WO2018117603A1 - Composition for artificial marble - Google Patents

Composition for artificial marble Download PDF

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Publication number
WO2018117603A1
WO2018117603A1 PCT/KR2017/015028 KR2017015028W WO2018117603A1 WO 2018117603 A1 WO2018117603 A1 WO 2018117603A1 KR 2017015028 W KR2017015028 W KR 2017015028W WO 2018117603 A1 WO2018117603 A1 WO 2018117603A1
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WO
WIPO (PCT)
Prior art keywords
composition
weight
artificial marble
parts
zinc oxide
Prior art date
Application number
PCT/KR2017/015028
Other languages
French (fr)
Korean (ko)
Inventor
정봉재
손창호
김주성
배승용
Original Assignee
롯데첨단소재(주)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by 롯데첨단소재(주) filed Critical 롯데첨단소재(주)
Priority to EP17885334.7A priority Critical patent/EP3560902A4/en
Priority to US16/470,317 priority patent/US11034620B2/en
Priority to JP2019530736A priority patent/JP6966550B2/en
Priority claimed from KR1020170174922A external-priority patent/KR101971371B1/en
Publication of WO2018117603A1 publication Critical patent/WO2018117603A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18—Polyesters; Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54—Substitutes for natural stone, artistic materials or the like
    • C04B2111/542—Artificial natural stone
    • C04B2111/545—Artificial marble
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80—Optical properties, e.g. transparency or reflexibility
    • C04B2111/82—Coloured materials

Definitions

  • the present invention relates to a composition for artificial marble. More specifically, the present invention relates to an artificial marble having excellent discoloration resistance and antibacterial property and a method of manufacturing the same.
  • Artificial marble is widely used as interior and exterior materials of construction. For example, its use is expanding as a material for sink counter tops, vanity tops, counters such as banks and general stores, interior walls, and interior sculptures. .
  • an inorganic antimicrobial agent containing a metal component such as silver or copper has been applied as an antimicrobial agent.
  • the inorganic antimicrobial agent is required to be excessively injected due to the lack of antimicrobial power, compared to the organic antimicrobial agent. Therefore, there are many disadvantages in use because of relatively high price, uniform dispersion problems during processing, and discoloration due to metal ions.
  • organic antimicrobial agent has the advantage of relatively low cost and good antibacterial effect even in small amount, but sometimes it is toxic to human body, and it is effective only for specific bacteria, and due to decomposition at high temperature resin processing temperature Most of the antimicrobial effect is lost, discoloration after processing, there is a shortcoming of the antimicrobial persistence due to elution problem, the range of organic antimicrobial agent that can be used for antimicrobial resin is extremely limited.
  • An object of the present invention is to provide a composition for artificial marble, which is excellent in discoloration resistance and excellent in antibacterial properties without impairing aesthetics.
  • the composition for artificial marble is a binder resin; Inorganic fillers except zinc oxide; And zinc oxide, wherein the zinc oxide has a size ratio (B / A) of peak A of 370 nm to 390 nm and peak B of 450 nm to 600 nm when measured for photo luminescence.
  • B / A size ratio of peak A of 370 nm to 390 nm and peak B of 450 nm to 600 nm when measured for photo luminescence.
  • the BET surface area measured by the BET analysis equipment is about 10 m 2 / g or less.
  • the composition for artificial marble may include 100 parts by weight of a binder resin, about 100 parts by weight to about 300 parts by weight of an inorganic filler except zinc oxide, and about 1 part by weight to about 10 parts by weight of zinc oxide.
  • the binder resin may include at least one of an acrylic resin and an unsaturated polyester resin.
  • the binder resin may be a mixture of poly (meth) acrylate and (meth) acrylate monomer.
  • the inorganic filler may include one or more of silica, alumina, calcium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, pearlite, vermiculite, smectite and bentonite.
  • the zinc oxide may have an average particle size of about 0.5 ⁇ m to about 3 ⁇ m.
  • the zinc oxide has a peak position 2 ⁇ of about 35 ° to about 37 ° when analyzed by X-ray diffraction (XRD), and the size of the microcrystal according to Equation 1 below. (crystallite size) value may be about 1,000 mm 3 to about 2,000 mm 3.
  • K is a shape factor
  • ⁇ is an X-ray wavelength
  • ⁇ is an FWHM value of an X-ray diffraction peak
  • ⁇ is a peak position value. (peak position degree).
  • the average particle size of the inorganic filler may be larger than the average particle size of the zinc oxide.
  • the inorganic filler and the zinc oxide may have a ratio of an average particle size of about 0.3: 1 to about 200: 1.
  • the artificial marble composition may further include one or more of a marble chip, a crosslinking agent, a crosslinking accelerator, a curing agent, a curing accelerator, a polymerization initiator, an antifoaming agent, a dispersing agent, a coupling agent, and a pigment.
  • the artificial marble composition measures an initial color (L 0 * , a 0 * , b 0 * ) using a colorimeter on an injection specimen of 50 mm ⁇ 90 mm ⁇ 3 mm size, and the injection specimen
  • an initial color L 0 * , a 0 * , b 0 *
  • the colorimeter may be from about 0 to about 3.
  • Equation 2 ⁇ L * is the difference between the L * values before and after the constant temperature and humidity test (L 1 * -L 0 * ), ⁇ a * is the difference between the a * value before and after the constant temperature and humidity test (a 1 * -a 0 * ⁇ b * is the difference (b 1 * -b 0 * ) of the b * value before and after the constant temperature and humidity test.
  • the composition for artificial marble is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm x 5 cm size specimen based on JIS Z 2801 antimicrobial evaluation method, and the antibacterial activity value against Staphylococcus aureus calculated according to Equation 3 below. Is about 2.0 to about 7.0, and the antimicrobial activity against E. coli may be about 2.0 to about 6.5.
  • Antimicrobial activity log (M1 / M2)
  • M1 is the number of bacteria after 24 hours incubation at 35 °C, RH 90% conditions for blank specimens, M2 is bacteria after 24 hours at 35 °C, RH 90% conditions for artificial marble specimens It is a number.
  • the artificial marble is formed from the composition for artificial marble.
  • This invention has the effect of providing the composition for artificial marble which is excellent in discoloration resistance and excellent in antibacterial property, without impairing aesthetics.
  • the binder resin of the present invention may include one or more of acrylic resins and unsaturated polyester resins.
  • the binder resin may be used in the form of a resin syrup in which a polymer is dissolved in a monomer.
  • the binder resin may be a mixture of a poly (meth) acrylate and a (meth) acrylate monomer.
  • the binder resin may include about 65 wt% to about 99 wt% of the (meth) acrylate monomer and about 1 wt% to about 35 wt% of the poly (meth) acrylate.
  • the (meth) acrylate monomer in the binder resin is 65%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99% by weight
  • Poly (meth) acrylate may be included in 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35% by weight.
  • the (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth).
  • Acrylate and glycidyl (meth) acrylate and the like can be used. These can be used individually or in mixture of 2 or more types.
  • the type of unsaturated polyester resin is not particularly limited, and in particular, an unsaturated polyester resin prepared through condensation of saturated or unsaturated dibasic acids and polyhydric alcohols may be used.
  • Saturated or unsaturated dibasic acids include maleic anhydride, citraconic acid, fumaric acid, itaconic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid or tetrahydrophthalic acid
  • polyhydric alcohols include ethylene glycol , Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, hydrogenated bisphenol A, trimethylol propane monoarylether, neopentyl glycol, 2,2 , 4-trimethyl-1,3-pentadiol and / or glycerin.
  • monobasic acids such as
  • silica, alumina, calcium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, pearlite, vermiculite, smectite and bentonite may be used, and zinc oxide is excluded.
  • the double aluminum hydroxide can be preferably applied in view of the transparent and beautiful appearance.
  • the inorganic filler has an average particle size of about 1 ⁇ m to about 100 ⁇ m, specifically about 3 ⁇ m to about 75 ⁇ m, for example, 3 ⁇ m, 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m , 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m, 55 ⁇ m, 60 ⁇ m, 65 ⁇ m, 70 ⁇ m, 75 ⁇ m. In the above range it may be excellent in appearance characteristics, texture, surface strength and the like of artificial marble.
  • the inorganic filler is about 100 parts by weight to about 300 parts by weight, specifically about 150 parts by weight to about 200 parts by weight, for example, 150 parts by weight, 155 parts by weight, 160 parts by weight, based on 100 parts by weight of the binder resin, It can be applied to 165 parts by weight, 170 parts by weight, 175 parts by weight, 180 parts by weight, 185 parts by weight, 190 parts by weight, 195 parts by weight, 200 parts by weight. Within this range, the process is easy and a beautiful appearance can be secured.
  • the zinc oxide used in the present invention has a size ratio (B / A) of peak A in the 370 nm to 390 nm region and peak B in the 450 nm to 600 nm region when measuring photo luminescence.
  • the BET surface area measured by BET analysis equipment is about 10 m 2 / g or less, specifically about 1 m 2 / g to about 10 m 2 / g, more specifically from about 1 m 2 / g to about 7 m 2 / g, for example, 1 m 2 / g, 2 m 2 / g, 3 m 2 / g, 4 m 2 /
  • the size ratio (B / A) of the zinc oxide is less than about 0.01, antimicrobial activity may be lowered, and when it exceeds about 1, discoloration resistance may not be secured.
  • zinc oxide having a BET surface area of more than 10 m 2 / g is applied, discoloration resistance and appearance of the object of the present invention cannot be secured.
  • the zinc oxide has an average particle size of about 0.5 ⁇ m to about 3 ⁇ m, specifically about 1 ⁇ m to about 3 ⁇ m, for example, 0.5 ⁇ m, 0.6 ⁇ m, measured using a Beckman coulter LS 13 320 Particle size analyzer particle size analyzer.
  • the average particle size of the inorganic filler is larger than the average particle size of the zinc oxide.
  • the ratio of the average particle size of the inorganic filler to the zinc oxide is about 0.3: 1 to about 200: 1, for example, about 1: 1 to about 100: 1, about 2: 1 to about 100 : 1, about 5: 1 to about 100: 1, about 5: 1 to about 30: 1.
  • the ratio of the average particle size of the inorganic filler to the zinc oxide is about 0.3: 1 to about 200: 1, for example, about 1: 1 to about 100: 1, about 2: 1 to about 100 : 1, about 5: 1 to about 100: 1, about 5: 1 to about 30: 1.
  • the zinc oxide has a peak position 2 ⁇ of about 35 ° to about 37 ° and a crystallite size according to Equation 1 below.
  • the initial color of artificial marble, weather resistance, antibacterial and the like can be excellent.
  • K is a shape factor
  • ⁇ is an X-ray wavelength
  • ⁇ is an FWHM value of an X-ray diffraction peak
  • ⁇ is a peak position value. (peak position degree).
