the monomer mixture in the preparation examples.

The particle size of the final product was measured. As a result, a microcapsule having an average particle size of 9.3 mu m, a latent heat capacity of 174.2 J / g, and a smooth surface was obtained.

[Comparative Production Example 1]

  In the same manner as in Production Example 1, except that 20.4 g of methyl methacrylate (MMA), 3.6 g of trimethylolpropane triacrylate (TMPTA) and 0.36 g of initiator Vazo 52G (ADVN, Dupont) Respectively.

As a result of measuring the particle size of the final product, the average particle size was 8.5 탆 and microcapsules with a latent heat capacity of 161.0 J / g were obtained. At this time, the surface of the microcapsule was uneven.

[Comparative Production Example 2]

  Except that 53.2 g of n-octadecane (RT28HC, RUBITHERM) and 55 g of n-octadecane (RT28HC, RUBITHERM) instead of 2.8 g of stearyl alcohol (AECOCEM) Respectively.

As a result of measuring the particle size of the final product, the average particle size was 7.6 mu m and a microcapsule having a latent heat capacity of 140.4 J / g was obtained. At this time, the surface of the microcapsule was uneven.

[Comparative Production Example 3]

Except that 20.4 g of methyl methacrylate (MMA) and 3.6 g of epoxy acrylate (Miramer PE 210, Miwon Specialty Chemical) and 0.36 g of initiator Vazo 52G (ADVN, Dupont) were used as the shell mixture in Comparative Preparation Example 1 Were carried out in the same manner.

As a result of measuring the particle size of the final product, the average particle size was 7.5 탆, and a microcapsule having a latent heat capacity of 99.1 J / g was obtained. At this time, the surface of the microcapsule was uneven.

It was confirmed that the phase transition microcapsule prepared in the above Preparation Example had excellent latent heat. Further, as shown in FIG. 1, spherical microcapsules having smooth surfaces were produced, and it was confirmed that the content of the heat storage material was maximized to exhibit more excellent latent heat characteristics.

The phase transition microcapsule of the present invention is further characterized in that the monomer mixture of the shell mixture contains 75 to 85% by weight of methyl methacrylate monomer, 10 to 20% by weight of the polyfunctional acrylate monomer and 1 to 10% by weight of the epoxy acrylate monomer , It was confirmed that the phase transition microcapsule formed a spherical surface with a more smooth surface and improved durability.

Further, polyvinyl alcohol was excellent as a continuous phase surfactant, but when polyvinylidone was used, it was confirmed that more uniform particles could be obtained.

Further, in the monomer mixture C ₈ to C ₂₀ alkyl acrylate based time to the monomer further comprises hayeoteul manufacturing microcapsules, C ₈ to C ₂₀ alkyl acrylate monomer micro the heat storage material due to expansion caused by high temperature and pressure The capsule was prevented from being damaged, and the microcapsules with better durability could be manufactured.

In Comparative Production Examples 1 and 2, microcapsules having low durability were prepared without epoxy acrylate. As shown in FIG. 2, shrinkage occurred and a rough and uneven shape like a concavo-convex structure was observed on the surface Respectively. In addition, the microcapsules having poor surface are low in the content of the heat storage material, widen the phase transition temperature range, and not only the heat storage effect is lowered, but also non-uniform microcapsules can not uniformly store the artificial marble in the artificial marble.

Further, when the multifunctional acrylate monomer is not contained, as in Comparative Production Example 3, the methyl methacrylate and the epoxy acrylate monomer are weakly bonded to each other, It is not preferable because it is exposed or spilled.

Also, when the shell mixture contains only the epoxy acrylate group, the adhesive strength between the microcapsules is improved by incorporating a large amount of unstable epoxy groups, so that the microcapsules are agglomerated to produce microcapsules having a large particle size. it's difficult. In addition, it may be necessary to add a curing agent according to an excessive amount of epoxy group. If a curing agent is added, heat is generated due to a rapid reaction and thermal decomposition of the heat storage material occurs.

[Example 1]

100 g of the phase change material (PCM) microcapsules prepared in Preparation Example 1, 20 wt% of polymethyl methacrylate (PMMA, atopia, AITOGLAS) and 80 wt% of methyl methacrylate (MMA, LGMMA) 300 g of the composition, 500 g of aluminum hydroxide powder (average particle diameter 20 m, CHALCO, special aluminum hydroxide), 6.9 g of lauroyl peroxide, 3.5 g of trimethylolpropane trimethacrylate and 3.0 g of hydroxyethyl methacrylate acid phosphate were added to a stirrer And the mixture was mixed at a rate of 300 rpm at 25 DEG C to prepare a composition.

