WO2013100452A1 - Preparation method of thermosetting resin, and molded product thereof - Google Patents

Preparation method of thermosetting resin, and molded product thereof Download PDF

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Publication number
WO2013100452A1
WO2013100452A1 PCT/KR2012/010908 KR2012010908W WO2013100452A1 WO 2013100452 A1 WO2013100452 A1 WO 2013100452A1 KR 2012010908 W KR2012010908 W KR 2012010908W WO 2013100452 A1 WO2013100452 A1 WO 2013100452A1
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Prior art keywords
resin
thermosetting
methacrylate
acrylate
acrylic
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PCT/KR2012/010908
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French (fr)
Korean (ko)
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반균하
정창도
장태욱
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제일모직주식회사
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Priority claimed from KR1020120145581A external-priority patent/KR101550199B1/en
Application filed by 제일모직주식회사 filed Critical 제일모직주식회사
Publication of WO2013100452A1 publication Critical patent/WO2013100452A1/en

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    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the present invention relates to a method for producing a thermosetting resin and molded articles thereof. More specifically, the present invention relates to a method for preparing a thermosetting resin having excellent scratch resistance and a thermosetting molded article having excellent scratch resistance.
  • Polycarbonate resin has excellent mechanical strength and is excellent in transparency, thermal stability, self-extinguishing and dimensional stability.It is widely used in electric and electronic products and automobile parts, and it is easy to achieve flame retardancy due to its chemical structure. It is easy to achieve flame retardancy with a small amount of flame retardant.
  • the scratch resistance of polycarbonate itself is not good at around the pencil hardness B, there is a problem in that the polycarbonate resin cannot achieve good scratch resistance.
  • the pencil hardness of the resin itself is very good, about 3H.
  • the present inventors mixed a low-viscosity acrylic resin with a polycarbonate resin to position the acrylic resin on the surface of the composition, and added a curing agent before molding to cure the acrylic resin moved to the surface. It is to develop a thermosetting molded article excellent in scratch resistance.
  • An object of the present invention is to provide a new method of producing a thermosetting resin that can be applied to a thermosetting molded article having excellent scratch resistance.
  • Another object of the present invention is to provide a method for producing a thermosetting resin that can be applied to a thermosetting molded article that does not require a painting and coating process.
  • Still another object of the present invention is to provide a thermosetting molded article having excellent scratch resistance.
  • thermoset molded article which does not require a painting and coating process.
  • Method for producing a thermosetting resin comprises the steps of (a) extruding a polycarbonate resin and an acrylic resin in the extruder to produce a thermoplastic resin; (b) mixing the thermoplastic resin composition with a curing agent in an injection molding machine to produce a thermosetting resin.
  • the acrylic resin has a melt flow index of 20 to 100 g / 10min, measured under a temperature of 230 ° C. and a load of 3 kg according to ASTM D1238.
  • thermosetting resin may be used 1 to 15 parts by weight of the curing agent based on 100 parts by weight of the thermoplastic resin consisting of 50 to 90% by weight of the polycarbonate resin and 10 to 50% by weight of the acrylic resin.
  • acrylic resin one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkylester monomers and methacrylic acid alkylester monomers may be used.
  • acrylic resins examples include polyacrylates, polymethacrylates, polymethylacrylates, polymethylmethacrylates, polyethylacrylates, polyethylmethacrylates, polypropylacrylates, polypropylmethacrylates, and polybutylacrylates. Latex, polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polycyclohexyl acrylate, polycyclohexyl methacrylate, poly n-hexyl acrylate, poly n-hexyl methacrylate, polyglycid Diacrylate, polyglycidyl methacrylate, poly acrylic acid, polymethacrylic acid, and mixtures thereof.
  • curing agent the hardening
  • the impact reinforcing material may be further included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin including the polycarbonate resin and the acrylic resin.
  • the impact modifier may be selected from the group consisting of rubber modified graft copolymers, olefin copolymers, and mixtures thereof.
  • thermosetting resin prepared by the method for producing a thermosetting resin.
  • Thermosetting molded article according to the present invention (A) polycarbonate resin; And (B) an acrylic resin, wherein the crosslinking degree of the acrylic resin is 50 to 95%.
  • thermosetting molded article may be made of 50 to 90 wt% of a polycarbonate resin (A) and 10 to 50 wt% of an acrylic resin (B).
  • acrylic resin one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkylester monomers and methacrylic acid alkylester monomers may be used.
  • acrylic resin polyacrylate, polymethacrylate, polymethylacrylate, polymethylmethacrylate, polyethylacrylate, polyethyl methacrylate, polypropylacrylate, polypropyl methacrylate, polybutyl Acrylate, polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polycyclohexyl acrylate, polycyclohexyl methacrylate, poly n-hexyl acrylate, poly n-hexyl methacrylate, polyglycol Cyl acrylate, polyglycidyl methacrylate, poly acrylic acid, polymethacrylic acid, and mixtures thereof.
  • Impact reinforcing material may be further included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the resin made of the polycarbonate-based resin (A) and the acrylic resin (B).
  • the impact modifier may be selected from the group consisting of rubber modified graft copolymers, olefin copolymers, and mixtures thereof.
  • the present invention provides a method for producing a new thermosetting resin capable of producing a thermosetting molded article excellent in scratch resistance, and further has the effect of the invention of providing a method for producing a thermosetting resin that does not require a coating or coating process for a thermosetting molded article.
  • thermosetting resin 1 is a view schematically showing a manufacturing process of a thermosetting resin according to the present invention.
  • the present invention relates to a method for producing a thermosetting resin having excellent scratch resistance, and provides a thermosetting molded article having excellent scratch resistance, thereby providing a method for producing a thermosetting resin without requiring a coating or coating process on the molded article. It is to.
  • Method for producing a thermosetting resin comprises the steps of (a) extruding a polycarbonate resin and an acrylic resin in the extruder to produce a thermoplastic resin; (b) mixing the thermoplastic resin composition with a curing agent in an injection molding machine to produce a thermosetting resin.
  • Method for producing a thermoplastic resin comprises the steps of (a) extruding a polycarbonate resin and an acrylic resin in the extruder to produce a thermoplastic resin; (b) mixing the thermoplastic resin composition with a curing agent in an injection molding machine to produce a thermosetting resin.
  • thermoplastic resin according to the present invention It is preferable to supply the acrylic resin to the side of the extruder, and to supply the curing agent to the side of the injection machine.
  • the curing agent When the curing agent is added in the manufacturing step of the thermoplastic resin, the curing agent is activated due to the heat generated during extrusion, and the acrylic resin is present in the form of particles in the polycarbonate resin, so that the scratch resistance of the thermosetting molded article cannot be improved.
  • the acrylic resin, the curing agent or both may be supplied to the side of the extruder, the injection machine or both.
  • the polycarbonate resin of the present invention may be prepared by reacting diphenols represented by the following formula (1) with phosgene, halogen formate, or carbonic acid diester:
  • A represents a single bond, C 1 -C 5 alkylene, C 1 -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -S- or -SO 2- .
  • the diphenol of Formula 1 is 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2- Methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5 -Dichloro-4-hydroxyphenyl) -propane, and the like, but is not necessarily limited thereto.
  • diphenol compound compounds such as hydroquinone and resorcinol can be used.
  • 2,2-bis- (4-hydroxyphenyl) -propane 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols, such as hydroxyphenyl) -cyclohexane, are preferable, and 2, 2-bis- (4-hydroxyphenyl) propane also called bisphenol-A is especially preferable.
  • the polycarbonate resin preferably has a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol, more preferably 15,000 to 80,000 g / mol.
  • polycarbonate resin a linear polycarbonate resin, a branched polycarbonate resin, or a mixture of linear and branched polycarbonate resins can be used without limitation.
  • Bisphenol-A polycarbonate resin may be used as the linear polycarbonate resin, but is not necessarily limited thereto.
  • the polycarbonate-based resin may be a branched chain, preferably 0.05 to 2 mol% of tri- or more polyfunctional compounds, such as trivalent or more, based on the total amount of diphenols used for polymerization. It can manufacture by adding the compound which has a phenol group.
  • the polycarbonate resin has a melt flow index (230 ° C./3 kg) of 5 to 25 g / 10 min, measured according to ASTM D1238.
  • the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indices.
  • a mixture of polycarbonate resins having a measured melt flow index greater than 10 g / 10 min and less than 50 g / 10 min can be used.
  • a mixture of a polycarbonate resin having a melt flow index of 8 g / 10 min and a polycarbonate resin having a melt flow index of 19 g / 10 min may be used.
  • the polycarbonate-based resin may form a base resin together with an acrylic resin, and may be included in an amount of 50 to 90 wt% based on 100 wt% of the base resin. Preferably, it may be included in 55.56 to 88.89% by weight. If it is less than 50 wt%, impact resistance may be lowered, and if it is more than 90 wt%, scratch resistance may not be improved.
  • the acrylic resin has a melt flow index of 20 to 100 g / 10 min, measured under a temperature of 230 ° C. and a load of 3 kg according to ASTM D1238.
  • the acrylic resin is moved to the surface in the blend with the polycarbonate resin, it is later cured by a curing agent may exhibit excellent scratch resistance compared to the general polymethyl methacrylate.
  • the melt flow index is less than 20 g / 10min, acrylic resin may enter into the polycarbonate resin, and thus scratch resistance may be lowered.
  • the melt flow index is higher than 100 g / 10min, mechanical properties such as impact resistance may be reduced. Can be.
  • the acrylic resin may be composed of one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkylester monomers and methacrylic acid alkylester monomers. Preferably, it may be a methacrylic acid methyl ester monomer.
  • the acrylic acid alkyl ester monomer or the methacrylic acid alkyl ester monomer may be methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxy methacrylate. , Phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and mixtures thereof, but is not necessarily limited thereto.
  • the acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer may be used alone or as a mixture of two or more thereof.
  • Acrylic resins include poly acrylate or methacrylate, polymethyl acrylate or methacrylate, polyethyl acrylate or methacrylate, polypropyl acrylate or methacrylate, polybutyl acrylate or methacrylate, polypentyl acrylic Consisting of latex or methacrylate, polycyclohexyl acrylate or methacrylate, polyn-hexyl acrylate or methacrylate, polyglycidyl acrylate or methacrylate, poly acrylic acid or methacrylic acid and mixtures thereof Can be selected from the group.
  • polymethyl methacrylate resin can be used.
  • the acrylic resin may form a base resin together with a polycarbonate resin, and may be included in an amount of 10 to 50 wt% based on 100 wt% of the base resin. Preferably, it may be included in 11.11 to 44.44% by weight. If it is less than 10% by weight, it is difficult to obtain the desired scratch resistance, and if it is more than 50% by weight, impact resistance may be lowered.
