WO2018088729A2 - Non-halogen flame-retardant resin composition - Google Patents

Non-halogen flame-retardant resin composition Download PDF

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Publication number
WO2018088729A2
WO2018088729A2 PCT/KR2017/011883 KR2017011883W WO2018088729A2 WO 2018088729 A2 WO2018088729 A2 WO 2018088729A2 KR 2017011883 W KR2017011883 W KR 2017011883W WO 2018088729 A2 WO2018088729 A2 WO 2018088729A2
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WO
WIPO (PCT)
Prior art keywords
weight
compound
halogen flame
resin composition
retardant resin
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PCT/KR2017/011883
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French (fr)
Korean (ko)
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WO2018088729A3 (en
Inventor
유제선
남기영
황용연
심재용
배선형
배재연
김인석
Original Assignee
(주) 엘지화학
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Priority claimed from KR1020170107355A external-priority patent/KR102092131B1/en
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to EP17868566.5A priority Critical patent/EP3412726B1/en
Priority to CN201780036906.0A priority patent/CN109312152B/en
Priority to JP2018565282A priority patent/JP6854300B2/en
Priority to US16/085,978 priority patent/US10836898B2/en
Publication of WO2018088729A2 publication Critical patent/WO2018088729A2/en
Publication of WO2018088729A3 publication Critical patent/WO2018088729A3/en

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    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to a non-halogen flame retardant resin composition, and more particularly, it is difficult to implement V-1 or higher under non-halogen flame retardant prescription, or solves the problem of flame retardant resins having poor colorability due to low gloss and whiteness.
  • the present invention relates to a non-halogen flame-retardant resin composition capable of simultaneously expressing whiteness and glossiness.
  • Flame retardancy is required in a variety of industrial plastic products, typically in acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, polystyrene, polyphenylene oxide and the like.
  • the acrylonitrile-butadiene-styrene-based copolymer has a problem that it is difficult to achieve flame retardancy of V-1 or higher under the non-halogen flame retardant prescription, and when blending with polyphenylene oxide or the like to implement flame retardancy, There is a problem that the colorability is poor.
  • polystyrene and polyphenylene oxide, etc. have a problem that both gloss and whiteness are inferior under the non-halogen flame retardant prescription.
  • Patent Document Korean Patent Publication No. 2013-0132004
  • the present invention is a non-halogen flame retardant capable of expressing excellent flame retardancy, whiteness and gloss at the same time by solving the problem of a flame retardant resin, which is difficult to implement V-1 or higher under a non-halogen flame retardant prescription, or is poor in colorability due to low gloss and whiteness. It is an object to provide a resin composition.
  • the present invention provides a blend resin comprising (A) a polyarylene ether polymer, a styrene polymer and a vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer, and (B) a non-halogen flame retardant Non-halogen flame-retardant resin composition comprising,
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer includes 1% by weight or more and less than 25% by weight of the vinyl cyan compound based on the total weight of the copolymer,
  • the surface glossiness (Gloss) of the specimen made by extruding the non-halogen flame-retardant resin composition at a 45 ° value is 80 or more, and the whiteness (L value) measured by the color CIELAB of the specimen prepared without the addition of a colorant.
  • the non-halogen flame retardant resin composition which is 75 or more is provided.
  • the present invention comprises (A) 14 to 64% by weight of polyarylene ether-based polymer, 20 to 70% by weight of styrene-based polymer and 16 to 40% by weight of vinylcyan compound-conjugated diene compound-vinylaromatic compound copolymer
  • a non-halogen flame-retardant composition comprising a blend resin, and (B) a non-halogen flame retardant,
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is a non-halogen flame-retardant resin composition characterized in that the vinyl cyan compound is contained in more than 1% by weight to less than 25% by weight relative to the total weight of the copolymer. to provide.
  • a non-halogen flame retardant formulation is difficult to implement more than V-1 grade, or solved the problem of the flame retardant resin was poor in colorability due to low gloss and whiteness to provide a molded article exhibiting excellent flame retardancy, whiteness and glossiness at the same time can do.
  • the non-halogen flame-retardant composition of the present disclosure is a blend resin comprising (A) a polyarylene ether polymer, a styrene polymer and a vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer, and (B) a non-halogen flame retardant,
  • a non-halogen flame-retardant resin composition comprising a, wherein the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is contained in the vinyl cyan compound at least 1% by weight to less than 25% by weight relative to the total weight of the copolymer
  • the surface glossiness (Gloss) of the specimen made by extruding the non-halogen flame-retardant resin composition at a 45 ° value is 80 or more, and the whiteness measured by color CIELAB of the specimen prepared without adding a colorant (L value) ) Is 75 or more.
  • the non-halogen flame-retardant composition of the present disclosure is (A) 14 to 64% by weight polyarylene ether polymer, 20 to 70% by weight styrene polymer and vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer
  • a non-halogen flame-retardant resin composition comprising a blend resin comprising 16 to 40 wt%, and (B) a non-halogen flame retardant, wherein the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is the total weight of the copolymer. It is characterized in that the vinyl cyan compound is contained in more than 1% by weight to less than 25% by weight.
  • the non-halogen flame-retardant resin composition means not adding a halogen or a halogen compound separately, and does not include naturally or through air, or even a very small amount of impurities, and specifically, a halogen content of 5,000 It means that it is ppm or less, Preferably it is 1,000 ppm or less.
  • the polyarylene ether-based polymer is not limited as long as it can be used as a flame-retardant resin, for example, a homopolymer of a compound represented by Formula 1 or Formula 2, or a copolymer comprising a compound of Formula 1 or Formula 2 Can be.
  • R a , R 1 , R 2 , R 3 and R 4 are substituents of arylene group (Ar) or phenylene group, each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl , Methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy or nitro group, n is an integer of 4 to 20, Ar is an arylene group having 7 to 20 carbon atoms.
  • R 1 and R 2 may be an alkyl group or an alkyl group having 1 to 4 carbon atoms
  • R 3 and R 4 may be hydrogen.
  • the polyarylene ether polymer may be, for example, a poly (phenylene ether) resin.
  • the poly (phenylene ether) -based resin means a poly (arylene ether) resin that can be represented by the following [Formula 3].
  • W, X, Y and Z are hydrogen or a substituent, n is a repeating unit.
  • W, X, Y and Z are each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, memeth Oxy, phenoxy or nitro group, wherein n is an integer from 4 to 20.
  • the homopolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenyl Ethylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl -1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2, 6-dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether and poly (2,5-dimethyl-1,4-phenylene) ether It may be one or more selected from the group consisting of.
  • the copolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol And a copolymer of 2,3,6-trimethylphenol and o-cresol, and the like.
  • the poly (arylene ether) resin may be 14 to 64% by weight, 20 to 50% by weight, or 30 to 40% by weight based on the total weight of the resin composition according to the present invention, for example, impact strength within this range Excellent mechanical properties, surface gloss and whiteness.
  • the poly (arylene ether) resin may have a weight average molecular weight of 5,000 to 100,000 g / mol, 20,000 to 80,000 g / mol, or 50,000 to 75,000 g / mol, dimensional stability and physical properties balance within this range Has an excellent effect.
  • the styrene-based polymer is not limited as long as it can be used as a flame retardant resin, for example, a polystyrene resin having a weight average molecular weight of 10,000 to 300,000 g / mol and a styrene content of 93 to 100% by weight, or 20,000 to 300,000 g / mol It may be a polystyrene resin having a weight average molecular weight of and a styrene content of 95 to 100% by weight.
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is not limited as long as it can be used as a flame retardant resin, and examples thereof include conjugated diene rubber polymers; And a shell polymerized by wrapping the rubbery polymer and including a vinylaromatic compound, a vinylcyan compound, and a fatty acid or a metal salt thereof, and a graft copolymer having a seed-shell structure.
  • the conjugated diene rubber polymer is selected from the group consisting of, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene It may be polymerized including one or more conjugated diene-based compounds.
  • the conjugated diene-based rubbery polymer (hereinafter referred to as 'seed') may be, for example, emulsion polymerization, and in this case, the mechanical properties are excellent, and are not particularly limited as long as they are manufactured according to a conventional emulsion polymerization method.
  • the seed may be in the form of a latex in which the polymerized rubbery polymer is dispersed in water in a colloidal state.
  • the average particle diameter is measured as an intensity value in Gaussian mode using a Nicomp 370HPL device manufactured by Nicomp, USA, using a dynamic laser light scattering method.
  • the gel content is determined by coagulation of polybutadiene rubber latex with dilute acid or metal salt, washing, drying in a vacuum oven at 60 ° C. for 24 hours, and then crushing the obtained rubber mass with scissors, and then removing 1 g of rubber sections. 100 g of toluene was stored in a dark room at room temperature for 48 hours, separated into sol and gel, dried, and then measured by the following equation.
  • the seed has, for example, an average particle diameter of more than 2,000 kPa to 3,500 kPa or less, 2,500 kPa or more to 3,500 kPa or less, or 3,000 kPa or more and 3,500 kPa or less, and a gel content of 60 to 95 wt%, 65 to 80 wt%, or 65 To 75% by weight large diameter seeds, for example, with an average particle diameter of 500 kPa to 2,000 kPa, 1,000 kPa to 2,000 kPa, or 1,000 kPa to 1,500 kPa, with a gel content of 60 to 95 wt%, 70 to 95 wt% or 80 to 95% by weight may be one or more selected from bimodal (bimodal) of the small diameter seed, there is an excellent impact strength and mechanical properties within this range.
  • bimodal bimodal
  • the large-diameter seed and the small-diameter seed constituting the seed may be 50:50 to 90:10, 60:40 to 75:25, 60:40 to 70:20, or 70:30 to 75:25 by weight, for example. Within this range, the dispersion and the surface properties are excellent.
  • the seed may be included in an amount of 40 to 60 wt%, 50 to 60 wt%, or 53 to 57 wt% based on 100 wt% of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. Mechanical properties and surface properties are excellent within.
  • the shell is emulsified graft polymerized to include the fatty acid having a mean carbon number and molecular weight or a metal salt thereof surrounding the bimodal seed, for example 100% by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound and vinyl cyan compound 40 to 60% by weight, 40 to 50% by weight, or 43 to 47% by weight may be included, and within this range there is an excellent mechanical and physical properties balance.
  • the fatty acid having a mean carbon number and molecular weight or a metal salt thereof surrounding the bimodal seed for example 100% by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound and vinyl cyan compound 40 to 60% by weight, 40 to 50% by weight, or 43 to 47% by weight may be included, and within this range there is an excellent mechanical and physical properties balance.
  • the aromatic vinyl compound includes, for example, styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene and derivatives thereof. It may be at least one selected from the group, and the vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof.
  • the derivative may mean a compound in which one or two or more hydrogen atoms of the original compound are substituted with a halogen group, an alkyl group, and a hydroxy group.
  • the vinyl cyan compound may be present in an amount of at least 1 wt% to less than 25 wt%, 1 wt% to 20 wt%, 1 wt% to 15 wt%, 1 wt% to 12 wt%, and 1 to 10 wt% based on the total weight of the copolymer. It may be preferable to mix in%, or 3 to 7% by weight, there is an effect that the mechanical and physical properties balance within this range is excellent.
  • the aromatic vinyl compound and the vinyl cyan compound included in the shell may be included, for example, in the range of 90:10 to 99: 1 based on the weight ratio.
  • the fatty acid may be, for example, a mixture of two or more kinds, two to ten kinds, or two to five kinds of fatty acid dimers or metal salts thereof having different carbon atoms in the chain.
  • the average carbon number of the chain of the fatty acid may be, for example, 10 or more, 33 or more, 33 to 44, or 33 to 36, and excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. have.
  • the fatty acid may include, for example, an unsaturated fatty acid dimer having an unsaturation of 1 to 20, 1 to 10, or 1 to 5, and in this range, there is little effect of volatile content during extrusion injection molding.
  • Unsaturation in the present description means double bond water.
  • the molecular weight of the fatty acid may be, for example, 100 g / mol or more, 100 to 2,000 g / mol, or 100 to 1,000 g / mol, and has excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. It is effective to let.
  • the molecular weight here refers to the weight average molecular weight measured by gel permeation chromatography (GPC).
  • the fatty acid may include, for example, one or more selected from the group consisting of oleic acid, oleic acid-based dimer, myristoleic acid, linoleic acid, and metal salts thereof.
  • the metal of the metal salt is, for example, an alkali metal or an alkaline earth metal, preferably an alkaline earth metal, and specifically, calcium, magnesium or a mixture thereof.
  • the fatty acid may be, for example, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, 0.1 to 1 parts by weight, or 0.1 to 0.3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. May be included.
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer of the present invention may have, for example, a weight average molecular weight of 20,000 to 100,000 g / mol, 30,000 g / mol to 85,000 g / mol, or 30,000 to 70,000 g / mol. In this range, it is excellent in surface gloss, whiteness and dispersion, and has excellent mechanical properties.
  • a weight average molecular weight refers to the molecular weight measured by gel permeation chromatography (GPC).
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer may include, for example, 45 to 60% by weight of a conjugated diene rubber polymer and a vinyl cyan compound (can be replaced or used in combination with an alkyl (meth) acrylate compound, if necessary). 10% by weight and 30-54% by weight of the vinylaromatic compound.
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is, for example, 50 to 60% by weight of a conjugated diene rubber polymer and a vinyl cyan compound (can be replaced or used in combination with an alkyl (meth) acrylate compound, if necessary). Graft copolymer of 8% by weight and from 32 to 48% by weight of vinylaromatic compounds.
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer has excellent thermal decomposition stability when used as a dry powder obtained by agglomeration with a salt, thereby reducing the amount of gas generated during extrusion and injection processing. It works.
  • the salt may be, for example, sulfate, carbonate or a mixture thereof.
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer of the present invention has a high glossiness by providing a composition that improves the graft density to increase the dispersibility of the polyarylene ether polymer and the styrene polymer. .
  • the blend resin may include 14 to 64 wt% of polyarylene ether polymer, 20 to 70 wt% of styrene polymer, and 16 to 40 wt% of vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer. Within this range, the whiteness and glossiness can be effectively improved while using the flame retardant resin.
  • the blend resin may include 20 to 50% by weight of polyarylene ether-based polymer, 30 to 50% by weight of styrene-based polymer and 20 to 30% by weight of vinylcyan compound-conjugated diene compound-vinylaromatic compound copolymer within this range, the whiteness and glossiness can be improved more efficiently while the flame retardant resin is used.
  • the blend resin may include 20 to 40 wt% of polyarylene ether polymer, 35 to 50 wt% of styrene polymer, and 22 to 30 wt% of vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer. .
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer of the present invention is not specifically prepared, but, for example, polymerizing a seed; And a fatty acid having a mean carbon number of 10 or more in the shell and a molecular weight of 500 to 2,000 g / mol or a metal salt thereof and preparing an shell by emulsion graft polymerization.
