KR20230115230A - Artificial marble composition and method for manufacturing artificial marble using the same - Google Patents

Abstract

An artificial marble composition according to an exemplary embodiment of the present invention includes a liquid binder resin including an unsaturated polyester resin; A thermosetting powder resin having a glass transition temperature (Tg) of 50° C. or higher and a melting temperature of 60° C. or higher; inorganic particles; and quartz powder.

Description

Artificial marble composition and method for manufacturing artificial marble using the same

This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0011437 filed with the Korean Intellectual Property Office on January 26, 2022, the entire contents of which are incorporated herein.

The present invention relates to an artificial marble composition and a method for manufacturing artificial marble using the same.

Representative types of artificial marble include polyester-based artificial marble, epoxy-based artificial marble, melamine-based artificial marble, and engineered stone-based artificial marble. Such artificial marble has a beautiful appearance and excellent workability, is lighter than natural marble, and has excellent strength, so it is widely used as counter tables and various interior materials. Artificial marble known to date mainly implements an appearance effect through a combination of opaque chips of a single color. However, in this way, there is a limit to implementing a pattern similar to natural marble or granite on artificial marble. Accordingly, many studies are being conducted to develop artificial marble having an appearance closer to that of natural marble.

In addition, engineered stone is an artificial marble, also called Easton, and is an interior material that has a texture and feel similar to that of natural stone. In the industry, studies have been conducted to enhance aesthetics by improving the color and shape of artificial marble. For example, Korean Patent Registration No. 10-1270415 discloses artificial marble with diversified patterns and appearances using marble chips. . Demand for engineered stone is gradually increasing for interior floors, wall decorations, kitchen tops, etc., and products imitating natural stone species such as granite and marble have been the main products.

However, interest in quartzite having a more luxurious pattern is gradually increasing in the recent interior market. Reflecting this trend, the Easton industry is making great efforts to implement the corresponding stone species.

Republic of Korea Patent No. 10-1270415

The present invention is to provide an artificial marble composition and a method for manufacturing artificial marble using the same. More specifically, the present invention is to provide an artificial marble composition capable of realizing a natural flow pattern and a method for manufacturing artificial marble using the same.

One embodiment of the present invention,

A liquid binder resin containing an unsaturated polyester resin;

A thermosetting powder resin having a glass transition temperature (Tg) of 50° C. or higher and a melting temperature of 60° C. or higher;

inorganic particles; and

quartz powder

It provides an artificial marble composition comprising a.

In addition, another embodiment of the present invention,

Forming a base layer in a plate shape by powdering a base composition in a horizontally oriented mold;

Forming a concave pattern on the base layer;

injecting the artificial marble composition into the intaglio pattern; and

After performing vibration and compression processes, performing a thermal curing process to form artificial marble having a vane pattern

It provides a method for manufacturing artificial marble comprising a.

In addition, another embodiment of the present invention provides an artificial marble that is manufactured by the manufacturing method of the artificial marble.

An artificial marble composition according to an exemplary embodiment of the present invention is obtained by simultaneously applying a liquid binder resin containing an unsaturated polyester resin and a thermosetting powder resin having a glass transition temperature (Tg) of 50 ° C. or higher and a melting temperature of 60 ° C. or higher. , It is possible to manufacture artificial marble capable of realizing a natural flow pattern without pinholes in the vane pattern of the artificial marble.

In addition, according to an exemplary embodiment of the present invention, since the thermosetting powder resin having a glass transition temperature (Tg) of 50 ° C. or more and a melting temperature of 60 ° C. or more can serve as an inorganic binder, a vane pattern of artificial marble is formed. occurrence of pinholes can be suppressed.

1 is a diagram schematically showing a thermal curing process in the manufacturing method of artificial marble of the present invention.

Hereinafter, the present invention will be described in more detail.

In the present invention, when a member is said to be located “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In the present invention, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

Conventionally, when forming a vein pattern of artificial marble, a composition containing inorganic particles such as silica particles and quartz particles and an inorganic pigment was used. However, since such a composition lacks a resin capable of holding inorganic materials such as inorganic particles and inorganic pigments, there is a problem in that pinholes are generated in the vein pattern of the artificial marble. In order to improve this, a liquid binder resin containing an unsaturated polyester resin was applied to the vane pattern forming composition, but boiling or bubbles were generated in the portion where the liquid binder resin was gathered, and thus, the vane pattern of the artificial marble was still formed. A pinhole occurred.

Accordingly, an object of the present invention is to provide an artificial marble composition capable of suppressing the occurrence of pinholes in a vane pattern of artificial marble and a method for manufacturing artificial marble using the same.

An artificial marble composition according to an exemplary embodiment of the present invention includes a liquid binder resin including an unsaturated polyester resin; A thermosetting powder resin having a glass transition temperature (Tg) of 50° C. or higher and a melting temperature of 60° C. or higher; inorganic particles; and quartz powder.

Hereinafter, each component of the artificial marble composition will be described.

liquid binder resin

In one embodiment of the present invention, the artificial marble composition includes a liquid binder resin containing an unsaturated polyester resin.

In one embodiment of the present invention, the liquid binder resin is an unsaturated polyester resin, based on 100 parts by weight of 0.4 parts by weight to 2.5 parts by weight of a curing agent, 0.05 parts by weight to 0.3 parts by weight of a catalyst, and 0.5 parts by weight to 7 parts by weight of a coupling agent. It can be prepared by mixing and dispersing parts.