  • the curing agent serves to cure the acrylic resin moved to the outside of the thermosetting resin composition to significantly improve scratch resistance.
  • the curing agent include benzoyl peroxide (BPO), dicumyl peroxide (DCP), di-tert-butyl peroxide (DTBP), azobisisobutylonitrile (AIBN), and the like. Can be used without limitation.
  • curing agent can use the hardening
  • the curing agent may be dicumyl peroxide.
  • the curing agent may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the base resin including the polycarbonate resin and the acrylic resin. Preferably it may be included in 5 to 10 parts by weight. If it is less than 1 part by weight, sufficient scratch resistance cannot be obtained, and if it is more than 15 parts by weight, physical properties such as scratch resistance, impact resistance, and workability are lowered.
  • thermosetting resin composition according to the present invention may further include an impact reinforcing material, if necessary, manufactured by a method known to those skilled in the art to which the present invention belongs, or commercially available impact reinforcing material Can be used without limitation.
  • the impact modifier may be a rubber modified graft copolymer, an olefin copolymer or a mixture thereof.
  • the rubber-modified graft copolymer is styrene, alpha-methyl styrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, alkyl or phenyl nucleosubstituted maleic acid which is capable of graft copolymerization to a rubbery polymer. It can be prepared by grafting one or more monomers selected from the group consisting of meads and mixtures thereof.
  • the rubber modified graft copolymer can be prepared by a conventional method.
  • the rubber content of the rubber-modified graphite copolymer is preferably 20 to 80% by weight.
  • the rubbery polymer may be selected from the group consisting of diene rubber, acrylic rubber, ethylene / propylene rubber, ethylene-propylene-diene terpolymer (EPDM), silicone rubber and mixtures thereof.
  • EPDM ethylene-propylene-diene terpolymer
  • a diene rubber can be used.
  • the diene rubber may include butadiene, isoprene, and the like, but is not limited thereto.
  • the acrylic rubber is a group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and mixtures thereof It may be selected from, but is not necessarily limited thereto.
  • the silicone rubber may be prepared from cyclosiloxane, for example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetra It may be selected from the group consisting of phenylcyclotetrosiloxane, octaphenylcyclotetrasiloxane and mixtures thereof, but is not necessarily limited thereto.
  • Polyolefin rubbers such as ethylene / propylene rubber and ethylene-propylene-diene terpolymer (EPDM), can be used.
  • the olefin copolymer is a chlorinated polyethylene (CPE) copolymer or an ethylene-vinyl-acetate (EVA) copolymer, but is not necessarily limited thereto.
  • the impact modifier is preferably a rubber modified graft copolymer, more preferably graft acrylonitrile-butadiene-styrene (g-ABS) copolymer or methyl methacrylate-butadiene-styrene (MBS) resin.
  • g-ABS graft acrylonitrile-butadiene-styrene
  • MFS methyl methacrylate-butadiene-styrene
  • the impact reinforcing material may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin consisting of the polycarbonate resin and the acrylic resin. Preferably it may be included in 5 to 15 parts by weight. If it is less than 1 part by weight, a sufficient impact reinforcing effect cannot be obtained. If it is more than 30 parts by weight, physical properties such as scratch resistance, transparency, and workability are lowered.
  • thermosetting resin composition of this invention may further contain an additive according to each use.
  • the thermosetting resin composition is selected from the group consisting of flame retardants, flame retardant aids, lubricants, anti-drip additives, antioxidants, plasticizers, heat stabilizers, light stabilizers, compatibilizers, weather stabilizers, pigments, dyes, colorants, inorganic additives and mixtures thereof.
  • the additive may further include, but is not necessarily limited to.
  • the additive may be used in an amount of 10 parts by weight or less, preferably 0.0001 to 10 parts by weight, based on 100 parts by weight of the base resin including the polycarbonate resin and the acrylic resin.
  • thermosetting resin can be obtained by the manufacturing method of the said thermosetting resin.
  • the present invention includes a polycarbonate resin and an acrylic resin, and provides a thermosetting molded article having a crosslinking degree of acrylic resin of 50 to 95%.
  • the thermosetting molded article may include 50 to 90 parts by weight of the polycarbonate resin and 10 to 50 parts by weight of the acrylic resin. If the degree of crosslinking of the acrylic resin is less than 50%, scratch resistance may be lowered, and if it is more than 95%, optical properties may be lowered by phase separation.
  • the degree of crosslinking can be measured using the Flory-Rehner formula below by immersing the specimen to be measured for 24 hours in toluene, measuring the swollen volume of the specimen after immersion. After immersion, the swollen volume of the specimen can be measured by dividing the mass increase in the swollen material by the density of the solvent when the density of the solvent is known.
  • v 1 is the molar volume of the solvent
  • v 2 is the volume fraction of the swollen material
  • ⁇ 1 is the Flory-Huggins interaction parameter
  • n is the degree of crosslinking.
  • thermosetting resin composition according to the present invention is (a) extrude a polycarbonate resin and an acrylic resin having a melt flow index of 20 to 100 g / 10min measured at a temperature of 230 °C and a load of 3 kg in accordance with ASTM D1238 in an extruder Preparing a thermoplastic resin composition; (b) mixing the thermoplastic resin composition and a curing agent in an injection molding machine to prepare a step of injecting a thermosetting resin composition. A thermosetting molded article is molded from the thermosetting resin composition.
  • the curing agent When the curing agent is added in the manufacturing step of the thermoplastic resin composition, the curing agent is activated due to the heat generated during extrusion, and the acrylic resin is present in the form of particles in the polycarbonate resin, so that the scratch resistance of the thermosetting molded article cannot be improved.
  • the acrylic resin, the curing agent or both may be supplied to the side of the extruder, the injection machine or both.
  • 1 is a view schematically showing a manufacturing process of the thermosetting resin composition according to the present invention.
  • thermosetting acrylic resin is positioned on the outermost surface of the thermosetting molded article, thereby improving scratch resistance of the thermosetting molded article.
  • curing agent is thrown in during injection of the said thermosetting resin composition. 1, it can be seen that the curing agent is injected during the injection.
  • Thermosetting the thermosetting resin composition may be performed for a time of 5 to 20 minutes at a temperature of 40 to 80 °C. For example, curing the thermosetting resin composition may be performed at 60 ° C. for 10 minutes. Curing the thermosetting resin composition may proceed simultaneously with the step of injecting the thermosetting resin composition. In addition, the step of curing the thermosetting resin composition may be progressed by the temperature at the time of injection of the thermosetting resin composition.
  • thermosetting molded article of the present invention has a pencil hardness of 2H to 4H measured according to JIS K 5401.
  • the thermosetting molded article may be applied to various products because of excellent scratch resistance. It can be widely used in the manufacture of electrical and electronic housings such as TVs, audio, cell phones, digital cameras, navigation, washing machines, computers, monitors, MP3s, video players, CD players, washing machines and office automation equipment.
  • thermosetting molded article is the same as that described in the method of manufacturing the thermosetting resin and is omitted in order to avoid duplication.
  • (A) Polycarbonate resin melt with SC-1080 having a weight average molecular weight of 25,000 g / mol, bisphenol-A linear polycarbonate resin, and a melt flow index manufactured by Cheil Industries Co., Ltd. A mixture of SC-1190 with a flow index of 19 g / 10 min was used. The pencil hardness measured according to JIS K 5401 is 3B.
  • (B) Acrylic resin The polymethyl methacrylate resin was used.
  • a curing agent was prepared in the same manner as in Example 1 except that the curing agent was added to the extruder together with the polycarbonate resin.
  • Table 1 shows the mixing ratio of (A) and (B) in parts by weight relative to the base resin including (A) and (B), and (C) and (D) in parts by weight based on 100 parts by weight of the base resin. It is shown.
  • Table 1 shows that in Examples 1 to 5 using the components of the present invention, the pencil hardness increases from 2H to 4H according to the increase in the content of the polymethylmethacrylate resin, so that excellent scratch resistance can be obtained. Can be.
  • Comparative Example 1 using only polycarbonate resin, the impact strength is excellent, but scratch resistance is not good.
  • Comparative Example 2 using only polymethyl methacrylate resin, the scratch resistance is excellent but impact strength is not good. It can be seen that.
  • thermosetting molded article according to the present invention exhibits excellent scratch resistance compared to acrylic resin alone, despite being a blend of polycarbonate resin and acrylic resin.

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Abstract

According to the present invention, a preparation method of thermosetting resin comprises the following steps: (a) extruding a polycarbonate-based resin and an acrylic resin from an extruder to prepare a thermoplastic resin; and (b) mixing the thermoplastic resin with a curing agent in an injection molding machine to prepare a thermosetting resin. According to the present invention, a thermosetting molded product comprises: (A) a polycarbonate-based resin; and (B) an acrylic resin, wherein the degree of cross-linking of the acrylic resin is 50-95% and the thermosetting molded product has excellent scratch resistance.

Description

열경화성 수지의 제조방법 및 이의 성형품Manufacturing method of thermosetting resin and molded article thereof
본 발명은 열경화성 수지의 제조방법 및 이의 성형품에 관한 것이다. 보다 구체적으로, 본 발명은 내스크래치성이 우수한 열경화성 수지의 제조방법 및 이로부터 제조된 내스크래치성이 우수한 열경화성 성형품에 관한 것이다.The present invention relates to a method for producing a thermosetting resin and molded articles thereof. More specifically, the present invention relates to a method for preparing a thermosetting resin having excellent scratch resistance and a thermosetting molded article having excellent scratch resistance.
전기 전자 제품은 대형화, 전문화, 경량화 추세에 따라 수지의 다양한 특성을 요구하고 있다. 특히 외장재료의 외관이 더욱 중요시되기 때문에 고광택 소재가 많이 요구됨에 따라 수지자체의 내스크래치 성능은 중요한 성능 중 하나이다. 일반적인 내스크래치성 소재는 일반소재에 도장 및 코팅 공정 등의 후가공 공정을 적용하거나, 내스크래치성이 뛰어난 소재를 블렌드하여 제조한다.Electric and electronic products require various characteristics of resins according to the trend of larger size, specialization and light weight. In particular, since the appearance of the exterior material is more important, the scratch resistance of the resin itself is one of the important performances as high gloss materials are required. General scratch-resistant materials are prepared by applying post-processing processes such as painting and coating processes to general materials, or by blending materials with excellent scratch resistance.