  • the zinc oxide may have a purity of about 99% or more. In the above range, the initial color of the artificial marble, weather resistance, antibacterial may be more excellent.
  • the zinc oxide is dissolved in zinc in the form of metal, and then vaporized by heating to about 850 ° C. to about 1,000 ° C., for example, about 900 ° C. to about 950 ° C., followed by injection of oxygen gas and about 20 ° C. After cooling to about 30 °C, if necessary, while the nitrogen / hydrogen gas is injected into the reactor, the heat treatment for about 30 minutes to about 150 minutes at about 700 °C to about 800 °C, and then room temperature (about 20 °C to Cooling to about 30 ° C.).
  • the zinc oxide is about 1 part by weight to about 10 parts by weight, more specifically, about 2 parts by weight to about 7 parts by weight, for example 1 part by weight, 2 parts by weight of 100 parts by weight of the binder resin. It can be included in parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight.
  • Weather resistance of the artificial marble in the above range may be excellent antibacterial and the like.
  • the artificial marble composition according to one embodiment of the present invention may further include one or more additives of a marble chip, a crosslinking agent, a crosslinking accelerator, a curing agent, a curing accelerator, a polymerization initiator, an antifoaming agent, a dispersing agent, a coupling agent, and a pigment, as necessary. have.
  • additive known additives used in artificial marble can be used without limitation.
  • the marble chip is formed by grinding artificial marble.
  • the marble chip may contain about 120 parts by weight to about 200 parts by weight of the inorganic filler, about 0.1 parts by weight to about 10 parts by weight of the crosslinking agent, and about 0.1 parts by weight to about 10 parts by weight of the polymerization initiator, based on 100 parts by weight of the acrylic resin syrup.
  • the parts are mixed, cured, and then broken up into pieces of about 0.1 mm to about 5 mm in size.
  • the mixing ratio of the marble chip may be mixed in an amount of about 0 parts by weight to about 150 parts by weight, more preferably about 0 parts by weight to about 70 parts by weight, based on 100 parts by weight of the binder resin.
  • a compound having a double bond in a molecule capable of crosslinking with the binder resin can be used without limitation.
  • the crosslinking agent is specifically about 0.1 part by weight to about 10 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, and 4 parts by weight based on 100 parts by weight of the binder resin. , 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight can be used.
  • the curing agent is not particularly limited as long as it is used for curing artificial marble.
  • the curing agent is specifically about 0.1 part by weight to about 5.0 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, based on 100 parts by weight of the binder resin, It can be used in 5 parts by weight.
  • the polymerization initiator serves to promote the polymerization and curing reaction of the resin composition in the artificial marble manufacturing process.
  • the polymerization initiator include diacyl peroxides such as benzoyl peroxide and dicumyl peroxide; Hydroperoxides such as butyl hydroperoxide, t-butyl hydroperoxide and cumyl hydroperoxide; t-butylperoxymaleic acid, t-butylperoxymaleate; t-butylhydroperoxybutylate; Acetyl peroxide; Lauroyl peroxide; Azobisisobutyronitrile; Azobisdimethylvaleronitrile; t-butylperoxyethylhexanoate; t-butylperoxy neodecanoate; t-amylperoxy-2-ethylhexanoate and the like can be used, but is not limited thereto.
  • the polymerization initiator is specifically about 0.1 part by weight to about 5.0 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight based on 100 parts by weight of the binder resin. 5 parts by weight can be used.
  • the coupling agent is to help the bonding of the inorganic filler and the binder resin, it can be easily carried out by those skilled in the art to which the present invention belongs.
  • the coupling agent may use a silane coupling agent such as 3- (trimethoxycyryl) propylmethacrylate, vinyltrimethoxysilane, vinyltriethoxysilane.
  • the coupling agent is specifically about 0.1 parts by weight to about 1.0 parts by weight, for example, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, based on 100 parts by weight of the binder resin, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, and 1 part by weight can be used.
  • the pigment may be an inorganic pigment, an organic pigment, a dye or the like. It is preferably used in this field such as reddish brown pigments such as iron oxide, yellow pigments such as iron hydroxide, green pigments such as chromium oxide, ultramarine pigments such as sodium aluminosilicate, white pigments such as titanium oxide, and black pigments such as carbon black. Ordinary things can be used.
  • the pigment is specifically about 0.0001 parts to about 5.0 parts by weight, for example, 0.0001 parts by weight, 0.001 parts by weight, 0.01 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, based on 100 parts by weight of the binder resin, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, and 5 parts by weight.
  • the artificial marble composition was 50 mm ⁇ 90 mm ⁇ 3 mm in size injection using a color difference meter for specimens to measure the early color (L 0 *, a 0 * , b 0 *), the injection specimen according to SAE J 1960, weather resistance test for 3,000 hours, and after the test using a colorimeter to measure the color (L 1 * , a 1 * , b 1 * ) and then the color change calculated according to the following Equation 2 ( ⁇ E) can be from about 0 to about 3, for example 0, 1, 2, 3.
  • Equation 2 ⁇ L * is the difference between the L * values before and after the constant temperature and humidity test (L 1 * -L 0 * ), ⁇ a * is the difference between the a * value before and after the constant temperature and humidity test (a 1 * -a 0 * ⁇ b * is the difference (b 1 * -b 0 * ) of the b * value before and after the constant temperature and humidity test.
  • the composition for artificial marble is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm x 5 cm size specimen based on JIS Z 2801 antimicrobial evaluation method, and the antibacterial activity value against Staphylococcus aureus calculated according to Equation 3 below.
  • the antimicrobial activity against E. coli is from about 2.0 to about 6.5, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5.
  • Antimicrobial activity log (M1 / M2)
  • M1 is the number of bacteria after 24 hours incubation at 35 °C, RH 90% conditions for blank specimens, M2 is bacteria after 24 hours at 35 °C, RH 90% conditions for artificial marble specimens It is a number.
  • Artificial marble according to the present invention can be prepared by curing the composition for artificial marble.
  • the curing temperature may be carried out at about 25 °C to about 180 °C.
  • an amine or sulfonic acid compound may be added together with a curing agent or a saponified salt of copper, cobalt, potassium, calcium, zirconium, and zinc may be added.
  • the method may further comprise defoaming before curing the composition for artificial marble.
  • the defoaming step may be degassed using a defoamer, and may be performed under a vacuum of about 760 mmHg.
  • a syrup made by dissolving 30% by weight of polymethylmethacrylate (PMMA) in 70% by weight of methylmethacrylate was used.
  • Aluminum hydroxide having an average particle size of 10 ⁇ m was used.
  • Zinc oxide of Table 1 was used.
  • Average particle size (unit: ⁇ m): The average particle size (volume average) was measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 instrument).
  • BET surface area (unit: m 2 / g): The BET surface area was measured by BET analysis equipment (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 equipment) using nitrogen gas adsorption.
  • Purity (Unit:%): Purity was measured using TGA thermal analysis with weight remaining at 800 ° C.
  • PL size ratio (B / A) According to the photo luminescence measuring method, a spectrum of light emitted by a He-Cd laser (Kimmon, 30mW) having a wavelength of 325 nm at room temperature is measured by a CCD detector. The temperature of the CCD detector was maintained at -70 ° C. The size ratio (B / A) of the peak A in the 370 to 390 nm region and the peak B in the 450 to 600 nm region was measured.
  • the injection specimen was subjected to PL analysis by injecting a laser into the specimen without any treatment, and the zinc oxide powder was placed in a pelletizer having a diameter of 6 mm and pressed to produce a flat specimen. It was.
  • K is a shape factor
  • ⁇ is an X-ray wavelength
  • ⁇ is an FWHM value of an X-ray diffraction peak
  • ⁇ is a peak position value. (peak position degree).
  • the composition for artificial marble mixed with trimethylolpropane trimethacrylate, normal dodecyl mercaptan, an antifoaming agent and a dispersing agent and a polymerization initiator After the preparation, the mixture was stirred and then cured at a temperature of 80 ° C. through vacuum degassing to prepare artificial marble.
  • Equation 2 ⁇ L * is the difference between the L * values before and after the constant temperature and humidity test (L 1 * -L 0 * ), ⁇ a * is the difference between the a * value before and after the constant temperature and humidity test (a 1 * -a 0 * ⁇ b * is the difference (b 1 * -b 0 * ) of the b * value before and after the constant temperature and humidity test.
  • Antibacterial activity value In accordance with JIS Z 2801 antimicrobial evaluation method, 5 cm x 5 cm size specimen was inoculated with Staphylococcus aureus and E. coli, and the antibacterial activity value was calculated according to the following formula (3).
  • Antimicrobial activity log (M1 / M2)
  • Equation 3 M1 is the number of bacteria after incubation for 24 hours at 35 °C, RH 90% conditions for blank specimens, M2 is bacteria after 24 hours at 35 °C, RH 90% conditions for artificial marble specimens It is a number.
  • Example 1 (A) binder resin 100 100 (B) inorganic filler 150 150 (C) zinc oxide (C1) 5 - (C2) - 5 Antimicrobial activity Staphylococcus aureus 4.6 4.6 Escherichia coli 6.3 6.3 Color change ( ⁇ E) 0.8 1.1
  • Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) binder resin 100 100 100 100 (B) inorganic filler 150 150 150 (C) zinc oxide (C1) - - - - (C2) - - - - (C3) - 5 - - (C4) - - 5 (C5) - - - 5 Antimicrobial activity Staphylococcus aureus 2.1 4.6 4.2 4.5 Escherichia coli 0 6.0 5.8 6.0 Color change ( ⁇ E) 8.4 7.6 9.2 8.7
  • Comparative Example 1 the antibacterial activity value showing the antimicrobial effect against Escherichia coli was 2 or less, and there was no antimicrobial effect, and color change occurred. Further, as in Comparative Examples 2 to 4, the size ratio (B / A) of the peak A in the 370 nm to 390 nm region and the peak B in the 450 nm to 600 nm region is outside the value of about 0.01 to about 1, or the BET surface area is When zinc oxide exceeding about 10 m 2 / g was used, antibacterial activity could be ensured, but the discoloration resistance was remarkably decreased.

Abstract

A composition for artificial marble, of the present invention, comprises: a binder resin; an inorganic filler excluding zinc oxide; and zinc oxide, wherein the zinc oxide has a size ratio (B/A), in which peak A is a 370 nm to 390 nm region and peak B is a 450 nm to 600 nm region, of approximately 0.01 to 1 during photoluminescence measurement, and has a BET surface area of approximately 10 m2/g or less.