In one embodiment of the present invention, the liquid binder resin contains 90% by weight or more of an unsaturated polyester resin, and the unsaturated polyester resin contains an unsaturated polyester polymer and a vinyl monomer in a weight ratio of 100: 30 to 70 It can be prepared using the composition. More preferably, the unsaturated polyester resin may be prepared using a composition comprising 60% to 75% by weight of an unsaturated polyester polymer and 25% to 40% by weight of a vinyl monomer.

The weight average molecular weight of the unsaturated polyester resin is 1,000 g/mol to 10,000 g/mol.

The unsaturated polyester polymer is not particularly limited, and includes, for example, saturated or unsaturated dibasic acids; and an unsaturated polyester polymer prepared through a condensation reaction of a polyhydric alcohol. Examples of the saturated or unsaturated dibasic acid include ortho-phthalic acid, isophthalic acid, maleic anhydride, citraconic acid, fumaric acid, itaconic acid, phthalic acid, phthalic anhydride, terephthalic acid, succinic acid, adipic acid, sebacic acid or tetrahydrophthalic acid. can be used In addition, as the polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, hydrogenated bisphenol A, trimethylolpropane monoaryl Ether, neopentyl glycol, 2,2,4-trimethyl-1,3-pentadiol and/or glycerin may be used. In addition, if necessary, a monobasic acid such as acrylic acid, propionic acid or benzoic acid; Alternatively, a polybasic acid such as trimellitic acid or tetracarboxylic acid of benzol may be further used.

As the type of the vinyl monomer, an alkyl acrylate monomer or an aromatic vinyl monomer may be used, but it is preferable to use an aromatic vinyl monomer in consideration of reactivity with an unsaturated polyester polymer. For example, as the aromatic vinyl monomer, at least one selected from styrene, α-methylstyrene, p-methylstyrene, vinyl toluene, alkyl styrene substituted with an alkyl group having 1 to 3 carbon atoms, and styrene substituted with a halogen may be used. may be used, and preferably, a styrene monomer may be used.

The curing agent may be included for the curing reaction of the binder, and may use a curing agent used in the manufacture of artificial marble, particularly engineered stone, and is not particularly limited. The curing agent may be an organic peroxide-based compound or an azo-based compound. The organic peroxide-based compound is a tert-butyl peroxybenzoate heat curing agent (TBPB, Trigonox C, akzo novel), diacyl peroxide, hydroperoxide, ketone peroxide, peroxy ester, peroxy ketal, dialkyl peroxide, It may be one or two or more selected from among alkyl peresters, percarbonates, and peroxydicarbonates. For example, the curing agent is tert-butyl peroxybenzoate thermal curing agent, benzoyl peroxide, dicumyl peroxide, butyl hydroperoxide, cumyl hydroperoxide, methyl ethyl ketone peroxide, t-butyl peroxy maleic acid, t-butyl It may be hydro peroxide, acetyl peroxide, lauroyl peroxide, t-butyl peroxy neodecanoate, or t-amyl peroxy 2-ethyl hexanoate, but is not limited thereto.

In addition, the azo-based compound may be azobisisobutyronitrile, but is not limited thereto.

The binder resin may include 0.4 to 2.5 parts by weight of a curing agent based on 100 parts by weight of the unsaturated polyester resin. When the curing agent is included in an amount of 0.4 parts by weight or more, the binder can be sufficiently cured, and when the content is 2.5 parts by weight or less, discoloration of the binder due to a high exothermic reaction and generation of bubbles due to boiling can be prevented.

The catalyst may be included to promote curing of the binder at a low temperature, and a catalyst used in the manufacture of artificial marble, particularly engineered stone, may be used and is not particularly limited. The catalyst may be metal soaps such as cobalt-based, vanadium-based, and manganese-based; tertiary amines; quaternary ammonium salts; And it may be one or two or more selected from mercaptans. For example, a cobalt 6% catalyst (Hex-Cem, Borchers) can be used. The binder resin may include 0.05 parts by weight to 0.3 parts by weight of the catalyst based on 100 parts by weight of the unsaturated polyester resin. When the catalyst is included in an amount of 0.05 parts by weight or more, it is advantageous to promote curing, and when included in an amount of 0.3 parts by weight or less, discoloration of the binder may be prevented.

The coupling agent may be included to improve bonding strength between the binder resin and inorganic particles and/or quartz powder, and may be silane-based or silicate-based. The binder resin may include 0.5 parts by weight to 7 parts by weight of the coupling agent based on 100 parts by weight of the unsaturated polyester resin. When the coupling agent is included in an amount of 0.5 parts by weight or more, it is advantageous to improve bonding strength with the inorganic particles and/or quartz powder, and when it is included in an amount of 7 parts by weight or less, it is advantageous to lower the cost of raw materials.

inorganic particles

In one embodiment of the present invention, the inorganic particles mean inorganic particles having a particle size of 0.1 mm to 4.0 mm. The inorganic particles may include two or more types of inorganic particles having different particle sizes, for example, a first inorganic particle having a particle size of 0.1 mm or more and less than 0.3 mm, and a second inorganic particle having a particle size of 0.3 mm or more and 0.7 mm or less. However, it is not limited thereto.

The inorganic particles may be mineral particles such as feldspar, quartz, and aluminum hydroxide, or may include at least one selected from amorphous silica particles, glass particles, and crystalline quartz particles as highly transparent inorganic particles.

