WO2018117473A1 - Composition de résine moussante, procédé de préparation associé et mousse utilisant celle-ci - Google Patents

Composition de résine moussante, procédé de préparation associé et mousse utilisant celle-ci Download PDF

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Publication number
WO2018117473A1
WO2018117473A1 PCT/KR2017/013955 KR2017013955W WO2018117473A1 WO 2018117473 A1 WO2018117473 A1 WO 2018117473A1 KR 2017013955 W KR2017013955 W KR 2017013955W WO 2018117473 A1 WO2018117473 A1 WO 2018117473A1
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WIPO (PCT)
Prior art keywords
zinc oxide
peak
resin composition
weight
foamable resin
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PCT/KR2017/013955
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English (en)
Korean (ko)
Inventor
김주성
김유현
김연경
박강열
배승용
정봉재
Original Assignee
롯데첨단소재(주)
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Priority claimed from KR1020170159551A external-priority patent/KR101991584B1/ko
Application filed by 롯데첨단소재(주) filed Critical 롯데첨단소재(주)
Priority to JP2019527892A priority Critical patent/JP2020514427A/ja
Priority to CN201780071570.1A priority patent/CN109983060B/zh
Priority to EP17883936.1A priority patent/EP3560989B1/fr
Priority to US16/347,929 priority patent/US11365304B2/en
Publication of WO2018117473A1 publication Critical patent/WO2018117473A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to a foamable resin composition, a method for producing the same, and a foam using the same. More specifically, the present invention relates to a foamable resin composition, a method for producing the same, and a foam using the same, which are excellent in antibacterial properties and are beneficial to a human body and are excellent in heat insulating properties.
  • Foaming resins in particular, polystyrene foaming resins, have excellent moldability, heat insulation, buffering properties, and thermal insulation properties, and the foams (foaming molded bodies) are used as packaging materials for home appliances, agricultural product boxes, processed food packaging, household goods, and house insulation materials. It is used in various ways.
  • foams applied to packaging materials for agricultural and marine products or processed foods or buffers used in infant play facilities improve long-term freshness when packaging, storing and transporting foods, and antibacterial and antimicrobial and antifungal properties against bacteria and fungi when used.
  • Techniques for adding antimicrobial agents to foams have been developed to give them.
  • KR 10-2014-0045782 discloses a technique for producing antimicrobial polystyrene by antimicrobial coating on the resin bead surface with an antimicrobial agent and a coating agent.
  • KR 10-0833453 discloses moldings that are beneficial to the human body containing silver nanoparticles and methods for their preparation.
  • KR 10-2005-0025186 discloses expanded polystyrene particles having a functional skin layer and a manufacturing method by coating a particle surface of expanded polystyrene with a functional coating composition.
  • the conventional invention has a problem that the process is cumbersome because a secondary process called coating process after EPS foaming is required.
  • the nano-sized particles are applied, the nano particles are lost after the coating process or flow out of the foam, which is rather harmful to the human body.
  • Another object of the present invention is to provide a foamable resin composition having excellent heat insulating properties.
  • Still another object of the present invention is to provide a method for producing a foamable resin composition having a simple process without a separate coating process.
  • the foamable resin composition is an aromatic vinyl resin; 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.
  • BET surface area measured by BET analysis equipment is about 1 m 2 / g to about 10 m 2 / g.
  • the expandable resin composition may include about 1 part by weight to about 10 parts by weight of zinc oxide based on 100 parts by weight of the aromatic vinyl resin.
  • the aromatic vinyl resin may be a polymer of a monomer comprising at least one of styrene, ⁇ -methylstyrene, vinyltoluene, and chlorostyrene.
  • 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 zinc oxide may have 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 by photo luminescence. Can be.
  • the foamable resin composition may include a blowing agent selected from at least one of a hydrocarbon compound and a hydrocarbon fluoride.
  • Another aspect of the present invention relates to a method for producing a expandable resin composition.
  • the method comprises mixing an aromatic vinyl-based resin and zinc oxide to form a mixed composition; And extruding by injecting a blowing agent into the mixed composition, wherein the zinc oxide has a size of peak A in a region of 370 nm to 390 nm and peak B in a region of 450 nm to 600 nm when measuring photo luminescence.