Description

인조대리석용 조성물Composition for artificial marble
본 발명은 인조대리석용 조성물에 관한 것이다. 보다 구체적으로 본 발명은 내변색성 및 항균성이 우수한 인조대리석 및 이의 제조방법에 관한 것이다.The present invention relates to a composition for artificial marble. More specifically, the present invention relates to an artificial marble having excellent discoloration resistance and antibacterial property and a method of manufacturing the same.
인조대리석은 건축 내외장재로 많이 사용되고 있으며, 예를 들면, 씽크대 상판, 세면 화장대의 상판, 은행 및 일반 매장의 접수대 등 각종 카운터의 상판, 내벽재, 각종 인테리어 조형물 등의 소재로서 그 사용이 확대되고 있다.Artificial marble is widely used as interior and exterior materials of construction. For example, its use is expanding as a material for sink counter tops, vanity tops, counters such as banks and general stores, interior walls, and interior sculptures. .
이처럼 인조대리석은 건축 내외장재에 적용되기 때문에 미감성뿐만 아니라, 내변색성이 요구되며, 각종 생활용품과 주방용품에도 사용이 확대됨에 따라 항균성 역시 요구되고 있다. Since artificial marble is applied to interior and exterior materials of buildings, it is required not only aesthetics but also discoloration resistance, and antibacterial activity is also required as the use of various household and kitchen appliances is expanded.
종래에는 항균제로 은이나 동 등의 금속 성분이 함유된 무기 항균제가 적용되었다. 이러한 무기 항균제는 유기 항균제에 비하여 항균력이 부족하여 과량 투입이 요구되며, 따라서 상대적으로 높은 가격과 가공 시 균일 분산 문제, 금속이온에 의한 변색 등의 단점이 있어 사용에 많은 제약이 있는 실정이다. 한편, 유기항균제는 상대적으로 가격이 싸고 적은 양으로도 항균 효과가 좋다는 장점이 있지만, 때로는 인체 독성을 지니며, 특정 균에 대하여만 효과가 있는 경우가 있고, 고온인 수지 가공 온도에서는 분해로 인해 항균 효과가 대부분 상실되며, 가공 후 변색 되며, 용출 문제로 항균 지속성이 짧은 단점이 있어 항균 수지용으로 사용될 수 있는 유기항균제의 범위는 극히 제한적이다.Conventionally, an inorganic antimicrobial agent containing a metal component such as silver or copper has been applied as an antimicrobial agent. The inorganic antimicrobial agent is required to be excessively injected due to the lack of antimicrobial power, compared to the organic antimicrobial agent. Therefore, there are many disadvantages in use because of relatively high price, uniform dispersion problems during processing, and discoloration due to metal ions. On the other hand, organic antimicrobial agent has the advantage of relatively low cost and good antibacterial effect even in small amount, but sometimes it is toxic to human body, and it is effective only for specific bacteria, and due to decomposition at high temperature resin processing temperature Most of the antimicrobial effect is lost, discoloration after processing, there is a shortcoming of the antimicrobial persistence due to elution problem, the range of organic antimicrobial agent that can be used for antimicrobial resin is extremely limited.
따라서, 미감성을 저해하지 않고 내변색성이 우수하면서, 항균성이 우수한 인조대리석의 개발이 필요한 실정이다. Therefore, it is necessary to develop artificial marble that is excellent in discoloration resistance and excellent in antibacterial properties without impairing aesthetics.
본 발명의 배경기술은 대한민국 특허 제815472호 등에 개시되어 있다.Background art of the present invention is disclosed in Korean Patent No. 815472 and the like.
본 발명의 목적은 미감성을 저해하지 않고 내변색성이 우수하면서, 항균성이 우수한 인조대리석용 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a composition for artificial marble, which is excellent in discoloration resistance and excellent in antibacterial properties without impairing aesthetics.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
본 발명의 하나의 관점은 인조대리석용 조성물에 관한 것이다. 상기 인조대리석용 조성물은 바인더 수지; 산화아연을 제외한 무기충전재; 및 산화아연;을 포함하고, 상기 산화아연은 광 발광(Photo Luminescence) 측정 시, 370 nm 내지 390 nm 영역의 피크 A와 450 nm 내지 600 nm 영역의 피크 B의 크기비(B/A)가 0.01 내지 1이고, BET 분석 장비로 측정한 BET 표면적이 약 10 m2/g 이하인 것을 특징으로 한다. One aspect of the present invention relates to a composition for artificial marble. The composition for artificial marble is a binder resin; Inorganic fillers except zinc oxide; And zinc oxide, wherein the zinc oxide has a size ratio (B / A) of peak A of 370 nm to 390 nm and peak B of 450 nm to 600 nm when measured for photo luminescence. To 1, and the BET surface area measured by the BET analysis equipment is about 10 m 2 / g or less.
구체예에서, 상기 인조대리석용 조성물은 바인더 수지 100 중량부, 산화아연을 제외한 무기충전재 약 100 중량부 내지 약 300 중량부, 및 산화아연 약 1 중량부 내지 약 10 중량부를 포함할 수 있다.In an embodiment, the composition for artificial marble may include 100 parts by weight of a binder resin, about 100 parts by weight to about 300 parts by weight of an inorganic filler except zinc oxide, and about 1 part by weight to about 10 parts by weight of zinc oxide.
구체예에서, 상기 바인더 수지는 아크릴계 수지 및 불포화 폴리에스테르 수지 중 1종 이상을 포함할 수 있다. In embodiments, the binder resin may include at least one of an acrylic resin and an unsaturated polyester resin.
구체예에서, 상기 바인더 수지는 폴리(메타)아크릴레이트와 (메타)아크릴레이트 모노머의 혼합물일 수 있다.In an embodiment, the binder resin may be a mixture of poly (meth) acrylate and (meth) acrylate monomer.
구체예에서, 상기 무기충전재는 실리카, 알루미나, 탄산칼슘, 수산화칼슘, 수산화알루미늄, 수산화마그네슘, 펄라이트, 버미큘라이트, 스멕타이트 및 벤토나이트 중 1종 이상을 포함할 수 있다.In embodiments, the inorganic filler may include one or more of silica, alumina, calcium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, pearlite, vermiculite, smectite and bentonite.
구체예에서, 상기 산화아연은 평균 입자 크기가 약 0.5 ㎛ 내지 약 3 ㎛일 수 있다.In embodiments, the zinc oxide may have an average particle size of about 0.5 μm to about 3 μm.
구체예에서, 상기 산화아연은 X선 회절(X-ray diffraction, XRD) 분석 시, 피크 위치(peak position) 2θ 값이 약 35° 내지 약 37° 범위이고, 하기 식 1에 의한 미소결정의 크기(crystallite size) 값이 약 1,000 Å 내지 약 2,000 Å일 수 있다.In embodiments, the zinc oxide has a peak position 2θ of about 35 ° to about 37 ° when analyzed by X-ray diffraction (XRD), and the size of the microcrystal according to Equation 1 below. (crystallite size) value may be about 1,000 mm 3 to about 2,000 mm 3.
[식 1][Equation 1]
미소결정 크기(D) =
Figure PCTKR2017015028-appb-I000001
Microcrystal size (D) =
Figure PCTKR2017015028-appb-I000001
상기 식 1에서, K는 형상 계수(shape factor)이고, λ는 X선 파장(X-ray wavelength)이고, β는 X선 회절 피크(peak)의 FWHM 값(degree)이며, θ는 피크 위치 값(peak position degree)이다.In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value of an X-ray diffraction peak, and θ is a peak position value. (peak position degree).
구체예에서, 상기 무기충전재의 평균입경크기는 상기 산화아연의 평균입경크기 보다 클 수 있다.In embodiments, the average particle size of the inorganic filler may be larger than the average particle size of the zinc oxide.
구체예에서, 상기 무기충전재와 상기 산화아연은 평균입경크기의 비가 약 0.3 : 1 내지 약 200 : 1 일 수 있다.In embodiments, the inorganic filler and the zinc oxide may have a ratio of an average particle size of about 0.3: 1 to about 200: 1.
구체예에서, 상기 인조대리석용 조성물은 마블칩, 가교제, 가교촉진제, 경화제, 경화촉진제, 중합개시제, 소포제, 분산제, 커플링제 및 안료 중 1종 이상을 더 포함할 수 있다. In embodiments, the artificial marble composition may further include one or more of a marble chip, a crosslinking agent, a crosslinking accelerator, a curing agent, a curing accelerator, a polymerization initiator, an antifoaming agent, a dispersing agent, a coupling agent, and a pigment.
구체예에서, 상기 인조대리석용 조성물은 50 mm × 90 mm × 3 mm 크기 사출 시편에 대해 색차계를 사용하여 초기 색상(L0 *, a0 *, b0 *)을 측정하고, 상기 사출 시편을 SAE J 1960에 의거하여, 3,000 시간 동안 내후성 테스트하고, 색차계를 사용하여 테스트 후 색상(L1 *, a1 *, b1 *)을 측정한 다음, 하기 식 2에 따라 산출한 색상 변화(ΔE)가 약 0 내지 약 3일 수 있다.In an embodiment, the artificial marble composition measures an initial color (L 0 * , a 0 * , b 0 * ) using a colorimeter on an injection specimen of 50 mm × 90 mm × 3 mm size, and the injection specimen According to SAE J 1960, weather resistance test for 3,000 hours, and after the test using a colorimeter to measure the color (L 1 * , a 1 * , b 1 * ) and then the color change calculated according to the following Equation 2 (ΔE) may be from about 0 to about 3.
[식 2][Equation 2]
색상 변화(ΔE) =
Figure PCTKR2017015028-appb-I000002
Color change (ΔE) =
Figure PCTKR2017015028-appb-I000002
상기 식 2에서, ΔL*는 항온 항습 시험 전후의 L* 값의 차이(L1 *-L0 *)이고, Δa*는 항온 항습 시험 전후의 a* 값의 차이(a1 *- a0 *) 이며, Δb*는 항온 항습 시험 전후의 b* 값의 차이(b1 *- b0 *)이다.In Equation 2, ΔL * is the difference between the L * values before and after the constant temperature and humidity test (L 1 * -L 0 * ), Δa * is the difference between the a * value before and after the constant temperature and humidity test (a 1 * -a 0 * Δb * is the difference (b 1 * -b 0 * ) of the b * value before and after the constant temperature and humidity test.
구체예에서, 상기 인조대리석용 조성물은 JIS Z 2801 항균 평가법에 의거하여, 5 cm x 5 cm 크기 시편에 황색포도상구균 및 대장균을 접종하고, 하기 식 3 에 따라 산출한 황색포도상구균에 대한 항균 활성치가 약 2.0 내지 약 7.0 이고, 대장균에 대한 항균 활성치가 약 2.0 내지 약 6.5 일 수 있다.In an embodiment, the composition for artificial marble is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm x 5 cm size specimen based on JIS Z 2801 antimicrobial evaluation method, and the antibacterial activity value against Staphylococcus aureus calculated according to Equation 3 below. Is about 2.0 to about 7.0, and the antimicrobial activity against E. coli may be about 2.0 to about 6.5.