폴리카보네이트 수지는 기계적 강도가 매우 우수하며 투명성, 열안정성, 자기 소화성, 치수 안정성 등이 우수한 수지로서 전기 전자 제품, 자동차 부품에 광범위하게 사용되고 있으며, 화학 구조상 난연성의 달성이 용이하기 때문에 범용고분자에 대비하여 적은 양의 난연제로 난연성을 달성하는 것이 용이하다. 그러나 폴리카보네이트 자체의 내스크래치 성능은 연필경도 B 내외로 좋지 않기 때문에 폴리카보네이트 수지만으로 양호한 내스크래치 특성을 달성할 수 없는 문제점이 있다. 반면, 내스크래치 특성이 우수한 폴리메틸메타크릴레이트 수지의 경우, 수지 자체의 연필 경도는 3H 정도로 매우 양호하다.Polycarbonate resin has excellent mechanical strength and is excellent in transparency, thermal stability, self-extinguishing and dimensional stability.It is widely used in electric and electronic products and automobile parts, and it is easy to achieve flame retardancy due to its chemical structure. It is easy to achieve flame retardancy with a small amount of flame retardant. However, since the scratch resistance of polycarbonate itself is not good at around the pencil hardness B, there is a problem in that the polycarbonate resin cannot achieve good scratch resistance. On the other hand, in the case of polymethyl methacrylate resin having excellent scratch resistance, the pencil hardness of the resin itself is very good, about 3H.
따라서, 폴리카보네이트 수지에 내스크래치성을 부여하기 위해서 폴리메틸메타크릴레이트 수지를 블렌드하는 방법이 일반적으로 사용되고 있다. 그러나, 폴리카보네이트 수지와 폴리메틸메타크릴레이트 수지의 일반적인 블렌드로는 내스크래치성에 있어서 점점 높아지고 있는 수요자의 요구를 만족시키기 어려운 실정이다.Therefore, in order to give a scratch resistance to polycarbonate resin, the method of blending polymethyl methacrylate resin is generally used. However, in general blends of polycarbonate resins and polymethyl methacrylate resins, it is difficult to meet the demands of consumers who are increasing in scratch resistance.
이에 따라, 본 발명자들은 상기 문제점을 해결하기 위하여 폴리카보네이트계 수지에 저점도 아크릴계 수지를 혼합하여 아크릴계 수지를 조성물의 표면에 위치시키고, 성형 전에 경화제를 투입하여 표면으로 이동한 아크릴계 수지를 경화시켜 내스크래치성이 우수한 열경화성 성형품을 개발하기에 이른 것이다.Accordingly, in order to solve the above problems, the present inventors mixed a low-viscosity acrylic resin with a polycarbonate resin to position the acrylic resin on the surface of the composition, and added a curing agent before molding to cure the acrylic resin moved to the surface. It is to develop a thermosetting molded article excellent in scratch resistance.
본 발명의 목적은 내스크래치성이 우수한 열경화성 성형품에 적용할 수 있는 새로운 열경화성 수지의 제조방법을 제공하는 것이다.An object of the present invention is to provide a new method of producing a thermosetting resin that can be applied to a thermosetting molded article having excellent scratch resistance.
본 발명의 다른 목적은 도장 및 코팅 공정이 필요없는 열경화성 성형품에 적용할 수 있는 열경화성 수지의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a method for producing a thermosetting resin that can be applied to a thermosetting molded article that does not require a painting and coating process.
본 발명의 또 다른 목적은 내스크래치성이 우수한 열경화성 성형품을 제공하는 것이다.Still another object of the present invention is to provide a thermosetting molded article having excellent scratch resistance.
본 발명의 또 다른 목적은 도장 및 코팅 공정이 필요없는 열경화성 성형품을 제공하는 것이다.It is yet another object of the present invention to provide a thermoset molded article which does not require a painting and coating process.
본 발명의 상기 및 기타의 목적들은 모두 하기 설명되는 본 발명에 의해서 달성될 수 있다.Both the above and other objects of the present invention can be achieved by the present invention described below.
본 발명에 따른 열경화성 수지의 제조방법은 (a) 압출기에서 폴리카보네이트계 수지 및 아크릴계 수지를 압출시켜 열가소성 수지를 제조하는 단계; (b) 사출기에서 상기 열가소성 수지 조성물을 경화제와 혼합하여 열경화성 수지를 제조하는 단계;로 이루어지는 것을 특징으로 한다.Method for producing a thermosetting resin according to the present invention comprises the steps of (a) extruding a polycarbonate resin and an acrylic resin in the extruder to produce a thermoplastic resin; (b) mixing the thermoplastic resin composition with a curing agent in an injection molding machine to produce a thermosetting resin.
상기 아크릴계 수지를 상기 압출기의 측면으로 공급하고, 상기 경화제를 상기 사출기의 측면으로 공급하는 것이 바람직하다.It is preferable to supply the acrylic resin to the side of the extruder, and to supply the curing agent to the side of the injection machine.
상기 아크릴계 수지는 ASTM D1238에 준하여 230 ℃의 온도 및 3 kg의 하중 하에서 측정한 용융흐름지수가 20 내지 100 g/10min의 범위이다.The acrylic resin has a melt flow index of 20 to 100 g / 10min, measured under a temperature of 230 ° C. and a load of 3 kg according to ASTM D1238.
상기 열경화성 수지는 상기 폴리카보네이트계 수지 50 내지 90 중량% 및 상기 아크릴계 수지 10 내지 50 중량%로 이루어진 열가소성 수지 100 중량부에 대하여, 상기 경화제 1 내지 15 중량부를 사용할 수 있다.The thermosetting resin may be used 1 to 15 parts by weight of the curing agent based on 100 parts by weight of the thermoplastic resin consisting of 50 to 90% by weight of the polycarbonate resin and 10 to 50% by weight of the acrylic resin.
상기 아크릴계 수지로는 아크릴산 단량체, 메타크릴산 단량체, 아크릴산 알킬에스테르 단량체 및 메타크릴산 알킬에스테르 단량체로 이루어진 군으로부터 선택된 하나 이상의 호모폴리머, 코폴리머 또는 이들의 혼합물이 사용될 수 있다.As the acrylic resin, one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkylester monomers and methacrylic acid alkylester monomers may be used.
상기 아크릴계 수지로는 폴리아크릴레이트, 폴리메타크릴레이트, 폴리메틸아크릴레이트, 폴리메틸메타크릴레이트, 폴리에틸아크릴레이트, 폴리에틸메타크릴레이트, 폴리프로필아크릴레이트, 폴리프로필메타크릴레이트, 폴리부틸아크릴레이트, 폴리부틸메타크릴레이트, 폴리펜틸아크릴레이트, 폴리펜틸메타크릴레이트, 폴리시클로헥실아크릴레이트, 폴리시클로헥실메타크릴레이트, 폴리n-헥실아크릴레이트, 폴리n-헥실메타크릴레이트, 폴리글리시딜아크릴레이트, 폴리글리시딜메타크릴레이트, 폴리 아크릴산, 폴리메타크릴산 및 이들의 혼합물로 이루어진 군으로부터 선택할 수 있다.Examples of the acrylic resins include polyacrylates, polymethacrylates, polymethylacrylates, polymethylmethacrylates, polyethylacrylates, polyethylmethacrylates, polypropylacrylates, polypropylmethacrylates, and polybutylacrylates. Latex, polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polycyclohexyl acrylate, polycyclohexyl methacrylate, poly n-hexyl acrylate, poly n-hexyl methacrylate, polyglycid Diacrylate, polyglycidyl methacrylate, poly acrylic acid, polymethacrylic acid, and mixtures thereof.
상기 경화제로는 아크릴계 수지용 경화제가 바람직하다.As said hardening | curing agent, the hardening | curing agent for acrylic resin is preferable.
상기 폴리카보네이트계 수지 및 상기 아크릴계 수지로 이루어진 열가소성 수지 100 중량부에 대하여, 충격보강재를 1 내지 30 중량부로 더 포함할 수 있다.The impact reinforcing material may be further included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin including the polycarbonate resin and the acrylic resin.
상기 충격보강재는 고무변성 그라프트 공중합체, 올레핀계 공중합체 및 이들의 혼합물로 이루어진 군으로부터 선택할 수 있다.The impact modifier may be selected from the group consisting of rubber modified graft copolymers, olefin copolymers, and mixtures thereof.
또한, 본 발명은 상기 열경화성 수지의 제조방법에 의하여 제조된 열경화성 수지를 제공한다.In addition, the present invention provides a thermosetting resin prepared by the method for producing a thermosetting resin.
본 발명에 따른 열경화성 성형품은 (A) 폴리카보네이트계 수지; 및 (B) 아크릴계 수지;로 이루어지며, 상기 아크릴계 수지의 가교화도가 50 내지 95%인 것을 특징으로 한다.Thermosetting molded article according to the present invention (A) polycarbonate resin; And (B) an acrylic resin, wherein the crosslinking degree of the acrylic resin is 50 to 95%.
열경화성 성형품은 폴리카보네이트계 수지(A) 50 내지 90 중량% 및 아크릴계 수지(B) 10 내지 50 중량%로 이루어질 수 있다.The thermosetting molded article may be made of 50 to 90 wt% of a polycarbonate resin (A) and 10 to 50 wt% of an acrylic resin (B).
아크릴계 수지로는 아크릴산 단량체, 메타크릴산 단량체, 아크릴산 알킬에스테르 단량체 및 메타크릴산 알킬에스테르 단량체로 이루어진 군으로부터 선택된 하나 이상의 호모폴리머, 코폴리머 또는 이들의 혼합물이 사용될 수 있다.As the acrylic resin, one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkylester monomers and methacrylic acid alkylester monomers may be used.
또한, 아크릴계 수지로는 폴리아크릴레이트, 폴리메타크릴레이트, 폴리메틸아크릴레이트, 폴리메틸메타크릴레이트, 폴리에틸아크릴레이트, 폴리에틸메타크릴레이트, 폴리프로필아크릴레이트, 폴리프로필메타크릴레이트, 폴리부틸아크릴레이트, 폴리부틸메타크릴레이트, 폴리펜틸아크릴레이트, 폴리펜틸메타크릴레이트, 폴리시클로헥실아크릴레이트, 폴리시클로헥실메타크릴레이트, 폴리n-헥실아크릴레이트, 폴리n-헥실메타크릴레이트, 폴리글리시딜아크릴레이트, 폴리글리시딜메타크릴레이트, 폴리 아크릴산, 폴리메타크릴산 및 이들의 혼합물로 이루어진 군으로부터 선택할 수 있다.Moreover, as acrylic resin, polyacrylate, polymethacrylate, polymethylacrylate, polymethylmethacrylate, polyethylacrylate, polyethyl methacrylate, polypropylacrylate, polypropyl methacrylate, polybutyl Acrylate, polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polycyclohexyl acrylate, polycyclohexyl methacrylate, poly n-hexyl acrylate, poly n-hexyl methacrylate, polyglycol Cyl acrylate, polyglycidyl methacrylate, poly acrylic acid, polymethacrylic acid, and mixtures thereof.
폴리카보네이트계 수지(A) 및 상기 아크릴계 수지(B)로 이루어진 수지 100 중량부에 대하여, (D) 충격보강재를 1 내지 30 중량부로 더 포함할 수 있다.(D) Impact reinforcing material may be further included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the resin made of the polycarbonate-based resin (A) and the acrylic resin (B).