(COLORCHIP-C001, Daicchon) 60 g, a defoamer (BYK-077 (BYK Japan KK) 6 g, an ultraviolet absorber (Tinuvin 1130, Ciba) 5.6 g, a pigment TONER HT WHITE 1000-1_GL300 ), And 5 g of a chain transfer agent (butylmercaptan).

The composition was applied on a steel belt with a polyvinyl alcohol (POVAL FILM (VF-KL), Kuraray, 30 탆) film on the bottom in a thickness of 12 mm on the cotta side. The coated composition was heat-treated in an oven controlled at a temperature of 100 캜 for 20 minutes to prepare artificial marble. The composition was applied on the surface of the artificial marble to a thickness of 0.1 mm, and then an aluminum panel was attached. Then, heat was applied at 30 DEG C for 30 minutes to perform a curing reaction to complete a two-layer composite panel. The content of formaldehyde in the finished panel was 0.005 mg / (m 2 h) using a UV / Vis spectrophotometer (OPTIZEN 3220UV, Mecasys).

[Example 2-6]

The phase transition microcapsules prepared in Preparation Example 1 in Example 1 were sequentially changed to Preparation Example 2-6.

[Example 7]

Except that 150 g of the phase-transition microcapsule in Example 1 was used.

[Example 8]

Except that 200 g of the phase-transition microcapsule in Example 1 was used.

[Example 9]

Except that 300 g of the phase-change microcapsules in Example 1 was used.

[Example 10]

300 g of an acrylic resin composition composed of a mixture of 20% by weight of polymethyl methacrylate (PMMA, Atopia, AITOGLAS) and 80% by weight of methyl methacrylate (MMA, LGMMA), 30 g of aluminum hydroxide powder (average particle diameter: 20 μm, CHALCO, special aluminum hydroxide, 6.9 g of lauroyl peroxide, 3.5 g of trimethylolpropane trimethacrylate and 3.0 g of hydroxyethyl methacrylate excipient phosphate were added to a stirrer and mixed at a rate of 300 rpm at 25 DEG C to prepare a comparative composition .

60 g of a chip (COLORCHIP-C001, Daicchon) for making a pattern, 6 g of BYK-077 (BYK Japan KK), 5.6 g of ultraviolet absorber (Tinuvin 1130, Ciba), 5 g of pigment (TONER HT WHITE 1000-1_GL300, , And 5 g of chain transfer agent (butylmercaptan) were added.

The comparative composition was applied on a steel belt with a polyvinyl alcohol (POVAL FILM (VF-KL), Kuraray, 30 탆) film laid on the floor at a thickness of 12 mm in the cotta section. The coated composition was heat-treated in an oven controlled at a temperature of 100 ° C for 20 minutes to produce artificial marble. The composition prepared in Example 1 was applied to the surface of the manufactured artificial marble to a thickness of 0.1 mm, and then an aluminum panel was attached. Then, heat was applied at 30 DEG C for 30 minutes to perform a curing reaction to complete a two-layer composite panel. The content of formaldehyde in the finished panel was 0.005 mg / (m 2 h) using a UV / Vis spectrophotometer (OPTIZEN 3220UV, Mecasys).

[Comparative Example 1-3]

The phase transfer microcapsules prepared in Preparation Example 1 in Example 1 were sequentially changed to Comparative Preparation Example 1-3, and the same procedure was carried out.

[Comparative Example 4]

Except that the phase transition microcapsules were not included in Example 1 above.

division Formability Power load
(kWh / mon.) Example 1 O 271 Example 2 O 266 Example 3 △ 268 Example 4 O 290 Example 5 O 273 Example 6 O 270 Example 7 O 258 Example 8 × - Example 9 × - Example 10 △ 290 Comparative Example 1 △ 285 Comparative Example 2 △ 288 Comparative Example 3 △ 299 Comparative Example 4 O 308

As shown in Table 1, the artificial marble prepared in the example according to the present invention is excellent in moldability and superior in its formability because it includes (a) phase transition microcapsule, (b) acrylic resin composition and (c) It is confirmed that energy saving effect can be realized because the power load is low due to the latent heat and heat storage effect.

Conventionally, a method of encapsulating a phase transition material by microencapsulation with melamine or formaldehyde resin is used. The melamine resin obtained by the polycondensation of melamine and formaldehyde has characteristics such as excellent mechanical strength and heat resistance. However, in this method, there is a possibility that formaldehyde, which is harmful to the human body, may remain because formaldehyde having a molar number twice or more of the melamine is added to increase the reaction rate of the melamine. On the contrary, when the phase transition microcapsule according to the present invention has a small possibility of residual formaldehyde and when it is confirmed that the amount of formaldehyde is less than 0.005 mg / (m 2 h) I was able to confirm that it was eco-friendly without harmful substances.