[식 3][Equation 3]
항균 활성치 = log(M1/M2)Antimicrobial activity = log (M1 / M2)
상기 식 3에서, M1은 블랭크(blank) 시편에 대한 35℃, RH 90% 조건에서 24 시간 배양 후 세균 수이고, M2는 인조대리석 시편에 대한 35℃, RH 90% 조건에서 24 시간 배양 후 세균 수이다.In Equation 3, M1 is the number of bacteria after 24 hours incubation at 35 ℃, RH 90% conditions for blank specimens, M2 is bacteria after 24 hours at 35 ℃, RH 90% conditions for artificial marble specimens It is a number.
본 발명의 다른 관점은 인조대리석에 관한 것이다. 상기 인조대리석은 상기 인조대리석용 조성물로부터 형성된다.Another aspect of the invention relates to artificial marble. The artificial marble is formed from the composition for artificial marble.
본 발명은 미감성을 저해하지 않고 내변색성이 우수하면서, 항균성이 우수한 인조대리석용 조성물을 제공하는 발명의 효과를 갖는다.This invention has the effect of providing the composition for artificial marble which is excellent in discoloration resistance and excellent in antibacterial property, without impairing aesthetics.
(A) 바인더 수지(A) binder resin
본 발명의 바인더 수지는 아크릴계 수지 및 불포화 폴리에스테르 수지 중 1종 이상을 포함할 수 있다. The binder resin of the present invention may include one or more of acrylic resins and unsaturated polyester resins.
상기 바인더 수지는 폴리머를 단량체에 용해한 수지 시럽의 형태로 사용될 수 있다.The binder resin may be used in the form of a resin syrup in which a polymer is dissolved in a monomer.
구체예에서는 상기 바인더 수지는 폴리(메타)아크릴레이트와 (메타)아크릴레이트 모노머의 혼합물일 수 있다. 구체적으로, 상기 바인더 수지는 (메타)아크릴레이트 모노머 약 65 중량% 내지 약 99 중량% 및 폴리(메타)아크릴레이트 약 1 중량% 내지 약 35 중량%를 포함할 수 있다. 예를 들면, 상기 바인더 수지 중 (메타)아크릴레이트 모노머는 65 중량%, 65 중량%, 70 중량%, 75 중량%, 80 중량, 85 중량%, 90 중량%, 95 중량%, 99 중량%로 포함될 수 있고, 폴리(메타)아크릴레이트는 1 중량%, 5 중량%, 10 중량%, 15 중량%, 20 중량%, 25 중량%, 30 중량%, 35 중량%로 포함될 수 있다. In an embodiment, the binder resin may be a mixture of a poly (meth) acrylate and a (meth) acrylate monomer. Specifically, the binder resin may include about 65 wt% to about 99 wt% of the (meth) acrylate monomer and about 1 wt% to about 35 wt% of the poly (meth) acrylate. For example, the (meth) acrylate monomer in the binder resin is 65%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99% by weight Poly (meth) acrylate may be included in 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35% by weight.
상기 (메타)아크릴레이트 모노머는 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 벤질(메타)아크릴레이트 및 글리시딜(메타)아크릴레이트 등이 사용될 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용될 수 있다. The (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth). ) Acrylate and glycidyl (meth) acrylate and the like can be used. These can be used individually or in mixture of 2 or more types.
불포화 폴리에스테르계 수지의 종류는 특별히 제한되지 않으며, 구체적으로 포화 또는 불포화 이염기산 및 다가 알코올의 축합반응을 통해 제조되는 불포화 폴리에스테르계 수지를 사용할 수 있다. 포화 또는 불포화 이염기산으로는 무수말레산, 시트라콘산, 푸마르산, 이타콘산, 프탈산, 무수프탈산, 이소프탈산, 테레프탈산, 호박산, 아디핀산, 세바신산 또는 테트라히드로프탈산이 있고, 다가 알코올로는 에틸렌 글리콜, 디에틸렌 글리콜, 트리에틸렌 글리콜, 프로필렌 글리콜, 디프로필렌 글리콜, 트리프로필렌 글리콜, 폴리프로필렌 글리콜, 1,3-부틸렌 글리콜, 수소화 비스페놀 A, 트리메틸롤 프로판 모노아릴에테르, 네오펜틸 글리콜, 2,2,4-트리메틸-1,3-펜타디올 및/또는 글리세린이 있다. 또한, 필요에 따라서 아크릴산, 프로피온산 또는 안식향산과 같은 일염기산 또는 트리멜리트산 및 벤졸의 테트라카본산과 같은 다염기산을 더 사용할 수 있다.The type of unsaturated polyester resin is not particularly limited, and in particular, an unsaturated polyester resin prepared through condensation of saturated or unsaturated dibasic acids and polyhydric alcohols may be used. Saturated or unsaturated dibasic acids include maleic anhydride, citraconic acid, fumaric acid, itaconic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid or tetrahydrophthalic acid, and polyhydric alcohols include ethylene glycol , Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, hydrogenated bisphenol A, trimethylol propane monoarylether, neopentyl glycol, 2,2 , 4-trimethyl-1,3-pentadiol and / or glycerin. In addition, monobasic acids such as acrylic acid, propionic acid or benzoic acid or polybasic acids such as trimellitic acid and tetracarboxylic acid of benzol may be further used as necessary.
(B) 무기충전재(B) inorganic filler
본 발명의 무기 충전물은 실리카, 알루미나, 탄산칼슘, 수산화칼슘, 수산화알루미늄, 수산화마그네슘, 펄라이트, 버미큘라이트, 스멕타이트 및 벤토나이트 등이 사용될 수 있으며, 산화아연은 제외된다. 이중 수산화알루미늄이 투명하고 미려한 외관 면에서 바람직하게 적용될 수 있다. As the inorganic filler of the present invention, silica, alumina, calcium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, pearlite, vermiculite, smectite and bentonite may be used, and zinc oxide is excluded. The double aluminum hydroxide can be preferably applied in view of the transparent and beautiful appearance.
구체예에서 상기 무기충전재는 평균입경크기가 약 1 ㎛ 내지 약 100 ㎛, 구체적으로 약 3 ㎛ 내지 약 75 ㎛, 예를 들면, 3 ㎛, 5 ㎛, 10 ㎛, 15 ㎛, 20 ㎛, 25 ㎛, 30 ㎛, 35 ㎛, 40 ㎛, 45 ㎛, 50 ㎛, 55 ㎛, 60 ㎛, 65 ㎛, 70 ㎛, 75 ㎛ 일 수 있다. 상기 범위에서 인조대리석의 외관 특성, 질감, 표면 강도 등이 우수할 수 있다. In embodiments, the inorganic filler has an average particle size of about 1 μm to about 100 μm, specifically about 3 μm to about 75 μm, for example, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm , 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm. In the above range it may be excellent in appearance characteristics, texture, surface strength and the like of artificial marble.
상기 무기충전재는 바인더 수지 100 중량부에 대하여, 약 100 중량부 내지 약 300 중량부, 구체적으로 약 150 중량부 내지 약 200 중량부, 예를 들면, 150 중량부, 155 중량부, 160중량부, 165 중량부, 170 중량부, 175 중량부, 180 중량부, 185 중량부, 190 중량부, 195 중량부, 200 중량부로 적용될 수 있다. 상기 범위에서 공정이 용이하고 미려한 외관을 확보할 수 있다. The inorganic filler is about 100 parts by weight to about 300 parts by weight, specifically about 150 parts by weight to about 200 parts by weight, for example, 150 parts by weight, 155 parts by weight, 160 parts by weight, based on 100 parts by weight of the binder resin, It can be applied to 165 parts by weight, 170 parts by weight, 175 parts by weight, 180 parts by weight, 185 parts by weight, 190 parts by weight, 195 parts by weight, 200 parts by weight. Within this range, the process is easy and a beautiful appearance can be secured.
(C) 산화아연(C) zinc oxide
본 발명에서 사용되는 산화아연은 광 발광(Photo Luminescence) 측정 시, 370 nm 내지 390 nm 영역의 피크 A와 450 nm 내지 600 nm 영역의 피크 B의 크기비(B/A)가 약 0.01 내지 약 1, 구체적으로 약 0.01 내지 약 0.5, 보다 구체적으로 약 0.1 내지 약 0.3, 예를 들면, 0.01, 0.05, 0.1, 0.15 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1 이고, 질소가스 흡착법을 사용하여, BET 분석 장비로 측정한 BET 표면적이 약 10 m2/g 이하, 구체적으로 약 1 m2/g 내지 약 10 m2/g, 보다 구체적으로 약 1 m2/g 내지 약 7 m2/g, 예를 들면, 1 m2/g, 2 m2/g, 3 m2/g, 4 m2/g, 5 m2/g, 6 m2/g, 7 m2/g, 8 m2/g, 9 m2/g, 10 m2/g 인 것이 사용될 수 있다. The zinc oxide used in the present invention has a size ratio (B / A) of peak A in the 370 nm to 390 nm region and peak B in the 450 nm to 600 nm region when measuring photo luminescence. Specifically about 0.01 to about 0.5, more specifically about 0.1 to about 0.3, for example 0.01, 0.05, 0.1, 0.15 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.65, 0.7, 0.75 , 0.8, 0.85, 0.9, 0.95, 1, and using a nitrogen gas adsorption method, the BET surface area measured by BET analysis equipment is about 10 m 2 / g or less, specifically about 1 m 2 / g to about 10 m 2 / g, more specifically from about 1 m 2 / g to about 7 m 2 / g, for example, 1 m 2 / g, 2 m 2 / g, 3 m 2 / g, 4 m 2 / g, 5 m 2 / g, 6 m 2 / g, 7 m 2 / g, 8 m 2 / g, 9 m 2 / g, 10 m 2 / g can be used.
만일 상기 산화아연의 크기비(B/A)가 약 0.01 미만일 경우 항균성이 저하될 수 있고, 약 1을 초과한 경우 내변색성을 확보할 수 없다. 또한, BET 표면적이 10 m2/g 을 초과하는 산화아연을 적용할 경우 본 발명에서 목적으로 하는 내변색성과 외관을 확보할 수 없다. If the size ratio (B / A) of the zinc oxide is less than about 0.01, antimicrobial activity may be lowered, and when it exceeds about 1, discoloration resistance may not be secured. In addition, when zinc oxide having a BET surface area of more than 10 m 2 / g is applied, discoloration resistance and appearance of the object of the present invention cannot be secured.