In particular, the high-transparency inorganic particles are amorphous silica particles, glass particles containing barium ions, and/or crystalline quartz particles having an SiO ₂ content of 99.5% to 100% by weight. Preferably, the inorganic particles of the present invention include amorphous silica particles, glass particles having a barium (Ba) ion content of 10% to 35% by weight in the particles, and/or crystalline quartz having a SiO ₂ content of 99.5% to 100% by weight. is a particle More preferably, the inorganic particles of the present invention are amorphous silica particles and glass particles having a barium (Ba) ion content of 10% to 35% by weight.

As an exemplary embodiment, artificial marble prepared using amorphous silica particles as inorganic particles or glass particles having a barium (Ba) ion content of 10% to 35% by weight in the particles has a SiO ₂ content of 99.5% by weight as inorganic particles. Light transmittance is higher than that of artificial marble prepared using crystalline quartz particles of 100% to 100% by weight. In addition, the artificial marble prepared using amorphous silica particles or glass particles having a barium (Ba) ion content of 10% to 35% by weight as the inorganic particles of the present invention has a SiO ₂ content of 99.5% by weight. It has higher luminance than artificial marble prepared using crystalline quartz particles of 100% to 100% by weight.

In one embodiment of the present invention, the inorganic particles may be amorphous silica particles. The silica particle is a term commonly used in the field of artificial marble, and generally means a SiO ₂ -based inorganic particle containing a small amount of other components such as minerals in addition to SiO ₂ as high as 90% by weight _or more. . The amorphous silica particles of the present invention may be amorphous fused silica particles, and the amorphous silica particles of the present invention may also be referred to herein as highly transparent amorphous fused silica particles. The amorphous fused silica particles may be amorphous fused silica particles having a particle size of 1.2 mm to 5.0 mm. In addition, the amorphous fused silica particles have a SiO ₂ content of 99.5% to 100% by weight, preferably 99.6% to 100% by weight, more preferably 99.7% to 100% by weight. In addition, the amorphous fused silica particles may have an alumina content of 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.3% by weight or less, and even more preferably 0.2% by weight or less. When the SiO ₂ content in the amorphous silica particles is 99.5% by weight or more, preferably 99.6% by weight or more, and more preferably 99.7% by weight or more, the light transmittance of the artificial marble is further improved.

The content of SiO ₂ in the amorphous silica particles and crystalline quartz particles of the present invention can be confirmed by quantitatively analyzing the content using XRF (X-Ray Fluorescence Spectroscopy). In addition, crystalline particles and amorphous particles can be confirmed by XRD (X-ray diffraction). XRF can generally be confirmed by measuring particles after making them into pellets, and XRD can be confirmed by measuring particles or artificial marble.

In one embodiment of the present invention, the inorganic particles may be glass particles containing barium ions. Preferably, the glass particles of the present invention have a barium (Ba) ion content of 10 wt% to 35 wt%, more preferably 15 wt% to 25 wt%.

Since glass is amorphous, the barium ion-containing glass particles of the present invention may also be referred to herein as highly transparent amorphous glass particles. At this time, high transparency means that the transmittance of visible light is 90% to 100%, and specifically, it means having a transmittance of 90% or more in the visible ray region when measured with a UV / VIS spectrophotometer on the basis of a glass plate before grinding into particles. do.

The content of barium ions in the glass particles can be measured by X-ray scanning. When detected by X-ray scanning, the content of barium (Ba) ions in the glass particles is preferably detected as 10% by weight to 35% by weight, more preferably 15% by weight to 25% by weight. Even if the barium ion content is out of the above range, the transparency of the glass particles themselves is good, but when artificial marble is manufactured using the glass particles, the artificial marble is unsuitable for use because it is blue or jade-colored even when viewed with the naked eye. That is, when artificial marble is made using glass particles whose barium (Ba) ion content is detected as 10% to 35% by weight when detected by X-ray scanning, it does not have bluish or jade-blue light, has good color and excellent product quality. Artificial marble can be manufactured.

The content of barium ions in artificial marble can be confirmed as follows. When artificial marble is manufactured using glass particles containing barium ions, barium ions are included in the artificial marble. When the artificial marble containing more than a certain amount of barium ions is scanned using X-rays, the artificial marble appears blue in the X-ray image. The barium ion content in the glass particles is also measured in the same way.

Preferably, the glass particles of the present invention may be glass particles having a particle size of 1.2 mm to 5.0 mm, and transmittance of 90% or more in the visible ray region when measured with a UV / VIS spectrophotometer on a glass plate basis before grinding into particles. It may be a highly transparent glass particle having.

The inorganic particles of the present invention may be crystalline quartz particles. The crystalline quartz particles of the present invention may also be referred to herein as high-transparency crystalline quartz particles.

At this time, the crystalline quartz particles may be highly transparent crystalline quartz particles having a particle size of 1.2 mm to 5.0 mm, and the SiO ₂ content is 99.5% to 100% by weight, preferably 99.6% to 100% by weight, more preferably is from 99.7% to 100% by weight. In addition, the crystalline quartz particles may have an alumina content of 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.3% by weight or less, and even more preferably 0.2% by weight or less.

When the content of SiO ₂ in the crystalline quartz particles is less than 99.5% by weight, for example, less than 99.4% by weight, light transmittance of the artificial marble may be lowered. Therefore, crystalline quartz particles having an SiO ₂ content of 99.5% by weight or more are preferred.

