WO2019151776A1 - Preparation method of graft copolymer, graft copolymer, and thermoplastic resin molded article - Google Patents

Preparation method of graft copolymer, graft copolymer, and thermoplastic resin molded article Download PDF

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WO2019151776A1
WO2019151776A1 PCT/KR2019/001304 KR2019001304W WO2019151776A1 WO 2019151776 A1 WO2019151776 A1 WO 2019151776A1 KR 2019001304 W KR2019001304 W KR 2019001304W WO 2019151776 A1 WO2019151776 A1 WO 2019151776A1
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weight
parts
graft copolymer
conjugated diene
polymer
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PCT/KR2019/001304
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French (fr)
Korean (ko)
Inventor
김종범
채주병
정유성
김창술
박은선
전태영
김영민
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주식회사 엘지화학
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Priority claimed from KR1020190011180A external-priority patent/KR102111120B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201980002501.4A priority Critical patent/CN110662780B/en
Priority to EP19747015.6A priority patent/EP3613783B1/en
Priority to US16/631,812 priority patent/US11104789B2/en
Publication of WO2019151776A1 publication Critical patent/WO2019151776A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
    • C08C1/065—Increasing the size of dispersed rubber particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/02—Alkylation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • 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
    • C08K5/01—Hydrocarbons
    • 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
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/24—Polymer with special particle form or size

Definitions

  • the present invention relates to a graft copolymer manufacturing method, a graft copolymer and a thermoplastic resin molded article, and more particularly to a graft copolymer capable of producing a molded article with improved surface properties and improved plating and coating properties. It is to provide a production method, graft copolymer and a thermoplastic resin molded article.
  • a method of controlling the content of acrylonitrile may be used to improve plating properties.
  • a method of improving the graft ratio or including a high gel content butadiene rubbery polymer is also used.
  • the method of introducing the small particle size butadiene rubbery polymer with a small average particle diameter during a graft reaction can also be used.
  • the method of using the small particle butadiene rubbery polymer can improve the adhesion to the plating, the increase of the content of the small particle butadiene rubbery polymer reduces the impact strength of the graft copolymer, and the graft ratio is lowered to reduce the fluidity. May occur.
  • the present invention includes the step of polymerizing a first conjugated diene polymer, a second conjugated diene polymer, an aromatic vinyl monomer and a vinyl cyan monomer, wherein the first conjugated diene polymer Distribution is 0.346 to 0.404, the second conjugated diene-based polymer provides a method for producing a graft copolymer having a particle size distribution of 0.196 to 0.304.
  • the present invention also provides a graft copolymer prepared by the above-described production method, having a graft ratio of at least 37%, and having a weight average molecular weight of the shell of at least 75,000 g / mol.
  • the present invention is a graft copolymer described above; And a copolymer comprising an aromatic vinyl monomer-derived unit and a vinyl cyan monomer-derived unit, and a thermoplastic resin molded article having a residual amount of volatile organic compound of 1,000 ppm or less.
  • the manufacturing method of the graft copolymer of the present invention it is possible to produce a molded article having excellent surface properties and improved plating and coating properties.
  • the manufacturing method of the graft copolymer of the present invention it is possible to produce a molded article excellent in both fluidity and mechanical properties, and minimized the residual amount of volatile organic compounds.
  • FIG. 1 is a graph showing a particle size distribution of a large particle butadiene rubbery polymer of Preparation Example 3.
  • Figure 2 is a graph showing the particle size distribution of the large particle butadiene rubber polymer of Preparation Example 8.
  • the average particle diameter and particle size distribution of the particles of the conjugated diene-based polymer may be measured using dynamic light scattering, and in detail, may be measured using a Nicomp 380 device (product name, manufacturer: PSS). Can be.
  • Average particle diameter or "Dv” as used in this specification means the arithmetic mean particle diameter in particle size distribution measured by the dynamic light scattering method.
  • the arithmetic mean particle size may be an intensity distribution mean particle size.
  • 90% particle size means the particle size (D 90 ) at the 90% position when the particle size is measured from 0 (minimum) to 100% (maximum) in order from the smaller one in the particle size distribution measured by the above measuring method. .
  • 50% particle size means the particle size (D 50 ) in which the larger and smaller ones become equivalent when the powder is divided into two from the particle size in the particle size distribution measured by the above measuring method.
  • “10% particle size” means the particle size (D 10 ) at the 10% position when the particle size distribution measured by the above-mentioned method is taken from 0 (minimum) to 100% (maximum) in order from the smaller one of the particle size. .
  • the measurement method by the dynamic light scattering method and the calculation method of the particle size distribution can be measured by a method well known in the art, and the particle size distribution in the present invention can also be calculated by the following equation (1).
  • Particle size distribution (PSD) [D 90 -D 10 ] / D 50
  • D 90 , D 50 and D 10 are as described above.
  • the gel content of the conjugated diene-based polymer latex coagulated with methanol washed, dried in a vacuum oven at 60 °C for 24 hours, and then obtained by cutting the lump (sample) obtained by scissors and then taking 1 g Toluene was added to 100 g of toluene and stored in a dark room at room temperature for 48 hours, and then separated into sol and gel.
  • the gel content can be measured by the following formula.
  • the graft rate is 2 g of the graft copolymer powder into 300 ml of acetone and stirred for 24 hours, the solution is added to an ultracentrifuge, the supernatant is separated, and the supernatant is dropped into methanol to be grafted. The unoccupied portion was obtained and dried at 85 ° C. to obtain a dried product. After the weight was measured, the graft ratio can be calculated by the following equation.
  • the weight average molecular weight of the shell of the graft copolymer is dried in a hot air oven at 50 °C of the supernatant obtained in the graft rate measuring method, the dried product in THF to prepare a solution (concentration: 0.1% by weight), It can be hung through a 0.1 ⁇ m filter and finally measured using a GPC.
  • the residual amount of volatile organic compounds can be measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
  • the polymerization may be any one selected from the group consisting of suspension polymerization, emulsion polymerization and bulk polymerization, of which emulsion polymerization is preferred.
  • the aromatic vinyl monomer derived unit may be a unit derived from an aromatic vinyl monomer.
  • the aromatic vinyl monomer may be at least one selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene, of which styrene is preferred.
  • the vinyl cyan-based monomer-derived unit may be a unit derived from the vinyl cyan-based monomer.
  • the vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile, of which acrylonitrile is preferable.
  • the conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, and 1,3-butadiene is preferable.
  • Method for producing a graft copolymer comprises the step of polymerizing a first conjugated diene polymer, a second conjugated diene polymer, an aromatic vinyl monomer and a vinyl cyan monomer, the first The conjugated diene polymer has a particle size distribution of 0.346 to 0.404, and the second conjugated diene polymer has a particle size distribution of 0.196 to 0.304.
  • the first conjugated diene-based polymer has a particle size distribution of 0.346 to 0.404, preferably 0.35 to 0.4. If the above conditions are satisfied, the coagulum in the first conjugated diene-based polymer is minimized.
  • a graft copolymer that implements excellent surface properties and impact strength may be prepared. If the particle size distribution is less than the above-mentioned range, the impact strength is lowered. If the particle size distribution exceeds the above-mentioned range, excessive surface projections occur.
  • the first conjugated diene polymer has an average particle diameter of 0.2 to 0.4 ⁇ m, 0.25 to 0.35 ⁇ m, or 0.3 to 0.33 ⁇ m, of which 0.3 to 0.33 ⁇ m is preferable. If the above conditions are satisfied, the coagulum in the first conjugated diene-based polymer can be minimized, and the impact strength and fluidity can be improved.
  • Particles included in the first conjugated diene-based polymer may have a standard deviation of 0.3 to 0.4 or 0.33 to 0.38, of which 0.33 to 0.38 are preferred. If the above conditions are satisfied, the first conjugated diene-based polymer includes particles having relatively various particle diameters, thereby making it possible to prepare a graft copolymer having excellent surface properties and impact strength.
  • the second conjugated diene-based polymer has a particle size distribution of 0.196 to 0.304, preferably 0.2 to 0.3. If the above conditions are satisfied, the graft copolymer can realize excellent impact strength and tensile strength. If the above range is not satisfied, the impact strength of the graft copolymer may decrease.
  • the second conjugated diene-based polymer has an average particle diameter of 0.2 to 0.4 ⁇ m, 0.25 to 0.35 ⁇ m, or 0.28 to 0.30 ⁇ m, of which 0.28 to 0.30 ⁇ m is preferable. If the above range is satisfied, the mechanical properties and fluidity of the graft copolymer may be further improved.
  • Particles included in the second conjugated diene-based polymer may have a standard deviation of 0.2 to 0.29 or 0.24 to 0.26, of which 0.24 to 0.26 is preferable.
  • the second conjugated diene-based polymer includes particles having a uniform particle size, thereby preparing a graft copolymer having excellent impact strength.
  • the first conjugated diene-based polymer and the second conjugated diene-based polymer are each prepared by 1) a method of polymerizing a conjugated diene monomer without performing an enlargement or 2) a small particle conjugated diene system by polymerizing a conjugated diene monomer After the polymer is prepared, the small particle conjugated diene polymer may be prepared by enlarging the polymer.
  • the average particle diameter of the small particle conjugated diene-based polymer may be 0.05 to 0.15 ⁇ m or 0.08 to 0.12 ⁇ m, of which 0.08 to 0.12 ⁇ m is preferred. If the above conditions are satisfied, it may be easy to prepare the first and second conjugated diene-based polymers.
  • the gel content of the small particle conjugated diene-based polymer may be 90% or more, 90% to 95% or 90% to 94%, of which 92% to 94% is preferred. If the above conditions are satisfied, excellent impact strength can be realized.
  • the preparation of the first and second conjugated diene-based polymers may be carried out over one or more steps, and the enlargement may be performed by adding a flocculant to the small particle conjugated diene-based polymer.
  • the flocculant may be acetic acid or phosphoric acid.
  • the flocculant may be added in an amount of 2.75 to 3.75 parts by weight or 3 to 3.5 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer, and 3 to 3.5 parts by weight of the flocculant. It is desirable to. When the above range is satisfied, a conjugated diene polymer that satisfies the particle size distribution and the average particle size of the first conjugated diene polymer can be prepared.
  • the weight ratio of the flocculant added at the time may be 85:15 to 95: 5 or 87:13 to 93: 7, of which 87:13 to 93: 7 is preferable.
  • the weight ratio of the flocculant added during primary and secondary enlargement is 65:35 to 80:20 or 70:30 to 75:25, of which 70:30 to 75:25 are preferred. If the above-mentioned range is satisfied, fluidity can be improved and excellent impact strength can be realized.
  • the flocculant may be added in an amount of 2 to 2.73 parts by weight or 2.5 to 2.7 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer when preparing the second conjugated diene polymer, and 2.5 to 2.7 parts by weight. It is preferable to add in a negative amount.
  • a conjugated diene polymer that satisfies the particle size distribution and the average particle size of the second conjugated diene polymer can be produced.
  • the weight ratio of the flocculant added at the time may be 90:10 to 99: 1 or 93: 7 to 97: 3, of which 93: 7 to 97: 3 is preferable.
  • the weight ratio of the flocculant added during the primary and secondary enlargement is 85:15 to 95: 5 or 87:13 to 93: 7, of which 87:13 to 93: 7 are preferred. If the above-mentioned range is satisfied, fluidity can be improved and excellent impact strength can be realized.
  • the second conjugated diene-based polymer when the second conjugated diene-based polymer is prepared by the method 1), it can be prepared by a known method, in order to satisfy the above-described particle size distribution and average particle size, the content of the emulsifier or electrolyte in the known method Can be adjusted appropriately.
  • the emulsifier may be one or more selected from the group consisting of alkali rosin acid metal salts, fatty acid alkali metal salts and fatty acid dimer alkali metal salts, of which fatty acid dimer alkali metal salts are preferred.
  • the rosin acid alkali metal salt may be one or more selected from the group consisting of potassium rosin acid salt and sodium rosin acid salt, and potassium rosin acid salt is preferable.
  • the fatty acid alkali metal salt may be a C 8 to C 20 fatty acid alkali metal salt, alkali metal salt of capric acid, alkali metal salt of lauric acid, alkali metal salt of palmitic acid, alkali metal salt of stearic acid, alkali metal salt and oleic acid and linol
  • alkali metal salts of leinic acid are more preferable.
  • the fatty acid dimer alkali metal salt may be a C 8 to C 20 fatty acid dimer alkali metal salt, preferably a C 8 to C 20 fatty acid dimer potassium salt, and more preferably an oleic acid dimer potassium salt.
  • the emulsifier may be added to 0.3 to 3.0 parts by weight or 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the conjugated diene monomer, of which 0.5 to 2.5 parts by weight is preferably added.
  • the polymerization stability is excellent and the polymerization conversion rate can be increased.
  • the electrolyte is KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 and Na 2 HPO 4 It may be at least one selected from the group consisting of, of which at least one selected from the group consisting of K 2 CO 3 and Na 2 CO 3 is preferred.