충격보강재는 고무변성 그라프트 공중합체, 올레핀계 공중합체 및 이들의 혼합물로 이루어진 군으로부터 선택할 수 있다.The impact modifier may be selected from the group consisting of rubber modified graft copolymers, olefin copolymers, and mixtures thereof.
이하 첨부된 도면을 참고로 본 발명의 구체적인 내용을 하기에 상세히 설명한다.Hereinafter, with reference to the accompanying drawings will be described in detail the present invention.
본 발명은 내스크래치성이 우수한 열경화성 성형품을 제조할 수 있는 새로운 열경화성 수지의 제조방법을 제공하며, 나아가 열경화성 성형품에 도장이나 코팅 공정이 필요없는 열경화성 수지의 제조방법을 제공하는 발명의 효과를 갖는다.The present invention provides a method for producing a new thermosetting resin capable of producing a thermosetting molded article excellent in scratch resistance, and further has the effect of the invention of providing a method for producing a thermosetting resin that does not require a coating or coating process for a thermosetting molded article.
도 1은 본 발명에 따른 열경화성 수지의 제조공정을 개략적으로 도시한 도면이다.1 is a view schematically showing a manufacturing process of a thermosetting resin according to the present invention.
본 발명은 내스크래치성이 우수한 열경화성 수지의 제조방법에 관한 것으로, 이로부터 제조된 내스크래치성이 우수한 열경화성 성형품을 제공하고, 그럼으로써 성형품에 도장이나 코팅 공정이 필요없는 열경화성 수지의 제조방법을 제공하기 위한 것이다.The present invention relates to a method for producing a thermosetting resin having excellent scratch resistance, and provides a thermosetting molded article having excellent scratch resistance, thereby providing a method for producing a thermosetting resin without requiring a coating or coating process on the molded article. It is to.
본 발명에 따른 열경화성 수지의 제조방법은 (a) 압출기에서 폴리카보네이트계 수지 및 아크릴계 수지를 압출시켜 열가소성 수지를 제조하는 단계; (b) 사출기에서 상기 열가소성 수지 조성물을 경화제와 혼합하여 열경화성 수지를 제조하는 단계;로 이루어지는 것을 특징으로 한다. 이하 본 발명의 구체적인 내용을 하기에서 상세히 설명한다.Method for producing a thermosetting resin according to the present invention comprises the steps of (a) extruding a polycarbonate resin and an acrylic resin in the extruder to produce a thermoplastic resin; (b) mixing the thermoplastic resin composition with a curing agent in an injection molding machine to produce a thermosetting resin. Hereinafter, specific contents of the present invention will be described in detail.
열경화성 수지의 제조방법Method for producing thermosetting resin
본 발명에 따른 열가소성 수지의 제조방법은 (a) 압출기에서 폴리카보네이트계 수지 및 아크릴계 수지를 압출시켜 열가소성 수지를 제조하는 단계; (b) 사출기에서 상기 열가소성 수지 조성물을 경화제와 혼합하여 열경화성 수지를 제조하는 단계;로 이루어진다.Method for producing a thermoplastic resin according to the present invention comprises the steps of (a) extruding a polycarbonate resin and an acrylic resin in the extruder to produce a thermoplastic resin; (b) mixing the thermoplastic resin composition with a curing agent in an injection molding machine to produce a thermosetting resin.
본 발명에 따른 열가소성 수지의 제조방법 상기 아크릴계 수지를 압출기의 측면으로 공급하고, 상기 경화제를 상기 사출기의 측면으로 공급하는 것이 바람직하다.Method for producing thermoplastic resin according to the present invention It is preferable to supply the acrylic resin to the side of the extruder, and to supply the curing agent to the side of the injection machine.
경화제를 상기 열가소성 수지의 제조 단계에서 투입하면 압출 시 발생한 열로 인하여 경화제가 활성화되고, 폴리카보네이트계 수지 안에 입자 형태로 아크릴계 수지가 존재하게 되어 열경화성 성형품의 내스크래치성을 향상시킬 수 없다.When the curing agent is added in the manufacturing step of the thermoplastic resin, the curing agent is activated due to the heat generated during extrusion, and the acrylic resin is present in the form of particles in the polycarbonate resin, so that the scratch resistance of the thermosetting molded article cannot be improved.
본 발명에서, 상기 아크릴계 수지, 경화제 또는 이들 모두를 압출기, 사출기 또는 이들 모두의 측면으로 공급할 수 있다. In the present invention, the acrylic resin, the curing agent or both may be supplied to the side of the extruder, the injection machine or both.
폴리카보네이트계 수지Polycarbonate resin
본 발명의 폴리카보네이트계 수지는 하기 화학식 1로 표시되는 디페놀류를 포스겐, 할로겐 포르메이트, 또는 탄산 디에스테르와 반응시킴으로써 제조될 수 있다:The polycarbonate resin of the present invention may be prepared by reacting diphenols represented by the following formula (1) with phosgene, halogen formate, or carbonic acid diester:
[화학식 1][Formula 1]
Figure PCTKR2012010908-appb-I000001
Figure PCTKR2012010908-appb-I000001
상기 식에서, A는 단일 결합, C1-C5의 알킬렌, C1-C5의 알킬리덴, C5-C6의 시클로알킬리덴, -S-또는 -SO2-를 나타낸다.Wherein A represents a single bond, C 1 -C 5 alkylene, C 1 -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -S- or -SO 2- .
상기 화학식 1의 디페놀은 4,4'-디히드록시디페닐, 2,2-비스-(4-히드록시페닐)-프로판, 2,4-비스-(4-히드록시페닐)-2-메틸부탄, 1,1-비스-(4-히드록시페닐)-시클로헥산, 2,2-비스-(3-클로로-4-히드록시페닐)-프로판, 2,2-비스-(3,5-디클로로-4-히드록시페닐)-프로판 등을 들 수 있으며, 반드시 이에 제한되는 것은 아니다. 디페놀 화합물로는 하이드로퀴논, 레조시놀과 같은 화합물을 사용할 수 있다. 이들 중, 2,2-비스-(4-히드록시페닐)-프로판, 2,2-비스-(3,5-디클로로-4-히드록시페닐)-프로판, 1,1-비스-(4-히드록시페닐)-시클로헥산 등의 비스페놀류가 바람직하며, 그 중 비스페놀-A라고도 불리는 2,2-비스-(4-히드록시페닐)-프로판이 특히 바람직하다.The diphenol of Formula 1 is 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2- Methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5 -Dichloro-4-hydroxyphenyl) -propane, and the like, but is not necessarily limited thereto. As the diphenol compound, compounds such as hydroquinone and resorcinol can be used. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols, such as hydroxyphenyl) -cyclohexane, are preferable, and 2, 2-bis- (4-hydroxyphenyl) propane also called bisphenol-A is especially preferable.
상기 폴리카보네이트계 수지는 중량평균분자량(Mw)이 10,000 내지 200,000 g/mol이 바람직하고, 더욱 바람직하게는 15,000 내지 80,000 g/mol이다. The polycarbonate resin preferably has a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol, more preferably 15,000 to 80,000 g / mol.
폴리카보네이트계 수지로는 선형 폴리카보네이트계 수지, 분지형 폴리카보네이트계 수지 또는 선형과 분지형 폴리카보네이트계 수지를 혼합한 것을 제한 없이 사용할 수 있다. 상기 선형 폴리카보네이트계 수지로는 비스페놀-A계 폴리카보네이트계 수지가 사용될 수 있으며, 반드시 이에 제한되는 것은 아니다. 상기 폴리카보네이트계 수지는 분지쇄가 있는 것이 사용될 수 있으며, 바람직하게는 중합에 사용되는 디페놀 전량에 대하여 0.05 내지 2 몰%의 트리- 또는 그 이상의 다관능 화합물, 예를 들면 3가 또는 그 이상의 페놀기를 가진 화합물을 첨가하여 제조할 수 있다. 상기 폴리카보네이트계 수지는 ASTM D1238에 준하여 측정한 용융흐름지수(230 ℃/3 kg)가 5 내지 25 g/10min이다. As the polycarbonate resin, a linear polycarbonate resin, a branched polycarbonate resin, or a mixture of linear and branched polycarbonate resins can be used without limitation. Bisphenol-A polycarbonate resin may be used as the linear polycarbonate resin, but is not necessarily limited thereto. The polycarbonate-based resin may be a branched chain, preferably 0.05 to 2 mol% of tri- or more polyfunctional compounds, such as trivalent or more, based on the total amount of diphenols used for polymerization. It can manufacture by adding the compound which has a phenol group. The polycarbonate resin has a melt flow index (230 ° C./3 kg) of 5 to 25 g / 10 min, measured according to ASTM D1238.
상기 폴리카보네이트계 수지는 용융흐름지수가 상이한 두 가지 이상의 폴리카보네이트계 수지 혼합물을 사용할 수 있다. 예를 들어, ASTM D1238에 준하여 230 ℃의 온도 및 3 kg의 하중 하에서 측정한 용융흐름지수가 5 내지 10 g/10min인 폴리카보네이트계 수지와 ASTM D1238에 준하여 230 ℃의 온도 및 3 kg의 하중 하에서 측정한 용융흐름지수가 10 g/10min 초과 50 g/10min 이하인 폴리카보네이트계 수지의 혼합물을 사용할 수 있다. 구체적으로, 용융흐름지수가 8 g/10min인 폴리카보네이트계 수지와 용융흐름지수가 19 g/10min인 폴리카보네이트계 수지의 혼합물을 사용할 수 있다.The polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indices. For example, a polycarbonate resin having a melt flow index of 5 to 10 g / 10min measured at a temperature of 230 ° C. and a load of 3 kg according to ASTM D1238 and a load of 3 kg and a temperature of 230 ° C. according to ASTM D1238. A mixture of polycarbonate resins having a measured melt flow index greater than 10 g / 10 min and less than 50 g / 10 min can be used. Specifically, a mixture of a polycarbonate resin having a melt flow index of 8 g / 10 min and a polycarbonate resin having a melt flow index of 19 g / 10 min may be used.
상기 폴리카보네이트계 수지는 아크릴계 수지와 함께 기초수지를 구성하며, 기초수지 100 중량%에 대하여 50 내지 90 중량%로 포함될 수 있다. 바람직하게는, 55.56 내지 88.89 중량%로 포함될 수 있다. 50 중량% 미만인 경우 내충격성이 저하될 수 있고, 90 중량% 초과인 경우 내스크래치성 향상을 기대할 수 없다.The polycarbonate-based resin may form a base resin together with an acrylic resin, and may be included in an amount of 50 to 90 wt% based on 100 wt% of the base resin. Preferably, it may be included in 55.56 to 88.89% by weight. If it is less than 50 wt%, impact resistance may be lowered, and if it is more than 90 wt%, scratch resistance may not be improved.
