WO2018088729A2 - Composition de résine ignifuge non halogénée - Google Patents

Composition de résine ignifuge non halogénée Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
weight
compound
halogen flame
resin composition
retardant resin
Prior art date
Application number
PCT/KR2017/011883
Other languages
English (en)
Korean (ko)
Other versions
WO2018088729A3 (fr
Inventor
유제선
남기영
황용연
심재용
배선형
배재연
김인석
Original Assignee
(주) 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170107355A external-priority patent/KR102092131B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to EP17868566.5A priority Critical patent/EP3412726B1/fr
Priority to JP2018565282A priority patent/JP6854300B2/ja
Priority to CN201780036906.0A priority patent/CN109312152B/zh
Priority to US16/085,978 priority patent/US10836898B2/en
Publication of WO2018088729A2 publication Critical patent/WO2018088729A2/fr
Publication of WO2018088729A3 publication Critical patent/WO2018088729A3/fr

Links

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine ignifuge non halogénée et plus particulièrement, a pour effet de pourvoir à une composition de résine ignifuge non halogénée qui peut simultanément présenter une excellente ininflammabilité, blancheur, et brillance. La solution selon l'invention permet de résoudre les problèmes d'une composition de résine ignifuge qui a du mal à atteindre la qualité V-1 ou plus avec une formulation ignifuge non halogénée, ou qui présente une faible brillance et blancheur, ce qui constitue de mauvaises propriétés colorantes.
PCT/KR2017/011883 2016-11-10 2017-10-26 Composition de résine ignifuge non halogénée WO2018088729A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP17868566.5A EP3412726B1 (fr) 2016-11-10 2017-10-26 Composition de résine ignifuge non halogénée
JP2018565282A JP6854300B2 (ja) 2016-11-10 2017-10-26 非ハロゲン難燃樹脂組成物
CN201780036906.0A CN109312152B (zh) 2016-11-10 2017-10-26 非卤素阻燃树脂组合物
US16/085,978 US10836898B2 (en) 2016-11-10 2017-10-26 Non-halogen flame retardant resin composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2016-0149369 2016-11-10
KR20160149369 2016-11-10
KR10-2017-0107355 2017-08-24
KR1020170107355A KR102092131B1 (ko) 2016-11-10 2017-08-24 비할로겐 난연수지 조성물

Publications (2)

Publication Number Publication Date
WO2018088729A2 true WO2018088729A2 (fr) 2018-05-17
WO2018088729A3 WO2018088729A3 (fr) 2018-08-09

Family

ID=62109898

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/011883 WO2018088729A2 (fr) 2016-11-10 2017-10-26 Composition de résine ignifuge non halogénée

Country Status (1)

Country Link
WO (1) WO2018088729A2 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130132004A (ko) 2012-05-25 2013-12-04 주식회사 삼양사 기계적 특성이 우수한 비할로겐 난연화 폴리에스테르 수지 조성물 및 이의 성형품

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1182198C (zh) * 2002-01-15 2004-12-29 上海金发科技发展有限公司 一种反应型、环保阻燃高光聚苯醚复合物及其制备方法
KR100602850B1 (ko) * 2003-12-16 2006-07-19 제일모직주식회사 열가소성 난연성 수지 조성물
KR100694980B1 (ko) * 2005-12-13 2007-03-14 제일모직주식회사 비할로겐계 난연성 열가소성 수지 조성물
US8771561B2 (en) * 2010-05-07 2014-07-08 Basf Se Aminoguanidinephenylphosphinate flame retardant compositions
WO2012113145A1 (fr) * 2011-02-24 2012-08-30 Rhodia (China) Co., Ltd. Compositions polymères ignifuges comprenant des sels d'hypophosphite stabilisés
KR101473774B1 (ko) * 2013-05-06 2014-12-17 현대이피 주식회사 고충격 난연 폴리페닐렌 에테르계 열가소성 수지 조성물

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130132004A (ko) 2012-05-25 2013-12-04 주식회사 삼양사 기계적 특성이 우수한 비할로겐 난연화 폴리에스테르 수지 조성물 및 이의 성형품

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3412726A4

Also Published As

Publication number Publication date
WO2018088729A3 (fr) 2018-08-09

Similar Documents

Publication Publication Date Title
WO2018084558A2 (fr) Composition de résine thermoplastique, son procédé de fabrication, et produit moulé la comprenant
WO2011081287A2 (fr) Composition de résine thermoplastique comprenant un composé de phosphore polymérisé, une pièce moulée en plastique fabriquée de la composition, et procédé pour fabriquer un composé de phosphore polymérisé
WO2014035055A1 (fr) Copolymère greffé acrylonitrile-acrylate-styrène et composition de résine thermoplastique le comprenant
WO2017039157A1 (fr) Composition de résine thermoplastique et son procédé de préparation
KR100778010B1 (ko) 비할로겐계 난연성 스티렌계 수지 조성물
WO2017142172A1 (fr) Polymère de caoutchouc et procédé de préparation correspondant, copolymère greffé et composition de résine thermoplastique
JP4790804B2 (ja) 難燃性成形組成物
KR101664842B1 (ko) 난연성 열가소성 수지조성물
WO2019083153A1 (fr) Copolymère greffé, composition de résine thermoplastique le comprenant et procédé de préparation associé
WO2017082649A1 (fr) Composition de résine thermoplastique présentant d'excellentes caractéristiques de faible brillance, de résistance aux intempéries, et de propriétés mécaniques, et produit extrudé fabriqué à partir de celle-ci
WO2021020741A1 (fr) Composition de résine thermoplastique et article moulé formé à partir de celle-ci
WO2010067926A1 (fr) Nouveaux composés de phosphate, leur procédé de préparation, et compositions de résine thermoplastique ignifuges utilisant de tels composés
WO2019132575A1 (fr) Composition de résine thermoplastique et article moulé fabriqué à partir de celle-ci
WO2021201444A1 (fr) Composition de résine thermoplastique et article moulé formé à partir de celle-ci
KR102092131B1 (ko) 비할로겐 난연수지 조성물
WO2018088729A2 (fr) Composition de résine ignifuge non halogénée
WO2022124513A1 (fr) Composition de résine thermoplastique, procédé de production de celle-ci et produit moulé fabriqué à partir de celle-ci
WO2020138802A1 (fr) Composition de résine thermoplastique et article moulé produit à partir de celle-ci
WO2020111618A1 (fr) Composition de résine thermoplastique et article produit à partir de celle-ci
WO2018088677A1 (fr) Résine thermoplastique et composition de résine thermoplastique
WO2022025409A1 (fr) Composition de résine thermoplastique et article moulé formé à partir de celle-ci
WO2019132572A1 (fr) Composition de résine thermoplastique et article moulé fabriqué avec celle-ci
WO2019194620A1 (fr) Composition de résine thermoplastique
WO2020149504A1 (fr) Composition de résine thermoplastique, procédé de préparation associé et produit moulé la comprenant
WO2016043424A1 (fr) Composition de résine thermoplastique et article moulé en résine thermoplastique préparé à partir de celle-ci

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2017868566

Country of ref document: EP

ENP Entry into the national phase in:

Ref document number: 2017868566

Country of ref document: EP

Effective date: 20180905

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17868566

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase in:

Ref document number: 2018565282

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase in:

Ref country code: DE