  • the electrolyte may be added in an amount of 0.1 to 1 part by weight or 0.2 to 0.5 part by weight based on 100 parts by weight of the conjugated diene-based monomer, of which 0.2 to 0.5 part by weight is preferable.
  • the polymerization stability is excellent and the polymerization conversion rate can be increased.
  • the weight ratio of the first conjugated diene-based polymer and the second conjugated diene-based polymer is 30:70 to 80:20, 50:50 to 80:20, 60:40 to 75:25 or 65:35 to 70:30 It may be, of which 65:35 to 70:30 is preferred.
  • the formation of protrusions on the surface may be minimized to manufacture a molded article having excellent surface characteristics, and thus, a molded article having excellent coating or plating characteristics may be manufactured.
  • the graft ratio is high, the graft copolymer with improved impact strength and fluidity can be prepared.
  • the total sum of the first conjugated diene-based polymer and the second conjugated diene-based polymer is 50 to 50, based on the total weight of the first conjugated diene-based polymer, the second conjugated diene-based polymer, an aromatic vinyl monomer, and a vinyl cyan monomer. It may be 65% by weight or 55 to 60% by weight, preferably 55 to 60% by weight. When the above-mentioned range is satisfied, it is possible to minimize the generation of coagulum during polymerization, and the impact strength of the graft copolymer may be further improved.
  • the first conjugated diene-based polymer and the second conjugated diene-based polymer may be in the form of latex dispersed in water in a colloidal state, and may be first introduced into a reactor before the polymerization starts.
  • the total sum of the aromatic vinyl monomer and the vinyl cyan monomer may be 35 to 50 wt%, based on the total weight of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. 40 to 45% by weight, of which 40 to 45% by weight is preferred. If the above range is satisfied, the chemical resistance, stiffness, impact strength, processability and surface gloss of the graft copolymer may be further improved.
  • the weight ratio of the aromatic vinyl monomer and the vinyl cyan monomer may be 80:20 to 65:35 or 75:25 to 70:30, of which 75:25 to 70:30 is preferable.
  • the polymerization conversion rate is increased, and the polymerization stability and the latex stability can be further improved.
  • the aromatic vinyl monomer and the vinyl cyan monomer may be emulsion-polymerized while continuously introduced at a constant rate into a reactor in which the first and second conjugated diene polymers are present.
  • the reaction heat generated during the polymerization may be dispersed.
  • At least one selected from the group consisting of a molecular weight regulator, an initiator, an emulsifier, a redox catalyst, and water may be further added to the reactor.
  • the molecular weight modifier may include a large reactive vinyl dimer having a high reactivity, a high decomposition rate mercaptan compound and a low reactivity rate, that is, a low decomposition rate.
  • the mercaptan compound may be at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan and octyl mercaptan, and t-dodecyl mercaptan is preferred.
  • the aromatic vinyl-based dimer may be at least one selected from the group consisting of ⁇ -methyl styrene dimer, ethyl styrene dimer and propyl styrene dimer, of which ⁇ -methyl styrene dimer is preferable.
  • the molecular weight modifier may be 0.30 to 0.50 parts by weight or 0.35 to 0.45 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Of these, 0.35 to 0.45 parts by weight is preferable. If the above-mentioned range is satisfied, the weight average molecular weight of the shell can be properly maintained to further improve the impact strength of the graft copolymer.
  • the mercaptan compound and the aromatic vinyl dimer may be added in a weight ratio of 60:40 to 70:30 or 65:35 to 70:30, and of the mercaptan compounds and 65:35 to 70:30. .
  • the mercaptan compound and the aromatic vinyl-based dimer can adjust the graft ratio of the graft copolymer to increase the falling ball impact strength and the notched Izod impact strength.
  • the initiators include potassium persulfate, sodium photosulphate, ammonium persulfate, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramentane hydroperoxide and benzoyl per At least one selected from the group consisting of oxides, and at least one selected from the group consisting of t-butyl hydroperoxide is preferred.
  • the initiator may be added in an amount of 0.5 to 0.8 parts by weight, or 0.6 to 0.7 parts by weight based on 100 parts by weight of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Among them, it is preferable to add 0.6 to 0.7 parts by weight. When the above range is satisfied, the latex stability is excellent and the emulsion polymerization is easily performed, while the residual amount in the graft copolymer can be minimized.
  • the emulsifier may be at least one selected from the group consisting of C 1 to C 20 mono carboxylic acid salts, C 12 to C 18 succinate metal salts, sulfonic acid metal salts and rosin acid alkali metal salts.
  • the mono carboxylate may be a C 8 to C 20 fatty acid soap.
  • the C 12 to C 18 succinate metal salt may be a C 12 to C 18 alkenyl succinate dipotassium salt.
  • the sulfonic acid metal salt may be at least one selected from the group consisting of sodium dodecyl sulfate, sodium lauric sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate. have.
  • the rosin acid alkali metal salt may be at least one selected from the group consisting of potassium rosin salt and sodium rosin salt.
  • an alkali metal rosin salt is preferable, and potassium rosin salt is more preferable.
  • the emulsifier may be added in an amount of 0.5 to 1.2 parts by weight, or 0.8 to 1.0 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Among them, it is preferable to add 0.8 to 1.0 parts by weight. If the above range is satisfied, while the emulsion polymerization is easily performed, the residual amount in the graft copolymer can be minimized.
  • the redox catalyst may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate and sodium sulfate.
  • ferrous sulfate, dextrose and sodium pyrophosphate are preferably one or more selected from the group consisting of.
  • the redox catalyst is 0.1 to 0.5 parts by weight, or 0.3 to 0.4 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyan monomer. It may be added, of which 0.3 to 0.4 parts by weight is preferably added. If the above range is satisfied, there is an advantage that the polymerization conversion rate is increased.
  • the water may be ion exchanged water.
  • At least one selected from the group consisting of the molecular weight regulator, the initiator, the emulsifier, the redox catalyst and the water is present in the reactor in which the first and second conjugated diene polymers are present together with the aromatic vinyl monomer and the vinyl cyan monomer. It can be fed continuously at a constant speed. When continuously added, the heat of reaction may be dispersed during polymerization, and thus, heat removal may be facilitated.
  • the graft copolymer prepared by the above-described manufacturing method has a graft ratio of at least 37%, and the weight average molecular weight of the shell is 75,000 g / mol or more, preferably 75,000 to 110,000 g / mol. If the above-mentioned range is satisfied, the surface characteristics may be excellent, and plating and painting characteristics may be further improved.
  • Thermoplastic resin composition according to another embodiment of the present invention is a graft copolymer prepared by the manufacturing method according to an embodiment of the present invention; And a copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit.
  • the copolymer may impart heat resistance, rigidity, and processability to the thermoplastic resin composition.
  • the copolymer may include the aromatic vinyl monomer derived unit and the vinyl cyan monomer derived unit in a weight ratio of 85:15 to 70:30 or 80:20 to 75:25, among which 80:20 to 75: It is preferable to include in the weight ratio of 25. If the above-mentioned range is satisfied, the thermoplastic resin composition can better realize the balance of heat resistance, impact strength and processability.
  • the copolymer may have a weight average molecular weight of 100,000 to 150,000 g / mol or 120,000 to 140,000 g / mol, of which 120,000 to 140,000 g / mol is preferred. When the above range is satisfied, the impact strength of the thermoplastic resin composition may be further improved.
  • the weight average molecular weight may be measured as a relative value for a standard polystyrene (PS) sample through GPC using THF (tetrahydrofuran) as an eluent.
  • PS polystyrene
  • THF tetrahydrofuran
  • the copolymer may be prepared by one or more methods selected from the group consisting of emulsion polymerization, suspension polymerization, and bulk polymerization, and preferably, the copolymer is prepared by bulk polymerization.
  • the weight ratio of the graft copolymer and the copolymer may be 20:80 to 35:65 or 25:75 to 30:70, of which 25:75 to 30:70 is preferable. If the above range is satisfied, the chemical resistance, impact strength, thermal stability, colorability, fatigue resistance, rigidity and workability of the molded article manufactured from the thermoplastic resin composition may be further improved.
  • thermoplastic resin molded article produced from the thermoplastic resin composition described above has a residual amount of volatile organic compound of 1,000 ppm or less. If the conditions mentioned above are satisfied, the molded article excellent in odor characteristic can be provided.
  • the residual amount of the volatile organic compound can be measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
  • aqueous acetic acid solution containing 2.4 parts by weight of acetic acid (concentration: 7% by weight) was stirred at 30 ° C. at a speed of 10 rpm for 1 hour. After continuous feeding at a constant rate, the mixture was stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.6 parts by weight was continuously added at a constant rate for 10 minutes, followed by secondary enlargement with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer A-1. .
  • the large particle size butadiene rubber polymer A-1 had a particle size distribution of 0.34 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.3 parts by weight was continuously added at a constant rate for 10 minutes, and then secondary enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer A-2.
  • the large particle size butadiene rubber polymer A-2 had a particle size distribution of 0.35 and an average particle diameter of 0.3 ⁇ m.
  • the large particle size butadiene rubbery polymer latex A-3 has a wide particle size distribution.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 1.05 parts by weight was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-4. It was.
  • the large-diameter butadiene rubbery polymer latex A-4 had a particle size distribution of 0.4 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing 0.4 parts by weight of acetic acid was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged while stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-5. It was.
  • the large particle butadiene rubber polymer latex A-5 had a particle size distribution of 0.41 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.25 parts by weight was continuously added at a constant rate for 10 minutes, followed by secondary enlargement with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-6. It was.
  • the large particle size butadiene rubbery polymer latex A-6 had a particle size distribution of 0.19 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing 0.125 parts by weight of acetic acid was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-7. It was.
  • the large particle size butadiene rubber polymer latex A-7 had a particle size distribution of 0.2 and an average particle diameter of 0.3 ⁇ m.
  • ion-exchanged water 100 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 1.5 parts by weight of potassium rosin salt as emulsifier, 0.3 parts by weight of Na 2 CO 3 as electrolyte, t-dodecylmer as molecular weight regulator 0.03 part by weight of captan and 0.5 part by weight of potassium persulfate were added as a batch, the temperature was raised to 50 ° C, and polymerization was started. When the polymerization conversion rate was about 35%, 0.7 parts by weight of potassium rosin salt, 0.5 parts by weight of potassium persulfate and 30 parts by weight of 1,3-butadiene were collectively added as an emulsifier to carry out polymerization.
  • the large-diameter butadiene rubbery polymer latex A-8 has a narrow particle size distribution.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.3 parts by weight was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-9. It was.
  • the large-diameter butadiene rubbery polymer latex A-9 had a particle size distribution of 0.3 and an average particle diameter of 0.3 ⁇ m.
  • aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.35 parts by weight was continuously added at a constant rate for 10 minutes, and then secondary enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-10. It was.
  • the large particle butadiene rubber polymer latex A-10 had a particle size distribution of 0.31 and an average particle diameter of 0.3 ⁇ m.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition ⁇ Production of the thermoplastic resin composition>
  • thermoplastic resin composition C-1 was prepared by mixing 30 parts by weight of the graft copolymer powder B-1 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • thermoplastic resin composition C-3 was prepared by mixing 30 parts by weight of the graft copolymer powder B-3 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-4 30 parts by weight of the graft copolymer powder B-4 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-4.
  • butadiene rubbery polymer latex A-3 40 parts by weight instead of 24 parts by weight (based on solids) of butadiene rubbery polymer latex Graft copolymer powder B-5 was prepared in the same manner as in Example 1 except for the addition.
  • thermoplastic resin composition C-5 was prepared by mixing 30 parts by weight of the graft copolymer powder B-5 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-6 30 parts by weight of the graft copolymer powder B-6 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-6.
  • Graft copolymer powder B-7 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-2 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-7 30 parts by weight of the graft copolymer powder B-7 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical Co., Ltd. were mixed to prepare a thermoplastic resin composition C-7.
  • Graft copolymer powder B-8 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-4 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-8 was prepared by mixing 30 parts by weight of the graft copolymer powder B-8 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-9 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-7 was added instead of the large particle butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-9 was prepared by mixing 30 parts by weight of the graft copolymer powder B-9 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-10 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-9 was added instead of the large particle butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-10 was prepared by mixing 30 parts by weight of the graft copolymer powder B-10 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-11 was prepared in the same manner as in 1.
  • thermoplastic resin composition C-11 was prepared by mixing 30 parts by weight of the graft copolymer powder B-11 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-12 was prepared in the same manner as in Example 1, except that 20 parts by weight of butadiene rubbery polymer latex A-9 (based on solids) was added instead.
  • thermoplastic resin composition C-12 was prepared by mixing 30 parts by weight of the graft copolymer powder B-12 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition was prepared by mixing 30 parts by weight of the graft copolymer powder B-13 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-14 was prepared by mixing 30 parts by weight of the graft copolymer powder B-14 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-15 was prepared by mixing 30 parts by weight of the graft copolymer powder B-15 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
  • thermoplastic resin composition C-16 was prepared by mixing 30 parts by weight of the graft copolymer powder B-16 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-17 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-1 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-17 30 parts by weight of the graft copolymer powder B-17 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-17.