  • the seed may include, for example, at least one of a large diameter rubbery polymer having an average particle diameter of more than 2,000 mm 3 and up to 3,500 mm 3, and a small diameter rubbery polymer having an average particle diameter of 500 mm 2 to 2,000 mm 3.
  • the seed polymerization may be carried out, for example, by emulsion polymerization.
  • the seed polymerization and emulsion graft polymerization method is not particularly limited in the case of seed polymerization and emulsion graft polymerization generally used in the production method of ABS resin.
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer production method of the present invention may be one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, and metal salts of unsaturated fatty acids. It may further include, the amount may be, for example, 0.01 to 3 parts by weight, 0.05 to 1 parts by weight or 0.05 to 0.5 parts by weight based on 100 parts by weight of the monomer (vinyl cyan + conjugated diene + aromatic vinyl).
  • a water-soluble initiator or a fat-soluble initiator may be used as an initiator.
  • the water-soluble initiator include sodium persulfate, potassium persulfate, ammonium persulfate, and the like.
  • the fat-soluble initiator includes cumene hydro peroxide, diisopropylbenzene hydro peroxide, tertiary butyl hydro peroxide, paramethane hydro peroxide, benzoyl peroxide, and the like, and if necessary, the combination thereof may be used. It may be possible.
  • the initiator may be used in an amount of 0.01 to 2 parts by weight, 0.05 to 1 part by weight, or 0.05 to 0.5 parts by weight, and does not cause overreaction within the above range, and may be a polymer having a desired particle size and size distribution. .
  • the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer production method of the present invention is, for example, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrrole as an oxidation-reduction catalyst. It may include one or more selected from the group consisting of sodium phosphate, sodium sulfite.
  • the oxidation-reduction catalyst may be used in an amount of 0.001 to 0.4 parts by weight, 0.005 to 0.2 parts by weight or 0.01 to 0.2 parts by weight based on 100 parts by weight of monomer, for example, may be prepared within a short time by promoting the polymerization reaction. have.
  • the reactants In the step of emulsion graft polymerization of the shell, it is preferable to add the reactants, and then to graft polymerization by reacting at 60 to 90 °C or 60 to 80 °C for 3 to 5 hours or 2 to 4 hours. This is because the polymerization reaction is initiated by the activation of the initiator within the above-mentioned range, and the heat removal is easy. In addition, when controlling the temperature and the reaction time in the above-described range, a polymer having a uniform size distribution can be prepared.
  • the step of emulsion graft polymerization of the shell may further comprise 0.1 to 1 parts by weight, 0.2 to 0.6 parts by weight or 0.3 to 0.5 parts by weight based on 100 parts by weight of the monomer, if necessary, in the above-described range
  • a molecular weight modifier may be advantageous to form a polymer having a desired average particle diameter, there is an effect that the size of the polymer is uniform.
  • mercaptan compounds such as tertiary dodecyl mercaptan, can be used as an example.
  • the entire amount of the initiator and the redox-based catalyst used in the graft polymerization reaction may be added at the beginning of the reaction. It is easy to defrost and suppress side reactions while reducing the content of the unreacted monomer can improve the quality and productivity of the polymer.
  • the second graft polymerization reaction may be performed by increasing the temperature to 60 to 100 ° C. or 70 to 90 ° C. under a temperature increase rate of 5 to 30 ° C./hr, or 10 to 20 ° C./hr.
  • a temperature increase rate of 5 to 30 ° C./hr, or 10 to 20 ° C./hr.
  • the polymerization reaction may be preferably terminated at 90 to 99%, 95 to 99%, or 97 to 99% of the polymerization conversion rate.
  • a polymer having a low unreacted monomer content and a high degree of polymerization in the product may be used. Can be prepared.
  • the polymerization conversion rate may be measured by a measurement method commonly used in the art to which the present invention pertains.
  • the weight loss method may be measured.
  • 1.5 g of a graft copolymer latex is 150 ° C. in a hot air dryer. After drying for 15 minutes, the weight is measured, and the total solid content (TSC) is calculated and measured by the following equation.
  • reaction conditions such as graft rate, reaction pressure, etc.
  • graft rate reaction pressure, etc.
  • reaction pressure reaction pressure
  • the graft copolymer latex prepared according to the present invention is prepared in the form of a powder through conventional processes such as salt agglomeration, washing, and drying, and the powder is made of a nonpolar material such as a polyarylene ether polymer and a styrene resin. It may be mixed with the resin and extruded and injected to produce a molded article.
  • the non-halogen flame-retardant resin composition is a kind that can improve the gloss and whiteness under the non-halogen flame-retardant formulation of the blend resin as an example, characterized in that using a combination of a metal salt-free hypophosphite compound and an organic flame retardant as the non-halogen flame retardant.
  • the non-halogen flame retardant may be, for example, 15 to 45 parts by weight, 15 to 31 parts by weight, 15 to 30 parts by weight, or 20 to 30 parts by weight based on 100 parts by weight of the blend resin, and within this range, flame retardant and sulfur resistance There is an excellent effect of denaturation.
  • the non-halogen flame retardant resin composition may include, for example, 0.1 to 5 parts by weight, 1 to 5 parts by weight, or 1 to 3 parts by weight of a metal salt-free hypophosphite compound based on 100 parts by weight of the blend resin. It has the effect of remarkably improving whiteness and glossiness while implementing flame retardant grade of V-1 or more within the range.
  • the metal salt-free hypophosphite compound may be any kind used as a stabilizer or a flame retardant aid for amorphous flame retardant resins, preferably a compound containing phosphine oxide.
  • the metal salt-free hypophosphite compound may be, for example, a compound represented by the following [Formula 4].
  • R 1 and R 2 are each independently a hydrogen atom, alkyl, cycloalkane, alkoxy, aryl, chlorine, bromine, iodine, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, phenoxy or nitro Qi.
  • the alkyl may be alkyl having 1 to 10 carbon atoms, or methyl, ethyl, propyl, and the alkoxy may have 1 to 20 carbon atoms, 1 to 16 carbon atoms, or 1 to 12 carbon atoms, and specifically, methoxy or ethoxy.
  • the aryl group may be an aryl having 6 to 24 carbon atoms, or a phenyl group, a naphthyl group, a phenanthrenyl group, a fluorene group, a dimethyl fluorene group, a triphenylene group, a benzoicene group or a fluoranthrene group, and the cycloalkane group. May have 3 to 30 carbon atoms or 3 to 18 carbon atoms.
  • metal salt-free hypophosphite compound examples include a group consisting of H-phosphonic acid, oxaphosphorine oxide, (3-chloropropyl) phosphonic acid, methyl cyclohexylphosphinate, butylphenylphosphinate, and derivatives thereof. It may be one or more selected from.
  • the non-halogen flame retardant resin composition may include, for example, 15 to 40 parts by weight, 15 to 30 parts by weight, or 15 to 25 parts by weight of an organophosphorus flame retardant based on 100 parts by weight of the blend resin, and within this range, V Effectively improves whiteness and gloss while achieving flame retardancy ratings above -1.
  • the organic phosphorus flame retardant can be used as all kinds of flame retardants for amorphous flame retardant resin, preferably an alkyl phosphonate ester having 1 to 20 carbon atoms, an aryl phosphonate ester having 6 to 30 carbon atoms, 1 to 10 carbon atoms It may be a compound selected from trialkyl phosphine, alkylphosphine oxide having 1 to 20 carbon atoms and arylphosphine oxide having 6 to 20 carbon atoms.
  • the organophosphorus flame retardant is considered to be used in combination with the aforementioned metal salt-free hypophosphite compound, triphenyl phosphate, resorcinol tetraphenyl-di-phosphate, bisphenol-A tetraphenoxy With bisphenol-A tetraphenoxy-di-phosphate, bisphenol-A tetracresyl-di-phosphate, resorcinol tetraxylyloxy-di-phosphate It is more preferable to use one or more selected from the group consisting of.
  • the non-halogen flame retardant resin composition may include, for example, a kind used as an antidropping agent for amorphous flame retardant resin, and preferably a fluorine-based polymer may be used.
  • the fluorine-based polymer may be, for example, Teflon, polyamide, polysilicon, PTFE, TFE-HFP copolymer, and the like, and in consideration of the effects of kneading and dispersion, it is more preferable to use a polymer having a particle size of 0.1 to 10 ⁇ m.
  • the fluorine-based polymer may include, for example, 2 parts by weight or less, 0.001 to 1 part by weight, or 0.01 to 1 part by weight based on 100 parts by weight of the blend resin, and the dropwise addition of the flame retardant additive (B) described above in this range.
  • the prevention effect can be optimized.
  • the non-halogen flame retardant resin composition may include, for example, a kind used as a melt index improver for an amorphous flame retardant resin, and for example, a lubricant such as magnesium stearate or wax may be used, and preferably a wax.
  • the wax is a compound having good compatibility with the flame retardant resin and having an extremely low viscosity at high heat, for example, having a melt viscosity of several tens to several hundred g / 10 minutes.
  • paraffin wax, polyethylene wax, and the like can be used.
  • the wax is used in an appropriate amount, the intrinsic properties of the flame retardant resin can be maintained and the melt index can be lowered at a relatively low cost.
  • the lubricant may be included in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the blend resin. Within this range, the melt index may be improved and the physical properties of the flame retardant may be maintained.
  • the non-halogen flame retardant resin composition may further include one or more selected from lubricants such as heat stabilizers, UV stabilizers, metal stearates, processing aids, pigments, colorants, molding aids, and fillers.
  • lubricants such as heat stabilizers, UV stabilizers, metal stearates, processing aids, pigments, colorants, molding aids, and fillers.
  • the amount used may be, for example, 0.05 to 5 parts by weight, 0.05 to 1 parts by weight, or 0.05 to 0.8 parts by weight based on 100 parts by weight of the blended resin.
  • the surface glossiness may have high glossiness of 80 or more, more than 91, or 99 or more with 45 ° gloss value.
  • the whiteness (L value) measured by the color CIELAB of the specimen may have an improved whiteness property of 75 or more, 84 or more, or 84 to 85.
  • the specimen may be manufactured by injection molding or extruding the non-halogen flame retardant resin composition at a processing temperature of 250 to 300 ° C., or by extruding to produce pellets.
  • a yellowing index ( ⁇ b) representing an increase in the b value measured by a hunter lab colormeter may have a yellowing resistance of 20 or less or 19 or less.
  • the non-halogen flame retardant resin composition may have a flame retardancy (UL-94, 2 mm) of V-0, V-1, or V-2, and has excellent flame retardancy and excellent balance of physical properties within this range.
  • the non-halogen flame retardant resin composition has, for example, an Izod impact strength (1/4 ") of 10 kgf ⁇ m / m or more, 12 kgf ⁇ m / m or more, or 12 to 20 kgf ⁇ m /, measured according to ASTM D256. It may be m, there is an effect of excellent impact strength and excellent balance of properties within this range.
  • the non-halogen flame-retardant resin composition of the present invention is not only excellent in mechanical strength but also excellent in whiteness and luster, so it is expected to be able to replace existing blending materials.
  • SB Graft polymerization of 45% by weight of styrene monomer to 55% by weight of polybutadiene rubber was made into powder through sulfate aggregation. At this time, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
  • ABS AN5%: Graft polymerization was performed by adding 0.01 part by weight of rosin soap to 55 parts by weight of polybutadiene rubber and 40 parts by weight of styrene monomer and 5 parts by weight of acrylonitrile. Prepared as a powder via sulfate aggregation. At this time, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
  • ABS (AN25%): Graft polymerization was performed by adding 55 parts by weight of polybutadiene rubber to 0.01 parts by weight of rosin soap based on 100 parts by weight of 20% by weight of styrene monomer and 25% by weight of acrylonitrile. Prepared as a powder via sulfate aggregation. At this time, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
  • ABS (AN5%) without fatty acid or metal salt thereof Graft polymerization of 40% by weight of styrene monomer and 5% by weight of acrylonitrile to 55% by weight of polybutadiene rubber without addition of fatty acid or metal salt thereof, followed by powdering through sulfate aggregation It was prepared as.
  • an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
  • PS A general propose polystyrene resin having a weight average molecular weight of 250,000 g / mol and a rubber content of 0% by weight was prepared.
  • HIPS A high impact polystyrene resin having a weight average molecular weight of 200,000 g / mol and a rubber content of 8% by weight was reinforced.
  • a polymer was prepared by bulk polymerization of 75% by weight of styrene monomer and 25% by weight of acrylonitrile monomer.
  • mPPO A phenylene oxide copolymer having Formula 2 and having a number average molecular weight of 24,000 g / mol was prepared.
  • Flame retardant 1 Phosphate compound: Bisphenol Abis (diphenyl phosphate) (CAS No. 181028-79-5)
  • Flame retardant 2 metal salt free hypophosphite compound: methyl cyclohexyl phosphinate
  • Flame retardant 3 Hypophosphite compound including metal salt: Calcium hypophosphite
  • Glidants Magnesium Stearate (CAS No. 557-04-0)
  • Stabilizer Iganox 1010 (CAS No. 6683-19-8)
  • Anti-dripping agent fluorine compound / teflon
  • Each component was mixed according to the following Tables 1 and 2 and extruded under a processing temperature of 200 to 250 ° C. to prepare pellets.
  • L value means the value of the coordinate axis representing the unique color
  • L can have a value of 0 to 100, the closer to 0 is black and the closer to 100 is white.
  • the specimens of Examples 1 to 5 prepared using the non-halogen flame-retardant resin composition of the blend resin and the resin additive according to the present invention have a ratio of the blend resin or resin additive deviated from the present invention.
  • the specimens of Comparative Examples 1 to 9 prepared using the halogen flame retardant resin composition it was confirmed that excellent performance in all physical properties of gloss, flame retardancy, impact strength, whiteness.

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Abstract

The present invention relates to a non-halogen flame-retardant resin composition. According to the present invention, there is an effect of providing a non-halogen flame retardant resin composition that can simultaneously exhibit excellent flame retardancy, whiteness, and glossiness by solving the problems of a flame-retardant resin composition which has difficultly in realizing the V-1 grade or higher with a non-halogen flame retardant formulation, or which has low glossiness and whiteness, thereby exhibiting poor coloring properties.

Description

비할로겐 난연수지 조성물Non-halogen flame retardant resin composition
〔출원(들)과의 상호 인용〕[Reciprocal citation with application (s)]
본 출원은 2016년 11월 10일자 한국특허출원 제10-2016-0149369호 및 2017년 8월 24일자 한국특허출원 제10-2017-0107355호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0149369 dated November 10, 2016 and Korean Patent Application No. 10-2017-0107355 dated August 24, 2017. All content disclosed in the literature is included as part of this specification.