The particle size may be measured using a Beckman coulter LS 13 320 Particle size analyzer particle size analyzer.

quartz powder

In one embodiment of the present invention, the artificial marble composition includes quartz powder. In this case, the quartz powder means quartz powder having a particle size of less than 0.1 mm. For example, the quartz powder may include either or both of powder having a particle size of less than 55 μm and powder having a particle size of 55 μm or more and less than 0.1 mm.

The particle size may be measured using a Beckman coulter LS 13 320 Particle size analyzer particle size analyzer. The quartz powder of the present invention may also be referred to herein as a highly transparent crystalline quartz powder.

The quartz powder of the present invention may be a general quartz powder having a SiO ₂ content of less than 99.5%, or a crystalline quartz powder to increase transparency. The crystalline quartz powder is preferably a crystalline quartz powder having a SiO ₂ content of 99.5% to 100% by weight. The crystalline quartz powder of the present invention has a SiO ₂ content of 99.5% to 100% by weight, preferably 99.6% to 100% by weight, more preferably 99.7% to 100% by weight, and an alumina content of 0.5% by weight or less. , preferably 0.4% by weight or less, more preferably 0.3% by weight or less, and even more preferably 0.2% by weight or less.

The crystalline quartz powder of the present invention preferably has an average SiO ₂ content of 99.5% to 100% by weight, and preferably an average alumina content of 0.5% by weight or less.

The content of SiO ₂ in the crystalline quartz powder of the present invention can be confirmed by quantitatively analyzing the content using XRF (X-Ray Fluorescence Spectroscopy). At this time, the powders are generally made into pellets and then measured and confirmed.

Since the crystalline quartz powder has a small particle size, self-scattering occurs. Therefore, in order to increase the internal light transmittance of the artificial marble, the artificial marble of the present invention may include crystalline quartz powder having a SiO ₂ content of 99.5% by weight or more. If the SiO ₂ content of the crystalline quartz powder is less than 99.5% by weight, the internal light transmittance of the artificial marble is low, and thus it may be difficult to manufacture artificial marble having high light transmittance.

powder resin

In one embodiment of the present invention, the artificial marble composition includes a thermosetting powder resin having a glass transition temperature (Tg) of 50°C or more and a melting temperature of 60°C or more.

The melting temperature of the powdered resin may be 60 °C or higher, 70 °C or higher, or 80 °C or higher. In addition, the melting temperature of the powdered resin may be 130 ℃ or less, may be 125 ℃ or less, may be 120 ℃ or less.

The glass transition temperature (Tg) of the powdered resin may be 50 °C or higher and 51 °C or higher. In addition, the glass transition temperature (Tg) of the powdered resin may be 70 ℃ or less, may be 65 ℃ or less.

The temperature at which curing of the powdered resin starts may be 118° C. or higher and may be 120° C. or higher. In addition, the temperature at which curing of the powdered resin starts may be 135° C. or less, and may be 130° C. or less.

The powder resin may use a thermosetting type powder resin. That is, the powdered resin does not react at room temperature and exists as a powder in a stable state, and when heat is applied to the powdered resin, the powdered resin melts and serves as a binder holding the inorganic substances included in the composition.

The powdered resin is an epoxy acrylate resin, a glycidyl methacrylate resin, a butyl methacrylate resin, a methyl methacrylate resin, a saturated polyester resin, a copolymer of methyl methacrylate resin and glycidyl methacrylate, A polymer resin, a copolymer resin obtained by polymerizing a methyl methacrylate resin and an epoxy acrylate resin, a polyester epoxy hybrid resin, and a resin in which glycidyl isocyanurate is mixed with polyester may be included. can

The average particle size of the powdered resin may be 5 μm to 25 μm, and may be about 15 μm. In addition, the powdered resin may undergo a curing reaction when heat is applied at a temperature of 118° C. or higher for 40 minutes or more.

inorganic pigment

In one embodiment of the present invention, the artificial marble composition may further include an inorganic pigment. As the inorganic pigment, inorganic pigments known in the art may be used, and are not particularly limited. For example, the inorganic pigment may include at least one selected from TiO ₂ , NiO•Sb ₂ O ₃ 20TiO ₂ , Fe ₂ O ₃ , and Fe ₃ O ₄ , but is not limited thereto.

The inorganic pigment may be gently mixed so as not to be uniformly distributed in the artificial marble composition. Since the inorganic pigment is non-uniformly present, the vein pattern can be maintained transparently, and the region including the inorganic pigment has a more transparent appearance due to the inorganic pigment.

At this time, in order to manufacture vane patterns having various colors, a plurality of artificial marble compositions to which inorganic pigments capable of representing each color are applied may be used.

In one embodiment of the present invention, based on the total weight of the artificial marble composition, the content of the liquid binder resin is 6% to 15% by weight, the content of the inorganic particles is 50% to 65% by weight, The content of the quartz powder may be 20% to 35% by weight, the content of the powdered resin may be 3% to 20% by weight, and the content of the inorganic pigment may be 0.01% to 3% by weight. More preferably, the content of the liquid binder resin is 6% to 12% by weight, the content of the inorganic particles is 50% to 60% by weight, the content of the quartz powder is 20% to 30% by weight, , The content of the powdered resin may be 3% to 15% by weight, and the content of the inorganic pigment may be 0.01% to 1.5% by weight.