In Examples 8 and 9, phase transition microcapsules were included. However, when they contained a large amount of phase transition microcapsules, the mechanical properties were increased and fracture occurred, resulting in poor moldability and difficulty in measuring the efficiency.

As shown in Example 10, when the conventional artificial marble not including the conventional phase transition microcapsule was used as the base layer and the phase transition microcapsule was included in the surface layer, it was confirmed that an excellent storage effect compared to the phase transition microcapsule content was exhibited.

More specifically, it was confirmed that the embodiment of the present invention including phase-transition microcapsules as compared with Comparative Example 4 has an energy saving rate of up to 27%.

Also, when the monomer mixture of the shell mixture contains 75 to 85% by weight of methyl methacrylate monomer, 10 to 20% by weight of the polyfunctional acrylate monomer and 1 to 10% by weight of the epoxy acrylate monomer, phase transition microcapsules are included The artificial marble has improved durability and moldability, and has excellent latent heat and heat storage effect, thereby further improving the energy saving rate.

Further, when the microcapsules prepared by further containing the C ₈ -C ₂₀ alkyl acrylate monomer in the monomer mixture were included in the artificial marble, the durability was further enhanced.

In addition, Comparative Examples 1 and 2 included microcapsules having poor surface smoothness, and the phase transition temperature range was widened, so that the heat storage effect was lowered, and unevenness was exhibited in the artificial marble.

In addition, the durability of Comparative Example 3 was low, so that it was vulnerable to an external impact, and the heat storage material was exposed or leaked to the outside.

Therefore, the artificial marble according to the present invention not only has excellent durability but also exhibits a high heat storage and latent heat effect, thereby providing an excellent energy saving rate.

As described above, the artificial marble and the manufacturing method thereof have been described in the present invention through the specified matters and the limited embodiments. However, the present invention is not limited to the above-described embodiments, It is to be understood that the invention is not limited thereto and that various modifications and changes may be made thereto by those skilled in the art.

Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (12)

(a) a core comprising a heat storage material and
Comprising a shell comprising an acrylic polymer prepared from a monomer mixture comprising 50 to 90% by weight of a methyl methacrylate monomer, 1 to 10% by weight of an epoxy acrylate monomer and 5 to 45% by weight of a polyfunctional acrylate monomer, capsule,
(b) an acrylic resin composition comprising polymethyl methacrylate and methyl methacrylate monomer, and
(c) an artificial marble which is cured by applying a composition comprising an inorganic filler. The method according to claim 1,
Wherein the composition comprises 10 to 40% by weight of phase transition microcapsules, 15 to 40% by weight of an acrylic resin composition and 30 to 65% by weight of an inorganic filler. The method according to claim 1,
Wherein the monomer mixture of the phase transfer microcapsules comprises 75 to 85% by weight of methyl methacrylate monomer, 10 to 20% by weight of the polyfunctional acrylate monomer and 1 to 10% by weight of the epoxy acrylate monomer. The method according to claim 1,
Wherein the acrylic resin composition comprises 10 to 30% by weight of polymethyl methacrylate and 70 to 90% by weight of methyl methacrylate. The method according to claim 1,
Wherein the inorganic filler is any one selected from aluminum hydroxide, calcium carbonate, silica, alumina, and magnesium hydroxide, or a mixture thereof. The method according to claim 1,
Wherein the composition further comprises a marble chip. The method according to claim 1,
The artificial marble is a double composite panel in which an aluminum panel is attached to the upper part of artificial marble. Phase transition microcapsule, an acrylic resin composition and an inorganic filler, and is cured by heat treatment,
The composition comprises (a) a core comprising a heat storage material and
Comprising a shell comprising an acrylic polymer prepared from a monomer mixture comprising 50 to 90% by weight of a methyl methacrylate monomer, 1 to 10% by weight of an epoxy acrylate monomer and 5 to 45% by weight of a polyfunctional acrylate monomer, capsule,
(b) an acrylic resin composition comprising polymethyl methacrylate and methyl methacrylate monomer, and
(c) an inorganic filler. 9. The method of claim 8,
Wherein an aluminum panel is attached to the upper part of the artificial marble to produce a double composite panel. 9. The method of claim 8,
Wherein the coating thickness is 0.01 to 1 mm. 9. The method of claim 8,
Wherein the heat treatment is performed at 80 to 120 占 폚. 9. The method of claim 8,
Wherein the inorganic filler is any one selected from aluminum hydroxide, calcium carbonate, silica, alumina, and magnesium hydroxide, or a mixture thereof.

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