본 발명은 비할로겐 난연수지 조성물에 관한 것으로, 보다 상세하게는 비할로겐 난연 처방 하에 V-1급 이상 구현이 어렵거나, 광택과 백색도가 낮아 착색성이 불량하던 난연 수지의 문제점을 해결하여 우수한 난연, 백색도 및 광택도를 동시에 발현할 수 있는 비할로겐 난연수지 조성물에 관한 것이다.The present invention relates to a non-halogen flame retardant resin composition, and more particularly, it is difficult to implement V-1 or higher under non-halogen flame retardant prescription, or solves the problem of flame retardant resins having poor colorability due to low gloss and whiteness. The present invention relates to a non-halogen flame-retardant resin composition capable of simultaneously expressing whiteness and glossiness.
난연성은 산업상 다양한 플라스틱 제품에서 요구되는 것으로, 대표적으로 아크릴로니트릴-부타디엔-스티렌계 공중합체, 스티렌-아크릴로니트릴계 공중합체, 폴리스티렌, 폴리페닐렌 옥사이드 등에서 요구된다.Flame retardancy is required in a variety of industrial plastic products, typically in acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, polystyrene, polyphenylene oxide and the like.
그러나, 이중에서 아크릴로니트릴-부타디엔-스티렌계 공중합체는 비할로겐 난연 처방 하에 V-1급 이상의 난연도 구현이 어려운 문제가 있고, 난연도 구현을 위해 폴리페닐렌 옥사이드 등과 블렌딩하는 경우에는 백색도가 낮아져 착색성이 불량한 문제가 있다.However, the acrylonitrile-butadiene-styrene-based copolymer has a problem that it is difficult to achieve flame retardancy of V-1 or higher under the non-halogen flame retardant prescription, and when blending with polyphenylene oxide or the like to implement flame retardancy, There is a problem that the colorability is poor.
또한, 상기 폴리스티렌과 폴리페닐렌 옥사이드 등은 비할로겐 난연 처방 하에 광택도와 백색도가 모두 떨어지는 문제가 있다.In addition, the polystyrene and polyphenylene oxide, etc. have a problem that both gloss and whiteness are inferior under the non-halogen flame retardant prescription.
이에 비할로겐 난연 처방 하에 난연성이 우수하면서도 뛰어난 광택도와 백색도를 제공할 수 있는 수지 조성물에 대한 필요성이 계속 요구되고 있는 실정이다.Accordingly, there is a continuing need for a resin composition capable of providing excellent gloss and whiteness with excellent flame retardancy under non-halogen flame retardant prescription.
〔선행기술문헌〕[Prior art document]
〔특허문헌〕한국특허공개 제2013-0132004호[Patent Document] Korean Patent Publication No. 2013-0132004
본 발명은 비할로겐 난연 처방 하에 V-1급 이상 구현이 어렵거나, 광택과 백색도가 낮아 착색성이 불량하던 난연 수지의 문제점을 해결하여 우수한 난연, 백색도 및 광택도를 동시에 발현할 수 있는 비할로겐 난연수지 조성물을 제공하는 것을 목적으로 한다.The present invention is a non-halogen flame retardant capable of expressing excellent flame retardancy, whiteness and gloss at the same time by solving the problem of a flame retardant resin, which is difficult to implement V-1 or higher under a non-halogen flame retardant prescription, or is poor in colorability due to low gloss and whiteness. It is an object to provide a resin composition.
본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
상기 목적을 달성하기 위하여, 본 발명은 (A) 폴리아릴렌 에테르계 중합체, 스티렌계 중합체 및 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체를 포함하는 블렌드 수지, 및 (B) 비할로겐 난연제, 를 포함하는 비할로겐 난연수지 조성물로서,In order to achieve the above object, the present invention provides a blend resin comprising (A) a polyarylene ether polymer, a styrene polymer and a vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer, and (B) a non-halogen flame retardant Non-halogen flame-retardant resin composition comprising,
상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 상기 공중합체의 전체 중량에 대해 상기 비닐시안 화합물이 1 중량% 이상 내지 25 중량% 미만으로 포함되고,The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer includes 1% by weight or more and less than 25% by weight of the vinyl cyan compound based on the total weight of the copolymer,
상기 비할로겐 난연수지 조성물을 압사출하여 만든 시편을 45°값으로 본 표면 광택도(Gloss)가 80 이상이고, 컬러런트의 별도 투입 없이 제작한 상기 시편을 컬러 CIELAB으로 측정한 백색도(L값)이 75 이상인 것을 특징으로 하는 비할로겐 난연수지 조성물을 제공한다.The surface glossiness (Gloss) of the specimen made by extruding the non-halogen flame-retardant resin composition at a 45 ° value is 80 or more, and the whiteness (L value) measured by the color CIELAB of the specimen prepared without the addition of a colorant. The non-halogen flame retardant resin composition which is 75 or more is provided.
또한, 본 발명은 (A) 폴리아릴렌 에테르계 중합체 14 내지 64 중량%, 스티렌계 중합체 20 내지 70 중량% 및 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 16 내지 40 중량%를 포함하는 블렌드 수지, 및 (B) 비할로겐 난연제, 를 포함하는 비할로겐 난연수지 조성물로서,In addition, the present invention comprises (A) 14 to 64% by weight of polyarylene ether-based polymer, 20 to 70% by weight of styrene-based polymer and 16 to 40% by weight of vinylcyan compound-conjugated diene compound-vinylaromatic compound copolymer A non-halogen flame-retardant composition comprising a blend resin, and (B) a non-halogen flame retardant,
상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 상기 공중합체의 전체 중량에 대해 상기 비닐시안 화합물이 1 중량% 이상 내지 25 중량% 미만으로 포함되는 것을 특징으로 하는 비할로겐 난연수지 조성물을 제공한다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is a non-halogen flame-retardant resin composition characterized in that the vinyl cyan compound is contained in more than 1% by weight to less than 25% by weight relative to the total weight of the copolymer. to provide.
본 발명에 따르면, 비할로겐 난연 처방 하에 V-1급 이상 구현이 어렵거나, 광택과 백색도가 낮아 착색성이 불량하던 난연 수지의 문제점을 해결하여 우수한 난연, 백색도 및 광택도가 동시에 발현된 성형품을 제공할 수 있다.According to the present invention, a non-halogen flame retardant formulation is difficult to implement more than V-1 grade, or solved the problem of the flame retardant resin was poor in colorability due to low gloss and whiteness to provide a molded article exhibiting excellent flame retardancy, whiteness and glossiness at the same time can do.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 기재의 비할로겐 난연수지 조성물은 (A) 폴리아릴렌 에테르계 중합체, 스티렌계 중합체 및 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체를 포함하는 블렌드 수지, 및 (B) 비할로겐 난연제, 를 포함하는 비할로겐 난연수지 조성물로서, 상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 상기 공중합체의 전체 중량에 대해 상기 비닐시안 화합물이 1 중량% 이상 내지 25 중량% 미만으로 포함되고, 상기 비할로겐 난연수지 조성물을 압사출하여 만든 시편을 45°값으로 본 표면 광택도(Gloss)가 80 이상이고, 컬러런트의 별도 투입 없이 제작한 상기 시편을 컬러 CIELAB으로 측정한 백색도(L값)이 75 이상인 것을 특징으로 한다.The non-halogen flame-retardant composition of the present disclosure is a blend resin comprising (A) a polyarylene ether polymer, a styrene polymer and a vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer, and (B) a non-halogen flame retardant, A non-halogen flame-retardant resin composition comprising a, wherein the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is contained in the vinyl cyan compound at least 1% by weight to less than 25% by weight relative to the total weight of the copolymer The surface glossiness (Gloss) of the specimen made by extruding the non-halogen flame-retardant resin composition at a 45 ° value is 80 or more, and the whiteness measured by color CIELAB of the specimen prepared without adding a colorant (L value) ) Is 75 or more.
또 다른 예로, 본 기재의 비할로겐 난연수지 조성물은 (A) 폴리아릴렌 에테르계 중합체 14 내지 64 중량%, 스티렌계 중합체 20 내지 70 중량% 및 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 16 내지 40 중량%를 포함하는 블렌드 수지, 및 (B) 비할로겐 난연제, 를 포함하는 비할로겐 난연수지 조성물로서, 상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 상기 공중합체의 전체 중량에 대해 상기 비닐시안 화합물이 1 중량% 이상 내지 25 중량% 미만으로 포함되는 것을 특징으로 한다.As another example, the non-halogen flame-retardant composition of the present disclosure is (A) 14 to 64% by weight polyarylene ether polymer, 20 to 70% by weight styrene polymer and vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer A non-halogen flame-retardant resin composition comprising a blend resin comprising 16 to 40 wt%, and (B) a non-halogen flame retardant, wherein the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is the total weight of the copolymer. It is characterized in that the vinyl cyan compound is contained in more than 1% by weight to less than 25% by weight.
본 기재에서 비할로겐 난연수지 조성물은 할로겐 또는 할로겐 화합물을 별도로 투입하지 않는 것을 의미하는 것으로, 자연적으로나 공기 등을 통해서, 또는 극미량의 불순물로 포함되는 것까지 포함하는 것은 아니며, 구체적으로 할로겐 함량이 5,000 ppm 이하, 바람직하게는 1,000 ppm 이하인 것을 의미한다.In the present description, the non-halogen flame-retardant resin composition means not adding a halogen or a halogen compound separately, and does not include naturally or through air, or even a very small amount of impurities, and specifically, a halogen content of 5,000 It means that it is ppm or less, Preferably it is 1,000 ppm or less.
상기 폴리아릴렌 에테르계 중합체는 난연 수지로 사용될 수 있는 종류라면 제한하지 않으며, 일례로 하기 화학식 1 또는 화학식 2로 표시되는 화합물의 단독 중합체, 또는 하기 화학식 1 또는 화학식 2의 화합물을 포함하는 공중합체일 수 있다.The polyarylene ether-based polymer is not limited as long as it can be used as a flame-retardant resin, for example, a homopolymer of a compound represented by Formula 1 or Formula 2, or a copolymer comprising a compound of Formula 1 or Formula 2 Can be.
Figure PCTKR2017011883-appb-C000001
Figure PCTKR2017011883-appb-C000001
Figure PCTKR2017011883-appb-C000002
Figure PCTKR2017011883-appb-C000002
상기 Ra, R1, R2, R3 및 R4는 아릴렌기(Ar) 또는 페닐렌기의 치환체로, 각각 독립적으로 또는 동시에 수소, 염소, 브롬, 요오드, 메틸, 에틸, 프로필, 알릴, 페닐, 메틸벤질, 클로로메틸, 브로모메틸, 시아노에틸, 시아노, 메톡시, 페녹시 또는 니트로기이며, 상기 n은 4 내지 20의 정수이고, Ar은 탄소수 7 내지 20의 아릴렌기이다. 일례로 R1 및 R2는 알킬기 또는 탄소수 1 내지 4의 알킬기이고, R3 및 R4는 수소일 수 있다.R a , R 1 , R 2 , R 3 and R 4 are substituents of arylene group (Ar) or phenylene group, each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl , Methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy or nitro group, n is an integer of 4 to 20, Ar is an arylene group having 7 to 20 carbon atoms. In an example, R 1 and R 2 may be an alkyl group or an alkyl group having 1 to 4 carbon atoms, and R 3 and R 4 may be hydrogen.
상기 폴리아릴렌 에테르계 중합체는 일례로 폴리(페닐렌 에테르)계 수지일 수 있다.The polyarylene ether polymer may be, for example, a poly (phenylene ether) resin.
상기 폴리(페닐렌 에테르)계 수지는 하기 [화학식 3]으로 표시될 수 있는 폴리(아릴렌 에테르) 수지를 의미한다.The poly (phenylene ether) -based resin means a poly (arylene ether) resin that can be represented by the following [Formula 3].
Figure PCTKR2017011883-appb-C000003
Figure PCTKR2017011883-appb-C000003
상기 W, X, Y 및 Z는 수소 또는 치환기이고, n은 반복단위이다.W, X, Y and Z are hydrogen or a substituent, n is a repeating unit.
상기 W, X, Y 및 Z는 각각 독립적으로 또는 동시에 수소, 염소, 브롬, 요오드, 메틸, 에틸, 프로필, 알릴, 페닐, 메틸벤질, 클로로메틸, 브로모메틸, 시아노에틸, 시아노, 메톡시, 페녹시 또는 니트로기이며, 상기 n은 4 내지 20의 정수이다.W, X, Y and Z are each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, memeth Oxy, phenoxy or nitro group, wherein n is an integer from 4 to 20.
상기 폴리(아릴렌 에테르) 수지의 단독 중합체는 특별히 제한하지는 않으나, 구체적인 예로 폴리(2,6-디메틸-1,4-페닐렌) 에테르, 폴리(2,6-디에틸-1,4-페닐렌) 에테르, 폴리(2-메틸-6-프로필-1,4-페닐렌) 에테르, 폴리(2,6-디프로필-1,4-페닐렌) 에테르, 폴리(2-에틸-6-프로필-1,4-페닐렌) 에테르, 폴리(2,6-디메톡시-1,4-페닐렌) 에테르, 폴리(2,6-디클로로메틸-1,4-페닐렌) 에테르, 폴리(2,6-디브로모메틸-1,4-페닐렌) 에테르, 폴리(2,6-디페닐-1,4-페닐렌) 에테르 및 폴리(2,5-디메틸-1,4-페닐렌) 에테르로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The homopolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenyl Ethylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl -1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2, 6-dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether and poly (2,5-dimethyl-1,4-phenylene) ether It may be one or more selected from the group consisting of.
또한, 상기 폴리(아릴렌 에테르) 수지의 공중합체는 특별히 제한하지는 않으나, 구체적인 예로 2,6-디메틸페놀과 2,3,6-트리메틸페놀의 공중합체, 2,6-디메틸페놀과 o-크레졸의 공중합체 및 2,3,6-트리메틸페놀과 o-크레졸의 공중합체 등으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.In addition, the copolymer of the poly (arylene ether) resin is not particularly limited, but specific examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol And a copolymer of 2,3,6-trimethylphenol and o-cresol, and the like.
상기 폴리(아릴렌 에테르) 수지는 일례로 본 발명에 따른 수지 조성물 총 중량을 기준으로 14 내지 64 중량%, 20 내지 50 중량%, 혹은 30 내지 40 중량%일 수 있고, 이 범위 내에서 충격강도, 기계적 물성과 표면 광택, 백색도가 우수한 효과가 있다. The poly (arylene ether) resin may be 14 to 64% by weight, 20 to 50% by weight, or 30 to 40% by weight based on the total weight of the resin composition according to the present invention, for example, impact strength within this range Excellent mechanical properties, surface gloss and whiteness.
상기 폴리(아릴렌 에테르) 수지는 일례로, 중량평균 분자량이 5,000 내지 100,000 g/mol, 20,000 내지 80,000 g/mol, 혹은 50,000 내지 75,000 g/mol일 수 있고, 이 범위 내에서 치수안정성 및 물성 밸런스가 뛰어난 효과가 있다.The poly (arylene ether) resin, for example, may have a weight average molecular weight of 5,000 to 100,000 g / mol, 20,000 to 80,000 g / mol, or 50,000 to 75,000 g / mol, dimensional stability and physical properties balance within this range Has an excellent effect.