아크릴계 수지Acrylic resin
본 발명에서, 아크릴계 수지는 ASTM D1238에 준하여 230 ℃의 온도 및 3 kg의 하중 하에서 측정한 용융흐름지수가 20 내지 100 g/10min이다. 또한, 아크릴계 수지는 폴리카보네이트계 수지와의 블렌드에서 표면으로 이동하며, 추후 경화제에 의해서 경화되어 일반 폴리메틸메타크릴레이트에 비해 우수한 내스크래치성을 나타낼 수 있다. 상기 용융흐름지수가 20 g/10min 미만인 경우 폴리카보네이트계 수지 안쪽으로 아크릴계 수지가 들어갈 수 있어 내스크래치성이 저하될 수 있고, 100 g/10min 초과인 경우 내충격성 등의 기계적 물성 저하의 원인이 될 수 있다.In the present invention, the acrylic resin has a melt flow index of 20 to 100 g / 10 min, measured under a temperature of 230 ° C. and a load of 3 kg according to ASTM D1238. In addition, the acrylic resin is moved to the surface in the blend with the polycarbonate resin, it is later cured by a curing agent may exhibit excellent scratch resistance compared to the general polymethyl methacrylate. When the melt flow index is less than 20 g / 10min, acrylic resin may enter into the polycarbonate resin, and thus scratch resistance may be lowered. When the melt flow index is higher than 100 g / 10min, mechanical properties such as impact resistance may be reduced. Can be.
아크릴계 수지는 아크릴산 단량체, 메타크릴산 단량체, 아크릴산 알킬에스테르 단량체 및 메타크릴산 알킬에스테르 단량체로 이루어진 군으로부터 선택된 하나 이상의 호모폴리머, 코폴리머 또는 이들의 혼합물로 구성될 수 있다. 바람직하게는, 메타크릴산 메틸에스테르 단량체일 수 있다.The acrylic resin may be composed of one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkylester monomers and methacrylic acid alkylester monomers. Preferably, it may be a methacrylic acid methyl ester monomer.
아크릴산 알킬에스테르 단량체 또는 메타크릴산 알킬 에스테르 단량체는 메틸메타크릴레이트, 에틸메타크릴레이트, n-프로필메타크릴레이트, 페닐메타크릴레이트, 벤질 메타크릴레이트, 시클로헥실메타크릴레이트, 페녹시메타크릴레이트, 페녹시에틸메타크릴레이트, 메틸아크릴레이트, 에틸아크릴레이트, 프로필아크릴레이트 및 이들의 혼합물로 이루어진 군으로부터 선택할 수 있으며, 반드시 이에 제한되는 것은 아니다. 상기 아크릴산 알킬에스테르 단량체 또는 메타크릴산 알킬 에스테르 단량체는 단독 또는 2종 이상의 혼합물로 사용할 수 있다.The acrylic acid alkyl ester monomer or the methacrylic acid alkyl ester monomer may be methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenoxy methacrylate. , Phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate and mixtures thereof, but is not necessarily limited thereto. The acrylic acid alkyl ester monomer or methacrylic acid alkyl ester monomer may be used alone or as a mixture of two or more thereof.
아크릴계 수지는 폴리 아크릴레이트 또는 메타크릴레이트, 폴리메틸 아크릴레이트 또는 메타크릴레이트, 폴리에틸 아크릴레이트 또는 메타크릴레이트, 폴리프로필 아크릴레이트 또는 메타크릴레이트, 폴리부틸 아크릴레이트 또는 메타크릴레이트, 폴리펜틸 아크릴레이트 또는 메타크릴레이트, 폴리시클로헥실 아크릴레이트 또는 메타크릴레이트, 폴리n-헥실 아크릴레이트 또는 메타크릴레이트, 폴리글리시딜 아크릴레이트 또는 메타크릴레이트, 폴리 아크릴산 또는 메타크릴산 및 이들의 혼합물로 이루어진 군으로부터 선택할 수 있다. 바람직하게는, 폴리메틸 메타크릴레이트 수지를 사용할 수 있다.Acrylic resins include poly acrylate or methacrylate, polymethyl acrylate or methacrylate, polyethyl acrylate or methacrylate, polypropyl acrylate or methacrylate, polybutyl acrylate or methacrylate, polypentyl acrylic Consisting of latex or methacrylate, polycyclohexyl acrylate or methacrylate, polyn-hexyl acrylate or methacrylate, polyglycidyl acrylate or methacrylate, poly acrylic acid or methacrylic acid and mixtures thereof Can be selected from the group. Preferably, polymethyl methacrylate resin can be used.
아크릴계 수지는 폴리카보네이트계 수지와 함께 기초수지를 구성하며, 기초수지 100 중량%에 대하여 10 내지 50 중량%로 포함될 수 있다. 바람직하게는, 11.11 내지 44.44 중량%로 포함될 수 있다. 10 중량% 미만인 경우 목적하는 내스크래치성을 얻기 어렵고, 50 중량% 초과인 경우 내충격성이 저하될 수 있다.The acrylic resin may form a base resin together with a polycarbonate resin, and may be included in an amount of 10 to 50 wt% based on 100 wt% of the base resin. Preferably, it may be included in 11.11 to 44.44% by weight. If it is less than 10% by weight, it is difficult to obtain the desired scratch resistance, and if it is more than 50% by weight, impact resistance may be lowered.
경화제Hardener
경화제는 상기 열경화성 수지 조성물의 외부로 이동한 아크릴계 수지를 경화시켜 내스크래치성을 현저히 개선하는 역할을 한다. 경화제의 예로는 벤조일퍼옥사이드(BPO), 디큐밀퍼옥사이드(DCP), 디-tert-부틸퍼옥사이드(DTBP), 아조비스이소부틸로니트릴(AIBN) 등이 있으나, 아크릴계 수지를 경화시킬 수 있는 것이라면 제한없이 사용할 수 있다.The curing agent serves to cure the acrylic resin moved to the outside of the thermosetting resin composition to significantly improve scratch resistance. Examples of the curing agent include benzoyl peroxide (BPO), dicumyl peroxide (DCP), di-tert-butyl peroxide (DTBP), azobisisobutylonitrile (AIBN), and the like. Can be used without limitation.
경화제는 아크릴계 수지용 경화제를 사용할 수 있다. 바람직하게는, 상기 경화제는 디큐밀퍼옥사이드를 사용할 수 있다.A hardening | curing agent can use the hardening | curing agent for acrylic resin. Preferably, the curing agent may be dicumyl peroxide.
경화제는 상기 폴리카보네이트계 수지 및 아크릴계 수지로 이루어진 기초수지 100 중량부에 대하여 1 내지 15 중량부로 포함될 수 있다. 바람직하게는 5 내지 10 중량부로 포함될 수 있다. 1 중량부 미만인 경우 충분한 내스크래치 특성을 얻을 수 없고, 15 중량부 초과인 경우 내스크래치성, 내충격성, 가공성 등의 물성이 저하된다.The curing agent may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the base resin including the polycarbonate resin and the acrylic resin. Preferably it may be included in 5 to 10 parts by weight. If it is less than 1 part by weight, sufficient scratch resistance cannot be obtained, and if it is more than 15 parts by weight, physical properties such as scratch resistance, impact resistance, and workability are lowered.
충격보강재Impact reinforcement
본 발명에 따른 열경화성 수지 조성물은 필요에 따라 충격보강재를 더 포함할 수 있으며, 본 발명에서 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 알려진 방법에 의해 제조되거나, 상업적으로 구입 가능한 충격보강재가 제한 없이 사용될 수 있다. The thermosetting resin composition according to the present invention may further include an impact reinforcing material, if necessary, manufactured by a method known to those skilled in the art to which the present invention belongs, or commercially available impact reinforcing material Can be used without limitation.
이 충격보강재는 고무변성 그라프트 공중합체, 올레핀계 공중합체 또는 이들의 혼합물을 사용할 수 있다. 상기 고무변성 그라프트 공중합체는 고무질 중합체에 그라프트 공중합이 가능한 스티렌, 알파-메틸 스티렌, 알킬 치환 스티렌, 아크릴로니트릴, 메타크릴로니트릴, 메틸메타크릴레이트, 무수말레인산, 알킬 또는 페닐 핵치환 말레이미드 및 이들의 혼합물로 이루어지는 군으로부터 선택되는 하나 이상의 단량체를 그라프트시켜 제조할 수 있다. 상기 고무변성 그라프트 공중합체는 통상의 방법으로 제조할 수 있다. 상기 고무변성 그라파트 공중합체 중 고무의 함량은 20 내지 80 중량%가 바람직하다. 상기 고무질 중합체는 디엔계 고무, 아크릴계 고무, 에틸렌/프로필렌 고무, 에틸렌-프로필렌-디엔의 삼원공중합체(EPDM), 실리콘계 고무 및 이들의 혼합물로 이루어지는 군으로부터 선택할 수 있다. 바람직하게는 디엔계 고무를 사용할 수 있다. 상기 디엔계 고무는 부타디엔 및 이소프렌 등이 사용될 수 있으며, 반드시 이에 제한되는 것은 아니다. 상기 아크릴계 고무는 메틸아크릴레이트, 에틸아크릴레이트, n-프로필아크릴레이트, n-부틸아크릴레이트, 2-에틸헥실아크릴레이트, 헥실메타크릴레이트, 2-에틸헥실메타아크릴레이트 및 이들의 혼합물로 이루어지는 군으로부터 선택할 수 있으며, 반드시 이에 제한되는 것은 아니다. 상기 실리콘계 고무는 시클로실록산으로부터 제조될 수 있으며, 예를 들어 헥사메틸시클로트리실록산, 옥타메틸시클로테트라실록산, 데카메틸시클로펜타실록산, 도데카메틸시클로헥사실록산, 트리메틸트리페닐시클로트리실록산, 테트라메틸테트라페닐시클로테트로실록산, 옥타페닐시클로테트라실록산 및 이들의 혼합물로 이루어지는 군으로부터 선택할 수 있으며, 반드시 이에 제한되는 것은 아니다. 에틸렌/프로필렌 고무, 에틸렌-프로필렌-디엔의 삼원공중합체(EPDM) 등의 폴리올레핀계 고무를 사용할 수 있다. 상기 올레핀계 공중합체는 염소화 폴리에틸렌(CPE) 공중합체 또는 에틸렌-비닐-아세테이트(EVA) 공중합체이며, 반드시 이에 제한되는 것은 아니다.The impact modifier may be a rubber modified graft copolymer, an olefin copolymer or a mixture thereof. The rubber-modified graft copolymer is styrene, alpha-methyl styrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, alkyl or phenyl nucleosubstituted maleic acid which is capable of graft copolymerization to a rubbery polymer. It can be prepared by grafting one or more monomers selected from the group consisting of meads and mixtures thereof. The rubber modified graft copolymer can be prepared by a conventional method. The rubber content of the rubber-modified graphite copolymer is preferably 20 to 80% by weight. The rubbery polymer may be selected from the group consisting of diene rubber, acrylic rubber, ethylene / propylene rubber, ethylene-propylene-diene terpolymer (EPDM), silicone rubber and mixtures thereof. Preferably, a diene rubber can be used. The diene rubber may include butadiene, isoprene, and the like, but is not limited thereto. The acrylic rubber is a group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and mixtures thereof It may be selected from, but is not necessarily limited thereto. The silicone rubber may be prepared from cyclosiloxane, for example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetra It may be selected from the group consisting of phenylcyclotetrosiloxane, octaphenylcyclotetrasiloxane and mixtures thereof, but is not necessarily limited thereto. Polyolefin rubbers, such as ethylene / propylene rubber and ethylene-propylene-diene terpolymer (EPDM), can be used. The olefin copolymer is a chlorinated polyethylene (CPE) copolymer or an ethylene-vinyl-acetate (EVA) copolymer, but is not necessarily limited thereto.