  • Graft copolymer powder B-18 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-5 was added instead of the large particle butadiene rubber polymer latex A-3.
  • thermoplastic resin composition C-18 was prepared by mixing 30 parts by weight of the graft copolymer powder B-18 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Graft copolymer powder B-19 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-6 was added instead of the large particle butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-19 30 parts by weight of the graft copolymer powder B-19 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-19.
  • Graft copolymer powder B-20 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-10 was added instead of butadiene rubber polymer latex A-8.
  • thermoplastic resin composition C-20 was prepared by mixing 30 parts by weight of the graft copolymer powder B-20 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
  • Polymerization Conversion Rate (%) [Total Solids Content (TSC) ⁇ (parts of monomers and subsidiary materials added) / 100]-(parts of subsidiary materials added to the monomer)
  • Graft rate (%) [(content of grafted SAN copolymer) / (sum of content of large particle butadiene rubbery polymer)] ⁇ 100
  • thermoplastic resin composition of the Example and the comparative example was put into the twin screw extruder set to 210 degreeC, and extruded, and the pellet was manufactured.
  • the physical properties of the pellets were measured in the following manner, and the results are shown in the following [Table 2] to [Table 5].
  • Residual amount of volatile organic compounds (ppm): The residual amount of volatile organic compounds was measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
  • the pellet prepared in Experimental Example 1 was injected to prepare a specimen, and the physical properties thereof were measured in the following manner, and the results are shown in the following [Table 2] to [Table 5].
  • the graft copolymers of Examples 1 to 12 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.35 to 0.4 and a large particle butadiene rubber polymer having a particle size distribution of 0.2 to 0.4 have a graft ratio of 37. It was confirmed that it was% or more and the weight average molecular weight of the shell was 75,000 g / mol or more.
  • the weight average molecular weight of the shell is 65,000 g / mol or less, and when the graft ratio is less than 37%, the weight average molecular weight is 75,000 g / mol or more.
  • the thermoplastic resin compositions of Examples 1 to 12 had a small amount of residual volatile organic compounds, so that the odor characteristics were excellent, and the number of surface protrusions was small, indicating that the surface characteristics were excellent. It was found that the falling ball impact strength and notched Izod impact strength were also excellent in mechanical properties.
  • Examples 1, 7 and 8 have a significantly lower residual amount of volatile organic compounds than Comparative Example 6 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.41 and a large particle butadiene rubber polymer having a particle size distribution of 0.23, and having a surface protrusion.
  • the number was remarkably small, and the fall impact strength and the notched Izod impact strength were excellent.
  • Examples 1, 9, and 10 had a significantly lower residual amount of volatile organic compounds compared to Comparative Example 8 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.37 and a large particle butadiene rubber polymer having a particle size distribution of 0.31.
  • the number of protrusions was remarkably small, and it was confirmed that the falling ball impact strength and the notched Izod impact strength were excellent.
  • Comparative Examples 1 to 4 made of only one type of large-diameter butadiene rubbery polymer, the amount of residual volatile organic compounds compared to the examples is not good because the odor characteristics are not good, and the number of surface projections is large, the surface properties are not good It could not be confirmed that falling ball impact strength and impact strength were reduced.

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Abstract

The present invention relates to a preparation method of a graft copolymer, a graft copolymer, and a thermoplastic resin molded article. The preparation method comprises a step of polymerizing a first conjugated diene-based polymer, a second conjugated diene-based polymer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer, wherein the first conjugated diene-based polymer has a particle size distribution between 0.346 and 0.404, and the second conjugated diene-based polymer has a particle size distribution between 0.196 and 0.304.

Description

그라프트 공중합체의 제조방법, 그라프트 공중합체 및 열가소성 수지 성형품Manufacturing method of graft copolymer, graft copolymer and thermoplastic resin molded article
[관련출원과의 상호인용][Citations with Related Applications]
본 발명은 2018.02.02에 출원된 한국 특허 출원 제10-2018-0013592호 및 2019.01.29에 출원된 한국 특허 출원 제10-2019-0011180호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용을 본 명세서의 일부로서 포함한다.The present invention claims the benefit of priority based on Korean Patent Application No. 10-2018-0013592 filed on Feb. 2, 2018 and Korean Patent Application No. 10-2019-0011180 filed on Jan. 29, 2019, All content disclosed in the literature is included as part of this specification.
[기술분야][Technical Field]
본 발명은 그라프트 공중합체의 제조방법, 그라프트 공중합체 및 열가소성 수지 성형품에 관한 것으로서, 보다 상세하게는 표면특성이 개선되어 도금 및 도장 특성이 개선된 성형품을 제조할 수 있는 그라프트 공중합체의 제조방법, 그라프트 공중합체 및 열가소성 수지 성형품을 제공하는 것이다.The present invention relates to a graft copolymer manufacturing method, a graft copolymer and a thermoplastic resin molded article, and more particularly to a graft copolymer capable of producing a molded article with improved surface properties and improved plating and coating properties. It is to provide a production method, graft copolymer and a thermoplastic resin molded article.
일반적으로 도금용 소재로 이용하는 ABS 그라프트 공중합체의 경우 도금 특성을 향상하기 위하여, 아크릴로니트릴의 함량을 조절하는 방법을 이용할 수 있다. 그리고, 도금 식각 시 앵커 홀(anchor hole)의 형상을 유지하기 위하여, 그라프트율을 향상시키거나, 겔 함량이 높은 부타디엔 고무질 중합체를 포함하는 방법도 이용한다. 그리고, 앵커 홀의 개수를 증가시켜 밀착성을 개선하기 위하여, 평균입경이 작은 소입경 부타디엔 고무질 중합체를 그라프트 반응 중에 도입하는 방법도 이용할 수 있다.In general, in the case of an ABS graft copolymer used as a plating material, a method of controlling the content of acrylonitrile may be used to improve plating properties. In addition, in order to maintain the shape of the anchor hole during the plating etching, a method of improving the graft ratio or including a high gel content butadiene rubbery polymer is also used. And in order to improve the adhesiveness by increasing the number of anchor holes, the method of introducing the small particle size butadiene rubbery polymer with a small average particle diameter during a graft reaction can also be used.
소입경 부타디엔 고무질 중합체를 이용하는 방법은 도금 밀착력을 향상시킬 수는 있지만, 소입경 부타디엔 고무질 중합체의 함량의 증가로 인해 그라프트 공중합체의 충격강도가 저하되고, 그라프트율이 저하되어 유동성이 저하되는 문제점이 발생할 수 있다.Although the method of using the small particle butadiene rubbery polymer can improve the adhesion to the plating, the increase of the content of the small particle butadiene rubbery polymer reduces the impact strength of the graft copolymer, and the graft ratio is lowered to reduce the fluidity. May occur.
그라프트율을 높이기 위하여 평균입경이 큰 대입경 부타디엔 고무질 중합체를 이용할 경우, 충격강도는 개선될 수 있으나 표면특성 및 유동성이 저하되어 도금 특성이 저하되는 문제가 발생할 수 있다.In order to increase the graft rate, when the large average butadiene rubbery polymer having a large average particle size is used, impact strength may be improved, but surface characteristics and fluidity may be degraded, thereby causing a problem of deterioration of plating characteristics.
본 발명의 목적은 표면특성이 개선되어 도금 및 도장 특성이 개선된 성형품을 제조할 수 있는 그라프트 공중합체의 제조방법을 제공하는 것이다.It is an object of the present invention to provide a method for producing a graft copolymer which can produce molded articles having improved surface properties and improved plating and coating properties.
또한, 본 발명의 목적은 그라프트율이 높으면서, 유동성 및 기계적 특성이 모두 우수하고, 휘발성 유기 화합물(Volatile Organic Compounds)의 잔류량이 최소화된 성형품을 제조할 수 있는 그라프트 공중합체의 제조방법을 제공하는 것이다.It is also an object of the present invention to provide a method for producing a graft copolymer having a high graft ratio, excellent fluidity and mechanical properties, and capable of producing a molded article having a minimum amount of volatile organic compounds. .
상기 과제를 해결하기 위하여, 본 발명은 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체를 중합하는 단계를 포함하며, 상기 제1 공액 디엔계 중합체는 입도분포가 0.346 내지 0.404이고, 상기 제2 공액 디엔계 중합체는 입도분포가 0.196 내지 0.304인 그라프트 공중합체의 제조방법을 제공한다.In order to solve the above problems, the present invention includes the step of polymerizing a first conjugated diene polymer, a second conjugated diene polymer, an aromatic vinyl monomer and a vinyl cyan monomer, wherein the first conjugated diene polymer Distribution is 0.346 to 0.404, the second conjugated diene-based polymer provides a method for producing a graft copolymer having a particle size distribution of 0.196 to 0.304.
또한, 본 발명은 상술한 제조방법으로 제조되고, 그라프트율이 37% 이상이고, 쉘의 중량평균분자량이 75,000 g/mol 이상인 그라프트 공중합체를 제공한다.The present invention also provides a graft copolymer prepared by the above-described production method, having a graft ratio of at least 37%, and having a weight average molecular weight of the shell of at least 75,000 g / mol.
또한, 본 발명은 상술한 그라프트 공중합체; 및 방향족 비닐계 단량체 유래 단위 및 비닐 시안계 단량체 유래 단위를 포함하는 공중합체를 포함하는 열가소성 수지 조성물로 제조되고, 휘발성 유기 화합물의 잔류량이 1,000 ppm 이하인 열가소성 수지 성형품을 제공한다.In addition, the present invention is a graft copolymer described above; And a copolymer comprising an aromatic vinyl monomer-derived unit and a vinyl cyan monomer-derived unit, and a thermoplastic resin molded article having a residual amount of volatile organic compound of 1,000 ppm or less.
본 발명의 그라프트 공중합체의 제조방법에 따르면, 표면 특성이 우수하여 도금 및 도장 특성이 개선된 성형품을 제조할 수 있다.According to the manufacturing method of the graft copolymer of the present invention, it is possible to produce a molded article having excellent surface properties and improved plating and coating properties.
또한, 본 발명의 그라프트 공중합체의 제조방법에 따르면, 유동성 및 기계적 특성이 모두 우수하고, 휘발성 유기 화합물의 잔류량이 최소화된 성형품을 제조할 수 있다.In addition, according to the manufacturing method of the graft copolymer of the present invention, it is possible to produce a molded article excellent in both fluidity and mechanical properties, and minimized the residual amount of volatile organic compounds.
도 1은 제조예 3의 대입경 부타디엔 고무질 중합체의 입도분포를 나타낸 그래프이다.1 is a graph showing a particle size distribution of a large particle butadiene rubbery polymer of Preparation Example 3. FIG.
도 2는 제조예 8의 대입경 부타디엔 고무질 중합체의 입도분포를 나타낸 그래프이다.Figure 2 is a graph showing the particle size distribution of the large particle butadiene rubber polymer of Preparation Example 8.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in this specification and claims are not to be construed as being limited to their ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.
본 발명에서 공액 디엔계 중합체의 입자의 평균입경과 입도분포는 동적 광산란(dynamic light scattering)법을 이용하여 측정할 수 있고, 상세하게는 Nicomp 380 장비(제품명, 제조사: PSS)를 이용하여 측정할 수 있다.In the present invention, the average particle diameter and particle size distribution of the particles of the conjugated diene-based polymer may be measured using dynamic light scattering, and in detail, may be measured using a Nicomp 380 device (product name, manufacturer: PSS). Can be.
본 명세서에서 말하는 「평균입경」또는 「Dv」란 동적 광산란법에 의해 측정되는 입도분포에 있어서의 산술 평균입경을 의미한다. 산술 평균입경은 산란강도(Intensity Distribution) 평균입경일 수 있다."Average particle diameter" or "Dv" as used in this specification means the arithmetic mean particle diameter in particle size distribution measured by the dynamic light scattering method. The arithmetic mean particle size may be an intensity distribution mean particle size.
「90% 입경」은 상기 측정법으로 측정되는 입도분포에 있어서 입경이 작은 쪽으로부터 순서대로 0(최소)~100%(최대)까지 셌을 때의 90% 위치에 있는 입경(D90)을 의미한다. "90% particle size" means the particle size (D 90 ) at the 90% position when the particle size is measured from 0 (minimum) to 100% (maximum) in order from the smaller one in the particle size distribution measured by the above measuring method. .
「50% 입경」은 상기 측정법으로 측정되는 입도 분포에 있어서 분체를 어느 입경으로부터 2개로 나누었을 때 큰 쪽과 작은 쪽이 등량으로 되는 입경(D50)을 의미한다. "50% particle size" means the particle size (D 50 ) in which the larger and smaller ones become equivalent when the powder is divided into two from the particle size in the particle size distribution measured by the above measuring method.
「10% 입경」은 상기 측정법으로 측정되는 입도분포에 있어서 입경의 작은 쪽으로부터 순서대로 0(최소)~100%(최대)까지 셌을 때의 10% 위치에 있는 입경(D10)을 의미한다. "10% particle size" means the particle size (D 10 ) at the 10% position when the particle size distribution measured by the above-mentioned method is taken from 0 (minimum) to 100% (maximum) in order from the smaller one of the particle size. .