상기 스티렌계 중합체는 난연수지로 사용될 수 있는 종류라면 제한하지 않으며, 일례로 10,000 내지 300,000 g/mol의 중량평균 분자량과 93~100 중량%의 스티렌 함량을 갖는 폴리스티렌 수지, 혹은 20,000 내지 300,000 g/mol의 중량평균 분자량과 95~100 중량%의 스티렌 함량을 갖는 폴리스티렌 수지일 수 있다. The styrene-based polymer is not limited as long as it can be used as a flame retardant resin, for example, a polystyrene resin having a weight average molecular weight of 10,000 to 300,000 g / mol and a styrene content of 93 to 100% by weight, or 20,000 to 300,000 g / mol It may be a polystyrene resin having a weight average molecular weight of and a styrene content of 95 to 100% by weight.
상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 난연 수지로 사용될 수 있는 종류라면 제한하지 않으며, 일례로 공액디엔계 고무질 중합체; 및 상기 고무질 중합체를 감싸고, 비닐방향족 화합물, 비닐시안 화합물, 및 지방산 또는 이의 금속염을 포함하여 중합된 쉘;을 포함하는 시드-쉘 구조의 그라프트 공중합체, 혹은 그 분체일 수 있다. The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is not limited as long as it can be used as a flame retardant resin, and examples thereof include conjugated diene rubber polymers; And a shell polymerized by wrapping the rubbery polymer and including a vinylaromatic compound, a vinylcyan compound, and a fatty acid or a metal salt thereof, and a graft copolymer having a seed-shell structure.
상기 공액디엔계 고무질 중합체는 일례로 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 2-에틸-1,3-부타디엔, 1,3-펜타디엔 및 이소프렌으로 이루어진 군으로부터 선택된 1종 이상의 공액디엔계 화합물을 포함하여 중합된 것일 수 있다.The conjugated diene rubber polymer is selected from the group consisting of, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene It may be polymerized including one or more conjugated diene-based compounds.
상기 공액디엔계 고무질 중합체(이하, '시드'라 함)는 일례로 유화 중합된 것일 수 있고, 이 경우 기계적 물성이 우수한 효과가 있으며, 통상의 유화 중합 방법에 따라 제조된 것이면 특별히 제한되지 않는다. 또 다른 예로 상기 시드는 중합된 고무질 중합체가 콜로이드 상태로 물에 분산된 라텍스의 형태일 수 있다.The conjugated diene-based rubbery polymer (hereinafter referred to as 'seed') may be, for example, emulsion polymerization, and in this case, the mechanical properties are excellent, and are not particularly limited as long as they are manufactured according to a conventional emulsion polymerization method. In another example, the seed may be in the form of a latex in which the polymerized rubbery polymer is dispersed in water in a colloidal state.
본 기재에서 평균 입경은 다이나믹 레이져 라이트 스케터링 방법으로 미국 Nicomp 사의 Nicomp 370HPL 기기를 이용하여 가우시안 모드로 인텐시티(intensity) 값으로 측정한다. In the present description, the average particle diameter is measured as an intensity value in Gaussian mode using a Nicomp 370HPL device manufactured by Nicomp, USA, using a dynamic laser light scattering method.
본 기재에서 겔 함량은 폴리부타디엔 고무 라텍스를 묽은 산이나 금속 염을 사용하여 응고한 후 세척하여 60 ℃의 진공 오븐에서 24 시간 동안 건조한 다음 얻어진 고무 덩어리를 가위로 잘게 자른 후 1 g의 고무 절편을 톨루엔 100 g에 넣고 48 시간 동안 실온의 암실에서 보관한 후 졸과 겔로 분리하여 각각 건조한 후, 하기 수학식에 의해 측정한다. In the present description, the gel content is determined by coagulation of polybutadiene rubber latex with dilute acid or metal salt, washing, drying in a vacuum oven at 60 ° C. for 24 hours, and then crushing the obtained rubber mass with scissors, and then removing 1 g of rubber sections. 100 g of toluene was stored in a dark room at room temperature for 48 hours, separated into sol and gel, dried, and then measured by the following equation.
Figure PCTKR2017011883-appb-I000001
Figure PCTKR2017011883-appb-I000001
상기 시드는 일례로 평균입경이 2,000 Å 초과 내지 3,500 Å 이하, 2,500 Å 이상 내지 3,500 Å 이하, 혹은 3,000 Å 이상 내지 3,500 Å 이하이고, 겔 함량이 60 내지 95 중량%, 65 내지 80 중량%, 혹은 65 내지 75 중량%인 대구경 시드와 일례로 평균입경이 500 Å 내지 2,000 Å, 1,000 Å 내지 2,000 Å, 혹은 1,000 Å 내지 1,500 Å이고, 겔 함량이 60 내지 95 중량%, 70 내지 95 중량% 혹은 80 내지 95 중량%인 소구경 시드의 바이모달(bimodal) 중에서 선택된 1종 이상일 수 있고, 이 범위 내에서 충격강도 및 기계적 물성이 우수한 효과가 있다.The seed has, for example, an average particle diameter of more than 2,000 kPa to 3,500 kPa or less, 2,500 kPa or more to 3,500 kPa or less, or 3,000 kPa or more and 3,500 kPa or less, and a gel content of 60 to 95 wt%, 65 to 80 wt%, or 65 To 75% by weight large diameter seeds, for example, with an average particle diameter of 500 kPa to 2,000 kPa, 1,000 kPa to 2,000 kPa, or 1,000 kPa to 1,500 kPa, with a gel content of 60 to 95 wt%, 70 to 95 wt% or 80 to 95% by weight may be one or more selected from bimodal (bimodal) of the small diameter seed, there is an excellent impact strength and mechanical properties within this range.
상기 시드를 구성하는 대구경 시드와 소구경 시드는 일례로 중량비로 50:50 내지 90:10, 60:40 내지 75:25, 60:40 내지 70:20, 혹은 70:30 내지 75:25일 수 있고, 이 범위 내에서 분산도와 표면 특성이 우수한 효과가 있다. The large-diameter seed and the small-diameter seed constituting the seed may be 50:50 to 90:10, 60:40 to 75:25, 60:40 to 70:20, or 70:30 to 75:25 by weight, for example. Within this range, the dispersion and the surface properties are excellent.
상기 시드는 일례로 공액디엔계 고무질 중합체, 방향족 비닐 화합물 및 비닐시안 화합물 총 함량 100 중량%를 기준으로 40 내지 60 중량%, 50 내지 60 중량%, 혹은 53 내지 57 중량%로 포함될 수 있고, 이 범위 내에서 기계적 물성 및 표면 특성이 우수한 효과가 있다.For example, the seed may be included in an amount of 40 to 60 wt%, 50 to 60 wt%, or 53 to 57 wt% based on 100 wt% of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. Mechanical properties and surface properties are excellent within.
상기 쉘은 상기 바이모달 시드를 감싸며 평균 탄소수와 분자량을 갖는 지방산 또는 이의 금속염을 포함하여 유화 그라프트 중합된 것으로, 일례로 공액디엔계 고무질 중합체, 방향족 비닐 화합물 및 비닐시안 화합물 총 함량 100 중량%를 기준으로 40 내지 60 중량%, 40 내지 50 중량%, 혹은 43 내지 47 중량%로 포함될 수 있으며, 이 범위 내에서 기계적 물성 및 물성 밸런스가 우수한 효과가 있다.The shell is emulsified graft polymerized to include the fatty acid having a mean carbon number and molecular weight or a metal salt thereof surrounding the bimodal seed, for example 100% by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound and vinyl cyan compound 40 to 60% by weight, 40 to 50% by weight, or 43 to 47% by weight may be included, and within this range there is an excellent mechanical and physical properties balance.
상기 방향족 비닐 화합물은 일례로 스티렌, α-메틸스티렌, α-에틸스티렌, p-메틸스티렌, o-메틸스티렌, o-t-부틸스티렌, 브로모스티렌, 클로로스티렌, 트리클로로스티렌 및 이들의 유도체로 이루어지는 군으로부터 선택된 1종 이상일 수 있고, 상기 비닐시안 화합물은 일례로 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 및 이들의 유도체로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The aromatic vinyl compound includes, for example, styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, o-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene and derivatives thereof. It may be at least one selected from the group, and the vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile and derivatives thereof.
본 기재에서 유도체라 함은 원 화합물의 수소 원자 중 하나 또는 둘 이상이 할로겐기, 알킬기, 히드록시기로 치환된 화합물을 의미할 수 있다. In the present description, the derivative may mean a compound in which one or two or more hydrogen atoms of the original compound are substituted with a halogen group, an alkyl group, and a hydroxy group.
상기 비닐시안 화합물은 상기 공중합체의 전체 중량에 1 중량% 이상 내지 25 중량% 미만, 1 중량% 내지 20 중량%, 1 중량% 내지 15 중량%, 1 중량% 내지 12 중량%, 1 내지 10 중량%, 혹은 3 내지 7 중량%로 혼합되는 것이 바람직할 수 있으며, 이 범위 내에서 기계적 물성 및 물성 밸런스가 우수하다는 효과가 있다. 상기 쉘에 포함되는 방향족 비닐 화합물 및 비닐시안 화합물은 일례로 중량비를 기준으로 90:10 내지 99:1 범위로 포함될 수 있다. The vinyl cyan compound may be present in an amount of at least 1 wt% to less than 25 wt%, 1 wt% to 20 wt%, 1 wt% to 15 wt%, 1 wt% to 12 wt%, and 1 to 10 wt% based on the total weight of the copolymer. It may be preferable to mix in%, or 3 to 7% by weight, there is an effect that the mechanical and physical properties balance within this range is excellent. The aromatic vinyl compound and the vinyl cyan compound included in the shell may be included, for example, in the range of 90:10 to 99: 1 based on the weight ratio.
상기 지방산은 일례로 사슬의 탄소수를 달리하는 2종 이상, 2종 내지 10종, 혹은 2종 내지 5종의 지방산 다이머 또는 이의 금속염의 혼합일 수 있다. 상기 지방산의 사슬의 평균 탄소수는 일례로 10 이상, 33 이상, 33 내지 44, 혹은 33 내지 36일 수 있고, 이 범위 내에서 열안정성이 우수하여, 압출 및 사출 가공 시 가스 발생량을 저감시키는 효과가 있다.The fatty acid may be, for example, a mixture of two or more kinds, two to ten kinds, or two to five kinds of fatty acid dimers or metal salts thereof having different carbon atoms in the chain. The average carbon number of the chain of the fatty acid may be, for example, 10 or more, 33 or more, 33 to 44, or 33 to 36, and excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. have.
상기 지방산은 일례로 불포화도가 1 내지 20, 1 내지 10, 혹은 1 내지 5인 불포화 지방산 다이머를 포함할 수 있고, 이 범위 내에서 압출 사출 성형시 휘발분이 적은 효과가 있다.The fatty acid may include, for example, an unsaturated fatty acid dimer having an unsaturation of 1 to 20, 1 to 10, or 1 to 5, and in this range, there is little effect of volatile content during extrusion injection molding.
본 기재에서 불포화도는 이중결합수를 의미한다. Unsaturation in the present description means double bond water.
상기 지방산의 분자량은 일례로 100 g/mol 이상, 100 내지 2,000 g/mol, 혹은 100 내지 1,000 g/mol일 수 있고, 이 범위 내에서 열안정성이 우수하여, 압출 및 사출 가공 시 가스 발생량을 저감시키는 효과가 있다.The molecular weight of the fatty acid may be, for example, 100 g / mol or more, 100 to 2,000 g / mol, or 100 to 1,000 g / mol, and has excellent thermal stability within this range, thereby reducing the amount of gas generated during extrusion and injection processing. It is effective to let.
여기서 분자량은 겔 침투 크로마토그래피(GPC)로 측정한 중량평균 분자량을 칭한다.The molecular weight here refers to the weight average molecular weight measured by gel permeation chromatography (GPC).
상기 지방산은 일례로 올레산, 올레산계 다이머, 미리스트올레산, 리놀레산, 및 이들의 금속염으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The fatty acid may include, for example, one or more selected from the group consisting of oleic acid, oleic acid-based dimer, myristoleic acid, linoleic acid, and metal salts thereof.
상기 금속염의 금속은 일례로, 알칼리 금속 또는 알칼리 토금속이고, 바람직하게는 알칼리 토금속이며, 구체적인 예로 칼슘, 마그네슘 또는 이들의 혼합일 수 있다. The metal of the metal salt is, for example, an alkali metal or an alkaline earth metal, preferably an alkaline earth metal, and specifically, calcium, magnesium or a mixture thereof.
상기 지방산은 일례로 상기 공액디엔계 고무질 중합체, 방향족 비닐 화합물 및 비닐시안 화합물 총 함량 100 중량부를 기준으로 0.1 내지 3 중량부, 0.1 내지 2 중량부, 0.1 내지 1 중량부, 혹은 0.1 내지 0.3 중량부로 포함될 수 있다.The fatty acid may be, for example, 0.1 to 3 parts by weight, 0.1 to 2 parts by weight, 0.1 to 1 parts by weight, or 0.1 to 0.3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound. May be included.
본 발명의 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 일례로 중량평균 분자량이 20,000 내지 100,000 g/mol, 30,000 g/mol 내지 85,000 g/mol, 혹은 30,000 내지 70,000 g/mol일 수 있고, 이 범위 내에서 표면 광택, 백색도 및 분산도가 우수하고, 기계적 물성이 뛰어난 효과가 있다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer of the present invention may have, for example, a weight average molecular weight of 20,000 to 100,000 g / mol, 30,000 g / mol to 85,000 g / mol, or 30,000 to 70,000 g / mol. In this range, it is excellent in surface gloss, whiteness and dispersion, and has excellent mechanical properties.
여기서 중량평균 분자량은 겔 침투 크로마토그래피(GPC)로 측정한 분자량을 칭한다.Here, a weight average molecular weight refers to the molecular weight measured by gel permeation chromatography (GPC).
상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는, 구체적인 예로 공액디엔 고무질 중합체 45 내지 60 중량% 및 비닐시안 화합물(필요에 따라 알킬 (메트)아크릴레이트 화합물로 대체하거나 병용 가능) 1 내지 10 중량% 및 비닐방향족 화합물 30 내지 54 중량%의 그라프트 공중합체일 수 있다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer may include, for example, 45 to 60% by weight of a conjugated diene rubber polymer and a vinyl cyan compound (can be replaced or used in combination with an alkyl (meth) acrylate compound, if necessary). 10% by weight and 30-54% by weight of the vinylaromatic compound.