  • the ratio (B / A) is about 0.01 to about 1 and the BET surface area is about 1 to about 10 m 2 / g.
  • the method comprises polymerizing a reaction solution comprising an aromatic vinyl monomer, an initiator and zinc oxide to form a polymer; And injecting a blowing agent into the polymer, wherein the zinc oxide has a size ratio (B) of peak A of 370 nm to 390 nm and peak B of 450 nm to 600 nm when measuring photo luminescence.
  • / A) is from about 0.01 to about 1 and the BET surface area is from about 1 m 2 / g to about 10 m 2 / g.
  • Another aspect of the present invention is a foam formed by foaming the foamable resin composition.
  • the thermal conductivity of the foam may be about 0.030 W / m ⁇ K to about 0.038 W / m ⁇ K based on KS L 9016.
  • the foam is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm X 5 cm size specimen according to the JIS Z 2801 antimicrobial evaluation method
  • the antibacterial activity value against Staphylococcus aureus calculated according to Equation 2 is about 2.0 To about 6.0
  • the antimicrobial activity against E. coli may be about 2.0 to about 5.0.
  • Antimicrobial activity log (M1 / M2)
  • Equation 2 M1 is the number of bacteria after 24 hours incubation at 35 °C, RH 90% conditions for the blank specimen, M2 is the number of bacteria after 24 hours incubation at 35 °C, RH 90% conditions for the foam specimens to be.
  • the present invention has the effect of the invention to provide a method for producing a foamable resin composition excellent in antibacterial and beneficial to the human body because the antimicrobial particles are not leaked or lost, and excellent in thermal insulation and a simple process without separate coating process. .
  • the foamable resin composition according to the present invention contains an aromatic vinyl resin and zinc oxide.
  • a conventional aromatic vinyl resin used in the foamable resin composition can be used without limitation.
  • polymerized the monomer mixture containing 1 or more types of styrene, (alpha) -methylstyrene, vinyltoluene, chlorostyrene, etc. can be used.
  • it may be a styrene resin such as general purpose polystyrene (GPPS), high impact polystyrene resin (HIPS).
  • GPPS general purpose polystyrene
  • HIPS high impact polystyrene resin
  • the weight average molecular weight of the aromatic vinyl-based resin is specifically about 120,000 g / mol to about 400,000 g / mol, more specifically about 150,000 g / mol to about 350,000 g / mol, for example 120,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol. It is possible to maintain foamability and strength in the above range.
  • 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 measured for photo luminescence.
  • the zinc oxide has an average particle size of about 0.5 ⁇ m to about 3 ⁇ m, more specifically about 1 ⁇ m to about 3 ⁇ m, for example, 0.5 ⁇ m, 0.6 ⁇ m, 0.7 as measured by Light Scattering (LS 13 320).
  • Zinc oxide can be prevented from being lost or leaked in the above range.
  • the zinc oxide has a peak position 2 ⁇ of about 35 ° to about 37 ° and a crystallite size according to Equation 1 below.
  • 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 99% or more. In the above range, the antimicrobial properties and thermal insulation of the foam may be more excellent.
  • the zinc oxide is dissolved in zinc in the form of metal, 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, specifically about 2 parts by weight to about 5 parts by weight, for example, 1 part by weight, based on 100 parts by weight of the aromatic vinyl 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.
  • Zinc oxide is uniformly dispersed in the aromatic vinyl resin in the above range, and excellent in weather resistance, antibacterial property, heat insulating property and the like of the foam.
  • a blowing agent used in a conventional foamable resin composition may be used.
  • hydrocarbons such as propane, butane, isobutane, normal pentane, isopentane, cyclopentane, hexane, and mixtures thereof. compound;
  • Hydrofluorinated hydrocarbons such as hydrochlorofluorocarbons (HCFC) such as HCFC-142b and HCFC-123, hydrofluorocarbons (HFC) such as HFC-123, and mixtures thereof;
  • HCFC hydrochlorofluorocarbons
  • HFC hydrofluorocarbons
  • the content of the blowing agent is specifically about 1 part by weight to 40 parts by weight, more specifically about 3 to about 20 parts by weight, for example, 1 part by weight, 5 parts by weight, and 10 parts by weight of 100 parts by weight of the aromatic vinyl resin. It is weight part, 15 weight part, 20 weight part, 25 weight part, 30 weight part, 35 weight part, 40 weight part. In the above range, the blowing agent and the zinc oxide may be uniformly dispersed in the aromatic vinyl resin.
  • the foamable resin composition according to the present invention if necessary, the usual additives such as foaming aids, compatibilizers, surfactants, gas barrier resins, dispersants, antiblocking agents, flame retardants, lubricants, nucleating agents, etc. It may further include.