동적 광산란법에 의한 측정 방법, 및 입도분포의 산출 방법에 대해서는 그 기술분야에 있어서 널리 알려진 방법으로 측정할 수 있고, 본 발명에서 입도분포는 하기 수학식 1에 의해 산출할 수도 있다.The measurement method by the dynamic light scattering method and the calculation method of the particle size distribution can be measured by a method well known in the art, and the particle size distribution in the present invention can also be calculated by the following equation (1).
[수학식 1][Equation 1]
입도분포(PSD)= [D90-D10]/D50 Particle size distribution (PSD) = [D 90 -D 10 ] / D 50
상기 수학식 1에서,In Equation 1,
D90, D50, D10의 정의는 상술한 바와 같다.The definitions of D 90 , D 50 and D 10 are as described above.
본 발명에서, 겔 함량은 공액 디엔계 중합체 라텍스를 메탄올을 사용하여 응고한 후 세척하여 60 ℃의 진공 오븐에서 24 시간 동안 건조한 후 수득된 덩어리(시료)를 가위로 잘게 자른 후 1 g을 취한 후, 톨루엔 100 g에 넣고 48 시간 동안 실온의 암실에서 보관 후 졸과 겔로 분리하고 다음 식으로 겔 함량을 측정할 수 있다.In the present invention, the gel content of the conjugated diene-based polymer latex coagulated with methanol, washed, dried in a vacuum oven at 60 ℃ for 24 hours, and then obtained by cutting the lump (sample) obtained by scissors and then taking 1 g Toluene was added to 100 g of toluene and stored in a dark room at room temperature for 48 hours, and then separated into sol and gel. The gel content can be measured by the following formula.
겔 함량(%) = [겔의 무게 / 시료의 무게] × 100Gel content (%) = [gel weight / sample weight] × 100
본 발명에서, 그라프트율은 그라프트 공중합체 분말 2 g을 아세톤 300 ㎖에 넣고 24 시간 동안 교반하고, 이 용액을 초원심분리기에 투입한 후, 상등액을 분리하고, 상등액에 메탄올에 떨어뜨려 그라프트되지 않은 부분을 수득하고, 이를 85 ℃에서 건조시켜 건조물을 수득한 후, 무게를 측정한 뒤, 다음 식으로 그라프트율을 산출할 수 있다.In the present invention, the graft rate is 2 g of the graft copolymer powder into 300 ml of acetone and stirred for 24 hours, the solution is added to an ultracentrifuge, the supernatant is separated, and the supernatant is dropped into methanol to be grafted. The unoccupied portion was obtained and dried at 85 ° C. to obtain a dried product. After the weight was measured, the graft ratio can be calculated by the following equation.
그라프트율(%) =Graft Rate (%) =
[(그라프트된 방향족 비닐계 단량체 및 비닐 시안계 단량체의 공중합체의 함량) / (제1 및 제2 공액 디엔계 중합체의 함량의 합)] × 100[(Content of copolymer of grafted aromatic vinyl monomer and vinyl cyan monomer) / (sum of contents of first and second conjugated diene polymer)] × 100
* 그라프트된 방향족 비닐계 단량체 및 비닐 시안계 단량체의 공중합체의 함량 = (수득된 건조물의 함량) - (제1 및 제2 공액 디엔계 중합체의 함량의 합)* Content of copolymer of grafted aromatic vinyl monomer and vinyl cyan monomer = (content of dry matter obtained)-(sum of contents of first and second conjugated diene polymer)
* 제1 및 제2 공액 디엔계 중합체의 함량의 합: 이론상 투입된 제1 및 제2 공액 디엔계 중합체의 고형분 함량의 합* Sum of contents of the first and second conjugated diene polymers: The sum of the solids contents of the first and second conjugated diene polymers theoretically added
본 발명에서, 그라프트 공중합체의 쉘의 중량평균분자량은 그라프트율 측정 방법에서 수득된 상등액을 50 ℃의 열풍 오븐에 건조한 후, 건조물을 THF에 녹여 용액(농도: 0.1 중량%)을 제조하고, 이를 0.1 ㎛ 필터를 통해 걸려낸 뒤 최종적으로 GPC를 이용하여 측정할 수 있다.In the present invention, the weight average molecular weight of the shell of the graft copolymer is dried in a hot air oven at 50 ℃ of the supernatant obtained in the graft rate measuring method, the dried product in THF to prepare a solution (concentration: 0.1% by weight), It can be hung through a 0.1 μm filter and finally measured using a GPC.
본 발명에서, 휘발성 유기 화합물의 잔류량은 가스 크로마토그라피 설비(상품명: GC, 제조사: Agilent)를 이용하여 측정할 수 있다.In the present invention, the residual amount of volatile organic compounds can be measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
본 발명에서, 중합은 현탁중합, 유화중합 및 괴상중합으로 이루어진 군에서 선택되는 어느 하나일 수 있고, 이 중 유화중합이 바람직하다.In the present invention, the polymerization may be any one selected from the group consisting of suspension polymerization, emulsion polymerization and bulk polymerization, of which emulsion polymerization is preferred.
본 발명에서, 방향족 비닐계 단량체 유래 단위는 방향족 비닐계 단량체로부터 유래된 단위일 수 있다. 상기 방향족 비닐계 단량체는 스티렌, α-메틸 스티렌, α-에틸 스티렌 및 p-메틸 스티렌으로 이루어진 군으로부터 선택되는 1종 이상일 수 있고, 이 중 스티렌이 바람직하다.In the present invention, the aromatic vinyl monomer derived unit may be a unit derived from an aromatic vinyl monomer. The aromatic vinyl monomer may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, of which styrene is preferred.
본 발명에서, 비닐 시안계 단량체 유래 단위는 비닐 시안계 단량체로부터 유래된 단위일 수 있다. 상기 비닐 시안계 단량체는 아크릴로니트릴, 메타크릴로니트릴, 페닐아크릴로니트릴 및 α-클로로아크릴로니트릴로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 아크릴로니트릴이 바람직하다.In the present invention, the vinyl cyan-based monomer-derived unit may be a unit derived from the vinyl cyan-based monomer. The vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and α-chloroacrylonitrile, of which acrylonitrile is preferable.
본 발명에서, 공액 디엔계 단량체는 1,3-부타디엔, 이소프렌, 클로로프렌 및 피퍼릴렌으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 이 중 1,3-부타디엔이 바람직하다.In the present invention, the conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, and 1,3-butadiene is preferable.
1. One. 그라프트Graft 공중합체의 제조방법 Method of Preparation of Copolymer
본 발명의 일실시예에 따른 그라프트 공중합체의 제조방법은 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체를 중합하는 단계를 포함하며, 상기 제1 공액 디엔계 중합체는 입도분포가 0.346 내지 0.404이고, 상기 제2 공액 디엔계 중합체는 입도분포가 0.196 내지 0.304이다.Method for producing a graft copolymer according to an embodiment of the present invention comprises the step of polymerizing a first conjugated diene polymer, a second conjugated diene polymer, an aromatic vinyl monomer and a vinyl cyan monomer, the first The conjugated diene polymer has a particle size distribution of 0.346 to 0.404, and the second conjugated diene polymer has a particle size distribution of 0.196 to 0.304.
상기 제1 공액 디엔계 중합체는 입도분포가 0.346 내지 0.404이고, 바람직하게는 0.35 내지 0.4이다. 상술한 조건을 만족하면, 제1 공액 디엔계 중합체 내 응고물이 최소화된다. 그리고, 우수한 표면 특성 및 충격강도를 구현하는 그라프트 공중합체를 제조할 수 있다. 입도분포가 상술한 범위 미만이면, 충격강도가 저하되고, 입도분포가 상술한 범위를 초과하면, 표면 돌기가 과도하게 발생한다.The first conjugated diene-based polymer has a particle size distribution of 0.346 to 0.404, preferably 0.35 to 0.4. If the above conditions are satisfied, the coagulum in the first conjugated diene-based polymer is minimized. In addition, a graft copolymer that implements excellent surface properties and impact strength may be prepared. If the particle size distribution is less than the above-mentioned range, the impact strength is lowered. If the particle size distribution exceeds the above-mentioned range, excessive surface projections occur.
상기 제1 공액 디엔계 중합체는 평균입경이 0.2 내지 0.4 ㎛, 0.25 내지 0.35 ㎛ 또는 0.3 내지 0.33 ㎛이고, 이 중 0.3 내지 0.33 ㎛가 바람직하다. 상술한 조건을 만족하면, 제1 공액 디엔계 중합체 내 응고물이 최소화되고, 충격강도 및 유동성이 개선될 수 있다.The first conjugated diene polymer has an average particle diameter of 0.2 to 0.4 µm, 0.25 to 0.35 µm, or 0.3 to 0.33 µm, of which 0.3 to 0.33 µm is preferable. If the above conditions are satisfied, the coagulum in the first conjugated diene-based polymer can be minimized, and the impact strength and fluidity can be improved.
상기 제1 공액 디엔계 중합체에 포함된 입자들은 표준편차가 0.3 내지 0.4 또는 0.33 내지 0.38일 수 있고, 이 중 0.33 내지 0.38이 바람직하다. 상술한 조건을 만족하면, 상기 제1 공액 디엔계 중합체가 비교적 다양한 입경을 가지는 입자들을 포함하므로, 표면특성 및 충격강도가 우수한 그라프트 공중합체를 제조할 수 있다.Particles included in the first conjugated diene-based polymer may have a standard deviation of 0.3 to 0.4 or 0.33 to 0.38, of which 0.33 to 0.38 are preferred. If the above conditions are satisfied, the first conjugated diene-based polymer includes particles having relatively various particle diameters, thereby making it possible to prepare a graft copolymer having excellent surface properties and impact strength.
한편, 상기 제2 공액 디엔계 중합체는 입도분포가 0.196 내지 0.304이고, 바람직하게는 0.2 내지 0.3이다. 상술한 조건을 만족하면, 그라프트 공중합체가 우수한 충격강도 및 인장강도를 구현할 수 있다. 상술한 범위를 만족하지 못하면, 그라프트 공중합체의 충격강도가 저하될 수 있다.On the other hand, the second conjugated diene-based polymer has a particle size distribution of 0.196 to 0.304, preferably 0.2 to 0.3. If the above conditions are satisfied, the graft copolymer can realize excellent impact strength and tensile strength. If the above range is not satisfied, the impact strength of the graft copolymer may decrease.
상기 제2 공액 디엔계 중합체는 평균입경이 0.2 내지 0.4 ㎛, 0.25 내지 0.35 ㎛ 또는 0.28 내지 0.30 ㎛이고, 이 중 0.28 내지 0.30 ㎛가 바람직하다. 상술한 범위를 만족하면, 그라프트 공중합체의 기계적 특성 및 유동성이 보다 개선될 수 있다.The second conjugated diene-based polymer has an average particle diameter of 0.2 to 0.4 µm, 0.25 to 0.35 µm, or 0.28 to 0.30 µm, of which 0.28 to 0.30 µm is preferable. If the above range is satisfied, the mechanical properties and fluidity of the graft copolymer may be further improved.
상기 제2 공액 디엔계 중합체에 포함된 입자들은 표준편차가 0.2 내지 0.29 또는 0.24 내지 0.26 일 수 있고, 이 중 0.24 내지 0.26 이 바람직하다. 상술한 조건을 만족하면, 상기 제2 공액 디엔계 중합체가 균일한 입경을 가지는 입자들을 포함하므로, 충격강도가 우수한 그라프트 공중합체를 제조할 수 있다.Particles included in the second conjugated diene-based polymer may have a standard deviation of 0.2 to 0.29 or 0.24 to 0.26, of which 0.24 to 0.26 is preferable. When the above conditions are satisfied, the second conjugated diene-based polymer includes particles having a uniform particle size, thereby preparing a graft copolymer having excellent impact strength.
한편, 상기 제1 공액 디엔계 중합체 및 제2 공액 디엔계 중합체는 각각 1) 공액 디엔계 단량체를 중합하여 비대화를 수행하지 않고 제조하는 방법 또는 2) 공액 디엔계 단량체를 중합하여 소입경 공액 디엔계 중합체를 제조한 후, 상기 소입경 공액 디엔계 중합체를 비대화하여 제조하는 방법으로 제조될 수 있다. On the other hand, the first conjugated diene-based polymer and the second conjugated diene-based polymer are each prepared by 1) a method of polymerizing a conjugated diene monomer without performing an enlargement or 2) a small particle conjugated diene system by polymerizing a conjugated diene monomer After the polymer is prepared, the small particle conjugated diene polymer may be prepared by enlarging the polymer.