상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는, 다른 예로 공액디엔 고무질 중합체 50 내지 60 중량% 및 비닐시안 화합물(필요에 따라 알킬(메트)아크릴레이트 화합물로 대체하거나 병용 가능) 2 내지 8 중량% 및 비닐방향족 화합물 32 내지 48 중량%의 그라프트 공중합체일 수 있다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is, for example, 50 to 60% by weight of a conjugated diene rubber polymer and a vinyl cyan compound (can be replaced or used in combination with an alkyl (meth) acrylate compound, if necessary). Graft copolymer of 8% by weight and from 32 to 48% by weight of vinylaromatic compounds.
상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 염을 사용하여 응집을 실시하여 수득된 분체(dry powder)로 사용하는 것이 열분해 안정성이 우수하여, 압출 및 사출 가공 시 가스 발생량을 저감시키는 효과가 있다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer has excellent thermal decomposition stability when used as a dry powder obtained by agglomeration with a salt, thereby reducing the amount of gas generated during extrusion and injection processing. It works.
상기 염은 일례로 황산염, 탄산염 또는 이들의 혼합일 수 있다.The salt may be, for example, sulfate, carbonate or a mixture thereof.
본 발명의 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 그라프트 밀도를 개선하는 조성을 제공하여 폴리아릴렌 에테르계 중합체와 스티렌계 중합체에 대한 분산도를 높임으로써 고광택성을 가지는 효과가 있다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer of the present invention has a high glossiness by providing a composition that improves the graft density to increase the dispersibility of the polyarylene ether polymer and the styrene polymer. .
일례로, 상기 블렌드 수지는 폴리아릴렌 에테르계 중합체 14 내지 64 중량%, 스티렌계 중합체 20 내지 70 중량%와 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 16 내지 40 중량%로 포함될 수 있고, 이 범위 내에서 난연 수지를 사용하면서도 백색도와 광택도를 효과적으로 개선할 수 있다.For example, the blend resin may include 14 to 64 wt% of polyarylene ether polymer, 20 to 70 wt% of styrene polymer, and 16 to 40 wt% of vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer. Within this range, the whiteness and glossiness can be effectively improved while using the flame retardant resin.
구체적인 예로, 상기 블렌드 수지는 폴리아릴렌 에테르계 중합체 20 내지 50 중량%, 스티렌계 중합체 30 내지 50 중량%와 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 20 내지 30 중량%로 포함될 수 있고, 이 범위 내에서 난연 수지를 사용하면서도 백색도와 광택도를 보다 효율적으로 개선할 수 있다.As a specific example, the blend resin may include 20 to 50% by weight of polyarylene ether-based polymer, 30 to 50% by weight of styrene-based polymer and 20 to 30% by weight of vinylcyan compound-conjugated diene compound-vinylaromatic compound copolymer Within this range, the whiteness and glossiness can be improved more efficiently while the flame retardant resin is used.
다른 예로, 상기 블렌드 수지는 폴리아릴렌 에테르계 중합체 20 내지 40 중량%, 스티렌계 중합체 35 내지 50 중량%와 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 22 내지 30 중량%로 포함될 수 있다.As another example, the blend resin may include 20 to 40 wt% of polyarylene ether polymer, 35 to 50 wt% of styrene polymer, and 22 to 30 wt% of vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer. .
본 발명의 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 제조방법이 특정되지 않으나, 일례로 시드를 중합하는 단계; 및 상기 쉘에 사슬(chain)의 평균 탄소수가 10 이상이고 분자량이 500 내지 2,000 g/mol인 지방산 또는 이의 금속염을 포함하고 유화 그라프트 중합시켜 쉘을 제조하는 단계;를 포함하여 구성될 수 있다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer of the present invention is not specifically prepared, but, for example, polymerizing a seed; And a fatty acid having a mean carbon number of 10 or more in the shell and a molecular weight of 500 to 2,000 g / mol or a metal salt thereof and preparing an shell by emulsion graft polymerization.
상기 시드는 일례로 평균입경이 2,000 Å 초과 내지 3,500 Å 이하의 대구경 고무질 중합체, 평균입경이 500 Å 내지 2,000 Å인 소구경 고무질 중합체 중에서 1종 이상을 포함할 수 있다. The seed may include, for example, at least one of a large diameter rubbery polymer having an average particle diameter of more than 2,000 mm 3 and up to 3,500 mm 3, and a small diameter rubbery polymer having an average particle diameter of 500 mm 2 to 2,000 mm 3.
상기 시드 중합은 일례로 유화 중합으로 실시될 수 있다.The seed polymerization may be carried out, for example, by emulsion polymerization.
상기 시드 중합 및 유화 그라프트 중합 방법은 일반적으로 ABS 수지의 제조방법에 사용되는 시드 중합 및 유화 그라프트 중합인 경우 특별히 제한되지 않는다.The seed polymerization and emulsion graft polymerization method is not particularly limited in the case of seed polymerization and emulsion graft polymerization generally used in the production method of ABS resin.
일례로 본 발명의 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 제조방법은 알킬 아릴 설포네이트, 알카리 메틸 알킬 설페이트, 설포네이트화된 알킬에스테르 및 불포화 지방산의 금속염으로 이루어지는 군으로부터 선택된 1종 이상을 추가로 포함할 수 있으며, 첨가량은 일례로 모노머(비닐시안+공액디엔+방향족비닐) 100 중량부 기준으로, 0.01 내지 3 중량부, 0.05 내지 1 중량부 또는 0.05 내지 0.5 중량부일 수 있다.For example, the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer production method of the present invention may be one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, and metal salts of unsaturated fatty acids. It may further include, the amount may be, for example, 0.01 to 3 parts by weight, 0.05 to 1 parts by weight or 0.05 to 0.5 parts by weight based on 100 parts by weight of the monomer (vinyl cyan + conjugated diene + aromatic vinyl).
본 발명의 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 제조방법은 개시제로서 수용성 개시제 또는 지용성 개시제를 사용할 수 있으며, 상기 수용성 개시제는 일례로 과황산 나트륨, 과황산 칼륨, 과황산 암모늄 등을 포함하며, 상기 지용성 개시제는 큐멘하이드로 퍼옥사이드, 디이소프로필벤젠하이드로 퍼옥사이드, 3급 부틸하이드로 퍼옥사이드, 파라메탄 하이드로 퍼옥사이드, 벤조일 퍼옥사이드 등을 포함하며, 필요에 따라 이들을 조합하여 사용하는 것이 가능할 수 있다.In the vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer production method of the present invention, a water-soluble initiator or a fat-soluble initiator may be used as an initiator. Examples of the water-soluble initiator include sodium persulfate, potassium persulfate, ammonium persulfate, and the like. The fat-soluble initiator includes cumene hydro peroxide, diisopropylbenzene hydro peroxide, tertiary butyl hydro peroxide, paramethane hydro peroxide, benzoyl peroxide, and the like, and if necessary, the combination thereof may be used. It may be possible.
상기 개시제는 일례로 0.01 내지 2 중량부, 0.05 내지 1 중량부 또는 0.05 내지 0.5 중량부 사용할 수 있으며, 상기 범위 내에서 과반응을 발생시키지 않으며, 목적하는 입경 및 크기분포를 갖는 중합체가 될 수 있다. For example, the initiator may be used in an amount of 0.01 to 2 parts by weight, 0.05 to 1 part by weight, or 0.05 to 0.5 parts by weight, and does not cause overreaction within the above range, and may be a polymer having a desired particle size and size distribution. .
본 발명의 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 제조방법은 일례로 산화-환원계 촉매로서 소듐포름알데히드 술폭실레이트, 소듐에틸렌디아민 테트라아세테이트, 황산 제1철, 덱스트로즈, 피롤인산나트륨, 아황산나트륨으로 이루어지는 군으로부터 선택된 1종 이상을 포함할 수 있다.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer production method of the present invention is, for example, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrrole as an oxidation-reduction catalyst. It may include one or more selected from the group consisting of sodium phosphate, sodium sulfite.
상기 산화-환원계 촉매는 일례로 모노머 100 중량부 기준으로 0.001 내지 0.4 중량부, 0.005 내지 0.2 중량부 또는 0.01 내지 0.2 중량부로 사용될 수 있으며, 상기 범위 내에서는 중합반응을 촉진하여 단시간 내에 제조할 수 있다.The oxidation-reduction catalyst may be used in an amount of 0.001 to 0.4 parts by weight, 0.005 to 0.2 parts by weight or 0.01 to 0.2 parts by weight based on 100 parts by weight of monomer, for example, may be prepared within a short time by promoting the polymerization reaction. have.
상기 쉘을 유화 그라프트 중합하는 단계에서는 상기 반응물들을 투입한 뒤, 60 내지 90 ℃ 또는 60 내지 80 ℃에서 3 내지 5 시간 또는 2 내지 4 시간 동안 반응시켜 그라프트 중합 시키는 것이 바람직할 수 있는데, 이는 상술한 범위 내에서 개시제의 활성화로 중합반응이 개시되고 제열이 용이하기 때문이다. 또한, 상술한 범위로 온도 및 반응시간을 제어하는 경우, 크기 분포가 고른 중합체가 제조될 수 있다.In the step of emulsion graft polymerization of the shell, it is preferable to add the reactants, and then to graft polymerization by reacting at 60 to 90 ℃ or 60 to 80 ℃ for 3 to 5 hours or 2 to 4 hours. This is because the polymerization reaction is initiated by the activation of the initiator within the above-mentioned range, and the heat removal is easy. In addition, when controlling the temperature and the reaction time in the above-described range, a polymer having a uniform size distribution can be prepared.
상기 쉘을 유화 그라프트 중합하는 단계는 필요에 따라 분자량조절제를 모노머 100 중량부 기준으로, 0.1 내지 1 중량부, 0.2 내지 0.6 중량부 또는 0.3 내지 0.5 중량부로 더 포함할 수 있으며, 상술한 범위로 분자량조절제를 더 포함하는 경우 목적하는 평균입경을 갖는 중합체를 형성하는데 유리할 수 있으며, 중합체의 크기가 균일해지는 효과가 있다.The step of emulsion graft polymerization of the shell may further comprise 0.1 to 1 parts by weight, 0.2 to 0.6 parts by weight or 0.3 to 0.5 parts by weight based on 100 parts by weight of the monomer, if necessary, in the above-described range When further comprising a molecular weight modifier may be advantageous to form a polymer having a desired average particle diameter, there is an effect that the size of the polymer is uniform.
상기 분자량조절제는 일례로 3급 도데실메르캅탄 등의 메르캅탄류 화합물을 사용할 수 있다.As said molecular weight modifier, mercaptan compounds, such as tertiary dodecyl mercaptan, can be used as an example.
본 발명의 다른 일례는 그라프트 중합반응에 사용되는 개시제 및 산화-환원계 촉매를 반응초기에 전량 투입하는 것이 가능할 수 있으나, 상술한 바와 같이 개시제 및 산화-환원계 촉매를 분할 투입하는 경우, 반응열의 제열이 용이하고 부반응을 억제하면서도 미반응 단량체의 함량이 감소하여 중합체의 품질 및 생산성이 향상될 수 있다.In another example of the present invention, it may be possible to add the entire amount of the initiator and the redox-based catalyst used in the graft polymerization reaction at the beginning of the reaction. It is easy to defrost and suppress side reactions while reducing the content of the unreacted monomer can improve the quality and productivity of the polymer.
전술한 투입 후, 승온 속도 5 내지 30 ℃/hr, 혹은 10 내지 20 ℃/hr 하에 60 내지 100 ℃, 혹은 70 내지 90 ℃까지 승온시켜 제 2차 그라프트 중합 반응을 수행할 수 있다. 상기와 같이 반응물의 온도를 승온시킴으로써 미반응 단량체의 반응을 촉진하여 보다 짧은 시간 내에 높은 전환율을 달성할 수 있다. After the above-mentioned charge, the second graft polymerization reaction may be performed by increasing the temperature to 60 to 100 ° C. or 70 to 90 ° C. under a temperature increase rate of 5 to 30 ° C./hr, or 10 to 20 ° C./hr. By raising the temperature of the reactants as described above, it is possible to promote the reaction of the unreacted monomer and achieve high conversion in a shorter time.
상기 중합반응은 일례로 중합전환율 90 내지 99 %, 95 내지 99 % 또는 97 내지 99 % 시점에서 반응을 종결하는 것이 바람직할 수 있으며, 상기 범위에서는 생성물 내에 미반응 단량체 함량이 적고 중합도가 높은 중합체가 제조될 수 있다.For example, the polymerization reaction may be preferably terminated at 90 to 99%, 95 to 99%, or 97 to 99% of the polymerization conversion rate. In the above range, a polymer having a low unreacted monomer content and a high degree of polymerization in the product may be used. Can be prepared.
본 기재에서 중합전환율은 본 발명이 속한 기술분야에서 통상적으로 사용되는 측정방법에 의하여 측정될 수 있고, 일례로 무게 감량법으로 측정할 수 있으며, 구체적인 예로 그라프트 공중합체 라텍스 1.5 g을 150 ℃ 열풍 건조기 내에서 15 분간 건조 후 무게를 측정하여 총 고형분 함량(TSC)을 구하고 하기 수학식에 의해 측정한다.In the present description, the polymerization conversion rate may be measured by a measurement method commonly used in the art to which the present invention pertains. For example, the weight loss method may be measured. As a specific example, 1.5 g of a graft copolymer latex is 150 ° C. in a hot air dryer. After drying for 15 minutes, the weight is measured, and the total solid content (TSC) is calculated and measured by the following equation.
Figure PCTKR2017011883-appb-I000002
Figure PCTKR2017011883-appb-I000002
TSC: 총 고형분 함량(%)TSC: Total solids content (%)
M: 투입된 총 단량체 함량(중량부)M: total monomer content added (parts by weight)
W: 투입된 물 함량(중량부)W: input water content (parts by weight)
S: 투입된 유화제 및 기타 부원료 함량(중량부)S: added emulsifiers and other minor ingredients (parts by weight)
전술한 기재 이외에 그라프트율, 반응압력 등과 같은 다른 반응 조건들은 본 발명이 속한 기술분야에서 통상적으로 실시되고 있는 범위 내인 경우 특별히 제한되지 않으며, 필요에 따라 적절히 선택하여 실시할 수 있다. Other reaction conditions, such as graft rate, reaction pressure, etc., in addition to the above-described substrates, are not particularly limited as long as they are within a range generally practiced in the art to which the present invention pertains, and may be appropriately selected and performed as necessary.
상기 본 발명에 따라 제조된 그라프트 공중합체 라텍스는 전술한 염 응집, 세척, 건조 등의 통상적인 공정을 거쳐 분말 형태로 제조되고, 이 분말은 폴리아릴렌 에테르계 중합체, 스티렌계 수지 등의 비극성 수지와 혼합하고 압출 및 사출하여 성형품으로 제조될 수 있다. The graft copolymer latex prepared according to the present invention is prepared in the form of a powder through conventional processes such as salt agglomeration, washing, and drying, and the powder is made of a nonpolar material such as a polyarylene ether polymer and a styrene resin. It may be mixed with the resin and extruded and injected to produce a molded article.