상기 산화아연은 Beckman coulter LS 13 320 Particle size analyzer 입도분석기를 사용하여 측정한 평균 입자 크기가 약 0.5 ㎛ 내지 약 3 ㎛, 구체적으로 약 1 ㎛ 내지 약 3 ㎛, 예를 들면, 0.5 ㎛, 0.6 ㎛, 0.7 ㎛, 0.8 ㎛, 0.9 ㎛, 1 ㎛, 1.1 ㎛, 1.2 ㎛, 1.3 ㎛, 1.4 ㎛, 1.5 ㎛, 1.6 ㎛, 1.7 ㎛, 1.8 ㎛, 1.9 ㎛, 2 ㎛, 2.1 ㎛, 2.2 ㎛, 2.3 ㎛, 2.4 ㎛, 2.5 ㎛, 2.6 ㎛, 2.7 ㎛, 2.8 ㎛, 2.9 ㎛, 3 ㎛일 수 있다. 상기 범위에서 우수한 외관을 가질 수 있다. The zinc oxide has an average particle size of about 0.5 μm to about 3 μm, specifically about 1 μm to about 3 μm, for example, 0.5 μm, 0.6 μm, measured using a Beckman coulter LS 13 320 Particle size analyzer particle size analyzer. , 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2 μm, 2.1 μm, 2.2 μm, 2.3 Micrometer, 2.4 micrometer, 2.5 micrometer, 2.6 micrometer, 2.7 micrometer, 2.8 micrometer, 2.9 micrometer, 3 micrometer. It may have an excellent appearance in the above range.
일 구체예에서, 상기 무기충전재의 평균입경크기는 상기 산화아연의 평균입경크기 보다 크다. In one embodiment, the average particle size of the inorganic filler is larger than the average particle size of the zinc oxide.
다른 구체예에서, 상기 무기충전재와 상기 산화아연은 평균입경크기의 비는 약 0.3 : 1 내지 약 200 : 1, 예를 들면, 약 1 : 1 내지 약 100 : 1, 약 2:1 내지 약 100 : 1, 약 5 : 1 내지 약 100 : 1, 약 5 : 1 내지 약 30 : 1 일 수 있다. 이러한 경우, 우수한 항균성과 유지하거나 향상시키면서도 인조대리석의 물성을 저하하지 않는 장점이 있다. In another embodiment, the ratio of the average particle size of the inorganic filler to the zinc oxide is about 0.3: 1 to about 200: 1, for example, about 1: 1 to about 100: 1, about 2: 1 to about 100 : 1, about 5: 1 to about 100: 1, about 5: 1 to about 30: 1. In this case, while maintaining or improving the excellent antimicrobial properties there is an advantage that does not lower the physical properties of artificial marble.
상기 산화아연은 X선 회절(X-ray diffraction, XRD) 분석 시, 피크 위치(peak position) 2θ 값이 약 35° 내지 약 37° 범위이고, 하기 식 1에 의한 미소결정의 크기(crystallite size) 값이 약 1,000 Å 내지 약 2,000 Å, 구체적으로 약 1,200 Å 내지 1,800 Å, 예를 들면, 1,100 Å, 1,200 Å, 1,300 Å, 1,400 Å, 1,500 Å, 1,600 Å, 1,700 Å, 1,800 Å, 1,900 Å, 2,000 Å 일 수 있다. 상기 범위에서, 인조대리석의 초기 색상, 내후성, 항균성 등이 우수할 수 있다. In the X-ray diffraction (XRD) analysis, the zinc oxide has a peak position 2θ of about 35 ° to about 37 ° and a crystallite size according to Equation 1 below. Value from about 1,000 kPa to about 2,000 kPa, specifically about 1,200 kPa to 1,800 kPa, for example 1,100 kPa, 1,200 kPa, 1,300 kPa, 1,400 kPa, 1,500 kPa, 1,600 kPa, 1,700 kPa, 1,800 kPa, 1,900 kPa, It can be 2,000 Å. In the above range, the initial color of artificial marble, weather resistance, antibacterial and the like can be excellent.
[식 1][Equation 1]
미소결정 크기(D) =
Figure PCTKR2017015028-appb-I000003
Microcrystal size (D) =
Figure PCTKR2017015028-appb-I000003
상기 식 1에서, K는 형상 계수(shape factor)이고, λ는 X선 파장(X-ray wavelength)이고, β는 X선 회절 피크(peak)의 FWHM 값(degree)이며, θ는 피크 위치 값(peak position degree)이다.In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value of an X-ray diffraction peak, and θ is a peak position value. (peak position degree).
상기 산화아연은 순도가 약 99%이상일 수 있다. 상기 범위에서, 인조대리석의 초기 색상, 내후성, 항균성 등이 더욱 우수할 수 있다. The zinc oxide may have a purity of about 99% or more. In the above range, the initial color of the artificial marble, weather resistance, antibacterial may be more excellent.
구체예에서, 상기 산화아연은 금속형태의 아연을 녹인 후, 약 850 ℃ 내지 약 1,000℃, 예를 들면 약 900℃ 내지 약 950℃로 가열하여 증기화시킨 후, 산소 가스를 주입하고 약 20℃ 내지 약 30℃로 냉각한 다음, 필요 시, 반응기에 질소/수소 가스를 주입하면서, 약 700℃ 내지 약 800℃에서 약 30분 내지 약 150분 동안 열처리를 진행한 후, 상온(약 20℃ 내지 약 30℃)으로 냉각하여 제조할 수 있다.In an embodiment, the zinc oxide is dissolved in zinc in the form of metal, and then vaporized by heating to about 850 ° C. to about 1,000 ° C., for example, about 900 ° C. to about 950 ° C., followed by injection of oxygen gas and about 20 ° C. After cooling to about 30 ℃, if necessary, while the nitrogen / hydrogen gas is injected into the reactor, the heat treatment for about 30 minutes to about 150 minutes at about 700 ℃ to about 800 ℃, and then room temperature (about 20 ℃ to Cooling to about 30 ° C.).
구체예에서, 상기 산화아연은 상기 바인더 수지 100 중량부에 대하여, 약 1 중량부 내지 약 10 중량부, 보다 구체적으로, 약 2 중량부 내지 약 7 중량부, 예를 들면, 1 중량부, 2 중량부, 3 중량부, 4 중량부, 5 중량부, 6 중량부, 7 중량부, 8 중량부, 9 중량부, 10 중량부로 포함될 수 있다. 상기 범위에서 인조대리석의 내후성, 항균성 등이 우수할 수 있다. In an embodiment, the zinc oxide is about 1 part by weight to about 10 parts by weight, more specifically, about 2 parts by weight to about 7 parts by weight, for example 1 part by weight, 2 parts by weight of 100 parts by weight of the binder resin. It can be included in parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight. Weather resistance of the artificial marble in the above range, may be excellent antibacterial and the like.
본 발명의 일 구체예에 따른 인조대리석 조성물은 필요에 따라, 마블칩, 가교제, 가교촉진제, 경화제, 경화촉진제, 중합개시제, 소포제, 분산제, 커플링제 및 안료 중 1종 이상의 첨가제를 더욱 포함할 수 있다. The artificial marble composition according to one embodiment of the present invention may further include one or more additives of a marble chip, a crosslinking agent, a crosslinking accelerator, a curing agent, a curing accelerator, a polymerization initiator, an antifoaming agent, a dispersing agent, a coupling agent, and a pigment, as necessary. have.
상기 첨가제로는 인조대리석에 사용되는 공지된 첨가제를 제한 없이 사용할 수 있다.As the additive, known additives used in artificial marble can be used without limitation.
상기 마블칩은 인조대리석을 분쇄하여 형성된 것이다. 예를 들면, 상기 마블칩은 아크릴 수지 시럽 100 중량부에 대하여, 무기 충전물 약 120 중량부 내지 약 200 중량부, 가교제 약 0.1 중량부 내지 약 10 중량부 및 중합개시제 약 0.1 중량부 내지 약 10 중량부를 혼합, 경화한 다음, 이를 파쇄한 후 약 0.1 mm 내지 약 5 mm크기로 분류한 것이다.The marble chip is formed by grinding artificial marble. For example, the marble chip may contain about 120 parts by weight to about 200 parts by weight of the inorganic filler, about 0.1 parts by weight to about 10 parts by weight of the crosslinking agent, and about 0.1 parts by weight to about 10 parts by weight of the polymerization initiator, based on 100 parts by weight of the acrylic resin syrup. The parts are mixed, cured, and then broken up into pieces of about 0.1 mm to about 5 mm in size.
상기 마블칩의 혼합비는 바인더 수지 100 중량부를 기준으로 약 0 중량부 약 150 중량부 더욱 바람직하기로는 약 0 중량부 내지 약 70 중량부로 혼합될 수 있다.The mixing ratio of the marble chip may be mixed in an amount of about 0 parts by weight to about 150 parts by weight, more preferably about 0 parts by weight to about 70 parts by weight, based on 100 parts by weight of the binder resin.
상기 가교제로는 상기 바인더 수지와 가교 결합이 가능한, 분자 내에 이중결합을 갖는 화합물을 제한 없이 사용할 수 있다. 예를 들면, 에틸렌글리콜디(메타)아크릴레이트(EDMA), 디에틸렌글리콜디(메타)아크릴레이트(2EDMA), 트리에틸렌글리콜디(메타)아크릴레이트(3EDMA), 테트라에틸렌글리콜디(메타)아크릴레이트(4EDMA), 트리메틸올프로판트리(메타)아크릴레이트(TMPMA), 1,6-헥산디올디(메타)아크릴레이트, 폴리부틸렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 이들의 혼합물 등을 사용할 수 있다. 상기 가교제는 구체적으로, 바인더 수지 100 중량부에 대하여 약 0.1 중량부 내지 약 10 중량부, 예를 들면, 0.1 중량부, 0.5 중량부, 1 중량부, 2 중량부, 3 중량부, 4 중량부, 5 중량부, 6 중량부, 7 중량부, 8 중량부, 9 중량부, 10 중량부로 사용될 수 있다. As the crosslinking agent, a compound having a double bond in a molecule capable of crosslinking with the binder resin can be used without limitation. For example, ethylene glycol di (meth) acrylate (EDMA), diethylene glycol di (meth) acrylate (2EDMA), triethylene glycol di (meth) acrylate (3EDMA), tetraethylene glycol di (meth) acrylic Rate (4EDMA), trimethylolpropane tri (meth) acrylate (TMPMA), 1,6-hexanediol di (meth) acrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylic Rates, mixtures thereof and the like can be used. The crosslinking agent is specifically about 0.1 part by weight to about 10 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, and 4 parts by weight based on 100 parts by weight of the binder resin. , 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight can be used.