상기 2) 단계에서, 상기 소입경 공액 디엔계 중합체의 평균입경은 0.05 내지 0.15 ㎛ 또는 0.08 내지 0.12 ㎛일 수 있고, 이 중 0.08 내지 0.12 ㎛가 바람직하다. 상술한 조건을 만족하면, 상기 제1 및 제2 공액 디엔계 중합체를 제조하기 용이할 수 있다.In step 2), the average particle diameter of the small particle conjugated diene-based polymer may be 0.05 to 0.15 ㎛ or 0.08 to 0.12 ㎛, of which 0.08 to 0.12 ㎛ is preferred. If the above conditions are satisfied, it may be easy to prepare the first and second conjugated diene-based polymers.
상기 소입경 공액 디엔계 중합체의 겔 함량은 90 % 이상, 90 % 내지 95 % 또는 90 % 내지 94 %일 수 있고, 이 중 92 % 내지 94 %인 것이 바람직하다. 상술한 조건을 만족하면, 우수한 충격강도를 구현할 수 있다.The gel content of the small particle conjugated diene-based polymer may be 90% or more, 90% to 95% or 90% to 94%, of which 92% to 94% is preferred. If the above conditions are satisfied, excellent impact strength can be realized.
한편, 상기 제1 및 제2 공액 디엔계 중합체의 제조 시 비대화는 1차 이상에 걸쳐 수행될 수 있고, 상기 비대화는 상기 소입경 공액 디엔계 중합체에 응집제를 투입함으로써 수행될 수 있다. 상기 응집제는 아세트산 또는 인산일 수 있다.Meanwhile, the preparation of the first and second conjugated diene-based polymers may be carried out over one or more steps, and the enlargement may be performed by adding a flocculant to the small particle conjugated diene-based polymer. The flocculant may be acetic acid or phosphoric acid.
상기 제1 공액 디엔계 중합체의 제조 시 상기 응집제는 상기 소입경 공액 디엔계 중합체 100 중량부에 대하여, 2.75 내지 3.75 중량부 또는 3 내지 3.5 중량부로 투입할 수 있고, 이 중 3 내지 3.5 중량부로 투입하는 것이 바람직하다. 상술한 범위를 만족하면, 제1 공액 디엔계 중합체의 입도분포 및 평균입경을 만족하는 공액 디엔계 중합체를 제조할 수 있다.In the preparation of the first conjugated diene polymer, the flocculant may be added in an amount of 2.75 to 3.75 parts by weight or 3 to 3.5 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer, and 3 to 3.5 parts by weight of the flocculant. It is desirable to. When the above range is satisfied, a conjugated diene polymer that satisfies the particle size distribution and the average particle size of the first conjugated diene polymer can be prepared.
상기 제1 공액 디엔계 중합체의 제조 시 상기 비대화가 2차에 걸쳐 수행될 경우, 상기 응집제의 총 투입량이 상기 소입경 공액 디엔계 중합체 100 중량부에 대하여 3 중량부일 때, 1차 및 2차 비대화 시 투입되는 응집제의 중량비가 85:15 내지 95:5 또는 87:13 내지 93:7일 수 있고, 이 중 87:13 내지 93:7이 바람직하다. 또한, 상기 응집제의 총 투입량이 상기 소입경 공액 디엔계 중합체 100 중량부에 대하여 3.5 중량부일 때, 1차 및 2차 비대화 시 투입되는 응집제의 중량비가 65:35 내지 80:20 또는 70:30 내지 75:25일 수 있고, 이 중 70:30 내지 75:25이 바람직하다. 상술한 범위를 만족하면, 유동성을 개선시킬 수 있고, 우수한 충격강도를 구현할 수 있다.When the enlargement is carried out in the second step in the production of the first conjugated diene polymer, when the total amount of the flocculant is 3 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer, primary and secondary enlargement The weight ratio of the flocculant added at the time may be 85:15 to 95: 5 or 87:13 to 93: 7, of which 87:13 to 93: 7 is preferable. In addition, when the total amount of the flocculant is 3.5 parts by weight based on 100 parts by weight of the small particle conjugated diene-based polymer, the weight ratio of the flocculant added during primary and secondary enlargement is 65:35 to 80:20 or 70:30 to 75:25, of which 70:30 to 75:25 are preferred. If the above-mentioned range is satisfied, fluidity can be improved and excellent impact strength can be realized.
한편, 상기 제2 공액 디엔계 중합체의 제조 시 상기 응집제는 상기 소입경 공액 디엔계 중합체 100 중량부에 대하여, 2 내지 2.73 중량부 또는 2.5 내지 2.7 중량부로 투입할 수 있고, 이 중 2.5 내지 2.7 중량부로 투입하는 것이 바람직하다. 상술한 범위를 만족하면, 제2 공액 디엔계 중합체의 입도분포 및 평균입경을 만족하는 공액 디엔계 중합체를 제조할 수 있다.Meanwhile, the flocculant may be added in an amount of 2 to 2.73 parts by weight or 2.5 to 2.7 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer when preparing the second conjugated diene polymer, and 2.5 to 2.7 parts by weight. It is preferable to add in a negative amount. When the above range is satisfied, a conjugated diene polymer that satisfies the particle size distribution and the average particle size of the second conjugated diene polymer can be produced.
상기 제2 공액 디엔계 중합체의 제조 시 상기 비대화가 2차에 걸쳐 수행될 경우, 상기 응집제의 총 투입량이 상기 소입경 공액 디엔계 중합체 100 중량부에 대하여 2.5 중량부일 때, 1차 및 2차 비대화 시 투입되는 응집제의 중량비가 90:10 내지 99:1 또는 93:7 내지 97:3일 수 있고, 이 중 93:7 내지 97:3이 바람직하다. 또한, 상기 응집제의 총 투입량이 상기 소입경 공액 디엔계 중합체 100 중량부에 대하여 2.7 중량부일 때, 1차 및 2차 비대화 시 투입되는 응집제의 중량비가 85:15 내지 95:5 또는 87:13 내지 93:7일 수 있고, 이 중 87:13 내지 93:7이 바람직하다. 상술한 범위를 만족하면, 유동성을 개선시킬 수 있고, 우수한 충격강도를 구현할 수 있다.When the enlargement is carried out in the second step in the preparation of the second conjugated diene polymer, when the total amount of the flocculant is 2.5 parts by weight based on 100 parts by weight of the small particle conjugated diene polymer, primary and secondary enlargement The weight ratio of the flocculant added at the time may be 90:10 to 99: 1 or 93: 7 to 97: 3, of which 93: 7 to 97: 3 is preferable. In addition, when the total amount of the flocculant is 2.7 parts by weight based on 100 parts by weight of the small particle conjugated diene-based polymer, the weight ratio of the flocculant added during the primary and secondary enlargement is 85:15 to 95: 5 or 87:13 to 93: 7, of which 87:13 to 93: 7 are preferred. If the above-mentioned range is satisfied, fluidity can be improved and excellent impact strength can be realized.
한편, 상기 제2 공액 디엔계 중합체가 상기 1) 제조방법으로 제조되는 경우, 공지의 방법으로 제조될 수 있으며, 상술한 입도분포 및 평균입경을 만족하기 위하여, 공지의 방법에서 유화제 또는 전해질의 함량을 적절히 조절할 수 있다.On the other hand, when the second conjugated diene-based polymer is prepared by the method 1), it can be prepared by a known method, in order to satisfy the above-described particle size distribution and average particle size, the content of the emulsifier or electrolyte in the known method Can be adjusted appropriately.
상기 유화제는 로진산 알칼리 금속염, 지방산 알칼리 금속염 및 지방산 다이머 알칼리 금속염으로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 지방산 다이머 알칼리 금속염이 바람직하다.The emulsifier may be one or more selected from the group consisting of alkali rosin acid metal salts, fatty acid alkali metal salts and fatty acid dimer alkali metal salts, of which fatty acid dimer alkali metal salts are preferred.
상기 로진산 알칼리 금속염은 로진산 칼륨염 및 로진산 나트륨염으로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 로진산 칼륨염이 바람직하다.The rosin acid alkali metal salt may be one or more selected from the group consisting of potassium rosin acid salt and sodium rosin acid salt, and potassium rosin acid salt is preferable.
상기 지방산 알칼리 금속염은 C8 내지 C20의 지방산 알칼리 금속염일 수 있고, 카프릭산의 알칼리 금속염, 라우릭산의 알칼리 금속염, 팔미틱산의 알칼리 금속염, 스테아릭산의 알칼리 금속염, 올레익산의 알칼리 금속염 및 리놀레인산의 알칼리 금속염으로 이루어진 군에서 선택되는 1종 이상이 보다 바람직하다.The fatty acid alkali metal salt may be a C 8 to C 20 fatty acid alkali metal salt, alkali metal salt of capric acid, alkali metal salt of lauric acid, alkali metal salt of palmitic acid, alkali metal salt of stearic acid, alkali metal salt and oleic acid and linol One or more types selected from the group consisting of alkali metal salts of leinic acid are more preferable.
상기 지방산 다이머 알칼리 금속염은 C8 내지 C20의 지방산 다이머 알칼리 금속염일 수 있고, C8 내지 C20의 지방산 다이머 칼륨염인 것이 바람직하고, 올레인산 다이머 칼륨염인 것이 보다 바람직하다.The fatty acid dimer alkali metal salt may be a C 8 to C 20 fatty acid dimer alkali metal salt, preferably a C 8 to C 20 fatty acid dimer potassium salt, and more preferably an oleic acid dimer potassium salt.
상기 유화제는 상기 공액 디엔계 단량체 100 중량부에 대하여, 0.3 내지 3.0 중량부 또는 0.5 내지 2.5 중량부로 투입될 수 있으며, 이 중 0.5 내지 2.5 중량부로 투입되는 것이 바람직하다. 상술한 범위를 만족하면, 중합 안정성이 우수해지고 중합전환율을 높일 수 있다.The emulsifier may be added to 0.3 to 3.0 parts by weight or 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the conjugated diene monomer, of which 0.5 to 2.5 parts by weight is preferably added. When the above range is satisfied, the polymerization stability is excellent and the polymerization conversion rate can be increased.
상기 전해질은 KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, NaHSO3, K4P2O7, K3PO4, Na3PO4 및 Na2HPO4로 이루어진 군에서 선택되는 1종 이상일 수 있으며, 이 중 K2CO3 및 Na2CO3로 이루어진 군에서 선택되는 1종 이상이 바람직하다.The electrolyte is KCl, NaCl, KHCO 3 , NaHCO 3 , K 2 CO 3 , Na 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , K 3 PO 4 , Na 3 PO 4 and Na 2 HPO 4 It may be at least one selected from the group consisting of, of which at least one selected from the group consisting of K 2 CO 3 and Na 2 CO 3 is preferred.
상기 전해질은 상기 공액 디엔계 단량체 100 중량부에 대하여, 0.1 내지 1 중량부 또는 0.2 내지 0.5 중량부로 투입될 수 있으며, 이 중 0.2 내지 0.5 중량부로 투입되는 것이 바람직하다. 상술한 범위를 만족하면, 중합 안정성이 우수해지고 중합전환율을 높일 수 있다.The electrolyte may be added in an amount of 0.1 to 1 part by weight or 0.2 to 0.5 part by weight based on 100 parts by weight of the conjugated diene-based monomer, of which 0.2 to 0.5 part by weight is preferable. When the above range is satisfied, the polymerization stability is excellent and the polymerization conversion rate can be increased.
한편, 상기 제1 공액 디엔계 중합체와 제2 공액 디엔계 중합체의 중량비는 30:70 내지 80:20, 50:50 내지 80:20, 60:40 내지 75:25 또는 65:35 내지 70:30일 수 있고, 이 중 65:35 내지 70:30인 것이 바람직하다. 상술한 범위를 만족하면, 표면에 돌기 생성이 최소화되어 표면 특성이 우수한 성형품을 제조할 수 있고, 이로 인해 도장 또는 도금 특성이 우수한 성형품을 제조할 수 있다. 그리고, 그라프트율이 높으면서 충격강도 및 유동성을 보다 개선된 그라프트 공중합체를 제조할 수 있다.On the other hand, the weight ratio of the first conjugated diene-based polymer and the second conjugated diene-based polymer is 30:70 to 80:20, 50:50 to 80:20, 60:40 to 75:25 or 65:35 to 70:30 It may be, of which 65:35 to 70:30 is preferred. When the above-described range is satisfied, the formation of protrusions on the surface may be minimized to manufacture a molded article having excellent surface characteristics, and thus, a molded article having excellent coating or plating characteristics may be manufactured. In addition, while the graft ratio is high, the graft copolymer with improved impact strength and fluidity can be prepared.
상기 제1 공액 디엔계 중합체와 제2 공액 디엔계 중합체의 총 합은 상기 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체의 총 중량에 대하여, 50 내지 65 중량% 또는 55 내지 60 중량%일 수 있고, 이 중 55 내지 60 중량%인 것이 바람직하다. 상술한 범위를 만족하면, 중합 중 응고물의 발생을 최소화할 수 있고, 그라프트 공중합체의 충격강도가 보다 개선될 수 있다.The total sum of the first conjugated diene-based polymer and the second conjugated diene-based polymer is 50 to 50, based on the total weight of the first conjugated diene-based polymer, the second conjugated diene-based polymer, an aromatic vinyl monomer, and a vinyl cyan monomer. It may be 65% by weight or 55 to 60% by weight, preferably 55 to 60% by weight. When the above-mentioned range is satisfied, it is possible to minimize the generation of coagulum during polymerization, and the impact strength of the graft copolymer may be further improved.