  • the foaming aid facilitates the foaming and molding of the expandable composite resin particles, and a conventional foaming aid can be used.
  • foaming aids such as toluene, cyclohexane, ethylbenzene, and the like can be used. have.
  • the content may be 0.01 to 10 parts by weight based on 100 parts by weight of the expandable resin composition, but is not limited thereto.
  • Method for producing a foamable resin composition is a step of mixing the aromatic vinyl resin and the zinc oxide in the content to form a mixed composition, injecting the blowing agent in the content to the mixed composition and extruded ( Extrusion step 1)).
  • the extruder used in the extrusion is not particularly limited, but the die plate hole diameter may be, for example, about 0.3 to about 2 mm, specifically about 0.5 mm to about 1.2 mm, for example, to obtain the desired grade.
  • the die plate hole diameter may be, for example, about 0.3 to about 2 mm, specifically about 0.5 mm to about 1.2 mm, for example, to obtain the desired grade.
  • 0.3 mm, 0.4 mm, 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1 mm, 1.1 mm 1.2 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2 can be mm.
  • the temperature of the melt kneading and the extruder is about 135 ° C to about 230 ° C, preferably about 150 ° C to about 200 ° C, for example, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C, and 200 ° C. Can be.
  • the temperature of the die plate is about 170 ° C to about 350 ° C, preferably about 190 ° C to about 300 ° C, for example, 190 ° C, 200 ° C, 210 ° C, 220 ° C, 230 ° C, 240 ° C, 250 ° C.
  • a foaming agent and the zinc oxide are uniformly dispersed in the aromatic vinyl resin, and a foam having physical properties such as excellent compressive strength and low thermal conductivity can be obtained.
  • the expandable resin composition may be pelletized by extrusion in water or the like during extrusion.
  • the average particle diameter of the pellets may be about 0.5 mm to about 5 mm.
  • the zinc oxide of the present invention has a structure uniformly distributed not only on the surface of the pellet but also inside. In the foamed foamed product, zinc oxide particles are uniformly distributed on the surface and inside of the cell.
  • the expandable resin composition may be prepared by polymerization.
  • the method comprises polymerizing a reaction solution containing an aromatic vinyl monomer, an initiator and zinc oxide to form a polymer; And injecting a blowing agent into the polymer.
  • the initiator benzoyl peroxide, dibenzoyl peroxide, lauryl peroxide, t-butylperoxybenzoate, tertyl amyl peroxy 2-ethyl hexyl carbonate, tert butyl peroxy isopropyl carbonate, cumene hydroxy per Oxides and the like may be used, but are not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.
  • the use amount of the initiator is about 0.01 to about 3 parts by weight, preferably about 0.05 to about 0.3 parts by weight, for example, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight of 100 parts by weight of the aromatic vinyl monomer. Parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, and 3 parts by weight. If the amount of the initiator is out of the above range it may be difficult to control the polymerization reaction.
  • Suspension polymerization may be applied to the polymerization, and dispersing agents may be used for dispersion stability and particle size control during suspension polymerization.
  • the dispersant polyvinyl alcohol, methyl cellulose, polyvinylpyrrolidone, tricalcium phosphate, magnesium pyrophosphate, and the like may be used, but are not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.
  • the dispersant is about 0.1 part by weight to about 3 parts by weight, for example, 0.1 part by weight, 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight based on 100 parts by weight of the aromatic vinyl monomer. 3 parts by weight can be used.
  • the manufacturing process is simple, and the loss of zinc oxide due to the coating can be minimized.
  • the foamed resin composition thus polymerized may have a bead shape having an average particle diameter of about 0.1 mm to about 5 mm.
  • the zinc oxide of the present invention has a structure uniformly distributed not only on the surface of the beads but also inside. In the foamed foamed beads, zinc oxide particles are uniformly distributed on the surface and inside of the cell.
  • Another aspect of the present invention is a foam formed by foaming the foamable resin composition.
  • the foam is filled (introduced) the foamable resin composition into a non-hermetic mold and, for example, using hot air or steam at a pressure of about 0.1 kgf / cm 2 to about 5 kgf / cm 2 .
  • a foam can be manufactured by fusing a foamable resin composition in a metal mold
  • the thermal conductivity of the foam is about 0.030 W / m ⁇ K to about 0.038 W / m ⁇ K, specifically about 0.030 W / m ⁇ K to about 0.033 W / m ⁇ K, based on KS L 9016, More specifically, from about 0.0310 W / mK to about 0.0325 W / mK, for example, 0.030 W / mK, 0.031 W / mK, 0.032 W / mK, 0.033 W / mK , 0.034 W / m ⁇ K, 0.035 W / m ⁇ K, 0.036 W / m ⁇ K, 0.037 W / m ⁇ K, 0.038 W / m ⁇ K.