충격보강재는 바람직하게는 고무변성 그라프트 공중합체이며, 더욱 바람직하게는 그라프트 아크릴로니트릴-부타디엔-스티렌(g-ABS) 공중합체 또는 메틸메타크릴레이트-부타디엔-스티렌(MBS) 수지이다.The impact modifier is preferably a rubber modified graft copolymer, more preferably graft acrylonitrile-butadiene-styrene (g-ABS) copolymer or methyl methacrylate-butadiene-styrene (MBS) resin.
충격보강재는 상기 폴리카보네이트계 수지 및 아크릴계 수지로 이루어진 기초수지 100 중량부에 대하여 1 내지 30 중량부로 포함될 수 있다. 바람직하게는 5 내지 15 중량부로 포함될 수 있다. 1 중량부 미만인 경우 충분한 충격보강 효과를 얻을 수 없고, 30 중량부 초과인 경우 내스크래치성, 투명성, 가공성 등의 물성이 저하된다.The impact reinforcing material may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the base resin consisting of the polycarbonate resin and the acrylic resin. Preferably it may be included in 5 to 15 parts by weight. If it is less than 1 part by weight, a sufficient impact reinforcing effect cannot be obtained. If it is more than 30 parts by weight, physical properties such as scratch resistance, transparency, and workability are lowered.
첨가제additive
본 발명의 열경화성 수지 조성물은 각각의 용도에 따라 첨가제를 더 포함할 수 있다. 상기 열경화성 수지 조성물은 난연제, 난연 보조제, 활제, 적하 방지제, 산화 방지제, 가소제, 열안정제, 광안정제, 상용화제, 내후안정제, 안료, 염료, 착색제, 무기물 첨가제 및 이들의 혼합물로 이루어진 군으로부터 선택되는 첨가제를 더 포함할 수 있으며, 반드시 이에 제한되는 것은 아니다.The thermosetting resin composition of this invention may further contain an additive according to each use. The thermosetting resin composition is selected from the group consisting of flame retardants, flame retardant aids, lubricants, anti-drip additives, antioxidants, plasticizers, heat stabilizers, light stabilizers, compatibilizers, weather stabilizers, pigments, dyes, colorants, inorganic additives and mixtures thereof. The additive may further include, but is not necessarily limited to.
상기 첨가제는 상기 폴리카보네이트계 수지 및 아크릴계 수지로 이루어진 기초수지 100 중량부에 대하여 10 중량부 이하, 바람직하게는 0.0001 내지 10 중량부로 사용할 수 있다.The additive may be used in an amount of 10 parts by weight or less, preferably 0.0001 to 10 parts by weight, based on 100 parts by weight of the base resin including the polycarbonate resin and the acrylic resin.
상기 열경화성 수지의 제조방법에 의하여 열경화성 수지를 얻을 수 있다.A thermosetting resin can be obtained by the manufacturing method of the said thermosetting resin.
열경화성 성형품Thermosetting moldings
본 발명은 폴리카보네이트계 수지 및 아크릴계 수지를 포함하며, 아크릴계 수지의 가교화도가 50 내지 95%인 열경화성 성형품을 제공한다. 상기 열경화성 성형품은 상기 폴리카보네이트계 수지 50 내지 90 중량부 및 상기 아크릴계 수지 10 내지 50 중량부를 포함할 수 있다. 상기 아크릴계 수지의 가교화도가 50% 미만인 경우 내스크래치성이 저하될 수 있고, 95% 초과인 경우 상분리에 의해서 광학특성이 저하될 수 있다.The present invention includes a polycarbonate resin and an acrylic resin, and provides a thermosetting molded article having a crosslinking degree of acrylic resin of 50 to 95%. The thermosetting molded article may include 50 to 90 parts by weight of the polycarbonate resin and 10 to 50 parts by weight of the acrylic resin. If the degree of crosslinking of the acrylic resin is less than 50%, scratch resistance may be lowered, and if it is more than 95%, optical properties may be lowered by phase separation.
상기 가교화도는 가교화도를 측정하고자 하는 시편을 톨루엔에 24시간 침지시키고, 침지후 시편의 팽윤된 부피를 측정하여, 하기 Flory-Rehner 공식을 이용해서 측정할 수 있다. 상기 침지후 시편의 팽윤된 부피는 용매의 밀도를 알 경우 팽윤된 물질에서 질량증가분을 용매의 밀도로 나누어 측정할 수 있다.The degree of crosslinking can be measured using the Flory-Rehner formula below by immersing the specimen to be measured for 24 hours in toluene, measuring the swollen volume of the specimen after immersion. After immersion, the swollen volume of the specimen can be measured by dividing the mass increase in the swollen material by the density of the solvent when the density of the solvent is known.
<Flory-Rehner 공식><Flory-Rehner Formula>
Figure PCTKR2012010908-appb-I000002
Figure PCTKR2012010908-appb-I000002
상기 식에서, v1은 용매의 몰부피, v2는 팽윤된 물질의 부피율, χ1은 Flory-Huggins 인터액션(interaction) 파라미터(parameter)이고, n은 가교화도이다.Wherein v 1 is the molar volume of the solvent, v 2 is the volume fraction of the swollen material, χ 1 is the Flory-Huggins interaction parameter, and n is the degree of crosslinking.
본 발명에 따른 열경화성 수지 조성물은 (a) 압출기에서 폴리카보네이트계 수지와 ASTM D1238에 준하여 230 ℃의 온도 및 3 kg의 하중 하에서 측정한 용융흐름지수가 20 내지 100 g/10min인 아크릴계 수지를 압출시켜 열가소성 수지 조성물을 제조하고; (b) 상기 열가소성 수지 조성물과 경화제를 사출기에서 혼합하여 열경화성 수지 조성물을 사출하는 단계에 의하여 제조한다. 상기 열경화성 수지 조성물로부터 열경화성 성형품을 성형한다.The thermosetting resin composition according to the present invention is (a) extrude a polycarbonate resin and an acrylic resin having a melt flow index of 20 to 100 g / 10min measured at a temperature of 230 ℃ and a load of 3 kg in accordance with ASTM D1238 in an extruder Preparing a thermoplastic resin composition; (b) mixing the thermoplastic resin composition and a curing agent in an injection molding machine to prepare a step of injecting a thermosetting resin composition. A thermosetting molded article is molded from the thermosetting resin composition.
상기 경화제를 상기 열가소성 수지 조성물의 제조 단계에서 투입하면 압출 시 발생한 열로 인하여 경화제가 활성화되고, 폴리카보네이트계 수지 안에 입자 형태로 아크릴계 수지가 존재하게 되어 열경화성 성형품의 내스크래치성을 향상시킬 수 없다.When the curing agent is added in the manufacturing step of the thermoplastic resin composition, the curing agent is activated due to the heat generated during extrusion, and the acrylic resin is present in the form of particles in the polycarbonate resin, so that the scratch resistance of the thermosetting molded article cannot be improved.
본 발명에서, 상기 아크릴계 수지, 경화제 또는 이들 모두를 압출기, 사출기 또는 이들 모두의 측면으로 공급할 수 있다. 도 1은 본 발명에 따른 열경화성 수지조성물의 제조공정을 개략적으로 도시한 도면이다.In the present invention, the acrylic resin, the curing agent or both may be supplied to the side of the extruder, the injection machine or both. 1 is a view schematically showing a manufacturing process of the thermosetting resin composition according to the present invention.
도 1을 보면, 폴리메틸메타크릴레이트(PMMA)가 압출기의 측면으로 공급되고, 경화제가 사출기의 측면으로 공급되는 것을 알 수 있다. 아크릴계 수지, 경화제 또는 이들 모두를 압출기, 사출기 또는 이들 모두의 측면으로 공급하는 경우 상기 열경화성 성형품의 최외각 표면에 열경화된 아크릴계 수지가 대부분 위치하여 열경화성 성형품의 내스크래치성을 향상시킬 수 있다. 상기 경화제는 상기 열경화성 수지 조성물의 사출 중에 투입한다. 도 1을 보면, 경화제가 사출 중에 투입되는 것을 알 수 있다.1, it can be seen that polymethyl methacrylate (PMMA) is supplied to the side of the extruder, and the curing agent is supplied to the side of the injection machine. When the acrylic resin, the curing agent, or both thereof is supplied to an extruder, an injection machine, or both sides thereof, most of the thermosetting acrylic resin is positioned on the outermost surface of the thermosetting molded article, thereby improving scratch resistance of the thermosetting molded article. The said hardening | curing agent is thrown in during injection of the said thermosetting resin composition. 1, it can be seen that the curing agent is injected during the injection.
상기 열경화성 수지 조성물을 열경화시키는 단계는 40 내지 80 ℃의 온도에서 5 내지 20분의 시간 동안 진행될 수 있다. 예를 들어, 상기 열경화성 수지 조성물을 경화시키는 단계는 60 ℃에서 10분 동안 진행될 수 있다. 상기 열경화성 수지 조성물을 경화시키는 단계는 상기 열경화성 수지 조성물을 사출하는 단계와 동시에 진행될 수 있다. 또한, 열경화성 수지 조성물을 경화시키는 단계는 상기 열경화성 수지 조성물의 사출시의 온도에 의해서 진행될 수 있다.Thermosetting the thermosetting resin composition may be performed for a time of 5 to 20 minutes at a temperature of 40 to 80 ℃. For example, curing the thermosetting resin composition may be performed at 60 ° C. for 10 minutes. Curing the thermosetting resin composition may proceed simultaneously with the step of injecting the thermosetting resin composition. In addition, the step of curing the thermosetting resin composition may be progressed by the temperature at the time of injection of the thermosetting resin composition.