상기 제1 공액 디엔계 중합체와 제2 공액 디엔계 중합체는 콜로이드 상태로 물에 분산된 라텍스 형태일 수 있으며, 중합 개시 전에 먼저 반응기에 투입될 수 있다.The first conjugated diene-based polymer and the second conjugated diene-based polymer may be in the form of latex dispersed in water in a colloidal state, and may be first introduced into a reactor before the polymerization starts.
상기 방향족 비닐계 단량체 및 비닐 시안계 단량체의 총 합은 상기 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체의 총 중량에 대하여, 35 내지 50 중량% 또는 40 내지 45 중량%일 수 있고, 이 중 40 내지 45 중량%인 것이 바람직하다. 상술한 범위를 만족하면, 그라프트 공중합체의 내화학성, 강성, 충격강도, 가공성 및 표면 광택이 보다 개선될 수 있다.The total sum of the aromatic vinyl monomer and the vinyl cyan monomer may be 35 to 50 wt%, based on the total weight of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. 40 to 45% by weight, of which 40 to 45% by weight is preferred. If the above range is satisfied, the chemical resistance, stiffness, impact strength, processability and surface gloss of the graft copolymer may be further improved.
상기 방향족 비닐계 단량체와 비닐 시안계 단량체의 중량비는 80:20 내지 65:35 또는 75:25 내지 70:30일 수 있고, 이 중 75:25 내지 70:30인 것이 바람직하다. 상술한 범위를 만족하면, 중합전환율이 높아지고, 중합 안정성 및 라텍스 안정성이 보다 개선될 수 있다.The weight ratio of the aromatic vinyl monomer and the vinyl cyan monomer may be 80:20 to 65:35 or 75:25 to 70:30, of which 75:25 to 70:30 is preferable. When the above range is satisfied, the polymerization conversion rate is increased, and the polymerization stability and the latex stability can be further improved.
상기 방향족 비닐계 단량체와 비닐 시안계 단량체는 상기 제1 및 제2 공액 디엔계 중합체가 존재하는 반응기에 일정한 속도로 연속 투입되면서 유화 중합될 수 있다. 상기 방향족 비닐계 단량체와 비닐 시안계 단량체가 연속 투입되면, 중합 중에 발생하는 반응열을 분산시킬 수 있다.The aromatic vinyl monomer and the vinyl cyan monomer may be emulsion-polymerized while continuously introduced at a constant rate into a reactor in which the first and second conjugated diene polymers are present. When the aromatic vinyl monomer and the vinyl cyan monomer are continuously added, the reaction heat generated during the polymerization may be dispersed.
상기 중합 시 상기 반응기에 분자량 조절제, 개시제, 유화제, 산화환원계 촉매 및 물로 이루어진 군에서 선택되는 1종 이상을 더 투입할 수 있다. In the polymerization, at least one selected from the group consisting of a molecular weight regulator, an initiator, an emulsifier, a redox catalyst, and water may be further added to the reactor.
상기 분자량 조절제는 반응성이 큰, 분해속도가 빠른 머캅탄류 화합물과 반응성이 작은, 즉 분해속도가 늦은 큰 방향족 비닐계 다이머를 포함할 수 있다.The molecular weight modifier may include a large reactive vinyl dimer having a high reactivity, a high decomposition rate mercaptan compound and a low reactivity rate, that is, a low decomposition rate.
상기 머캅탄류 화합물은 t-도데실 머캅탄, n-도데실 머캅탄 및 옥틸 머캅탄으로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 t-도데실 머캅탄이 바람직하다.The mercaptan compound may be at least one selected from the group consisting of t-dodecyl mercaptan, n-dodecyl mercaptan and octyl mercaptan, and t-dodecyl mercaptan is preferred.
상기 방향족 비닐계 다이머는 α-메틸 스티렌 다이머, 에틸 스티렌 다이머 및 프로필 스티렌 다이머로 이루어진 군으로부터 선택되는 1종 이상일 수 있고, 이 중 α-메틸 스티렌 다이머가 바람직하다.The aromatic vinyl-based dimer may be at least one selected from the group consisting of α-methyl styrene dimer, ethyl styrene dimer and propyl styrene dimer, of which α-methyl styrene dimer is preferable.
상기 분자량 조절제는 상기 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체의 합 100 중량부에 대하여, 0.30 내지 0.50 중량부 또는 0.35 내지 0.45 중량부일 수 있으며, 이 중 0.35 내지 0.45 중량부가 바람직하다. 상술한 범위를 만족하면, 쉘의 중량평균분자량을 적절하게 유지하여 그라프트 공중합체의 충격강도를 보다 개선시킬 수 있다.The molecular weight modifier may be 0.30 to 0.50 parts by weight or 0.35 to 0.45 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Of these, 0.35 to 0.45 parts by weight is preferable. If the above-mentioned range is satisfied, the weight average molecular weight of the shell can be properly maintained to further improve the impact strength of the graft copolymer.
상기 머캅탄류 화합물과 방향족 비닐계 다이머는 60:40 내지 70:30 또는 65:35 내지 70:30의 중량비로 투입할 수 있고, 이 중 65:35 내지 70:30의 중량비로 투입되는 것이 바람직하다. 상술한 조건을 만족하면, 머캅탄류 화합물과 방향쪽 비닐계 다이머가 그라프트 공중합체의 그라프트율을 조절할 수 있어서 낙구 충격강도 및 노치드 아이조드 충격강도를 높여 줄 수 있다.The mercaptan compound and the aromatic vinyl dimer may be added in a weight ratio of 60:40 to 70:30 or 65:35 to 70:30, and of the mercaptan compounds and 65:35 to 70:30. . When the above conditions are satisfied, the mercaptan compound and the aromatic vinyl-based dimer can adjust the graft ratio of the graft copolymer to increase the falling ball impact strength and the notched Izod impact strength.
상기 개시제는 과황산칼륨, 광황산나트륨, 과황산암모늄, 큐멘 하이드로 퍼옥사이드, 디이소프로필 벤젠 하이드로퍼옥사이드, 아조비스 이소부틸로니트릴, t-부틸 하이드로퍼옥사이드, 파라멘탄 하이드로퍼옥사이드 및 벤조일퍼옥사이드로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 t-부틸 하이드로퍼옥사이드로 이루어진 군에서 선택되는 1종 이상이 바람직하다.The initiators include potassium persulfate, sodium photosulphate, ammonium persulfate, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramentane hydroperoxide and benzoyl per At least one selected from the group consisting of oxides, and at least one selected from the group consisting of t-butyl hydroperoxide is preferred.
상기 개시제는 상기 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체의 합 100 중량부에 대하여, 0.5 내지 0.8 중량부, 또는 0.6 내지 0.7 중량부로 투입될 수 있고, 이 중 0.6 내지 0.7 중량부로 투입되는 것이 바람직하다. 상술한 범위를 만족하면, 라텍스 안정성이 우수하고 유화 중합이 용이하게 수행되면서, 그라프트 공중합체 내 잔류량은 최소화할 수 있다.The initiator may be added in an amount of 0.5 to 0.8 parts by weight, or 0.6 to 0.7 parts by weight based on 100 parts by weight of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Among them, it is preferable to add 0.6 to 0.7 parts by weight. When the above range is satisfied, the latex stability is excellent and the emulsion polymerization is easily performed, while the residual amount in the graft copolymer can be minimized.
상기 유화제는 C1 내지 C20의 모노 카르복실산염, C12 내지 C18의 숙시네이트 금속염, 설폰산 금속염 및 로진산 알칼리 금속염으로 이루어진 군에서 선택되는 1종 이상일 수 있다. The emulsifier may be at least one selected from the group consisting of C 1 to C 20 mono carboxylic acid salts, C 12 to C 18 succinate metal salts, sulfonic acid metal salts and rosin acid alkali metal salts.
상기 모노 카르복실산염은 C8 내지 C20의 지방산 비누일 수 있다.The mono carboxylate may be a C 8 to C 20 fatty acid soap.
상기 C12 내지 C18의 숙시네이트 금속염은 C12 내지 C18의 알케닐 숙신산 디칼륨염일 수 있다. The C 12 to C 18 succinate metal salt may be a C 12 to C 18 alkenyl succinate dipotassium salt.
상기 설폰산 금속염은 나트륨 도데실 설페이트, 나트륨 라우릭 설페이트, 나트륨 도데실 벤젠 설페이트, 나트륨 옥타데실 설페이트, 나트륨 올레익 설페이트, 칼륨 도데실 설페이트 및 칼륨 옥타데실 설페이트로 이루어진 군에서 선택되는 1종 이상일 수 있다. The sulfonic acid metal salt may be at least one selected from the group consisting of sodium dodecyl sulfate, sodium lauric sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate. have.
상기 로진산 알칼리 금속염은 로진산 칼륨염 및 로진산 나트륨염으로 이루어진 군에서 선택되는 1종 이상일 수 있다.The rosin acid alkali metal salt may be at least one selected from the group consisting of potassium rosin salt and sodium rosin salt.
상기 유화제로는 로진산 알칼리 금속염이 바람직하고, 로진산 칼륨염이 보다 바람직하다.As said emulsifier, an alkali metal rosin salt is preferable, and potassium rosin salt is more preferable.
상기 유화제는 상기 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체의 합 100 중량부에 대하여, 0.5 내지 1.2 중량부, 또는 0.8 내지 1.0 중량부로 투입될 수 있고, 이 중 0.8 내지 1.0 중량부로 투입되는 것이 바람직하다. 상술한 범위를 만족하면, 유화 중합이 용이하게 수행되면서, 그라프트 공중합체 내 잔류량은 최소화할 수 있다.The emulsifier may be added in an amount of 0.5 to 1.2 parts by weight, or 0.8 to 1.0 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer, and the vinyl cyan monomer. Among them, it is preferable to add 0.8 to 1.0 parts by weight. If the above range is satisfied, while the emulsion polymerization is easily performed, the residual amount in the graft copolymer can be minimized.
상기 산화환원계 촉매는 나트륨 포름알데히드 설폭실레이트, 나트륨 에틸렌디아민 테트라아세테이트, 황산제1철, 덱스트로즈, 피로인산나트륨, 무수 피로인산나트륨 및 나트륨 설페이트로 이루어진 군에서 선택되는 1종 이상일 수 있고, 이 중 황산제1철, 덱스트로즈 및 피로인산나트륨으로 이루어진 군에서 선택되는 1종 이상인 것이 바람직하다.The redox catalyst may be at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, anhydrous sodium pyrophosphate and sodium sulfate. Of these, ferrous sulfate, dextrose and sodium pyrophosphate are preferably one or more selected from the group consisting of.
상기 산화환원계 촉매는 상기 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체의 합 100 중량부에 대하여, 0.1 내지 0.5 중량부, 또는 0.3 내지 0.4 중량부로 투입될 수 있고, 이 중 0.3 내지 0.4 중량부로 투입되는 것이 바람직하다. 상술한 범위를 만족하면, 중합전환율이 높아지는 이점이 있다.The redox catalyst is 0.1 to 0.5 parts by weight, or 0.3 to 0.4 parts by weight based on 100 parts by weight of the sum of the first conjugated diene polymer, the second conjugated diene polymer, the aromatic vinyl monomer and the vinyl cyan monomer. It may be added, of which 0.3 to 0.4 parts by weight is preferably added. If the above range is satisfied, there is an advantage that the polymerization conversion rate is increased.
상기 물은 이온교환수일 수 있다.The water may be ion exchanged water.
상기 분자량 조절제, 개시제, 유화제, 산화환원계 촉매 및 물로 이루어진 군에서 선택되는 1종 이상은 상기 방향족 비닐계 단량체와 비닐 시안계 단량체와 함께 상기 제1 및 제2 공액 디엔계 중합체가 존재하는 반응기에 일정한 속도로 연속 투입될 수 있다. 연속 투입되면, 중합 시 반응열이 분산될 수 있어 제열이 용이할 수 있다.At least one selected from the group consisting of the molecular weight regulator, the initiator, the emulsifier, the redox catalyst and the water is present in the reactor in which the first and second conjugated diene polymers are present together with the aromatic vinyl monomer and the vinyl cyan monomer. It can be fed continuously at a constant speed. When continuously added, the heat of reaction may be dispersed during polymerization, and thus, heat removal may be facilitated.
상술한 제조방법으로 제조된 그라프트 공중합체는 그라프트율이 37% 이상이고, 쉘의 중량평균분자량이 75,000 g/mol 이상, 바람직하게는 75,000 내지 110,000 g/mol이다. 상술한 범위를 만족하면, 표면특성이 우수해져 도금 및 도장특성이 보다 개선될 수 있다.The graft copolymer prepared by the above-described manufacturing method has a graft ratio of at least 37%, and the weight average molecular weight of the shell is 75,000 g / mol or more, preferably 75,000 to 110,000 g / mol. If the above-mentioned range is satisfied, the surface characteristics may be excellent, and plating and painting characteristics may be further improved.