In the artificial marble composition, the quartz powder is evenly distributed in the liquid binder resin and the powder resin to prevent excessive shrinkage of the resin during the thermal curing process and at the same time prevent the formation of empty spaces between inorganic particles. Therefore, based on the total weight of the artificial marble composition, if the content of the quartz powder is less than 20% by weight, curing shrinkage of the resin may not be prevented and wrinkles in the form of valleys may be formed, and if the content exceeds 35% by weight As the specific surface area increases, pinholes may occur in a partial region where the liquid binder resin and the powder resin do not exist.

In one embodiment of the present invention, the total content of the liquid binder resin and the powdered resin may be 9% by weight or more, 10% by weight or more, and 23% by weight or less based on the total weight of the artificial marble composition. .

Based on the total weight of the artificial marble composition, when the total content of the liquid binder resin and the powdered resin is less than 9% by weight, the content of the resin is low, making it difficult to obtain a product in the form of transparent particles attached, and in the heat curing process after high pressure Pinholes may occur due to insufficient binding. In addition, based on the total weight of the artificial marble composition, when the total content of the liquid binder resin and the powder resin exceeds 23% by weight, quartz powder and solid powder may adhere to the surface of the inorganic particles to form a large dough, However, since a dough with poor flowability is formed, it is undesirable because it may be difficult to transfer the belt and mold in the process.

In one embodiment of the present application, the artificial marble composition may be used to form a vein pattern of artificial marble.

In addition, the method for manufacturing artificial marble according to an exemplary embodiment of the present application includes forming a base layer in a plate shape by dividing a base composition in a horizontally oriented mold; Forming a concave pattern on the base layer; injecting the artificial marble composition into the intaglio pattern; and forming artificial marble having a vane pattern by performing a vibration and compression process and then a thermal curing process.

A method for manufacturing artificial marble according to an exemplary embodiment of the present invention includes forming a base layer in a plate shape by powdering a base composition in a horizontally oriented mold.

The mold may be a container having a predetermined shape so that the artificial marble composition discharged from the hopper can be contained in a predetermined shape. In particular, in one embodiment of the present invention, the mold is oriented horizontally to form the base layer in a plate-like shape, and as in the prior art, different types of mixtures of natural quartz, unsaturated polyester liquid resin and solid pigment are prepared to vertically It is different from the manufacturing process by layering with

The base layer may be formed by injecting a base composition into a plurality of hoppers controlled by a digital divider and then dividing the base composition into a mold.

The base composition may include a liquid binder resin, inorganic particles, and quartz powder. Details of the liquid binder resin, inorganic particles, and quartz powder of the base composition are the same as described above.

The manufacturing method of artificial marble according to an exemplary embodiment of the present invention includes forming a concave pattern on the base layer. Forming the concave portion pattern on the base layer may use a method known in the art. For example, the step of forming the concave portion pattern on the base layer may use a knife for producing a vane pattern, but is not limited thereto. In this case, the depth of the concave portion pattern may be 100% or less, 80% or less, 75% or less, or 50% or more of the thickness of the base layer.

When the depth of the concave pattern exceeds 80% of the thickness of the base layer, the knife for manufacturing the intaglio pattern may touch the lower floor during the formation process of the intaglio pattern in the base layer, and the width of the intaglio pattern is 15 mm. Complete drying is possible at 70mm to 70mm. In addition, when the depth of the concave pattern is 100%, it is possible to implement a design pattern in which the concave pattern can be seen even from the side when the artificial marble is cut in a vertical plane. In addition, when the depth of the concave portion pattern is less than 50% of the thickness of the base layer, the vane pattern may be removed during subsequent processes such as bending and cut down of the manufactured artificial marble, which is not preferable.

When forming a pattern on artificial marble, in order to form a pattern with a relatively wide width, it is common to separately mix a composition of different colors using pigments, prepare a position to form a pattern, and then powder the position at that position. am. In addition, it is common for patterns at the level of thin ornamental lines to sprinkle liquid pigment directly on a powdered base or to form a shallow path by dipping lightly with a pre-prepared embossed frame and then sprinkle liquid pigment on it.

The process of forming the concave portion pattern of the present invention refers to a step of preparing a position to form a pattern, especially in the case of the former having a separate composition, among the above-described pattern formation processes for imparting a pattern to artificial marble. The process of forming the concave portion pattern to secure the position where the pattern is to be formed is exemplarily the following method, but is not limited thereto.

1) Use of tools

With a tool shaped like a shovel or chisel, it is possible to set aside the pattern along the length of the pattern to be formed, or to remove it by means such as an aspirator to secure the intaglio pattern. Even after securing the intaglio pattern, the composition for the base on the side often collapses and is mixed, so it can give a natural feeling when used when implementing a stone species or design with unclear boundaries.

2) Embossed frame (embossed plate)

The composition in the pattern area is not pushed aside or removed, but is pressed to make space. A pre-designed embossed frame (emboss plate) can be placed on the divided base and applied pressure to form a concave pattern.

The embossed frame (emboss plate) can be used alone, but various auxiliary means can be utilized. For example, when an auxiliary mask with a barrier rib is additionally used, an embossed frame having the same shape as the perforation position of the auxiliary mask can be applied, and at this time, even after removing the embossed frame, the composition on the side is mixed into the pattern area by the auxiliary mask barrier rib. can form a neat pattern.

3) Use of a specific tool to secure a pattern of intaglios of a specific shape

When the shape in the depth direction as well as the surface of artificial marble is important, it is possible to secure the concave pattern with the shape in the depth direction controlled by using a precisely designed tool. For example, an asymmetric concave portion pattern may be formed by pressing using a tool designed with one side vertical and one side diagonal. When an asymmetrical pattern is filled with a highly transparent (glass or highly transparent composition, etc.) pattern, a gradation effect can be exhibited in the depth direction.