상기 비할로겐 난연수지 조성물은 일례로 상기 블렌드 수지의 비할로겐 난연 처방 하에 광택도와 백색도를 개선할 수 있는 종류들로서, 상기 비할로겐 난연제로서 금속염 프리 하이포포스파이트 화합물과 유기인 난연제의 조합을 사용함에 특징을 갖는다. The non-halogen flame-retardant resin composition is a kind that can improve the gloss and whiteness under the non-halogen flame-retardant formulation of the blend resin as an example, characterized in that using a combination of a metal salt-free hypophosphite compound and an organic flame retardant as the non-halogen flame retardant. Has
상기 비할로겐 난연제는 일례로, 상기 블렌드 수지 100 중량부 기준으로 15 내지 45 중량부, 15 내지 31 중량부, 15 내지 30 중량부, 혹은 20 내지 30 중량부일 수 있고, 이 범위 내에서 난연성 및 내황변성이 우수한 효과가 있다.The non-halogen flame retardant may be, for example, 15 to 45 parts by weight, 15 to 31 parts by weight, 15 to 30 parts by weight, or 20 to 30 parts by weight based on 100 parts by weight of the blend resin, and within this range, flame retardant and sulfur resistance There is an excellent effect of denaturation.
상기 비할로겐 난연수지 조성물은 일례로, 상기 블렌드 수지 100 중량부 기준으로, 금속염 프리 하이포포스파이트 화합물을 0.1 내지 5 중량부, 1 내지 5 중량부, 혹은 1 내지 3 중량부 포함할 수 있고, 이 범위 내에서 V-1 이상의 난연 등급을 구현하면서 백색도와 광택도를 현저하게 개선시키는 효과가 있다. The non-halogen flame retardant resin composition may include, for example, 0.1 to 5 parts by weight, 1 to 5 parts by weight, or 1 to 3 parts by weight of a metal salt-free hypophosphite compound based on 100 parts by weight of the blend resin. It has the effect of remarkably improving whiteness and glossiness while implementing flame retardant grade of V-1 or more within the range.
상기 금속염 프리 하이포포스파이트 화합물은 비정질 난연수지에 대한 안정화제 혹은 난연조제로 사용되는 모든 종류를 사용가능한 것으로, 바람직하게는 포스핀옥사이드를 포함하는 화합물일 수 있다.The metal salt-free hypophosphite compound may be any kind used as a stabilizer or a flame retardant aid for amorphous flame retardant resins, preferably a compound containing phosphine oxide.
상기 금속염 프리 하이포포스파이트 화합물은 일례로 하기 [화학식 4]로 표시되는 화합물일 수 있다.The metal salt-free hypophosphite compound may be, for example, a compound represented by the following [Formula 4].
Figure PCTKR2017011883-appb-C000004
Figure PCTKR2017011883-appb-C000004
상기 R1 및 R2는 각각 독립적으로 수소 원자, 알킬, 싸이클로알케인, 알콕시, 아릴, 염소, 브롬, 요오드, 메틸벤질, 클로로메틸, 브로모메틸, 시아노에틸, 시아노, 페녹시 또는 니트로기이다.R 1 and R 2 are each independently a hydrogen atom, alkyl, cycloalkane, alkoxy, aryl, chlorine, bromine, iodine, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, phenoxy or nitro Qi.
상기 알킬은 탄소수 1 내지 10의 알킬, 또는 메틸, 에틸, 프로필일 수 있고, 상기 알콕시는 탄소수 1 내지 20, 탄소수 1 내지 16 또는 탄소수 1 내지 12일 수 있고, 구체적인 예로 메톡시 또는 에톡시일 수 있고, 상기 아릴기는 탄소수 6 내지 24의 아릴, 또는 페닐기, 나프틸기, 페난트레닐기, 플루오렌기, 디메틸플루오렌기, 트리페닐렌기, 벤조크라이센기 또는 플루오안트렌기일 수 있고, 상기 싸이클로알케인은 탄소수 3 내지 30 또는 탄소수 3 내지 18일 수 있다.The alkyl may be alkyl having 1 to 10 carbon atoms, or methyl, ethyl, propyl, and the alkoxy may have 1 to 20 carbon atoms, 1 to 16 carbon atoms, or 1 to 12 carbon atoms, and specifically, methoxy or ethoxy. The aryl group may be an aryl having 6 to 24 carbon atoms, or a phenyl group, a naphthyl group, a phenanthrenyl group, a fluorene group, a dimethyl fluorene group, a triphenylene group, a benzoicene group or a fluoranthrene group, and the cycloalkane group. May have 3 to 30 carbon atoms or 3 to 18 carbon atoms.
구체적인 예로 상기 금속염 프리 하이포포스파이트 화합물은 H-포스피닉산, 옥사포스포린 옥사이드, (3-클로로프로필)포스피닉산, 메틸 사이클로헥실포스피네이트, 부틸페닐포스피네이트 및 이들의 유도체로 이루어진 군으로부터 선택된 1종 이상일 수 있다.Specific examples of the metal salt-free hypophosphite compound include a group consisting of H-phosphonic acid, oxaphosphorine oxide, (3-chloropropyl) phosphonic acid, methyl cyclohexylphosphinate, butylphenylphosphinate, and derivatives thereof. It may be one or more selected from.
상기 비할로겐 난연수지 조성물은 일례로, 상기 블렌드 수지 100 중량부 기준으로, 유기인 난연제 15 내지 40 중량부, 15 내지 30 중량부, 혹은 15 내지 25 중량부를 포함할 수 있고, 이 범위 내에서 V-1 이상의 난연 등급을 구현하면서 백색도와 광택도를 효율적으로 개선시킬 수 있다.The non-halogen flame retardant resin composition may include, for example, 15 to 40 parts by weight, 15 to 30 parts by weight, or 15 to 25 parts by weight of an organophosphorus flame retardant based on 100 parts by weight of the blend resin, and within this range, V Effectively improves whiteness and gloss while achieving flame retardancy ratings above -1.
상기 유기인 난연제는 비정질 난연수지에 대한 난연제로 사용되는 모든 종류가 사용가능한 것으로, 바람직하게는 탄소수 1 내지 20의 알킬 포스포네이트 에스테르, 탄소수 6 내지 30의 아릴 포스포네이트 에스테르, 탄소수 1 내지 10의 트리알킬 포스핀, 탄소수 1 내지 20의 알킬포스핀 옥사이드 및 탄소수 6 내지 20의 아릴포스핀 옥사이드 중에서 선택된 화합물일 수 있다. The organic phosphorus flame retardant can be used as all kinds of flame retardants for amorphous flame retardant resin, preferably an alkyl phosphonate ester having 1 to 20 carbon atoms, an aryl phosphonate ester having 6 to 30 carbon atoms, 1 to 10 carbon atoms It may be a compound selected from trialkyl phosphine, alkylphosphine oxide having 1 to 20 carbon atoms and arylphosphine oxide having 6 to 20 carbon atoms.
상기 유기인 난연제는 전술한 금속염 프리 하이포포스파이트 화합물과의 병용 사용을 고려할 때, 트리페닐 포스페이트(Triphenyl phosphate), 레조르시놀 테트라페닐 디포스페이트(Resorcinol tetraphenyl-di-phosphate), 비스페놀-A 테트라페녹시 디포스페이트(Bisphenol-A tetraphenoxy-di-phosphate), 비스페놀- A 테트라크레실 디포스페이트(Bisphenol-A tetracresyl-di-phosphate), 레조르시놀 테트라자일리옥시 디포스페이트(Resorcinol tetraxylyloxy-di-phosphate)로 이루어진 군으로부터 선택된 1종 이상을 사용하는 것이 보다 바람직하다. The organophosphorus flame retardant is considered to be used in combination with the aforementioned metal salt-free hypophosphite compound, triphenyl phosphate, resorcinol tetraphenyl-di-phosphate, bisphenol-A tetraphenoxy With bisphenol-A tetraphenoxy-di-phosphate, bisphenol-A tetracresyl-di-phosphate, resorcinol tetraxylyloxy-di-phosphate It is more preferable to use one or more selected from the group consisting of.
상기 비할로겐 난연수지 조성물은 일례로 비정질 난연수지에 대한 적하방지제로 사용되는 종류를 포함할 수 있고, 바람직하게는 불소계 폴리머를 사용할 수 있다. The non-halogen flame retardant resin composition may include, for example, a kind used as an antidropping agent for amorphous flame retardant resin, and preferably a fluorine-based polymer may be used.
상기 불소계 폴리머는 일례로 테프론, 폴리아마이드, 폴리실리콘, PTFE, TFE-HFP 공중합체 등일 수 있고, 혼련 및 분산의 효과를 고려할 때 입자크기 0.1~10 ㎛를 갖는 폴리머를 사용하는 것이 보다 바람직하다.The fluorine-based polymer may be, for example, Teflon, polyamide, polysilicon, PTFE, TFE-HFP copolymer, and the like, and in consideration of the effects of kneading and dispersion, it is more preferable to use a polymer having a particle size of 0.1 to 10 μm.
상기 불소계 폴리머는 일례로 블렌드 수지 100 중량부 기준으로 2 중량부 이하, 0.001 내지 1 중량부, 혹은 0.01 내지 1 중량부 범위로 포함할 수 있고, 이 범위에서 전술한 (B) 난연수지 첨가제의 적하방지 효과를 최적화할 수 있다.The fluorine-based polymer may include, for example, 2 parts by weight or less, 0.001 to 1 part by weight, or 0.01 to 1 part by weight based on 100 parts by weight of the blend resin, and the dropwise addition of the flame retardant additive (B) described above in this range. The prevention effect can be optimized.
상기 비할로겐 난연수지 조성물은 일례로 비정질 난연수지에 대한 용융지수 개선제로 사용되는 종류를 포함할 수 있고, 일례로 마그네슘 스테아레이트, 왁스 등의 활제를 사용할 수 있고, 바람직하게는 왁스이다.The non-halogen flame retardant resin composition may include, for example, a kind used as a melt index improver for an amorphous flame retardant resin, and for example, a lubricant such as magnesium stearate or wax may be used, and preferably a wax.
상기 왁스는 난연수지와 상용성이 좋고 고열시 극히 저점도의 화합물로서 일례로 수십 내지 수백 g/10분의 용융점도를 갖는 것으로, 일례로 파라핀 왁스, 폴리에틸렌 왁스 등을 사용할 수 있다. 상기 왁스는 적절한 양을 사용하면 난연수지 고유의 물성을 유지하며 비교적 낮은 비용으로 용융지수를 낮출 수 있다.The wax is a compound having good compatibility with the flame retardant resin and having an extremely low viscosity at high heat, for example, having a melt viscosity of several tens to several hundred g / 10 minutes. For example, paraffin wax, polyethylene wax, and the like can be used. When the wax is used in an appropriate amount, the intrinsic properties of the flame retardant resin can be maintained and the melt index can be lowered at a relatively low cost.
상기 활제는 일례로 블렌드 수지 100 중량부 기준으로 0.5 내지 5 중량부 포함될 수 있고, 이 범위 내에서 용융지수 개선 효과가 탁월하며 난연수지 고유의 물성은 유지할 수 있다.For example, the lubricant may be included in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the blend resin. Within this range, the melt index may be improved and the physical properties of the flame retardant may be maintained.
상기 비할로겐 난연수지 조성물은 열 안정제, UV 안정제, 메탈 스테아레이트 등의 활제, 가공조제, 안료, 착색제, 성형조제 및 충전제 중에서 선택된 1종 이상을 더 포함할 수 있다. The non-halogen flame retardant resin composition may further include one or more selected from lubricants such as heat stabilizers, UV stabilizers, metal stearates, processing aids, pigments, colorants, molding aids, and fillers.
그 사용량은 일례로, 블렌드 수지 100 중량부 기준으로 0.05 내지 5 중량부, 0.05 내지 1 중량부, 혹은 0.05 내지 0.8 중량부 범위로 포함할 수 있다. The amount used may be, for example, 0.05 to 5 parts by weight, 0.05 to 1 parts by weight, or 0.05 to 0.8 parts by weight based on 100 parts by weight of the blended resin.
본 발명의 비할로겐 난연수지 조성물을 용융압출한 시편의 경우 45°광택도값으로 본 표면광택도가 80 이상, 91 초과, 혹은 99 이상의 고광택성을 가질 수 있다. In the case of the melt-extruded specimen of the non-halogen flame-retardant resin composition of the present invention, the surface glossiness may have high glossiness of 80 or more, more than 91, or 99 or more with 45 ° gloss value.
상기 시편을 컬러 CIELAB으로 측정한 백색도(L값)이 75 이상, 84 이상, 혹은 84 내지 85의 개선된 백색도 물성을 가질 수 있다. The whiteness (L value) measured by the color CIELAB of the specimen may have an improved whiteness property of 75 or more, 84 or more, or 84 to 85.
상기 시편은 비할로겐 난연수지 조성물을 250~300 ℃의 가공온도에서 사출 성형하거나, 압출하여 펠릿을 제조한 후 사출성형 및 금형 공정을 통해 제조할 수 있다. The specimen may be manufactured by injection molding or extruding the non-halogen flame retardant resin composition at a processing temperature of 250 to 300 ° C., or by extruding to produce pellets.
상기 시편을 90 ℃ 오븐에서 100 시간 방치 후 헌터랩 칼라미터(hunter lab colormeter)로 측정한 b값이 증가한 것을 표현한 황변지수(△b)가 20 이하 또는 19 이하의 내황변성을 가질 수 있다. After leaving the specimen in an oven at 90 ° C. for 100 hours, a yellowing index (Δb) representing an increase in the b value measured by a hunter lab colormeter may have a yellowing resistance of 20 or less or 19 or less.
상기 비할로겐 난연수지 조성물은 일례로 난연도(UL-94, 2mm)가 V-0, V-1 또는 V-2일 수 있고, 이 범위 내에서 난연성이 우수하면서도 물성 밸런스가 뛰어난 효과가 있다.For example, the non-halogen flame retardant resin composition may have a flame retardancy (UL-94, 2 mm) of V-0, V-1, or V-2, and has excellent flame retardancy and excellent balance of physical properties within this range.
상기 비할로겐 난연수지 조성물은 일례로 ASTM D256에 의거하여 측정한 Izod 충격강도(1/4")가 10 kgfㆍm/m 이상, 12 kgfㆍm/m 이상, 또는 12 내지 20 kgfㆍm/m일 수 있고, 이 범위 내에서 충격강도가 우수하면서도 물성 밸런스가 뛰어난 효과가 있다.The non-halogen flame retardant resin composition has, for example, an Izod impact strength (1/4 ") of 10 kgf · m / m or more, 12 kgf · m / m or more, or 12 to 20 kgf · m /, measured according to ASTM D256. It may be m, there is an effect of excellent impact strength and excellent balance of properties within this range.