2. 열가소성 수지 조성물2. Thermoplastic Composition
본 발명의 다른 일실시예에 따른 열가소성 수지 조성물은 본 발명의 일실시예에 따른 제조방법으로 제조된 그라프트 공중합체; 및 방향족 비닐계 단량체 유래 단위 및 비닐 시안계 단량체 유래 단위를 포함하는 공중합체를 포함한다.Thermoplastic resin composition according to another embodiment of the present invention is a graft copolymer prepared by the manufacturing method according to an embodiment of the present invention; And a copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit.
상기 공중합체는 열가소성 수지 조성물에 내열성, 강성, 가공성을 부여해 줄 수 있다.The copolymer may impart heat resistance, rigidity, and processability to the thermoplastic resin composition.
상기 공중합체는 상기 방향족 비닐계 단량체 유래 단위와 비닐 시안계 단량체 유래 단위를 85:15 내지 70:30 또는 80:20 내지 75:25의 중량비로 포함할 수 있고, 이 중 80:20 내지 75:25의 중량비로 포함하는 것이 바람직하다. 상술한 범위를 만족하면, 열가소성 수지 조성물이 내열성, 충격강도 및 가공성의 균형을 보다 잘 구현할 수 있다.The copolymer may include the aromatic vinyl monomer derived unit and the vinyl cyan monomer derived unit in a weight ratio of 85:15 to 70:30 or 80:20 to 75:25, among which 80:20 to 75: It is preferable to include in the weight ratio of 25. If the above-mentioned range is satisfied, the thermoplastic resin composition can better realize the balance of heat resistance, impact strength and processability.
상기 공중합체는 중량평균분자량이 100,000 내지 150,000g/mol 또는 120,000 내지 140,000g/mol일 수 있고, 이 중 120,000 내지 140,000g/mol가 바람직하다. 상술한 범위를 만족하면, 열가소성 수지 조성물의 충격강도가 보다 개선될 수 있다.The copolymer may have a weight average molecular weight of 100,000 to 150,000 g / mol or 120,000 to 140,000 g / mol, of which 120,000 to 140,000 g / mol is preferred. When the above range is satisfied, the impact strength of the thermoplastic resin composition may be further improved.
상기 중량평균분자량은 용출액으로 THF(테트라하이드로퓨란)을 이용하여 GPC을 통해 표준 PS(standard polystyrene) 시료에 대한 상대 값으로 측정할 수 있다.The weight average molecular weight may be measured as a relative value for a standard polystyrene (PS) sample through GPC using THF (tetrahydrofuran) as an eluent.
상기 공중합체는 유화중합, 현탁중합 및 괴상중합으로 이루어진 군에서 선택되는 1종 이상의 방법으로 제조될 수 있고, 이 중 괴상중합으로 제조되는 것이 바람직하다.The copolymer may be prepared by one or more methods selected from the group consisting of emulsion polymerization, suspension polymerization, and bulk polymerization, and preferably, the copolymer is prepared by bulk polymerization.
상기 그라프트 공중합체와 공중합체의 중량비는 20:80 내지 35:65 또는 25:75 내지 30:70일 수 있고, 이 중 25:75 내지 30:70이 바람직하다. 상술한 범위를 만족하면, 열가소성 수지 조성물로 제조된 성형품의 내화학성, 충격강도, 열안정성, 착색성, 내피로성, 강성 및 가공성이 보다 개선될 수 있다.The weight ratio of the graft copolymer and the copolymer may be 20:80 to 35:65 or 25:75 to 30:70, of which 25:75 to 30:70 is preferable. If the above range is satisfied, the chemical resistance, impact strength, thermal stability, colorability, fatigue resistance, rigidity and workability of the molded article manufactured from the thermoplastic resin composition may be further improved.
상술한 열가소성 수지 조성물로 제조된 열가소성 수지 성형품은 휘발성 유기 화합물의 잔류량이 1,000 ppm 이하이다. 상술한 조건을 만족하면, 냄새 특성이 우수한 성형품을 제공할 수 있다.The thermoplastic resin molded article produced from the thermoplastic resin composition described above has a residual amount of volatile organic compound of 1,000 ppm or less. If the conditions mentioned above are satisfied, the molded article excellent in odor characteristic can be provided.
여기서, 휘발성 유기 화합물의 잔류량은 가스 크로마토그라피 설비(상품명: GC, 제조사: Agilent)를 이용하여 측정할 수 있다.Here, the residual amount of the volatile organic compound can be measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
제조예Production Example 1 One
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질소로 치환된 중합 반응기에 이온교환수 120 중량부, 1,3-부타디엔 100 중량부, 유화제로 로진산 칼륨염 2 중량부, 분자량 조절제로 t-도데실 머캅탄 0.1 중량부, 전해질로 Na2CO3 0.2 중량부를 투입한 후 충분히 혼합시킨 후 반응기의 내부 온도가 50 ℃가 되도록 승온하였다. 승온 완료 후, 개시제로 과황산칼륨 0.2 중량부를 일괄 투입하고 중합을 7 시간 동안 수행하였다. 이어서, 분자량 조절제로 t-도데실 머캅탄 0.05 중량부를 투입하고 70 ℃로 승온한 후, 중합을 8 시간 동안 수행한 후 중합을 종료하여 소입경 부타디엔 고무질 중합체 라텍스(평균입경: 0.1 ㎛, 겔 함량: 98 %)를 수득하였다. 120 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene, 2 parts by weight of potassium rosin salt as emulsifier, 0.1 parts by weight of t-dodecyl mercaptan as molecular weight modifier, Na 2 as electrolyte After adding 0.2 parts by weight of CO 3, the mixture was sufficiently mixed and the temperature of the reactor was increased to 50 ° C. After completion of the temperature increase, 0.2 part by weight of potassium persulfate was added as an initiator in a batch, and polymerization was performed for 7 hours. Subsequently, 0.05 parts by weight of t-dodecyl mercaptan was added as a molecular weight modifier, the temperature was raised to 70 ° C, the polymerization was carried out for 8 hours, and the polymerization was terminated. : 98%) was obtained.
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상기 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 2.4 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1 시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 0.6 중량부로 포함하는 아세트산 수용액(농도: 7중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 A-1을 제조하였다. 상기 대입경 부타디엔 고무질 중합체 A-1은 입도분포가 0.34 이고, 평균입경이 0.3 ㎛이었다.100 parts by weight of the small-diameter butadiene rubbery polymer latex (based on solids) was added to the reaction tank, and an aqueous acetic acid solution containing 2.4 parts by weight of acetic acid (concentration: 7% by weight) was stirred at 30 ° C. at a speed of 10 rpm for 1 hour. After continuous feeding at a constant rate, the mixture was stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.6 parts by weight was continuously added at a constant rate for 10 minutes, followed by secondary enlargement with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer A-1. . The large particle size butadiene rubber polymer A-1 had a particle size distribution of 0.34 and an average particle diameter of 0.3 μm.
제조예Production Example 2 2
<< 대입경Large particle size 공액Conjugate 디엔계Diene 중합체의 제조> Preparation of Polymer>
제조예 1에서 제조된 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 2.7 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1 시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 0.3 중량부로 포함하는 아세트산 수용액(농도: 7중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 A-2를 제조하였다. 상기 대입경 부타디엔 고무질 중합체 A-2는 입도분포가 0.35이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubbery polymer latex prepared in Preparation Example 1 was added to the reactor, and an aqueous acetic acid solution containing 2.7 parts by weight of acetic acid was stirred at a speed of 10 rpm at 30 ° C. (concentration: 7% by weight). ) Was continuously added at a constant rate for 1 hour, and then stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.3 parts by weight was continuously added at a constant rate for 10 minutes, and then secondary enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer A-2. . The large particle size butadiene rubber polymer A-2 had a particle size distribution of 0.35 and an average particle diameter of 0.3 μm.
제조예Production Example 3 3
제조예 1에서 제조한 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 3 중량부로 포함하는 아세트산 수용액(농도: 7중량%)을 1 시간 동안 일정한 속도로 투입하였다. 투입이 완료되면 교반을 중지한 후, 30 분 동안 방치하여 비대화하여 대입경 부타디엔 고무질 중합체 A-3를 제조하였다. 상기 대입경 부타디엔 고무질 중합체 A-3는 입도분포가 0.37이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubbery polymer latex prepared in Preparation Example 1 was added to the reactor, and an acetic acid aqueous solution containing 3 parts by weight of acetic acid while stirring at 30 rpm at a speed of 10 rpm (concentration: 7% by weight) ) Was added at a constant rate for 1 hour. After the addition was completed, the stirring was stopped, and the mixture was left for 30 minutes to enlarge to prepare a large particle butadiene rubbery polymer A-3. The large particle size butadiene rubber polymer A-3 had a particle size distribution of 0.37 and an average particle diameter of 0.3 μm.
도 1에 상기 대입경 부타디엔 고무질 중합체 라텍스 A-3의 입도분포를 나타내었다.1 shows the particle size distribution of the large-diameter butadiene rubbery polymer latex A-3.
도 1을 참조하면, 대입경 부타디엔 고무질 중합체 라텍스 A-3이 넓은 입도분포를 갖는 것을 확인할 수 있다.Referring to Figure 1, it can be seen that the large particle size butadiene rubbery polymer latex A-3 has a wide particle size distribution.
제조예Production Example 4 4
제조예 1에서 제조한 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 2.45 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 1.05 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 라텍스 A-4를 제조하였다. 상기 대입경 부타디엔 고무질 중합체 라텍스 A-4는 입도분포가 0.4이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubber polymer latex prepared in Preparation Example 1 was added to the reactor, and an aqueous acetic acid solution containing 2.45 parts by weight of acetic acid was stirred at a speed of 10 rpm at 30 ° C (concentration: 7% by weight). ) Was continuously added at a constant rate for 1 hour, and then stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 1.05 parts by weight was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-4. It was. The large-diameter butadiene rubbery polymer latex A-4 had a particle size distribution of 0.4 and an average particle diameter of 0.3 μm.
제조예Production Example 5 5
제조예 1에서 제조한 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 3.6 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1 시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 0.4 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 라텍스 A-5를 제조하였다. 상기 대입경 부타디엔 고무질 중합체 라텍스 A-5는 입도분포가 0.41이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubbery polymer latex prepared in Preparation Example 1 was added to the reactor, and an aqueous acetic acid solution containing 3.6 parts by weight of acetic acid was stirred at a speed of 10 rpm at 30 ° C (concentration: 7% by weight). ) Was continuously added at a constant rate for 1 hour, and then stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing 0.4 parts by weight of acetic acid was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged while stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-5. It was. The large particle butadiene rubber polymer latex A-5 had a particle size distribution of 0.41 and an average particle diameter of 0.3 μm.
제조예Production Example 6 6
제조예 1에서 제조한 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 2.25 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1 시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 0.25 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 라텍스 A-6을 제조하였다. 상기 대입경 부타디엔 고무질 중합체 라텍스 A-6은 입도분포가 0.19이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubbery polymer latex prepared in Preparation Example 1 was added to the reactor, and an aqueous acetic acid solution containing 2.25 parts by weight of acetic acid was stirred at a speed of 10 rpm at 30 ° C (concentration: 7% by weight). ) Was continuously added at a constant rate for 1 hour, and then stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.25 parts by weight was continuously added at a constant rate for 10 minutes, followed by secondary enlargement with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-6. It was. The large particle size butadiene rubbery polymer latex A-6 had a particle size distribution of 0.19 and an average particle diameter of 0.3 μm.
제조예Production Example 7 7
제조예 1에서 제조한 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 2.375 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1 시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 0.125 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 라텍스 A-7을 제조하였다. 상기 대입경 부타디엔 고무질 중합체 라텍스 A-7은 입도분포가 0.2 이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubbery polymer latex prepared in Preparation Example 1 was added to the reactor, and an aqueous acetic acid solution containing 2.375 parts by weight of acetic acid was stirred at a speed of 10 rpm at 30 ° C (concentration: 7% by weight). ) Was continuously added at a constant rate for 1 hour, and then stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing 0.125 parts by weight of acetic acid was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-7. It was. The large particle size butadiene rubber polymer latex A-7 had a particle size distribution of 0.2 and an average particle diameter of 0.3 μm.