상기 경화제는 인조대리석의 경화에 사용되는 것이라면 특별히 제한되지 않는다. 상기 경화제는 구체적으로 바인더 수지 100 중량부에 대하여 약 0.1 중량부 내지 약 5.0 중량부, 예를 들면, 0.1 중량부, 0.5 중량부, 1 중량부, 2 중량부, 3 중량부, 4 중량부, 5 중량부로 사용될 수 있다. The curing agent is not particularly limited as long as it is used for curing artificial marble. The curing agent is specifically about 0.1 part by weight to about 5.0 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, based on 100 parts by weight of the binder resin, It can be used in 5 parts by weight.
상기 중합개시제는 인조대리석 제조 과정에서 수지 조성물의 중합 및 경화 반응을 촉진시키는 역할을 한다. 상기 중합개시제로는 벤조일퍼옥사이드 및 디쿠밀퍼옥사이드 등의 디아실퍼옥사이드; 부틸히드로퍼옥사이드, t-부틸히드로퍼옥사이드 및 쿠밀히드로퍼옥사이드 등의 히드로퍼옥사이드; t-부틸퍼옥시말레인산, t-부틸퍼옥시말레이트; t-부틸히드로퍼옥시부틸레이트; 아세틸퍼옥사이드; 라우로일퍼옥사이드; 아조비스이소부티로니트릴; 아조비스디메틸발레로니트릴; t-부틸퍼옥시에틸헥사노에이트; t-부틸퍼옥시네오데카노에이트; t-아밀퍼옥시-2-에틸헥사노에이트 등을 사용할 수 있으나, 이에 제한되지 않는다. 상기 중합개시제는 구체적으로 바인더 수지 100 중량부에 대하여 약 0.1 중량부 내지 약 5.0 중량부, 예를 들면, 0.1 중량부, 0.5 중량부, 1 중량부, 2 중량부, 3 중량부, 4 중량부, 5 중량부로 사용될 수 있다. The polymerization initiator serves to promote the polymerization and curing reaction of the resin composition in the artificial marble manufacturing process. Examples of the polymerization initiator include diacyl peroxides such as benzoyl peroxide and dicumyl peroxide; Hydroperoxides such as butyl hydroperoxide, t-butyl hydroperoxide and cumyl hydroperoxide; t-butylperoxymaleic acid, t-butylperoxymaleate; t-butylhydroperoxybutylate; Acetyl peroxide; Lauroyl peroxide; Azobisisobutyronitrile; Azobisdimethylvaleronitrile; t-butylperoxyethylhexanoate; t-butylperoxy neodecanoate; t-amylperoxy-2-ethylhexanoate and the like can be used, but is not limited thereto. The polymerization initiator is specifically about 0.1 part by weight to about 5.0 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight based on 100 parts by weight of the binder resin. 5 parts by weight can be used.
상기 커플링제는 무기충전재와 바인더 수지와의 결합을 돕기 위한 것으로, 본 발명이 속하는 분야의 통상의 지식을 가진 자에 의해 용이하게 실시될 수 있다. 바람직하게, 커플링제는 3-(트리메톡시사이릴)프로필메타아크릴레이트, 비닐트리메톡시실란, 비닐트리에톡시실란과 같은 실란계 커플링제를 사용할 수 있다. 커플링제는 구체적으로 바인더 수지 100 중량부에 대하여 약 0.1 중량부 내지 약 1.0 중량부, 예를 들면, 0.1 중량부, 0.2 중량부, 0.3 중량부, 0.4 중량부, 0.5 중량부, 0.6 중량부, 0.7 중량부, 0.8 중량부, 0.9 중량부, 1 중량부로 사용될 수 있다. The coupling agent is to help the bonding of the inorganic filler and the binder resin, it can be easily carried out by those skilled in the art to which the present invention belongs. Preferably, the coupling agent may use a silane coupling agent such as 3- (trimethoxycyryl) propylmethacrylate, vinyltrimethoxysilane, vinyltriethoxysilane. The coupling agent is specifically about 0.1 parts by weight to about 1.0 parts by weight, for example, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, based on 100 parts by weight of the binder resin, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, and 1 part by weight can be used.
상기 안료는 무기안료, 유기 안료, 염료 등이 사용될 수 있다. 바람직하게는 산화철 등의 적갈색안료, 수산화철 등의 황색안료, 산화크롬 등의 녹색안료, 나트륨알루미노실리케이트 등의 군청색안료, 산화티탄 등의 백색안료, 카본블랙 등의 흑색안료와 같이 이 분야에서 사용되는 통상의 것을 사용할 수 있다. 상기 안료는 구체적으로 바인더 수지 100 중량부에 대하여 약 0.0001 중량부 내지 약 5.0 중량부, 예를 들면, 0.0001 중량부, 0.001 중량부, 0.01 중량부, 0.1 중량부, 0.5 중량부, 1 중량부, 1.5 중량부, 2 중량부, 2.5 중량부, 3 중량부, 3.5 중량부, 4 중량부, 4.5 중량부, 5 중량부로 로 포함될 수 있다. The pigment may be an inorganic pigment, an organic pigment, a dye or the like. It is preferably used in this field such as reddish brown pigments such as iron oxide, yellow pigments such as iron hydroxide, green pigments such as chromium oxide, ultramarine pigments such as sodium aluminosilicate, white pigments such as titanium oxide, and black pigments such as carbon black. Ordinary things can be used. The pigment is specifically about 0.0001 parts to about 5.0 parts by weight, for example, 0.0001 parts by weight, 0.001 parts by weight, 0.01 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, based on 100 parts by weight of the binder resin, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, and 5 parts by weight.
구체예에서, 상기 인조대리석용 조성물은 50 mm × 90 mm × 3 mm 크기 사출 시편에 대해 색차계를 사용하여 초기 색상(L0 *, a0 *, b0 *)을 측정하고, 상기 사출 시편을 SAE J 1960에 의거하여, 3,000 시간 동안 내후성 테스트하고, 색차계를 사용하여 테스트 후 색상(L1 *, a1 *, b1 *)을 측정한 다음, 하기 식 2에 따라 산출한 색상 변화(ΔE)가 약 0 내지 약 3, 예를 들면, 0, 1, 2, 3일 수 있다.In embodiments, the artificial marble composition was 50 mm × 90 mm × 3 mm in size injection using a color difference meter for specimens to measure the early color (L 0 *, a 0 * , b 0 *), the injection specimen According to SAE J 1960, weather resistance test for 3,000 hours, and after the test using a colorimeter to measure the color (L 1 * , a 1 * , b 1 * ) and then the color change calculated according to the following Equation 2 (ΔE) can be from about 0 to about 3, for example 0, 1, 2, 3.
[식 2][Equation 2]
색상 변화(ΔE) =
Figure PCTKR2017015028-appb-I000004
Color change (ΔE) =
Figure PCTKR2017015028-appb-I000004
상기 식 2에서, ΔL*는 항온 항습 시험 전후의 L* 값의 차이(L1 *-L0 *)이고, Δa*는 항온 항습 시험 전후의 a* 값의 차이(a1 *- a0 *) 이며, Δb*는 항온 항습 시험 전후의 b* 값의 차이(b1 *- b0 *)이다.In Equation 2, ΔL * is the difference between the L * values before and after the constant temperature and humidity test (L 1 * -L 0 * ), Δa * is the difference between the a * value before and after the constant temperature and humidity test (a 1 * -a 0 * Δb * is the difference (b 1 * -b 0 * ) of the b * value before and after the constant temperature and humidity test.
구체예에서, 상기 인조대리석용 조성물은 JIS Z 2801 항균 평가법에 의거하여, 5 cm x 5 cm 크기 시편에 황색포도상구균 및 대장균을 접종하고, 하기 식 3 에 따라 산출한 황색포도상구균에 대한 항균 활성치가 약 2.0 내지 약 7.0, 예를 들면, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7이고, 대장균에 대한 항균 활성치가 약 2.0 내지 약 6.5, 예를 들면, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 일 수 있다. In an embodiment, the composition for artificial marble is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm x 5 cm size specimen based on JIS Z 2801 antimicrobial evaluation method, and the antibacterial activity value against Staphylococcus aureus calculated according to Equation 3 below. Is from about 2.0 to about 7.0, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7 and the antimicrobial activity against E. coli is from about 2.0 to about 6.5, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5.
[식 3][Equation 3]
항균 활성치 = log(M1/M2)Antimicrobial activity = log (M1 / M2)
상기 식 3에서, M1은 블랭크(blank) 시편에 대한 35℃, RH 90% 조건에서 24 시간 배양 후 세균 수이고, M2는 인조대리석 시편에 대한 35℃, RH 90% 조건에서 24 시간 배양 후 세균 수이다.In Equation 3, M1 is the number of bacteria after 24 hours incubation at 35 ℃, RH 90% conditions for blank specimens, M2 is bacteria after 24 hours at 35 ℃, RH 90% conditions for artificial marble specimens It is a number.
본 발명에 따른 인조대리석은 상기 인조대리석용 조성물을 경화시켜 제조될 수 있다. 상기 경화 온도는 약 25 ℃ 내지 약 180 ℃ 에서 경화를 수행할 수 있다. 이 때, 경화성을 조절하기 위해 경화제와 함께 아민 또는 술폰산 화합물을 추가하여 사용하거나 또는 구리, 코발트, 칼륨, 칼슘, 지르코늄, 아연의 비누화염을 추가하여 사용할 수 있다. Artificial marble according to the present invention can be prepared by curing the composition for artificial marble. The curing temperature may be carried out at about 25 ℃ to about 180 ℃. At this time, in order to adjust the curability, an amine or sulfonic acid compound may be added together with a curing agent or a saponified salt of copper, cobalt, potassium, calcium, zirconium, and zinc may be added.
구체예에서는 상기 인조대리석용 조성물을 경화시키기 전에 탈포하는 단계를 더 포함할 수 있다. 상기 탈포 단계는 탈포제를 사용하여 탈포할 수 있으며, 약 760 ㎜Hg 진공 하에서 할 수 있다.In embodiments, the method may further comprise defoaming before curing the composition for artificial marble. The defoaming step may be degassed using a defoamer, and may be performed under a vacuum of about 760 mmHg.
이하, 본 발명의 바람직한 실시예를 통해 본 발명의 구성 및 작용을 더욱 상세히 설명하기로 한다. 다만, 이는 본 발명의 바람직한 예시로 제시된 것이며 어떠한 의미로도 이에 의해 본 발명이 제한되는 것으로 해석될 수는 없다.Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.
여기에 기재되지 않은 내용은 이 기술 분야에서 숙련된 자이면 충분히 기술적으로 유추할 수 있는 것이므로 그 설명을 생략하기로 한다.Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.
실시예Example
(A) 바인더 수지(A) binder resin
폴리메틸메타아크릴레이트(PMMA) 30 중량%를 메틸메타아크릴레이트 70 중량%에 용해하여 만든 시럽을 사용하였다. A syrup made by dissolving 30% by weight of polymethylmethacrylate (PMMA) in 70% by weight of methylmethacrylate was used.