본 발명의 비할로겐 난연수지 조성물은 기계적 강도가 우수할 뿐 아니라 백색도와 광택이 매우 우수하므로 기존의 블렌딩 소재를 대체할 수 있을 것으로 기대된다. The non-halogen flame-retardant resin composition of the present invention is not only excellent in mechanical strength but also excellent in whiteness and luster, so it is expected to be able to replace existing blending materials.
이하 본 발명을 바람직한 실시예 및 비교예를 통해 설명한다. 그러나 하기의 실시예는 본 발명의 설명을 돕기 위해 편의상 소개되는 것일 뿐 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described through preferred examples and comparative examples. However, the following examples are merely introduced for convenience of description of the present invention, and the present invention is not limited to the following examples.
[실시예]EXAMPLE
<제조예><Production example>
이하 실험을 위하여 다음과 같은 성분들을 준비하였다:The following components were prepared for the following experiments:
1) SB: 폴리부타디엔 고무 55 중량%에 스티렌 모노머 45 중량%를 그라프트 중합한 다음 황산염 응집을 통해 분체로 준비하였다. 이때 유화제로는 탄소수 36, 불포화도 1의 올레산 다이머를 사용하였다.1) SB: Graft polymerization of 45% by weight of styrene monomer to 55% by weight of polybutadiene rubber was made into powder through sulfate aggregation. At this time, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
2) ABS(AN5%): 폴리부타디엔 고무 55 중량%에 스티렌 모노머 40 중량%와 아크릴로니트릴 5 중량%의 총 100 중량부에 대해 로진 솝(Rosin soap) 0.01 중량부를 투입하여 그라프트 중합한 다음 황산염 응집을 통해 분체로서 준비하였다. 이때 유화제로는 탄소수 36, 불포화도 1의 올레산 다이머를 사용하였다.2) ABS (AN5%): Graft polymerization was performed by adding 0.01 part by weight of rosin soap to 55 parts by weight of polybutadiene rubber and 40 parts by weight of styrene monomer and 5 parts by weight of acrylonitrile. Prepared as a powder via sulfate aggregation. At this time, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
3) ABS(AN12%): 폴리부타디엔 고무 55 중량%에 스티렌 모노머 33 중량%와 아크릴로니트릴 12 중량%의 총 100 중량부에 대해 로진 솝(Rosin soap) 0.01 중량부를 투입하여 그라프트 중합한 다음 황산염 응집을 통해 분체로서 준비하였다. 이때 유화제로는 탄소수 36, 불포화도 1의 올레산 다이머를 사용하였다.3) ABS (AN12%): Graft polymerization was performed by adding 55 parts by weight of polybutadiene rubber to 0.01 parts by weight of rosin soap based on 100 parts by weight of 33% by weight of styrene monomer and 12% by weight of acrylonitrile. Prepared as a powder via sulfate aggregation. At this time, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
4) ABS(AN25%): 폴리부타디엔 고무 55 중량%에 스티렌 모노머 20 중량%와 아크릴로니트릴 25 중량%의 총 100 중량부에 대해 로진 솝(Rosin soap) 0.01 중량부를 투입하여 그라프트 중합한 다음 황산염 응집을 통해 분체로서 준비하였다. 이때 유화제로는 탄소수 36, 불포화도 1의 올레산 다이머를 사용하였다.4) ABS (AN25%): Graft polymerization was performed by adding 55 parts by weight of polybutadiene rubber to 0.01 parts by weight of rosin soap based on 100 parts by weight of 20% by weight of styrene monomer and 25% by weight of acrylonitrile. Prepared as a powder via sulfate aggregation. At this time, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
5) 지방산 또는 이의 금속염 미포함 ABS(AN5%): 폴리부타디엔 고무 55 중량%에 스티렌 모노머 40 중량%와 아크릴로니트릴 5 중량%를 지방산 또는 이의 금속염의 투입없이 그라프트 중합한 다음 황산염 응집을 통해 분체로서 준비하였다. P2015-0552PCUS이때 유화제로는 탄소수 36, 불포화도 1의 올레산 다이머를 사용하였다.5) ABS (AN5%) without fatty acid or metal salt thereof: Graft polymerization of 40% by weight of styrene monomer and 5% by weight of acrylonitrile to 55% by weight of polybutadiene rubber without addition of fatty acid or metal salt thereof, followed by powdering through sulfate aggregation It was prepared as. In the case of P2015-0552PCUS, an oleic acid dimer having 36 carbon atoms and 1 degree of unsaturation was used as an emulsifier.
6) PS: 중량평균 분자량이 250,000 g/mol이고, 고무 함량이 0 중량%인 범용(general propose) 폴리스티렌 수지를 준비하였다. 6) PS: A general propose polystyrene resin having a weight average molecular weight of 250,000 g / mol and a rubber content of 0% by weight was prepared.
7) HIPS: 중량평균 분자량이 200,000 g/mol이고, 고무 함량이 8 중량%으로서 내충격성이 보강된 고충격(high impact) 폴리스티렌 수지를 준비하였다. 7) HIPS: A high impact polystyrene resin having a weight average molecular weight of 200,000 g / mol and a rubber content of 8% by weight was reinforced.
8) SAN: 스티렌 모노머 75 중량%와 아크릴로니트릴 모노머 25 중량%를 괴상 중합시켜 중합체를 준비하였다. 8) SAN: A polymer was prepared by bulk polymerization of 75% by weight of styrene monomer and 25% by weight of acrylonitrile monomer.
9) mPPO: 화학식 2를 갖고, 수평균 분자량이 24,000 g/mol인 페닐렌 옥사이드 공중합체를 준비하였다. 9) mPPO: A phenylene oxide copolymer having Formula 2 and having a number average molecular weight of 24,000 g / mol was prepared.
10) 난연1: 포스페이트 화합물: 비스페놀 에이 비스(다이페닐 포스페이트) (CAS No. 181028-79-5)10) Flame retardant 1: Phosphate compound: Bisphenol Abis (diphenyl phosphate) (CAS No. 181028-79-5)
11) 난연2: 금속염 프리 하이포포스파이트 화합물: 메틸 사이클로헥실포스피네이트11) Flame retardant 2: metal salt free hypophosphite compound: methyl cyclohexyl phosphinate
12) 난연3: 금속염 포함 하이포포스파이트 화합물: 차아인산 칼슘염 12) Flame retardant 3: Hypophosphite compound including metal salt: Calcium hypophosphite
13) 활제: 마그네슘 스테아레이트 (CAS No. 557-04-0)13) Glidants: Magnesium Stearate (CAS No. 557-04-0)
14) 안정제: 이가녹스 1010 (CAS No. 6683-19-8)14) Stabilizer: Iganox 1010 (CAS No. 6683-19-8)
15) 적하방지제: 불소계 화합물/테프론15) Anti-dripping agent: fluorine compound / teflon
<실시예 1-5, 비교예 1-9, 추가예 1 내지 4><Example 1-5, Comparative Example 1-9, Additional Examples 1-4>
하기 표 1, 2에 따라 각 성분들을 혼합하고 200 내지 250 ℃의 가공 온도 하에 압출 가공하여 펠렛을 제조하였다.Each component was mixed according to the following Tables 1 and 2 and extruded under a processing temperature of 200 to 250 ° C. to prepare pellets.
상기 압출로 제조된 펠렛으로 표면광택/충격강도용 ASTM 및 난연도용 UL 규격에 맞는 시편을 사출기를 통하여 250 내지 300 ℃의 가공 온도 하에 제조하였다. As a pellet prepared by the extrusion, a specimen meeting the ASTM standard for surface gloss / impact strength and the UL standard for flame retardancy was prepared at a processing temperature of 250 to 300 ° C. through an injection machine.
구분division 실시예Example 비교예Comparative example
1One 22 33 44 55 1One 22 33 44
1)SB(AN0%)1) SB (AN0%) 2525
2)ABS(AN5%)2) ABS (AN5%) 2525 2525 3030
3)ABS(AN12%)3) ABS (AN12%) 3030 2525
4)ABS(AN25%)4) ABS (AN25%) 2525 2525
5)금속염 미포함 ABS(AN5%)5) ABS without metal salt (AN5%)
6)PS6) PS 4040 4040 3535 4040 4444 4040 4040
7)HIPS7) HIPS 6565
8)SAN(AN25%)8) SAN (AN25%) 4040
9)mPPO9) mPPO 3535 3535 3535 3030 3131 3535 3535 3535 3535
10)난연110) Flame retardant 1 2222 2626 2222 2626 2525 2222 2222 2222 2222
11)난연211) Flame Retardant 2 22 22 1One 0.50.5 4.54.5 0.010.01
12)난연312) Flame retardant 3
13)활제13) lubricant 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
14)안정제14) Stabilizer 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
15)적하방지제15) anti-dripping agent 0.10.1 0.10.1 0.10.1 0.10.1 00 0.10.1 0.10.1 0.10.1 0.10.1
구분division 비교예Comparative example 추가예Additional example
55 66 77 88 99 1One 22 33 44
1)SB(AN0%)1) SB (AN0%)
2)ABS(AN5%)2) ABS (AN5%) 2525 55 55 2525
3)ABS(AN12%)3) ABS (AN12%) 2525 2525 2525
4)ABS(AN25%)4) ABS (AN25%) 2525 1010 1010
5)금속염 미포함 ABS(AN5%)5) ABS without metal salt (AN5%) 2525
6)PS6) PS 4040 4545 4545 6565 4040 4040 4040 4040
7)HIPS7) HIPS
8)SAN(AN25%)8) SAN (AN25%) 4040
9)mPPO9) mPPO 3535 3535 4040 4040 1010 3535 3535 3535 3535
10)난연110) Flame retardant 1 2222 2222 2222 1212 2222 2222 2222 5050 2222
11)난연211) Flame Retardant 2 66 22 22 1010 22
12)난연312) Flame retardant 3 22
13)활제13) lubricant 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
14)안정제14) Stabilizer 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5
15)적하방지제15) anti-dripping agent 0.10.1 0.10.1 0.10.1 0.10.1 0.10.1 0.10.1 0.10.1
<물성 테스트><Property test>
실시예 1 내지 5, 비교예 1 내지 9, 추가예 1 내지 4의 시편을 아래와 같은 방법으로 물성을 테스트하였다. The specimens of Examples 1 to 5, Comparative Examples 1 to 9 and Additional Examples 1 to 4 were tested for physical properties in the following manner.
* 표면 광택도(Gloss, 45°): 시편을 이용하여 표준측정 ASTM D523에 의거하여 45° 각도에서 측정하였다.* Surface glossiness (Gloss, 45 °): The specimen was measured at a 45 ° angle according to the standard measurement ASTM D523.
* 난연도: UL-94 수직법에 따라 2 mm 두께의 시편을 제작한 다음 난연 등급을 측정하였다. * Flame retardancy: 2 mm thick specimens were prepared according to the UL-94 vertical method and then flame retardant grades were measured.
* 충격강도(Notched Izod Impact Strength, kgfㆍm/m): 1/4"의 시편을 이용하여 표준측정 ASTM D256에 의거하여 측정하였다.* Notched Izod Impact Strength (kgf · m / m): Measured according to standard measurement ASTM D256 using a 1/4 "specimen.
* 백색도(수지 착색성): 두께 1/8 inch의 시편에 대하여 컬러 CIELAB 테스트를 수행하고 L값에 대한 색도를 측정하였다. * Whiteness (resin colorability): A color CIELAB test was performed on specimens 1/8 inch thick and the chromaticity for the L value was measured.
L값은 고유의 색상을 나타내는 좌표축의 값을 의미하며 L은 0에서 100의 값을 가질 수 있으며, 0에 가까울수록 검은색을 나타내고 100에 가까울수록 흰색을 나타낸다. L value means the value of the coordinate axis representing the unique color, L can have a value of 0 to 100, the closer to 0 is black and the closer to 100 is white.
* 황변지수(△b): 시편을 90 ℃ 오븐에서 100 시간 동안 방치하여 변색되는 정도를 hunter Lab값으로 측정하였다.* Yellowness index (△ b): The degree of discoloration by leaving the specimen in a 90 ℃ oven for 100 hours was measured by the Hunter Lab value.
상기 방법으로 테스트한 결과를 하기 표 3, 4로 정리하였다.The test results by the above method are summarized in Tables 3 and 4 below.
물성Properties 실시예Example 비교예Comparative example
1One 22 33 44 55 1One 22 33 44
광택도Glossiness 9999 9999 9999 9999 9999 7373 1111 7373 9595
난연Flame Retardant V-1V-1 V-0V-0 V-1V-1 V-1V-1 V-2V-2 V-1V-1 V-1V-1 NGNG NGNG
충격강도Impact strength 1717 1515 1818 1616 1212 1818 77 33 44
백색도(L값)Whiteness (L value) 8585 8484 8383 7777 8787 7272 6565 6363 7171
황변지수(?b)Yellowness Index (? B) 1616 1818 1919 1414 1313 1818 1414 1313 1414
물성Properties 비교예Comparative example 추가예Additional example
55 66 77 88 99 1One 22 33 44
광택도Glossiness 9191 7777 8282 8080 9999 9999 100100 100100 9999
난연Flame Retardant NGNG NGNG NGNG NGNG NGNG V-1V-1 V-1V-1 V-1V-1 V-1V-1
충격강도Impact strength 33 77 33 55 1111 2020 66 44 1616
백색도(L값)Whiteness (L value) 6565 6363 8282 8080 8888 6767 8686 8787 8181
황변지수(?b)Yellowness Index (? B) 1515 1717 1414 1414 1111 1010 2424 2525 2424
상기 표 3, 4에서 보듯이, 본 발명에 따른 블렌드 수지와 수지 첨가제로 된 비할로겐 난연수지 조성물을 이용하여 제조한 실시예 1 내지 5의 시편은 본 발명에서 벗어난 블렌드 수지 혹은 수지 첨가제로 된 비할로겐 난연수지 조성물을 이용하여 제조한 비교예 1 내지 9의 시편 대비, 광택도, 난연, 충격강도, 백색도의 모든 물성에서 우수한 성능을 나타내는 것을 확인할 수 있었다.As shown in Tables 3 and 4, the specimens of Examples 1 to 5 prepared using the non-halogen flame-retardant resin composition of the blend resin and the resin additive according to the present invention have a ratio of the blend resin or resin additive deviated from the present invention. Compared with the specimens of Comparative Examples 1 to 9 prepared using the halogen flame retardant resin composition, it was confirmed that excellent performance in all physical properties of gloss, flame retardancy, impact strength, whiteness.
또한, ABS 수지 제조시 지방산 또는 이의 금속염을 포함한 실시에 1 내지 5는 착색제를 포함하지 않았음에도 불구하고 황변지수가 20 이하로 내황변성이 우수하였지만, ABS 수지 제조시 금속염을 포함하지 않은 추가예 1은 황변지수가 열악해졌다.In addition, in the production of the ABS resin including fatty acids or metal salts thereof 1 to 5, although the yellowing index was excellent in yellowing resistance of 20 or less, even though it did not contain a coloring agent, additional example 1 containing no metal salt in the production of ABS resin The yellowing index was poor.