  • the foam is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm X 5 cm size specimen according to the JIS Z 2801 antimicrobial evaluation method
  • the antibacterial activity value against Staphylococcus aureus calculated according to Equation 2 is about 2.0 To about 6.0, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, and the antimicrobial activity against E. coli is about 2.0 to about 5.0, for example, 2, 2.5, 3, 3.5 Can be 4, 4.5, 5.
  • Antimicrobial activity log (M1 / M2)
  • Equation 2 M1 is the number of bacteria after 24 hours incubation at 35 °C, RH 90% conditions for the blank specimen, M2 is the number of bacteria after 24 hours incubation at 35 °C, RH 90% conditions for the foam specimens to be.
  • the foam may have an average size of a cell cut from a cross section of the foam and measured using an optical microscope at 200 magnification, about 8 ⁇ m to about 100 ⁇ m, for example, about 10 ⁇ m to about 50 ⁇ m.
  • Zinc oxide of Table 1 was used.
  • n-pentane gas was used.
  • TCP / ADP was used as a dispersant by mixing at a weight ratio of 1.5 / 3.0
  • the TCP is Tricalcium phosphate (Hydroxyapatite), manufacturer: Samzo Industries; the ADP is Ammonium dihydrogen phosphate manufacturer: Finechemtech, product name: Fincol ).
  • D12 / DN was used as a dispersant by mixing at a weight ratio of 800/200 ppm
  • D12 is sodium alkyl aryl sulfonate, manufacturer: DAI-ICHI KOGYO SEIYAKU, product name: Neogen SCF
  • DN is sodium 2-naphthalenesulfonate, manufactured by KAO, trade name: Demol-L).
  • 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).
  • GPPS pellet manufactured by Cheil Industries, product name: GP HR-2390P00
  • lubricant POLYWAX 660 PETROLITE
  • TINUBIN 770 CIBA
  • the mixed composition which mixed 2 weight part of zinc oxide (Z1) of Table 1 was extruded and pelletized.
  • 100 parts by weight of the prepared pellet, 100 parts by weight of water, TCP / ADP 1.5 / 3.0 parts by weight, and D12 / DN 800/200 ppm were dispersed in a pressurized reactor. The pellets thus dispersed were heated up to 90 ° C.
  • a polymer was prepared by polymerization at 120 ° C. under pressure of 0.5 kgf nitrogen. 40 parts by weight of n-pentane was injected into the polymer at a pressure of 10 kgf of nitrogen as a blowing agent, and then stirred at 120 ° C. for 6 hours and then cooled to less than 60 ° C. to synthesize a foamable resin composition.
  • Defoamed and dried process to prepare a non-foamed EPS powder was subjected to the usual process steps such as foam aging and molding to obtain a density of 15.5 kg / m 3 foam.
  • Example 1 The same procedure as in Example 1 was carried out except that zinc oxide was not used.
  • Example 2 The same procedure as in Example 2 was conducted except that no zinc oxide was used.
  • Example 2 The same procedure as in Example 1 was carried out except that zinc oxide (Z3) was used.
  • Example 2 The same procedure as in Example 1 was carried out except that zinc oxide (Z5) was used.
  • Antibacterial activity value In accordance with JIS Z 2801 antibacterial evaluation method, 5 cm X 5 cm size specimen was inoculated with Staphylococcus aureus and E. coli, and the antimicrobial activity value was calculated according to the following formula 2.
  • Antimicrobial activity log (M1 / M2)
  • Equation 2 M1 is the bacterial count after 24 hours incubation at 35 °C, RH 90% conditions for the blank specimen (Stomacher, 400 POLY-BAG), M2 is 35 °C, RH 90 for the foam specimens Number of bacteria after 24 hours incubation at% conditions.
  • Foam average cell size (unit: ⁇ m): The cross section of the foams prepared in the above Examples and Comparative Examples was cut out, and the cell size of the foam was confirmed by using an optical microscope at 200 magnification. The average cell size was chosen as the average value by arbitrarily selecting / measuring 10 cell sizes in three or more foam granules.
  • Foamability (unit: times): After foaming by supplying 0.2 kg / cm 2 steam for 5 minutes to the foamable resin composition (mini-pellet) prepared in the above Examples and Comparative Examples, the foam chamber 60 °C After drying for 2 hours at foaming magnification was measured. Measurement of the expansion ratio is a measuring cylinder, and then by measuring the weight and volume of the foamed granules (foamed), dried using the scale of calculating the density of the expanded granules, foam former density 1 g / basis cm 3 1-fold by the expansion ratio Was converted.
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Zinc oxide type Z1 Z2 - - Z3 Z4 Z5 Average cell size ( ⁇ m) 10 40 10 40 8 5 40 Density (kg / m3) 17 15.5 16 14.5 18 16 15.5 Thermal Conductivity (W / mK) 0.038 0.037 0.038 0.038 0.17 0.15 0.16 Effervescent (pear) 20 65 20 65 3 5 19 Antimicrobial activity Staphylococcus aureus 4.6 4.6 1.2 1.3 2.1 2.3 5.0 Escherichia coli 3.4 3.4 0.5 0.8 1.3 1.0 3.8