4) Pattern frame

Before dividing the base, a pattern frame having a pattern area is installed in advance, and then the base is divided. Thereafter, when the pattern frame is removed, the same intaglio pattern as the pattern frame can be secured.

The method for manufacturing artificial marble according to an exemplary embodiment of the present invention includes introducing the artificial marble composition according to the present invention to the intaglio pattern.

Mixing of the artificial marble composition may be performed by a dry mixer or wet mixer applied in a ceramic powder mixing process.

In one embodiment of the present invention, the step of injecting the artificial marble composition into the concave portion pattern may be performed by a powdering process of a discharge method of the artificial marble composition. Through this process, the vane patterns of the artificial marble can be implemented in the form of various colors, and thin and clear vane patterns having one or more colors can be formed adjacent to each other, as well as gradation There is a feature that can implement shapes such as natural flow patterns and smeared patterns, such as colors. Accordingly, a vane pattern according to an exemplary embodiment of the present invention may have two or more colors, gradation colors, or a combination thereof. Also, the vane pattern according to an exemplary embodiment of the present invention may include a straight line pattern, a curved pattern, or a combination pattern thereof.

The step of discharging the composition is a step of filling the concave portions formed by discharging the composition after the step of forming the concave portion patterns. In the step of discharging the composition, a machine or equipment capable of discharging the composition may be used.

In the step of discharging the composition, the size of the outlet may be appropriately adjusted. When the width of the concave portion is large, a discharge port having a large size may be used, and when the width of the intaglio portion is small, a discharge port having a small size may be used.

In one embodiment of the present invention, after the step of injecting the artificial marble composition into the concave portion pattern, performing a vibration and compression process, and then performing a thermal curing process to form artificial marble having a vane pattern. includes

The solid phase having a pattern is positioned by the vibration and compression process, and then the powder resin is melted and converted into a liquid resin by a thermal curing process. In particular, the liquid resin in which the powder resin is melted may play a role of connecting spaces between inorganic particles, and since the liquid resin in which the powder resin is melted is transparent, the inorganic particles may be connected to each other as a whole.

In one embodiment of the present invention, the compression molding process may use a process known in the art. For example, the compression may be performed by vibrating compression at an initial 2,600 rpm for 30 seconds, then continuously raised to 3,100 rpm and vibrating vibrator press for 120 seconds, based on manufacturing a slab having a size of 300 mm × 300 mm × 20 mm. At this time, the pressure can be set to about 1.5 bar, which is a range in which the vibration vibrator is not damaged. The compression molding process may be performed according to the above description, but is not limited thereto.

The thermal curing process may be performed at a temperature of 118° C. or higher for 40 minutes or more. By such a heat curing process, the powdered resin of the artificial marble composition is melted and converted into a liquid resin, and then cured. Therefore, in one embodiment of the present invention, the melting and curing process of the powdered resin may be performed simultaneously.

In the manufacturing method of the artificial marble of the present invention, the thermal curing process is schematically shown in FIG. 1 below. As shown in FIG. 1, the artificial marble composition according to the present invention includes a liquid binder resin 10 including an unsaturated polyester resin; powdered resin 40; inorganic particles 20; and quartz powder 30, and the powdered resin 40 is melted and converted into a liquid resin 50 by a thermal curing process, and then cured.

The manufacturing method of artificial marble according to an exemplary embodiment of the present invention includes the steps of curing the artificial marble composition and then removing the mold to manufacture artificial marble; and a post-processing step of cutting the artificial marble and polishing the surface smoothly. A method of removing the mold, a post-processing method, and the like are not particularly limited, and methods known in the art may be used.

In addition, one embodiment of the present invention provides artificial marble that is manufactured by the method for manufacturing artificial marble.

An artificial marble composition according to an exemplary embodiment of the present invention is obtained by simultaneously applying a liquid binder resin containing an unsaturated polyester resin and a thermosetting powder resin having a glass transition temperature (Tg) of 50 ° C. or higher and a melting temperature of 60 ° C. or higher. , It is possible to manufacture artificial marble capable of realizing a natural flow pattern without pinholes in the vane pattern of the artificial marble.

In addition, according to an exemplary embodiment of the present invention, since the thermosetting powder resin having a glass transition temperature (Tg) of 50 ° C. or more and a melting temperature of 60 ° C. or more can serve as an inorganic binder, a vane pattern of artificial marble is formed. occurrence of pinholes can be suppressed.

In manufacturing the artificial marble as described above, the composition of the resin composition for the base and the resin composition for the pattern may be different from each other. Preferably, the pigments or binder resins in the composition may be different from each other, and more preferably, the binder resins may be different from each other. In addition, the meaning of being different may mean that the content is different, including the presence or absence of the composition. The difference in content is more than the level of error accepted in the industry, and may be exemplified by a difference of 10% or more, preferably 5% or more. If it is difficult to absolutely distinguish the difference in content, a relative comparison can be made with the resin composition for a base and the resin composition for a pattern prepared in the same way in a device that can be measured under the same conditions. Illustratively, relative comparison of content may be possible by comparing areas using GC, which is not subjected to quantitative analysis. At this time, when the area difference is 5% or more, it can be said that there is a difference in content.