상술한 바와 같이, 본 발명에서는 비할로겐 난연 처방 하에 V-1급 이상 구현이 어렵거나, 광택과 백색도가 낮아 착색성이 불량하던 난연 수지의 문제점을 해결하고 우수한 난연, 백색도, 광택도 및 내황변성을 동시에 발현할 수 있으므로 기존의 블렌딩 소재를 효과적으로 대체할 수 있을 것으로 기대된다.As described above, in the present invention, it is difficult to implement V-1 or higher under the non-halogen flame retardant prescription, or it solves the problem of the flame retardant resin, which is poor in colorability due to low gloss and whiteness, and excellent flame retardancy, whiteness, gloss and yellowing resistance It can be expressed at the same time, it is expected to be able to effectively replace the existing blending material.

Claims (19)

  1. (A) 폴리아릴렌 에테르계 중합체, 스티렌계 중합체 및 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체를 포함하는 블렌드 수지, 및 (B) 비할로겐 난연제, 를 포함하는 비할로겐 난연수지 조성물로서, A non-halogen flame-retardant composition comprising (A) a polyarylene ether polymer, a styrene polymer and a blend resin comprising a vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer, and (B) a non-halogen flame retardant. ,
    상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 상기 공중합체의 전체 중량에 대해 상기 비닐시안 화합물이 1 중량% 이상 내지 25 중량% 미만으로 포함되고,The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer includes 1% by weight or more and less than 25% by weight of the vinyl cyan compound based on the total weight of the copolymer,
    상기 비할로겐 난연수지 조성물을 압사출하여 만든 시편을 광택도 45°값으로 본 표면 광택도(Gloss)가 80 이상이고, 상기 시편을 컬러 CIELAB으로 측정한 백색도(L값)이 75 이상인 것을 특징으로 하는 비할로겐 난연수지 조성물.The surface glossiness (Gloss) of the specimen produced by extruding the non-halogen flame-retardant resin composition at a glossiness of 45 ° is 80 or more, and the whiteness (L value) of the specimen measured by color CIELAB is 75 or more. Non-halogen flame-retardant resin composition.
  2. 제1항에 있어서, The method of claim 1,
    상기 폴리아릴렌 에테르계 중합체는 하기 [화학식 1] 또는 [화학식 2]로 표시되는 단위의 단독 중합체; 또는 하기 [화학식 1] 또는 [화학식 2]로 표시되는 단위를 포함하는 공중합체;인 것을 특징으로 하는 비할로겐 난연수지 조성물:The polyarylene ether polymer may be a homopolymer of a unit represented by the following [Formula 1] or [Formula 2]; Or a copolymer comprising a unit represented by the following [Formula 1] or [Formula 2]; a non-halogen flame-retardant resin composition, characterized in that:
    [화학식 1][Formula 1]
    Figure PCTKR2017011883-appb-I000003
    Figure PCTKR2017011883-appb-I000003
    [화학식 2][Formula 2]
    Figure PCTKR2017011883-appb-I000004
    Figure PCTKR2017011883-appb-I000004
    (상기 Ra, R1, R2, R3 및 R4는 아릴렌기(Ar) 또는 페닐렌기의 치환체로, 각각 독립적으로 또는 동시에 수소, 염소, 브롬, 요오드, 메틸, 에틸, 프로필, 알릴, 페닐, 메틸벤질, 클로로메틸, 브로모메틸, 시아노에틸, 시아노, 메톡시, 페녹시 또는 니트로기이며, 상기 n은 4 내지 20의 정수이고, Ar은 탄소수 7 내지 20의 아릴렌기이다.) (The R a , R 1 , R 2 , R 3 and R 4 are substituents of arylene group (Ar) or phenylene group, each independently or simultaneously hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, Phenyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, phenoxy or nitro group, n is an integer of 4 to 20, Ar is an arylene group having 7 to 20 carbon atoms. )
  3. 제1항에 있어서,The method of claim 1,
    상기 폴리아릴렌 에테르계 중합체는 중량평균 분자량이 5,000 내지 100,000 g/mol인 폴리페닐렌 에테르계 중합체인 것을 특징으로 하는 비할로겐 난연수지 조성물. The polyarylene ether polymer is a non-halogen flame-retardant resin composition, characterized in that the polyphenylene ether polymer having a weight average molecular weight of 5,000 to 100,000 g / mol.
  4. 제1항에 있어서,The method of claim 1,
    상기 스티렌계 중합체는 10,000 내지 300,000 g/mol의 중량평균 분자량과 93~100 중량%의 스티렌 함량을 갖는 폴리스티렌 수지인 것을 특징으로 하는 비할로겐 난연수지 조성물.The styrene polymer is a non-halogen flame-retardant resin composition, characterized in that the polystyrene resin having a weight average molecular weight of 10,000 to 300,000 g / mol and a styrene content of 93 to 100% by weight.
  5. 제1항에 있어서,The method of claim 1,
    상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 공액디엔계 고무질 중합체를 포함하는 시드; 및 상기 시드를 감싸고, 비닐방향족 화합물, 비닐시안 화합물 및, 지방산 또는 이의 금속염을 포함하여 중합된 쉘;을 포함하는 시드-쉘 구조의 그라프트 공중합체인 것을 특징으로 하는 비할로겐 난연수지 조성물.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer may include a seed comprising a conjugated diene rubber polymer; And a seed-shell structured graft copolymer comprising: a shell surrounding the seed, and a polymerized shell comprising a vinylaromatic compound, a vinylcyan compound, and a fatty acid or a metal salt thereof.
  6. 제5항에 있어서,The method of claim 5,
    상기 공액디엔계 고무질 중합체는 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 2-에틸-1,3-부타디엔, 1,3-펜타디엔 및 이소프렌으로 이루어진 군으로부터 선택된 1종 이상의 공액디엔계 화합물을 포함하여 중합된 것을 특징으로 하는 비할로겐 난연수지 조성물.The conjugated diene rubber polymer is one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene A non-halogen flame-retardant resin composition characterized by polymerizing including the conjugated diene-based compound.
  7. 제1항에 있어서,The method of claim 1,
    상기 비할로겐 난연수지 조성물은 황변지수(90 ℃, 100 시간) △b값이 20 이하인 것을 특징으로 하는 비할로겐 난연수지 조성물.The non-halogen flame-retardant resin composition is a non-halogen flame-retardant resin, characterized in that the yellowing index (90 ℃, 100 hours) Δb value of 20 or less.
  8. 제5항에 있어서,The method of claim 5,
    상기 공액디엔계 고무질 중합체, 비닐방향족 화합물 및 비닐시안 화합물 총 함량 100 중량%를 기준으로 상기 (a) 시드는 40 내지 60 중량%로 포함되고, 상기 (b) 쉘은 40 내지 60 중량%로 포함되고, 상기 (b) 쉘에 포함되는 비닐방향족 화합물과 비닐시안 화합물의 함량은 중량비로 90:10 내지 99:1로 포함된 것을 특징으로 하는 비할로겐 난연수지 조성물.The (a) seed may be included in an amount of 40 to 60% by weight, and the shell (b) may be included in an amount of 40 to 60% by weight based on 100% by weight of the total content of the conjugated diene-based rubbery polymer, vinylaromatic compound, and vinylcyan compound. , (B) The non-halogen flame-retardant resin composition, characterized in that the content of the vinyl aromatic compound and the vinyl cyan compound contained in the shell is contained in a weight ratio of 90:10 to 99: 1.
  9. 제5항에 있어서,The method of claim 5,
    상기 지방산 또는 이의 금속염은 사슬의 탄소수가 10 이상인 지방산, 지방산 금속염 또는 이들의 혼합물인 것을 특징으로 하는 비할로겐 난연수지 조성물.The fatty acid or metal salt thereof is a non-halogen flame-retardant resin composition, characterized in that the fatty acid having 10 or more carbon atoms in the chain, fatty acid metal salts or mixtures thereof.
  10. 제5항에 있어서,The method of claim 5,
    상기 지방산 또는 이의 금속염은 불포화도가 1 내지 20인 불포화 지방산 또는 이의 금속염을 포함하는 것을 특징으로 하는 비할로겐 난연수지 조성물.The fatty acid or a metal salt thereof is a non-halogen flame retardant resin composition, characterized in that it comprises an unsaturated fatty acid having a degree of unsaturation of 1 to 20 or a metal salt thereof.
  11. 제5항에 있어서,The method of claim 5,
    상기 지방산 또는 이의 금속염은 상기 공액디엔계 고무질 중합체, 방향족 비닐 화합물 및 비닐시안 화합물 총 함량 100 중량부를 기준으로 0.1 내지 3 중량부로 포함되는 것을 특징으로 하는 비할로겐 난연수지 조성물.The fatty acid or a metal salt thereof is non-halogen flame-retardant resin composition, characterized in that it comprises 0.1 to 3 parts by weight based on 100 parts by weight of the total content of the conjugated diene rubber polymer, aromatic vinyl compound and vinyl cyan compound.
  12. 제1항에 있어서,The method of claim 1,
    상기 블렌드 수지는 폴리아릴렌 에테르계 중합체 14 내지 64 중량%, 스티렌계 중합체 20 내지 70 중량%와 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 16 내지 40 중량%로 구성된 것을 특징으로 하는 비할로겐 난연수지 조성물. The blend resin is 14 to 64% by weight of polyarylene ether-based polymer, 20 to 70% by weight of styrene-based polymer and vinyl cyanide compound-conjugated diene compound-vinylaromatic compound copolymer, characterized in that the ratio consisting of Halogen flame retardant resin composition.
  13. 제1항에 있어서, The method of claim 1,
    상기 비할로겐 난연수지 조성물은 상기 블렌드 수지 100 중량부 기준으로, 포스핀 옥사이드를 포함하는 금속염 프리 하이포포스파이트 화합물을 0.1 내지 5 중량부로 포함하는 것을 특징으로 하는 비할로겐 난연수지 조성물. The non-halogen flame-retardant resin composition is a non-halogen flame-retardant resin composition comprising 0.1 to 5 parts by weight of a metal salt-free hypophosphite compound containing a phosphine oxide based on 100 parts by weight of the blend resin.
  14. 제1항에 있어서, The method of claim 1,
    상기 비할로겐 난연수지 조성물은 상기 블렌드 수지 100 중량부 기준으로, 탄소수 1 내지 20의 알킬 포스포네이트 에스테르, 탄소수 6 내지 30의 아릴 포스포네이트 에스테르, 및 탄소수 1 내지 10의 트리알킬 포스핀 중에서 선택된 1 이상의 유기인 난연제를 15 내지 40 중량부로 포함하는 것을 특징으로 하는 비할로겐 난연수지 조성물. The non-halogen flame retardant resin composition is selected from an alkyl phosphonate ester having 1 to 20 carbon atoms, an aryl phosphonate ester having 6 to 30 carbon atoms, and a trialkyl phosphine having 1 to 10 carbon atoms based on 100 parts by weight of the blend resin. Non-halogen flame-retardant resin composition comprising 15 to 40 parts by weight of one or more organic phosphorus flame retardant.
  15. 제1항에 있어서,The method of claim 1,
    상기 비할로겐 난연제는 금속염 프리 하이포포스파이트 화합물과 유기인 난연제를 포함하는 것을 특징으로 하는 비할로겐 난연수지 조성물.The non-halogen flame retardant is a non-halogen flame retardant resin composition comprising a metal salt free hypophosphite compound and an organic phosphorus flame retardant.
  16. 제15항에 있어서,The method of claim 15,
    상기 금속염 프리 하이포포스파이트 화합물은 하기 [화학식 4]로 표시되는 화합물인 것을 특징으로 하는 비할로겐 난연수지 조성물.The metal salt free hypophosphite compound is a non-halogen flame-retardant resin composition, characterized in that the compound represented by the following [Formula 4].
    [화학식 4][Formula 4]
    Figure PCTKR2017011883-appb-I000005
    Figure PCTKR2017011883-appb-I000005
    (상기 R1 및 R2는 각각 독립적으로 수소 원자, 알킬기, 싸이클로알케인, 알콕시, 아릴, 염소, 브롬, 요오드, 메틸벤질, 클로로메틸, 브로모메틸, 시아노에틸, 시아노, 페녹시 또는 니트로기이다.)R 1 and R 2 are each independently a hydrogen atom, an alkyl group, a cycloalkane, alkoxy, aryl, chlorine, bromine, iodine, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, phenoxy or Nitro group.)
  17. 제1항에 있어서,The method of claim 1,
    상기 비할로겐 난연수지 조성물은 상기 블렌드 수지 100 중량부 기준으로, 불소계 적하방지제를 2 중량부 이하로 포함하는 것을 특징으로 하는 비할로겐 난연수지 조성물.The non-halogen flame-retardant resin composition is a non-halogen flame-retardant resin composition, characterized in that containing less than 2 parts by weight of a fluorine-based anti-dropping agent based on 100 parts by weight of the blend resin.
  18. 제1항에 있어서,The method of claim 1,
    상기 비할로겐 난연수지 조성물은 상기 블렌드 수지 100 중량부 기준으로, 안정제, 활제, 가공조제, 안료, 착색제, 성형조제, 왁스 및 충전제 중에서 선택된 1종 이상을 0.5 내지 5 중량부로 포함하는 것을 특징으로 하는 비할로겐 난연수지 조성물.The non-halogen flame retardant resin composition is based on 100 parts by weight of the blend resin, characterized in that it comprises 0.5 to 5 parts by weight of at least one selected from stabilizers, lubricants, processing aids, pigments, colorants, molding aids, waxes and fillers. Non-halogen flame retardant resin composition.
  19. (A) 폴리아릴렌 에테르계 중합체 14 내지 64 중량%, 스티렌계 중합체 20 내지 70 중량% 및 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체 16 내지 40 중량%를 포함하는 블렌드 수지, 및 (B) 비할로겐 난연제, 를 포함하는 비할로겐 난연수지 조성물로서, (A) a blend resin comprising 14 to 64% by weight polyarylene ether polymer, 20 to 70% by weight styrene polymer and 16 to 40% by weight vinylcyan compound-conjugated diene compound-vinylaromatic compound copolymer, and ( B) A non-halogen flame-retardant composition comprising a non-halogen flame retardant,
    상기 비닐시안 화합물-공액디엔 화합물-비닐방향족 화합물 공중합체는 상기 공중합체의 전체 중량에 대해 상기 비닐시안 화합물이 1 중량% 이상 내지 25 중량% 미만으로 포함되는 것을 특징으로 하는 비할로겐 난연수지 조성물.The vinyl cyan compound-conjugated diene compound-vinylaromatic compound copolymer is a non-halogen flame-retardant resin composition, characterized in that the vinyl cyan compound is contained in more than 1% to 25% by weight based on the total weight of the copolymer.
PCT/KR2017/011883 2016-11-10 2017-10-26 Non-halogen flame-retardant resin composition WO2018088729A2 (en)

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