본 발명의 상기 열경화성 성형품은 JIS K 5401에 준하여 측정한 연필경도가 2H 내지 4H이다. 상기 열경화성 성형품은 내스크래치성이 우수하기 때문에 여러 가지 제품에 적용될 수 있다. TV, 오디오, 핸드폰, 디지털 카메라, 내비게이션, 세탁기, 컴퓨터, 모니터, MP3, 비디오 플레이어, CD 플레이어, 세척기 및 사무자동화 기기와 같은 전기, 전자의 하우징 제조에 널리 이용될 수 있다.The thermosetting molded article of the present invention has a pencil hardness of 2H to 4H measured according to JIS K 5401. The thermosetting molded article may be applied to various products because of excellent scratch resistance. It can be widely used in the manufacture of electrical and electronic housings such as TVs, audio, cell phones, digital cameras, navigation, washing machines, computers, monitors, MP3s, video players, CD players, washing machines and office automation equipment.
상기 열경화성 성형품의 각 성분들은 상기 열경화성 수지의 제조방법에서 설명된 것과 동일한 것으로 중복을 피하기 위해서 생략하였다.Each component of the thermosetting molded article is the same as that described in the method of manufacturing the thermosetting resin and is omitted in order to avoid duplication.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예EXAMPLE
하기의 실시예 및 비교실시예에서 사용된 각 성분의 사양은 다음과 같다:The specifications of each component used in the following Examples and Comparative Examples are as follows:
(A) 폴리카보네이트계 수지: 중량평균분자량이 25,000 g/mol이고, 비스페놀-A 선형 폴리카보네이트계 수지이고, 제일모직(주)에서 제조한 용융흐름지수가 8 g/10min인 SC-1080과 용융흐름지수가 19 g/10min인 SC-1190의 혼합물을 사용하였다. JIS K 5401에 준하여 측정한 연필경도는 3B이다.(A) Polycarbonate resin: melt with SC-1080 having a weight average molecular weight of 25,000 g / mol, bisphenol-A linear polycarbonate resin, and a melt flow index manufactured by Cheil Industries Co., Ltd. A mixture of SC-1190 with a flow index of 19 g / 10 min was used. The pencil hardness measured according to JIS K 5401 is 3B.
(B) 아크릴계 수지: 폴리메틸메타크릴레이트 수지를 사용하였다.(B) Acrylic resin: The polymethyl methacrylate resin was used.
(B1) 용융흐름지수가 20 g/10min인 LG MMA사의 IF870 Grade를 사용하였다.(B1) The IF870 Grade of LG MMA, with a melt flow index of 20 g / 10 min, was used.
(B2) 용융흐름지수가 100 g/10min인 LG MMA사의 IH830B grade를 사용하였다.(B2) LG MMA's IH830B grade with a melt flow index of 100 g / 10 min was used.
(B3) 중량평균분자량이 110,000 g/mol이고, 용융흐름지수가 2.2 g/10min인 LG MMA사의 IH830 Grade를 사용하였다. JIS K 5401에 준하여 측정한 연필경도는 3H이다.(B3) LG MMA's IH830 Grade with a weight average molecular weight of 110,000 g / mol and a melt flow index of 2.2 g / 10min was used. The pencil hardness measured according to JIS K 5401 is 3H.
(B4) 용융흐름지수가 11 g/10min인 LG MMA사의 IF850을 사용하였다.(B4) IF850 of LG MMA with a melt flow index of 11 g / 10 min was used.
(C) 경화제: 디큐밀퍼옥사이드로 Aldrich사의 Luperox DCP를 사용하였다.(C) Curing agent: Aldrich's Luperox DCP was used as the dicumyl peroxide.
(D) 충격보강재: 일본 MRC사의 Metablen C223-A Grade를 사용하였다(D) Impact reinforcing material: Metablen C223-A Grade manufactured by MRC of Japan was used.
하기의 실시예 및 비교실시예의 물성은 다음과 같은 방법으로 측정하였다:The physical properties of the following Examples and Comparative Examples were measured by the following method:
(1) 내충격성: ASTM D256에 준하여 3.715 mm 두께 시편의 노치 아이조드 충격강도를 측정하였다(단위: kgf·cm/cm). (1) Impact resistance: According to ASTM D256, the notched Izod impact strength of the 3.715 mm thick specimen was measured (unit: kgf · cm / cm).
(2) 내스크래치성: 10×10 cm2의 시편에 대하여, 23 ℃ 및 상대습도 50%에서 48시간 방치한 후 JIS K 5401에 준하여 연필경도를 측정하였다. 내스크래치성은 연필경도 결과에 따라 3B, 2B B, HB, F, H, 2H, 3H 등으로 평가되며, 높은 H 값을 보일수록 내스크래치 성능이 우수하며, 높은 B 값을 보일수록 스크래치 물성이 저하되는 경향을 보인다.(2) Scratch resistance: After leaving for 48 hours at 23 degreeC and 50% of the relative humidity with respect to the specimen of 10x10 cm <2> , pencil hardness was measured according to JISK5401. Scratch resistance is evaluated as 3B, 2B B, HB, F, H, 2H, 3H, etc. according to the result of pencil hardness.The higher the H value, the better the scratch resistance. Tends to be.
열경화성 성형품의 제조Manufacture of thermosetting molded parts
실시예 1-5 및 비교실시예 1-5Example 1-5 and Comparative Example 1-5
하기 표 1 및 표 2의 조성으로 폴리카보네이트계 수지 및 충격보강재를 혼합하고 L/D=36, ø=45 mm인 이축 압출기에 투입하였다(main feeding). 아크릴계 수지는 이축 압출기에 측면으로 공급하였다(side feeding). 상기 혼합물을 압출시켜 펠렛을 제조하였다. 제조된 펠렛을 80 ℃에서 6시간 건조 후 6 oz 사출기에 투입하고(main feeding), 사출 중에 경화제를 측면으로 투입하여(side feeding), 금형 내에서 시편을 제조하면서 경화시켰다. 제조된 시편의 물성을 상기 측정방법에 따라 측정하였으며, 그 결과를 하기 표 1 및 표 2에 나타내었다.To the composition of Table 1 and Table 2, polycarbonate-based resins and impact modifiers were mixed and fed to a twin screw extruder having L / D = 36 and ø = 45 mm (main feeding). Acrylic resin was side fed to the twin screw extruder. The mixture was extruded to prepare pellets. The prepared pellets were dried at 80 ° C. for 6 hours and then fed into a 6 oz injection machine (main feeding), and the curing agent was added to the side during injection (side feeding), and cured while preparing the specimen in the mold. The physical properties of the prepared specimens were measured according to the measurement method, and the results are shown in Tables 1 and 2 below.
비교실시예 6Comparative Example 6
경화제를 폴리카보네이트계 수지와 함께 압출기에 투입한 것을 제외하고 실시예 1과 동일한 방법으로 제조하였다. A curing agent was prepared in the same manner as in Example 1 except that the curing agent was added to the extruder together with the polycarbonate resin.
하기 표 1은 (A) 및 (B)의 혼합비는 (A) 및 (B)를 포함하는 기초수지에 대하여 중량부로 나타낸 것이고, (C) 및 (D)는 기초수지 100 중량부에 대하여 중량부로 나타낸 것이다.Table 1 shows the mixing ratio of (A) and (B) in parts by weight relative to the base resin including (A) and (B), and (C) and (D) in parts by weight based on 100 parts by weight of the base resin. It is shown.
표 1
Figure PCTKR2012010908-appb-T000001
 Table 1
Figure PCTKR2012010908-appb-T000001
표 2
Figure PCTKR2012010908-appb-T000002
 TABLE 2
Figure PCTKR2012010908-appb-T000002
표 1을 보면, 본원발명의 구성성분을 사용한 실시예 1 내지 5의 경우, 폴리메틸메타크릴레이트 수지의 함량증가에 따라 연필경도가 2H에서 4H로 증가하여 우수한 내스크래치성을 얻을 수 있다는 것을 알 수 있다.Table 1 shows that in Examples 1 to 5 using the components of the present invention, the pencil hardness increases from 2H to 4H according to the increase in the content of the polymethylmethacrylate resin, so that excellent scratch resistance can be obtained. Can be.
폴리카보네이트계 수지만을 사용한 비교실시예 1의 경우 충격강도는 우수하나 내스크래치성이 좋지 못하고, 폴리메틸메타크릴레이트 수지만을 사용한 비교실시예 2의 경우 내스크래치성은 우수하나 충격강도가 좋지 못하다는 것을 알 수 있다.In Comparative Example 1 using only polycarbonate resin, the impact strength is excellent, but scratch resistance is not good. In Comparative Example 2 using only polymethyl methacrylate resin, the scratch resistance is excellent but impact strength is not good. It can be seen that.
경화제를 사용하지 않고 본원발명의 용융흐름지수의 범위를 벗어난 폴리메틸메타크릴레이트를 사용한 비교실시예 3 및 4의 경우, 본원발명이 목적하는 우수한 내스크래치성을 갖지 못한다는 것을 알 수 있다.In the case of Comparative Examples 3 and 4 using polymethyl methacrylate outside the melt flow index of the present invention without using a curing agent, it can be seen that the present invention does not have the desired excellent scratch resistance.
본원발명의 용융흐름지수의 범위를 벗어난 폴리메틸메타크릴레이트 수지를 사용한 비교실시예 5의 경우, 내스크래치성이 저하된다는 것을 알 수 있다.In the case of Comparative Example 5 using a polymethyl methacrylate resin outside the range of the melt flow index of the present invention, it can be seen that scratch resistance is lowered.
폴리카보네이트계 수지와 함께 경화제를 투입한 비교실시예 6의 경우, 경화반응이 사출전에 일어나 내스크래치성이 발현되지 못하는 것을 알 수 있다.In Comparative Example 6 in which a curing agent was added together with the polycarbonate resin, a curing reaction occurs before injection, and it can be seen that scratch resistance is not expressed.
또한, 실시예 4와 비교실시예 2를 비교해 보면, 본원발명에 따른 열경화성 성형품은 폴리카보네이트계 수지와 아크릴계 수지의 블렌드임에도 불구하고, 아크릴계 수지 단독에 비해 우수한 내스크래치성을 나타냄을 알 수 있다.In addition, when comparing Example 4 and Comparative Example 2, it can be seen that the thermosetting molded article according to the present invention exhibits excellent scratch resistance compared to acrylic resin alone, despite being a blend of polycarbonate resin and acrylic resin.
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 (19)

  1. (a) 압출기에서 폴리카보네이트계 수지 및 아크릴계 수지를 압출시켜 열가소성 수지를 제조하는 단계;(a) extruding a polycarbonate resin and an acrylic resin in an extruder to produce a thermoplastic resin;
    (b) 사출기에서 상기 열가소성 수지 조성물을 경화제와 혼합하여 열경화성 수지를 제조하는 단계;(b) mixing the thermoplastic resin composition with a curing agent in an injection molding machine to produce a thermosetting resin;
    를 포함하는 것을 특징으로 하는 열경화성 수지의 제조방법.Method for producing a thermosetting resin comprising a.