The resin composition for the base is powdered on the entire pattern frame, and the resin composition for the pattern may select a composition suitable for discharging through a narrow inlet. Using the resin composition for patterns only in some patterns does not have a significant effect on the physical properties of artificial marble, but if the resin composition for patterns is the same for all patterns, there may be problems with the physical properties, and the process is performed while additionally using a binder. Because it is added, it may not be suitable in terms of cost.

Hereinafter, examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention is not construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

<Example>

<Example 1>

1) Preparation of base composition

First inorganic particles (quartz sand) having a particle size of 0.1 mm to 0.3 mm and second inorganic particles (quartz sand) having a particle size of 0.3 mm to 0.7 mm are mixed in a weight ratio of 1: 2.5 and inorganic particles and a liquid binder resin (Polynt, USA) unsaturated polyester resin) was mixed uniformly for 1 minute. Thereafter, quartz powder (Sibelco's quartz powder) having a particle size of 45 μm or less was added and mixed repeatedly twice for 1 minute to prepare a base composition.

At this time, based on the total weight of the base composition, 12% by weight of a liquid binder resin, 57% by weight of inorganic particles, and 31% by weight of quartz powder were used.

2) Preparation of artificial marble composition for vein patterns

After mixing the first inorganic particles (quartz sand) having a particle size of 0.1 mm to 0.3 mm and the second inorganic particle (quartz sand) having a particle size of 0.3 mm to 0.7 mm, a white inorganic pigment (TiO ₂ ) is added and maintained for 1 minute. Mixed evenly. Thereafter, an unsaturated polyester resin was added and mixed uniformly for 1 minute, and quartz powder having a particle size of 45 μm or less (Sibelco's quartz powder) was added and mixed twice for 1 minute. Finally, powdered resin was added and mixed for 2 minutes to prepare an artificial marble composition for a vane pattern. The powdered resin has a glass transition temperature of 53°C, a melting temperature of 119°C, and a curing reaction that starts at 123°C and ends at 180°C, and has a maximum exothermic temperature of 166°C during curing.

At this time, based on the total weight of the artificial marble composition for the vane pattern, 6.4% by weight of liquid binder resin, 17.8% by weight of first inorganic particles, 39.3% by weight of second inorganic particles, 1% by weight of inorganic pigment, 28.3% by weight of quartz powder, and 7.2% by weight of powdered resin.

3) Manufacture of artificial marble

The base composition was put into a rubber mold having a width of 300 mm, a length of 300 mm and a height of 18 mm, and the surface was compacted while pressing with a roller. After that, a concave pattern having a width of 15 mm and a length of 300 mm was formed using a spatula. After adding the artificial marble composition for the vane pattern prepared above to the concave portion pattern, vibration and pressure were applied for 1 minute under conditions of 2,900 rpm using a vibrating vibrator press to compact them.

The minced mixture was placed between hot plates with upper and lower portions heated to 130° C. and pressed from above and below with a force of 1 atm or less, and heat was applied for 50 minutes.

After curing was completed, it was cooled to room temperature and then removed from the mold to prepare artificial marble. After cutting the four sides of the artificial marble, the surface was polished smoothly to manufacture artificial marble having a vane pattern.

As a result of checking the prepared artificial marble, it was confirmed that a vane pattern having a width of 15 mm and a length of 300 mm and a smooth surface was manufactured.

<Example 2>

Except for applying a powder resin having a glass transition temperature of 57 ° C, a melting temperature of 60 ° C, and a curing reaction starting at 128 ° C and ending at 180 ° C and having a maximum exothermic temperature of 172 ° C during curing, the same as in Example 1 The same was done.

As a result of checking the prepared artificial marble, it was confirmed that a vane pattern having a width of 15 mm and a length of 300 mm and a smooth surface was manufactured.

<Example 3>

Except for applying a powder resin having a glass transition temperature of 63 ° C, a melting temperature of 67 ° C, and a curing reaction starting at 121 ° C and ending at 182 ° C and having a maximum exothermic temperature of 174 ° C during curing, the same as in Example 1 The same was done.

As a result of checking the prepared artificial marble, it was confirmed that a vane pattern having a width of 15 mm and a length of 300 mm and a smooth surface was manufactured.

<Example 4>

Except for applying a powder resin having a glass transition temperature of 51 ° C, a melting temperature of 116 ° C, and a curing reaction starting at 118 ° C and ending at 182 ° C and having a maximum exothermic temperature of 169 ° C during curing, the same as in Example 1 The same was done.

As a result of checking the prepared artificial marble, it was confirmed that a vane pattern having a width of 15 mm and a length of 300 mm and a smooth surface was manufactured.

<Example 5>

The same procedure as in Example 1 was performed, except that 10.4% by weight of the liquid binder resin and 3.2% by weight of the powdered resin were applied.

As a result of checking the prepared artificial marble, it was confirmed that a vane pattern having a width of 15 mm and a length of 300 mm and a smooth surface was manufactured.

<Example 6>

The glass transition temperature was 66 ° C, the melting temperature was 69 ° C, and the curing reaction was carried out in the same manner as in Example 1, except that the powdered resin was applied, starting at 160 ° C and ending at 184 ° C.

In Example 6, since the temperature at which the curing of the powdered resin starts is too high, the surface of the vane pattern is not smooth and the inorganic particles are easily separated. Therefore, it can be confirmed that it is more preferable that the temperature at which the curing of the powdered resin starts is 118° C. to 135° C. in order to have a smooth surface of the vane pattern of the artificial marble.

<Comparative Example 1>

It was carried out in the same manner as in Example 1, except that a thermoplastic resin having a glass transition temperature of 86 °C and a melting temperature of 90 °C was applied as a powder resin.