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La composition de résine moussante de la présente invention contient une résine à base de vinyle aromatique et de l'oxyde de zinc. Le rapport dimensionnel (B/A) de l'oxyde de zinc, la valeur A maximale représentant une région comprise entre 370 nm et 390 nm, et la valeur B maximale représentant une région comprise entre 450 nm et 600 nm, est d'environ 0,01 à environ 1 lorsque la photoluminescence est mesurée, et la surface BET correspondante est d'environ 1 m2/g à environ 10 m2/g.
PCT/KR2017/013955 2016-12-23 2017-11-30 Composition de résine moussante, procédé de préparation associé et mousse utilisant celle-ci WO2018117473A1 (fr)

Priority Applications (4)

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JP2019527892A JP2020514427A (ja) 2016-12-23 2017-11-30 発泡性樹脂組成物、その製造方法及びこれを用いた発泡体
CN201780071570.1A CN109983060B (zh) 2016-12-23 2017-11-30 发泡树脂组合物、其制备方法和使用其的发泡体
EP17883936.1A EP3560989B1 (fr) 2016-12-23 2017-11-30 Composition de résine moussante, procédé de préparation associé et mousse utilisant celle-ci
US16/347,929 US11365304B2 (en) 2016-12-23 2017-11-30 Foaming resin composition, preparation method therefor, and foam using same

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KR20160177858 2016-12-23
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KR1020170159551A KR101991584B1 (ko) 2016-12-23 2017-11-27 발포성 수지 조성물, 그 제조방법 및 이를 이용한 발포체

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Publication number Priority date Publication date Assignee Title
US11124643B2 (en) 2016-12-27 2021-09-21 Lotte Chemical Corporation Thermoplastic resin composition and molded article manufactured therefrom
US11365304B2 (en) 2016-12-23 2022-06-21 Lotte Chemical Corporation Foaming resin composition, preparation method therefor, and foam using same

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11365304B2 (en) 2016-12-23 2022-06-21 Lotte Chemical Corporation Foaming resin composition, preparation method therefor, and foam using same
US11124643B2 (en) 2016-12-27 2021-09-21 Lotte Chemical Corporation Thermoplastic resin composition and molded article manufactured therefrom

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