  2. 제1항에 있어서, 상기 아크릴계 수지를 상기 압출기의 측면으로 공급하고, 상기 경화제를 상기 사출기의 측면으로 공급하는 것을 특징으로 하는 열경화성 수지의 제조방법.The method of claim 1, wherein the acrylic resin is supplied to the side of the extruder, and the curing agent is supplied to the side of the injection machine.
  3. 제1항에 있어서, 상기 아크릴계 수지는 ASTM D1238에 준하여 230 ℃의 온도 및 3 kg의 하중 하에서 측정한 용융흐름지수가 20 내지 100 g/10min인 것을 특징으로 하는 열경화성 수지의 제조방법.The method of claim 1, wherein the acrylic resin has a melt flow index of 20 to 100 g / 10min measured at a temperature of 230 ° C. and a load of 3 kg according to ASTM D1238.
  4. 제1항에 있어서, 상기 열경화성 수지는 상기 폴리카보네이트계 수지 50 내지 90 중량% 및 상기 아크릴계 수지 10 내지 50 중량%로 이루어진 열가소성 수지 100 중량부에 대하여, 상기 경화제 1 내지 15 중량부를 포함하는 것을 특징으로 하는 열경화성 수지의 제조방법.The thermosetting resin of claim 1, wherein the thermosetting resin comprises 1 to 15 parts by weight of the curing agent based on 100 parts by weight of the thermoplastic resin consisting of 50 to 90% by weight of the polycarbonate resin and 10 to 50% by weight of the acrylic resin. The manufacturing method of thermosetting resin made into.
  5. 제1항에 있어서, 상기 아크릴계 수지는 아크릴산 단량체, 메타크릴산 단량체, 아크릴산 알킬에스테르 단량체 및 메타크릴산 알킬에스테르 단량체로 이루어진 군으로부터 선택된 하나 이상의 호모폴리머, 코폴리머 또는 이들의 혼합물인 것을 특징으로 하는 열경화성 수지의 제조방법.The method of claim 1, wherein the acrylic resin is one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkyl ester monomers and methacrylic acid alkyl ester monomers. Method for producing a thermosetting resin.
  6. 제1항에 있어서, 상기 아크릴계 수지는 폴리아크릴레이트, 폴리메타크릴레이트, 폴리메틸아크릴레이트, 폴리메틸메타크릴레이트, 폴리에틸아크릴레이트, 폴리에틸메타크릴레이트, 폴리프로필아크릴레이트, 폴리프로필메타크릴레이트, 폴리부틸아크릴레이트, 폴리부틸메타크릴레이트, 폴리펜틸아크릴레이트, 폴리펜틸메타크릴레이트, 폴리시클로헥실아크릴레이트, 폴리시클로헥실메타크릴레이트, 폴리n-헥실아크릴레이트, 폴리n-헥실메타크릴레이트, 폴리글리시딜아크릴레이트, 폴리글리시딜메타크릴레이트, 폴리 아크릴산, 폴리메타크릴산 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 열경화성 수지의 제조방법.The method of claim 1, wherein the acrylic resin is polyacrylate, polymethacrylate, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, polypropyl acrylate, polypropyl methacrylate Latex, polybutyl acrylate, polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polycyclohexyl acrylate, polycyclohexyl methacrylate, polyn-hexyl acrylate, polyn-hexyl methacrylate A method for producing a thermosetting resin, characterized in that it is selected from the group consisting of latex, polyglycidyl acrylate, polyglycidyl methacrylate, poly acrylic acid, polymethacrylic acid and mixtures thereof.
  7. 제1항에 있어서, 상기 경화제가 아크릴계 수지용 경화제인 것을 특징으로 하는 열경화성 수지 조성물.The thermosetting resin composition according to claim 1, wherein the curing agent is a curing agent for acrylic resin.
  8. 제1항에 있어서, 상기 폴리카보네이트계 수지 및 상기 아크릴계 수지로 이루어진 열가소성 수지 100 중량부에 대하여, 충격보강재를 1 내지 30 중량부로 더 포함하는 것을 특징으로 하는 열경화성 수지의 제조방법.The method of manufacturing a thermosetting resin according to claim 1, further comprising 1 to 30 parts by weight of an impact modifier, based on 100 parts by weight of the thermoplastic resin consisting of the polycarbonate resin and the acrylic resin.
  9. 제8항에 있어서, 상기 충격보강재는 고무변성 그라프트 공중합체, 올레핀계 공중합체 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 열경화성 수지의 제조방법.The method of claim 8, wherein the impact modifier is selected from the group consisting of rubber-modified graft copolymers, olefin copolymers, and mixtures thereof.
  10. 제1항에 있어서, 난연제, 난연보조제, 활제, 적하방지제, 산화방지제, 가소제, 열안정제, 광안정제, 상용화제, 내후안정제, 안료, 염료, 착색제, 무기물 첨가제 및 이들의 혼합물로 이루어진 군으로부터 선택되는 첨가제를 더 포함하는 것을 특징으로 하는 열경화성 수지의 제조방법.A flame retardant, flame retardant aid, lubricant, anti-drip agent, antioxidant, plasticizer, heat stabilizer, light stabilizer, compatibilizer, weather stabilizer, pigment, dye, colorant, inorganic additive and mixtures thereof. Method for producing a thermosetting resin, characterized in that it further comprises an additive.
  11. 제1항 내지 제10항 중 어느 한 항에 따른 열경화성 수지의 제조방법에 의하여 제조된 열경화성 수지.A thermosetting resin prepared by the method for producing a thermosetting resin according to any one of claims 1 to 10.
  12. (A) 폴리카보네이트계 수지; 및(A) polycarbonate resin; And
    (B) 아크릴계 수지;(B) acrylic resin;
    를 포함하며, 상기 아크릴계 수지의 가교화도가 50 내지 95%인 것을 특징으로 하는 열경화성 성형품.And a crosslinking degree of the acrylic resin is 50 to 95%.
  13. 제12항에 있어서, 상기 열경화성 성형품은 상기 폴리카보네이트계 수지(A) 50 내지 90 중량% 및 상기 아크릴계 수지(B) 10 내지 50 중량%를 포함하는 것을 특징으로 하는 열경화성 성형품.The thermosetting molded article according to claim 12, wherein the thermosetting molded article comprises 50 to 90 wt% of the polycarbonate resin (A) and 10 to 50 wt% of the acrylic resin (B).
  14. 제12항에 있어서, 상기 아크릴계 수지는 아크릴산 단량체, 메타크릴산 단량체, 아크릴산 알킬에스테르 단량체 및 메타크릴산 알킬에스테르 단량체로 이루어진 군으로부터 선택된 하나 이상의 호모폴리머, 코폴리머 또는 이들의 혼합물인 것을 특징으로 하는 열경화성 성형품.The method of claim 12, wherein the acrylic resin is one or more homopolymers, copolymers or mixtures thereof selected from the group consisting of acrylic acid monomers, methacrylic acid monomers, acrylic acid alkyl ester monomers and methacrylic acid alkyl ester monomers. Thermosetting moldings.
  15. 제12항에 있어서, 상기 아크릴계 수지는 폴리아크릴레이트, 폴리메타크릴레이트, 폴리메틸아크릴레이트, 폴리메틸메타크릴레이트, 폴리에틸아크릴레이트, 폴리에틸메타크릴레이트, 폴리프로필아크릴레이트, 폴리프로필메타크릴레이트, 폴리부틸아크릴레이트, 폴리부틸메타크릴레이트, 폴리펜틸아크릴레이트, 폴리펜틸메타크릴레이트, 폴리시클로헥실아크릴레이트, 폴리시클로헥실메타크릴레이트, 폴리n-헥실아크릴레이트, 폴리n-헥실메타크릴레이트, 폴리글리시딜아크릴레이트, 폴리글리시딜메타크릴레이트, 폴리 아크릴산, 폴리메타크릴산 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 열경화성 성형품.The method of claim 12, wherein the acrylic resin is polyacrylate, polymethacrylate, polymethyl acrylate, polymethyl methacrylate, polyethyl acrylate, polyethyl methacrylate, polypropyl acrylate, polypropyl methacrylate Latex, polybutyl acrylate, polybutyl methacrylate, polypentyl acrylate, polypentyl methacrylate, polycyclohexyl acrylate, polycyclohexyl methacrylate, polyn-hexyl acrylate, polyn-hexyl methacrylate A thermosetting molded article, characterized in that it is selected from the group consisting of latex, polyglycidyl acrylate, polyglycidyl methacrylate, poly acrylic acid, polymethacrylic acid and mixtures thereof.
  16. 제12항에 있어서, 상기 폴리카보네이트계 수지(A) 및 상기 아크릴계 수지(B)로 이루어진 수지 100 중량부에 대하여, (D) 충격보강재를 1 내지 30 중량부로 더 포함하는 것을 특징으로 하는 열경화성 성형품.The thermosetting molded article according to claim 12, further comprising (D) an impact modifier in an amount of 1 to 30 parts by weight based on 100 parts by weight of the resin made of the polycarbonate resin (A) and the acrylic resin (B). .
  17. 제16항에 있어서, 상기 충격보강재는 고무변성 그라프트 공중합체, 올레핀계 공중합체 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 열경화성 성형품.17. The thermosetting molded article according to claim 16, wherein the impact modifier is selected from the group consisting of rubber modified graft copolymers, olefin copolymers, and mixtures thereof.
  18. 제12항에 있어서, 난연제, 난연보조제, 활제, 적하방지제, 산화방지제, 가소제, 열안정제, 광안정제, 상용화제, 내후안정제, 안료, 염료, 착색제, 무기물 첨가제 및 이들의 혼합물로 이루어진 군으로부터 선택되는 첨가제를 더 포함하는 것을 특징으로 하는 열경화성 성형품.The method according to claim 12, selected from the group consisting of flame retardants, flame retardant aids, lubricants, anti-drip agents, antioxidants, plasticizers, heat stabilizers, light stabilizers, compatibilizers, weather stabilizers, pigments, dyes, colorants, inorganic additives and mixtures thereof. Thermosetting molded article, characterized in that it further comprises an additive.
  19. 제12항에 있어서, JIS K 5401에 준하여 측정한 연필경도가 2H 내지 4H인 것을 특징으로 하는 열경화성 성형품.The thermosetting molded article according to claim 12, wherein the pencil hardness measured in accordance with JIS K 5401 is 2H to 4H.
PCT/KR2012/010908 2011-12-29 2012-12-14 Preparation method of thermosetting resin, and molded product thereof WO2013100452A1 (en)

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