(B) 무기충전재(B) inorganic filler
평균입경크기가 10 ㎛인 수산화 알루미늄을 사용하였다. Aluminum hydroxide having an average particle size of 10 μm was used.
(C) 산화아연(C) zinc oxide
하기 표 1의 산화아연을 사용하였다.Zinc oxide of Table 1 was used.
(C1)(C1) (C2)(C2) (C3)(C3) (C4)(C4) (C5)(C5)
평균 입자 크기 (㎛)Average particle size (μm) 1.21.2 1.01.0 1.11.1 1.01.0 1.01.0
BET 표면적 (m2/g)BET surface area (m 2 / g) 44 66 1515 1111 44
순도 (%)Purity (%) 9999 9999 9797 9999 9999
PL 크기비(B/A)PL size ratio (B / A) 0.280.28 0.50.5 9.89.8 0.30.3 1.51.5
미소결정 크기 (Å)Microcrystalline Size (Å) 14171417 12291229 503503 15001500 16001600
산화아연의 물성 측정 방법How to measure the physical properties of zinc oxide
(1) 평균 입자 크기(단위: ㎛): 입도분석기(Beckman Coulter社 Laser Diffraction Particle Size Analyzer LS I3 320 장비)를 사용하여, 평균 입자 크기(부피 평균)를 측정하였다.(1) Average particle size (unit: μm): The average particle size (volume average) was measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 instrument).
(2) BET 표면적(단위: m2/g): 질소가스 흡착법을 사용하여, BET 분석 장비(Micromeritics社 Surface Area and Porosity Analyzer ASAP 2020 장비)로 BET 표면적을 측정하였다.(2) BET surface area (unit: m 2 / g): The BET surface area was measured by BET analysis equipment (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 equipment) using nitrogen gas adsorption.
(3) 순도 (단위: %): TGA 열분석법을 사용하여, 800℃ 온도에서 잔류하는 무게를 가지고 순도를 측정하였다.(3) Purity (Unit:%): Purity was measured using TGA thermal analysis with weight remaining at 800 ° C.
(4) PL 크기비(B/A): 광 발광(Photo Luminescence) 측정법에 따라, 실온에서 325 nm 파장의 He-Cd laser (KIMMON사, 30mW)를 시편에 입사해서 발광되는 스펙트럼을 CCD detector를 이용하여 검출하였으며, 이때 CCD detector의 온도는 -70℃ 를 유지하였다. 370 내지 390 nm 영역의 피크 A와 450 내지 600 nm 영역의 피크 B의 크기비(B/A)를 측정하였다. 여기서, 사출 시편은 별도의 처리 없이 레이저(laser)를 시편에 입사시켜 PL 분석을 진행하였고, 산화아연 파우더는 6 mm 직경의 펠렛타이저(pelletizer)에 넣고 압착하여 편평하게 시편을 제작한 뒤 측정하였다.(4) PL size ratio (B / A): According to the photo luminescence measuring method, a spectrum of light emitted by a He-Cd laser (Kimmon, 30mW) having a wavelength of 325 nm at room temperature is measured by a CCD detector. The temperature of the CCD detector was maintained at -70 ° C. The size ratio (B / A) of the peak A in the 370 to 390 nm region and the peak B in the 450 to 600 nm region was measured. Here, the injection specimen was subjected to PL analysis by injecting a laser into the specimen without any treatment, and the zinc oxide powder was placed in a pelletizer having a diameter of 6 mm and pressed to produce a flat specimen. It was.
(5) 미소결정 크기(crystallite size, 단위: Å): 고분해능 X-선 회절분석기(High Resolution X-Ray Diffractometer, 제조사: X'pert사, 장치명: PRO-MRD)을 사용하였으며, 피크 위치(peak position) 2θ 값이 35° 내지 37° 범위이고, 측정된 FWHM 값(회절 피크(peak)의 Full width at Half Maximum)을 기준으로 Scherrer's equation(하기 식 1)에 적용하여 연산하였다. 여기서, 파우더 형태 및 사출 시편 모두 측정이 가능하며, 더욱 정확한 분석을 위하여, 사출 시편의 경우, 600℃, 에어(air) 상태에서 2시간 열처리하여 고분자 수지를 제거한 후, XRD 분석을 진행하였다. (5) Crystallite size (unit: Å): High Resolution X-Ray Diffractometer (manufacturer: X'pert, device name: PRO-MRD) was used, peak position (peak position) 2θ values range from 35 ° to 37 °, and were calculated by applying to the Scherrer's equation (Equation 1) based on the measured FWHM value (Full width at Half Maximum of the diffraction peak). Here, both the powder form and the injection specimen can be measured. For more accurate analysis, the injection specimen was subjected to heat treatment at 600 ° C. for 2 hours under air (air) to remove the polymer resin, followed by XRD analysis.
[식 1][Equation 1]
미소결정 크기(D) =
Figure PCTKR2017015028-appb-I000005
Microcrystal size (D) =
Figure PCTKR2017015028-appb-I000005
상기 식 1에서, K는 형상 계수(shape factor)이고, λ는 X선 파장(X-ray wavelength)이고, β는 X선 회절 피크(peak)의 FWHM 값(degree)이며, θ는 피크 위치 값(peak position degree)이다.In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value of an X-ray diffraction peak, and θ is a peak position value. (peak position degree).
실시예 1~2 및 비교예 1~4: 인조대리석의 제조Examples 1-2 and Comparative Examples 1-4: Preparation of Artificial Marble
상기 각 구성 성분을 하기 표 2 및 3에 기재된 조성에 따라 함량을 조절하고, 트리메틸올프로판트리메타크릴레이트, 노르말도데실메르캡탄, 소포제와 분산제 및 중합개시제를 첨가하여 혼합한 인조대리석용 조성물을 제조한 후, 교반시킨 후 진공탈포흘 거쳐 80℃의 온도에서 경화시켜 인조대리석을 제조 하였다.To adjust the content according to the composition shown in the following Tables 2 and 3, the composition for artificial marble mixed with trimethylolpropane trimethacrylate, normal dodecyl mercaptan, an antifoaming agent and a dispersing agent and a polymerization initiator After the preparation, the mixture was stirred and then cured at a temperature of 80 ° C. through vacuum degassing to prepare artificial marble.
물성 평가 방법Property evaluation method
(1) 내후성 평가(색상 변화(ΔE)): 50 mm × 90 mm × 3 mm 크기 사출 시편에 대해 색차계(KONICA MINOLTA, CM-3700A)를 사용하여 초기 색상(L0 *, a0 *, b0 *)을 측정하고, 상기 사출 시편을 SAE J 1960에 의거하여, 3,000 시간 동안 내후성 테스트하고, 색차계를 사용하여 테스트 후 색상(L1 *, a1 *, b1 *)을 측정한 다음, 하기 식 2에 따라 색상 변화(ΔE)를 산출하였다.(1) Weather resistance evaluation (color change (ΔE)): Initial color (L 0 * , a 0 * , using a color difference meter (KONICA MINOLTA, CM-3700A) for 50 mm × 90 mm × 3 mm injection molded specimens. measuring the b 0 *) and, on the basis of the injection specimen to SAE J 1960, after the test to weather resistance testing, using a color difference meter for 3000 hours the color (L 1 *, a 1 * , b 1 *) was measured Next, the color change ΔE was calculated according to the following Equation 2.
[식 2][Equation 2]
색상 변화(ΔE) =
Figure PCTKR2017015028-appb-I000006
Color change (ΔE) =
Figure PCTKR2017015028-appb-I000006
상기 식 2에서, ΔL*는 항온 항습 시험 전후의 L* 값의 차이(L1 *-L0 *)이고, Δa*는 항온 항습 시험 전후의 a* 값의 차이(a1 *- a0 *) 이며, Δb*는 항온 항습 시험 전후의 b* 값의 차이(b1 *- b0 *)이다.In Equation 2, ΔL * is the difference between the L * values before and after the constant temperature and humidity test (L 1 * -L 0 * ), Δa * is the difference between the a * value before and after the constant temperature and humidity test (a 1 * -a 0 * Δb * is the difference (b 1 * -b 0 * ) of the b * value before and after the constant temperature and humidity test.
(2) 항균 활성치: JIS Z 2801 항균 평가법에 의거하여, 5 cm x 5 cm 크기 시편에 황색포도상구균 및 대장균을 접종하고, 하기 식 3 에 따라 항균 활성치를 구하였다.(2) Antibacterial activity value: In accordance with JIS Z 2801 antimicrobial evaluation method, 5 cm x 5 cm size specimen was inoculated with Staphylococcus aureus and E. coli, and the antibacterial activity value was calculated according to the following formula (3).
[식 3][Equation 3]
항균 활성치 = log(M1/M2)Antimicrobial activity = log (M1 / M2)
상기 식 3에서, M1은 블랭크(blank) 시편에 대한 35℃, RH 90% 조건에서 24시간 배양 후 세균 수이고, M2는 인조대리석 시편에 대한 35℃, RH 90% 조건에서 24시간 배양 후 세균 수이다.In Equation 3, M1 is the number of bacteria after incubation for 24 hours at 35 ℃, RH 90% conditions for blank specimens, M2 is bacteria after 24 hours at 35 ℃, RH 90% conditions for artificial marble specimens It is a number.