In Comparative Example 1, it was confirmed that the liquid resin was separated during the heating and curing process, and boiling bubbles were generated due to heat during the reaction of the unsaturated polyester, so that a large number of bubbles were formed on the surface of the vane pattern.

<Comparative Example 2>

It was carried out in the same manner as in Example 1, except that a thermoplastic resin having a glass transition temperature of 101 °C and a melting temperature of 109 °C was applied as a powder resin.

In Comparative Example 2, it was confirmed that the liquid resin was separated during the heating and curing process, and boiling bubbles were generated due to heat during the reaction of the unsaturated polyester, so that a large number of bubbles were formed on the surface of the vane pattern.

<Comparative Example 3>

The glass transition temperature was 48 ° C, the melting temperature was 125 ° C, and the curing reaction was carried out in the same manner as in Example 1, except that the powdered resin was applied starting at 140 ° C and ending at 180 ° C.

In Comparative Example 3, the powdered resin was not completely melted for a given curing time and curing did not occur, resulting in a rough surface that could be touched by hand in a powder state. Therefore, when the glass transition temperature of the powdered resin is less than 50° C. or the melting temperature is too high, it can be confirmed that the powdered resin is not sufficiently melted and cannot function as a binder.

<Comparative Example 4>

The glass transition temperature was 43 ° C, the melting temperature was 55 ° C, and the curing reaction was carried out in the same manner as in Example 1, except that the powdered resin was applied starting at 105 ° C and ending at 140 ° C.

In Comparative Example 4, the melting temperature of the powdered resin was too low and hardening occurred too quickly, and the phenomenon of aggregation due to instantaneous heat during the mixing process appeared as a problem. In this case, a rough surface partially formed by firmly aggregating inside the final cured vane pattern appeared, which is called a dry spot. That is, it was observed that when melted at too low a temperature, partial instantaneous hardening occurs and a normal surface state cannot be made.

As a result, the artificial marble composition according to an exemplary embodiment of the present invention has a liquid binder resin containing an unsaturated polyester resin and a glass transition temperature (Tg) of 50 ° C or higher and a melting temperature of 60 ° C or higher. By simultaneously applying the resin, it is possible to manufacture artificial marble capable of realizing a natural flow pattern without generating pinholes in the vane pattern of the artificial marble.

In addition, according to an exemplary embodiment of the present invention, since the thermosetting powder resin having a glass transition temperature (Tg) of 50 ° C. or more and a melting temperature of 60 ° C. or more can serve as an inorganic binder, a vane pattern of artificial marble is formed. occurrence of pinholes can be suppressed.

10: liquid binder resin containing an unsaturated polyester resin
20: inorganic particles
30: quartz powder
40: powdered resin
50: liquid resin converted by melting powder resin

Claims (13)

A liquid binder resin containing an unsaturated polyester resin;
A thermosetting powder resin having a glass transition temperature (Tg) of 50° C. or higher and a melting temperature of 60° C. or higher;
inorganic particles; and
quartz powder
An artificial marble composition comprising: The artificial marble composition according to claim 1, wherein the temperature at which the curing of the powdered resin starts is 118°C to 135°C. The method according to claim 1, wherein the powder resin is an epoxy acrylate resin, glycidyl methacrylate resin, butyl methacrylate resin, methyl methacrylate resin, saturated polyester resin, methyl methacrylate resin and glycidyl methacrylate 1 selected from a copolymer resin obtained by polymerizing a rate, a copolymer resin obtained by polymerizing a methyl methacrylate resin and an epoxy acrylate resin, a polyester epoxy hybrid resin, and a resin in which glycidyl isocyanurate is mixed with polyester An artificial marble composition comprising at least one species. The artificial marble composition of claim 1, wherein the inorganic particles include at least one selected from amorphous silica particles, glass particles, and crystalline quartz particles. The artificial marble composition according to claim 1, further comprising an inorganic pigment. The artificial marble composition according to claim 5, wherein the inorganic pigment includes at least one selected from TiO ₂ , NiO•Sb ₂ O ₃ 20TiO ₂ , Fe ₂ O ₃ , and Fe ₃ O ₄ . The method according to claim 5, based on the total weight of the artificial marble composition,
The content of the liquid binder resin is 6% to 15% by weight, the content of the powdered resin is 3% to 20% by weight, the content of the inorganic particles is 50% to 65% by weight, and the quartz powder The content of the artificial marble composition is 20% to 35% by weight, and the content of the inorganic pigment is 0.01% to 3% by weight. The artificial marble composition according to claim 1, wherein the artificial marble composition is for forming a vein pattern of artificial marble. Forming a base layer in a plate shape by powdering a base composition in a horizontally oriented mold;
Forming a concave pattern on the base layer;
Injecting the artificial marble composition according to any one of claims 1 to 8 into the intaglio pattern; and
After performing vibration and compression processes, performing a thermal curing process to form artificial marble having a vane pattern
Method for manufacturing artificial marble comprising a. The method of claim 9, wherein the thermal curing process is performed at a temperature of 118° C. or higher for 40 minutes or more. The method of manufacturing artificial marble according to claim 9, wherein the powdered resin of the artificial marble composition is melted by the heat curing process, converted into a liquid resin, and then cured. The method of claim 9, wherein the vane pattern is a straight line pattern, a curved pattern, or a combination pattern thereof. Artificial marble manufactured by the method of manufacturing artificial marble of claim 9.