실시예 1Example 1 실시예 2Example 2
(A) 바인더 수지(A) binder resin 100100 100100
(B) 무기충전재(B) inorganic filler 150150 150150
(C) 산화아연(C) zinc oxide (C1)(C1) 55 --
(C2)(C2) -- 55
항균활성치Antimicrobial activity 황색 포도상 구균Staphylococcus aureus 4.64.6 4.64.6
대장균Escherichia coli 6.36.3 6.36.3
색상 변화 (ΔE)Color change (ΔE) 0.80.8 1.11.1
비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4
(A) 바인더 수지(A) binder resin 100100 100100 100100 100100
(B) 무기충전재(B) inorganic filler 150150 150150 150150 150150
(C) 산화아연(C) zinc oxide (C1)(C1) -- -- -- --
(C2)(C2) -- -- -- --
(C3)(C3) -- 55 -- --
(C4)(C4) -- -- 55
(C5)(C5) -- -- -- 55
항균활성치Antimicrobial activity 황색 포도상 구균Staphylococcus aureus 2.12.1 4.64.6 4.24.2 4.54.5
대장균Escherichia coli 00 6.06.0 5.85.8 6.06.0
색상 변화 (ΔE)Color change (ΔE) 8.48.4 7.67.6 9.29.2 8.78.7
상기 결과로부터, 비교예 1에서는 대장균에 대해 항균효과를 나타내는 항균 활성치가 2 이하로 항균 효과가 없으며, 색상 변화가 발생하였다. 또한, 비교예 2 내지 4와 같이 370 nm 내지 390 nm 영역의 피크 A와 450 nm 내지 600 nm 영역의 피크 B의 크기비(B/A)가 약 0.01 내지 약 1 값을 벗어나거나 혹은 BET 표면적이 약 10 m2/g을 초과하는 산화아연을 사용한 경우 항균성은 확보할 수 있었지만 내변색성이 현저하게 저하된 것을 확인할 수 있었다. From the above results, in Comparative Example 1, the antibacterial activity value showing the antimicrobial effect against Escherichia coli was 2 or less, and there was no antimicrobial effect, and color change occurred. Further, as in Comparative Examples 2 to 4, the size ratio (B / A) of the peak A in the 370 nm to 390 nm region and the peak B in the 450 nm to 600 nm region is outside the value of about 0.01 to about 1, or the BET surface area is When zinc oxide exceeding about 10 m 2 / g was used, antibacterial activity could be ensured, but the discoloration resistance was remarkably decreased.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (13)

  1. 바인더 수지;Binder resins;
    산화아연을 제외한 무기충전재; 및Inorganic fillers except zinc oxide; And
    산화아연;을 포함하고,Zinc oxide;
    상기 산화아연은 광 발광(Photo Luminescence) 측정 시, 370 nm 내지 390 nm 영역의 피크 A와 450 nm 내지 600 nm 영역의 피크 B의 크기비(B/A)가 약 0.01 내지 약 1이고, BET 분석 장비로 측정한 BET 표면적이 약 10 m2/g 이하인 인조대리석용 조성물. The zinc oxide has a size ratio (B / A) of peak A in the 370 nm to 390 nm region and peak B in the 450 nm to 600 nm region when measured for photo luminescence, and is BET analysis. Composition for artificial marble having a BET surface area of about 10 m 2 / g or less as measured by the equipment.
  2. 제1항에 있어서, 상기 인조대리석용 조성물은 바인더 수지 100 중량부, 산화아연을 제외한 무기충전재 약 100 중량부 내지 약 300 중량부, 및 산화아연 약 1 중량부 내지 약 10 중량부를 포함하는 인조대리석용 조성물.The artificial marble according to claim 1, wherein the composition for artificial marble comprises 100 parts by weight of a binder resin, about 100 parts by weight to about 300 parts by weight of an inorganic filler excluding zinc oxide, and about 1 part by weight to about 10 parts by weight of zinc oxide. Composition.
  3. 제1항에 있어서, 상기 바인더 수지는 아크릴계 수지 및 불포화 폴리에스테르 수지 중 1종 이상을 포함하는 인조대리석용 조성물. The composition of claim 1, wherein the binder resin comprises at least one of an acrylic resin and an unsaturated polyester resin.
  4. 제1항에 있어서, 상기 바인더 수지는 폴리(메타)아크릴레이트와 (메타)아크릴레이트 모노머의 혼합물인 것을 특징으로 하는 인조대리석용 조성물.The composition for artificial marble according to claim 1, wherein the binder resin is a mixture of a poly (meth) acrylate and a (meth) acrylate monomer.
  5. 제1항에 있어서, 상기 무기충전재는 실리카, 알루미나, 탄산칼슘, 수산화칼슘, 수산화알루미늄, 수산화마그네슘, 펄라이트, 버미큘라이트, 스멕타이트 및 벤토나이트 중 1종 이상을 포함하는 인조대리석용 조성물.The composition of claim 1, wherein the inorganic filler comprises at least one of silica, alumina, calcium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, pearlite, vermiculite, smectite, and bentonite.
  6. 제1항에 있어서, 상기 산화아연은 평균 입자 크기가 약 0.5 ㎛ 내지 약 3 ㎛인 인조대리석용 조성물.The composition of claim 1, wherein the zinc oxide has an average particle size of about 0.5 μm to about 3 μm.
  7. 제1항에 있어서, 상기 산화아연은 X선 회절(X-ray diffraction, XRD) 분석 시, 피크 위치(peak position) 2θ 값이 약 35° 내지 약 37° 범위이고, 하기 식 1에 의한 미소결정의 크기(crystallite size) 값이 약 1,000 Å 내지 약 2,000 Å인 것을 특징으로 하는 인조대리석용 조성물:The method of claim 1, wherein the zinc oxide has a peak position 2θ of about 35 ° to about 37 ° in X-ray diffraction (XRD) analysis, and the microcrystals according to Equation 1 below. A composition for artificial marble, characterized in that the crystallite size value is from about 1,000 mm 3 to about 2,000 mm 3:
    [식 1][Equation 1]
    미소결정 크기(D) =
    Figure PCTKR2017015028-appb-I000007
    Microcrystal size (D) =
    Figure PCTKR2017015028-appb-I000007
    상기 식 1에서, K는 형상 계수(shape factor)이고, λ는 X선 파장(X-ray wavelength)이고, β는 X선 회절 피크(peak)의 FWHM 값(degree)이며, θ는 피크 위치 값(peak position degree)이다.In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is an FWHM value of an X-ray diffraction peak, and θ is a peak position value. (peak position degree).
  8. 제1항에 있어서, 상기 무기충전재의 평균입경크기는 상기 산화아연의 평균입경크기 보다 큰 것을 특징으로 하는 인조대리석용 조성물.The composition of claim 1, wherein the average particle size of the inorganic filler is larger than the average particle size of the zinc oxide.
  9. 제8항에 있어서, 상기 무기충전재와 상기 산화아연은 평균입경크기의 비가 약 0.3 : 1 내지 약 200 : 1 인 인조대리석용 조성물. The composition of claim 8, wherein the inorganic filler and the zinc oxide have a ratio of an average particle size of about 0.3: 1 to about 200: 1.
  10. 제1항에 있어서, 상기 인조대리석용 조성물은 마블칩, 가교제, 가교촉진제, 경화제, 경화촉진제, 중합개시제, 소포제, 분산제, 커플링제 및 안료 중 1종 이상을 더 포함하는 것을 특징으로 하는 인조대리석용 조성물.The artificial marble according to claim 1, wherein the artificial marble composition further comprises at least one of a marble chip, a crosslinking agent, a crosslinking accelerator, a curing agent, a curing accelerator, a polymerization initiator, an antifoaming agent, a dispersing agent, a coupling agent, and a pigment. Composition.
  11. 제1항에 있어서, 상기 인조대리석용 조성물은 50 mm × 90 mm × 3 mm 크기 사출 시편에 대해 색차계를 사용하여 초기 색상(L0 *, a0 *, b0 *)을 측정하고, 상기 사출 시편을 SAE J 1960에 의거하여, 3,000 시간 동안 내후성 테스트하고, 색차계를 사용하여 테스트 후 색상(L1 *, a1 *, b1 *)을 측정한 다음, 하기 식 2에 따라 산출한 색상 변화(ΔE)가 약 0 내지 약 3인 인조대리석용 조성물:The method of claim 1, wherein the artificial marble composition for using the color difference meter for a 50 mm × 90 mm × 3 mm in size injection specimen measuring the initial color (L 0 *, a 0 * , b 0 *), the The injection specimen was subjected to weather resistance testing for 3,000 hours according to SAE J 1960, and the color after test (L 1 * , a 1 * , b 1 * ) was measured using a colorimeter, and then calculated according to Equation 2 below. Composition for artificial marble having a color change (ΔE) of about 0 to about 3:
    [식 2][Equation 2]
    색상 변화(ΔE) =
    Figure PCTKR2017015028-appb-I000008
    Color change (ΔE) =
    Figure PCTKR2017015028-appb-I000008
    상기 식 2에서, ΔL*는 항온 항습 시험 전후의 L* 값의 차이(L1 *-L0 *)이고, Δa*는 항온 항습 시험 전후의 a* 값의 차이(a1 *- a0 *)이며, Δb*는 항온 항습 시험 전후의 b* 값의 차이(b1 *- b0 *)이다.In Equation 2, ΔL * is the difference between the L * values before and after the constant temperature and humidity test (L 1 * -L 0 * ), Δa * is the difference between the a * value before and after the constant temperature and humidity test (a 1 * -a 0 * Δb * is the difference (b 1 * -b 0 * ) of the b * value before and after the constant temperature and humidity test.
  12. 제1항에 있어서, 상기 인조대리석용 조성물은 JIS Z 2801 항균 평가법에 의거하여, 5 cm x 5 cm 크기 시편에 황색포도상구균 및 대장균을 접종하고, 하기 식 3 에 따라 산출한 황색포도상구균에 대한 항균 활성치가 약 2.0 내지 약 7.0 이고, 대장균에 대한 항균 활성치가 약 2.0 내지 약 6.5 인 인조대리석용 조성물: According to claim 1, wherein the composition for artificial marble is inoculated with Staphylococcus aureus and E. coli in 5 cm x 5 cm size specimens based on the antimicrobial evaluation method JIS Z 2801 for Staphylococcus aureus calculated according to the following formula 3 A composition for artificial marble having an antimicrobial activity of about 2.0 to about 7.0 and an antimicrobial activity of E. coli of about 2.0 to about 6.5:
    [식 3][Equation 3]
    항균 활성치 = log(M1/M2)Antimicrobial activity = log (M1 / M2)
    상기 식 3에서, M1은 블랭크(blank) 시편에 대한 35℃, RH 90% 조건에서 24시간 배양 후 세균 수이고, M2는 인조대리석 시편에 대한 35℃, RH 90% 조건에서 24시간 배양 후 세균 수이다.In Equation 3, M1 is the number of bacteria after incubation for 24 hours at 35 ℃, RH 90% conditions for blank specimens, M2 is bacteria after 24 hours at 35 ℃, RH 90% conditions for artificial marble specimens It is a number.
  13. 제1항 내지 제12항 중 어느 한 항에 따른 인조대리석용 조성물로부터 형성된 인조대리석.Artificial marble formed from the composition for artificial marble according to any one of claims 1 to 12.
PCT/KR2017/015028 2016-12-20 2017-12-19 Composition for artificial marble WO2018117603A1 (en)

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US16/470,317 US11034620B2 (en) 2016-12-20 2017-12-19 Composition for artificial marble
JP2019530736A JP6966550B2 (en) 2016-12-20 2017-12-19 Composition for terrazzo

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US11034620B2 (en) 2016-12-20 2021-06-15 Lotte Chemical Corporation Composition for artificial marble
US11505674B2 (en) 2017-11-08 2022-11-22 Lotte Chemical Corporation Thermoplastic resin composition and molded article produced from same

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US11034620B2 (en) 2016-12-20 2021-06-15 Lotte Chemical Corporation Composition for artificial marble
US11505674B2 (en) 2017-11-08 2022-11-22 Lotte Chemical Corporation Thermoplastic resin composition and molded article produced from same

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