제조예Production Example 8 8
질소 치환된 중합 반응기에 이온교환수 100 중량부, 1,3-부타디엔 70 중량부, 유화제로 로진산 칼륨염 1.5 중량부, 전해질로 Na2CO3 0.3 중량부, 분자량 조절제로 t-도데실 머캅탄 0.03 중량부 및 개시제로 과황산칼륨 0.5 중량부를 일괄 투입하고, 50 ℃로 승온시킨 후 중합을 개시하였다. 중합 전환율이 약 35%인 시점에서 유화제로 로진산 칼륨염 0.7 중량부, 과황산칼륨 0.5 중량부 및 1,3-부타디엔 30 중량부를 일괄 투입하고 중합을 수행하였다. 중합 전환율이 약 60 %인 시점에서 75 ℃로 승온한 후, 중합 전환율이 약 65%인 시점에서 유화제로 로진산 칼륨염 0.3 중량부를 일괄 투입하고, 중합을 지속하였다. 중합 전환율이 약 97 %인 시점에서 반응을 종료하여, 입도분포가 0.23이고, 평균입경이 0.3 ㎛인 대입경 부타디엔 고무질 중합체 라텍스 A-8를 제조하였다.100 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene, 1.5 parts by weight of potassium rosin salt as emulsifier, 0.3 parts by weight of Na 2 CO 3 as electrolyte, t-dodecylmer as molecular weight regulator 0.03 part by weight of captan and 0.5 part by weight of potassium persulfate were added as a batch, the temperature was raised to 50 ° C, and polymerization was started. When the polymerization conversion rate was about 35%, 0.7 parts by weight of potassium rosin salt, 0.5 parts by weight of potassium persulfate and 30 parts by weight of 1,3-butadiene were collectively added as an emulsifier to carry out polymerization. After heating up at 75 degreeC when the polymerization conversion rate was about 60%, 0.3 weight part of potassium rosin salts were added collectively as an emulsifier at the time of a polymerization conversion rate of about 65%, and superposition | polymerization was continued. The reaction was terminated when the polymerization conversion was about 97% to prepare a large particle butadiene rubbery polymer latex A-8 having a particle size distribution of 0.23 and an average particle diameter of 0.3 μm.
도 2에 대입경 부타디엔 고무질 중합체 라텍스 A-8의 입도분포를 나타내었다.2 shows the particle size distribution of the large-diameter butadiene rubbery polymer latex A-8.
도 2를 참조하면, 대입경 부타디엔 고무질 중합체 라텍스 A-8이 좁은 입도분포를 갖는 것을 확인할 수 있다.Referring to FIG. 2, it can be seen that the large-diameter butadiene rubbery polymer latex A-8 has a narrow particle size distribution.
제조예Production Example 9 9
제조예 1에서 제조한 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 2.7 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1 시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 0.3 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 라텍스 A-9를 제조하였다. 상기 대입경 부타디엔 고무질 중합체 라텍스 A-9는 입도분포가 0.3 이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubbery polymer latex prepared in Preparation Example 1 was added to the reactor, and an aqueous acetic acid solution containing 2.7 parts by weight of acetic acid was stirred at a speed of 10 rpm at 30 ° C (concentration: 7% by weight). ) Was continuously added at a constant rate for 1 hour, and then stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.3 parts by weight was continuously added at a constant rate for 10 minutes, and then secondaryly enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-9. It was. The large-diameter butadiene rubbery polymer latex A-9 had a particle size distribution of 0.3 and an average particle diameter of 0.3 μm.
제조예Production Example 10 10
제조예 1에서 제조한 소입경 부타디엔 고무질 중합체 라텍스 100 중량부(고형분 기준)를 반응조에 투입하고, 30 ℃에서 10 rpm의 속도로 교반하면서 아세트산을 3.15 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 1 시간 동안 일정한 속도로 연속 투입한 후, 25 분 동안 교반하여 1차 비대화하였다. 이어서, 아세트산을 0.35 중량부로 포함하는 아세트산 수용액(농도: 7 중량%)을 10 분 동안 일정한 속도로 연속 투입한 후, 10 분 동안 교반하면서 2차 비대화하여 대입경 부타디엔 고무질 중합체 라텍스 A-10을 제조하였다. 상기 대입경 부타디엔 고무질 중합체 라텍스 A-10은 입도분포가 0.31이고, 평균입경이 0.3 ㎛이었다.100 parts by weight (based on solids) of the small-diameter butadiene rubbery polymer latex prepared in Preparation Example 1 was added to the reactor, and an aqueous acetic acid solution containing 3.15 parts by weight of acetic acid was stirred at a speed of 10 rpm at 30 ° C (concentration: 7% by weight). ) Was continuously added at a constant rate for 1 hour, and then stirred for 25 minutes to firstly enlarge. Subsequently, an aqueous acetic acid solution (concentration: 7% by weight) containing acetic acid at 0.35 parts by weight was continuously added at a constant rate for 10 minutes, and then secondary enlarged with stirring for 10 minutes to prepare a large particle butadiene rubbery polymer latex A-10. It was. The large particle butadiene rubber polymer latex A-10 had a particle size distribution of 0.31 and an average particle diameter of 0.3 μm.
이하, 제조예의 대입경 부타디엔 고무질 중합체의 제조에서 투입되는 아세트산의 함량 및 중량비, 대입경 부타디엔 고무질 중합체의 입도분포 및 평균입경을 하기 [표 1]에 기재하였다. Hereinafter, the content and weight ratio of acetic acid introduced in the preparation of the large-diameter butadiene rubbery polymer of the preparation example, the particle size distribution and the average particle diameter of the large-diameter butadiene rubbery polymer are described in the following [Table 1].
구분division 제조예Production Example
1One 22 33 44 55 66 77 88 99 1010
대입경 부타디엔 고무질 중합체Large particle butadiene rubbery polymer A-1A-1 A-2A-2 A-3A-3 A-4A-4 A-5A-5 A-6A-6 A-7A-7 A-8A-8 A-9A-9 A-10A-10
아세트산(중량부)Acetic acid (parts by weight) 총 투입량Total input 33 33 33 3.53.5 4.04.0 2.52.5 2.52.5 -- 2.72.7 3.53.5
1차 비대화1st enlargement 2.42.4 2.72.7 33 2.452.45 3.63.6 2.252.25 2.3752.375 -- 0.30.3 3.153.15
2차 비대화2nd enlargement 0.60.6 0.30.3 -- 1.051.05 0.40.4 0.250.25 0.1250.125 -- 33 0.350.35
중량비Weight ratio 8:28: 2 9:19: 1 -- 7:37: 3 9:19: 1 9:19: 1 95:595: 5 -- 9:19: 1 9:19: 1
입도분포Particle size distribution 0.340.34 0.350.35 0.370.37 0.40.4 0.410.41 0.190.19 0.20.2 0.230.23 0.30.3 0.310.31
평균입경Average particle diameter 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3
실시예Example 1 One
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
스티렌 30 중량부, 아크릴로니트릴 10 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.6 중량부, 유화제로 로진산 칼륨염 1.0 중량부, 분자량 조절제로 t-도데실 머캅탄 0.26 중량부와 α-메틸 스티렌 다이머 0.14 중량부 및 이온교환수 25 중량부를 포함하는 제1 혼합물을 준비하였다.30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.6 parts by weight of t-butyl hydroperoxide as an initiator, 1.0 parts by weight of potassium rosin salt as an emulsifier, 0.26 parts by weight of t-dodecyl mercaptan as a molecular weight modifier and α-methyl A first mixture including 0.14 parts by weight of styrene dimer and 25 parts by weight of ion-exchanged water was prepared.
또한, 덱스트로즈 0.027 중량부, 피로인산 나트륨 0.002 중량부 및 황산제1철 0.001 중량부를 포함하는 제2 혼합물을 준비하였다.In addition, a second mixture including 0.027 parts by weight of dextrose, 0.002 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate was prepared.
질소 치환된 반응기에 대입경 부타디엔 고무질 중합체 라텍스 A-3 36 중량부(고형분 기준), 대입경 부타디엔 고무질 중합체 라텍스 A-8 24 중량부(고형분 기준) 및 이온교환수 100 중량부를 투입하였다. 36 parts by weight of the large-diameter butadiene rubbery polymer latex A-3 (based on solids), 24 parts by weight of the large-diameter butadiene rubbery polymer latex A-8 (based on the solids), and 100 parts by weight of ion-exchanged water were added to the nitrogen-substituted reactor.
이어서, 상기 반응기에 상기 제1 혼합물과 제2 혼합물을 70 ℃에서 일정한 속도로 2시간 동안 연속 투입하면서 중합하였다.Subsequently, the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
이어서, 상기 반응기에 산화환원계 촉매로 덱스트로즈 0.05 중량부, 피로인산 나트륨 0.03 중량부 및 황산제1철 0.001 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.05 중량부를 일괄 투입하고, 80 ℃로 1 시간에 걸쳐 승온하면서 중합을 수행한 후, 중합을 종료하여, 그라프트 공중합체 라텍스를 제조하였다. 수득된 그라프트 공중합체 라텍스를 응집, 숙성, 세척, 탈수 및 건조하고 그라프트 공중합체 분말 B-1을 수득하였다.Subsequently, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide as an initiator were collectively added to the reactor at 80 ° C. After the polymerization was carried out while raising the temperature over 1 hour, the polymerization was terminated to prepare a graft copolymer latex. The graft copolymer latex obtained was coagulated, aged, washed, dehydrated and dried to obtain graft copolymer powder B-1.
<열가소성 수지 조성물의 제조><Production of the thermoplastic resin composition>
상기 그라프트 공중합체 분말 B-1 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-1을 제조하였다.The thermoplastic resin composition C-1 was prepared by mixing 30 parts by weight of the graft copolymer powder B-1 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실시예Example 2 2
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 36 중량부(고형분 기준) 대신에 40 중량부(고형분 기준)를 투입하고, 대입경 부타디엔 고무질 중합체 라텍스 A-8 24 중량부(고형분 기준) 대신에 20 중량부(고형분 기준)를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-2를 제조하였다.40 parts by weight (based on solids) instead of 36 parts by weight (based on solids) of butadiene rubber polymer latex A-3, 20 parts by weight instead of 24 parts by weight (based on solids) of butadiene rubbery polymer latex Graft copolymer powder B-2 was prepared in the same manner as in Example 1 except that (Solid content basis) was added.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-2 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-2를 제조하였다.30 parts by weight of the graft copolymer powder B-2 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-2.
실시예Example 3 3
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 36 중량부(고형분 기준) 대신에 45 중량부(고형분 기준)를 투입하고, 대입경 부타디엔 고무질 중합체 라텍스 A-8 24 중량부(고형분 기준) 대신에 15 중량부(고형분 기준)를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-3을 제조하였다.45 parts by weight (based on solids) instead of 36 parts by weight (based on solids) of butadiene rubbery polymer latex A-3, 15 parts by weight instead of 24 parts by weight (based on solids) of butadiene rubbery polymer Graft copolymer powder B-3 was prepared in the same manner as in Example 1 except that (Solid content basis) was added.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-3 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-3을 제조하였다.The thermoplastic resin composition C-3 was prepared by mixing 30 parts by weight of the graft copolymer powder B-3 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실시예Example 4 4
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
스티렌 30 중량부, 아크릴로니트릴 10 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.6 중량부, 유화제로 로진산 칼륨염 1.0 중량부, 분자량 조절제로 t-도데실 머캅탄 0.14 중량부와 α-메틸 스티렌 다이머 0.26 중량부 및 이온교환수 25 중량부를 포함하는 제1 혼합물을 준비하였다.30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.6 parts by weight of t-butyl hydroperoxide as an initiator, 1.0 parts by weight of potassium rosin acid as an emulsifier, 0.14 parts by weight of t-dodecyl mercaptan as a molecular weight modifier and α-methyl A first mixture including 0.26 parts by weight of styrene dimer and 25 parts by weight of ion-exchanged water was prepared.
또한, 덱스트로즈 0.027 중량부, 피로인산 나트륨 0.002 중량부 및 황산제1철 0.001 중량부를 포함하는 제2 혼합물을 준비하였다.In addition, a second mixture including 0.027 parts by weight of dextrose, 0.002 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate was prepared.
질소 치환된 반응기에 대입경 부타디엔 고무질 중합체 라텍스 A-3 40 중량부(고형분 기준), 대입경 부타디엔 고무질 중합체 라텍스 A-8 20 중량부(고형분 기준) 및 이온교환수 100 중량부를 투입하였다. 40 parts by weight of the large-diameter butadiene rubbery polymer latex A-3 (based on solids), 20 parts by weight of the large-diameter butadiene rubbery polymer latex A-8 (based on the solids), and 100 parts by weight of ion-exchanged water were added to the nitrogen-substituted reactor.
이어서, 상기 반응기에 상기 제1 혼합물과 제2 혼합물을 70 ℃에서 일정한 속도로 2시간 동안 연속 투입하면서 중합하였다.Subsequently, the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
이어서, 상기 반응기에 산화환원계 촉매로 덱스트로즈 0.05 중량부, 피로인산 나트륨 0.03 중량부 및 황산제1철 0.001 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.05 중량부를 일괄 투입하고, 80 ℃로 1 시간에 걸쳐 승온하면서 중합을 수행한 후, 중합을 종료하여, 그라프트 공중합체 라텍스를 제조하였다. 수득된 그라프트 공중합체 라텍스를 응집, 숙성, 세척, 탈수 및 건조하고 그라프트 공중합체 분말 B-4를 수득하였다.Subsequently, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide as an initiator were collectively added to the reactor at 80 ° C. After the polymerization was carried out while raising the temperature over 1 hour, the polymerization was terminated to prepare a graft copolymer latex. The graft copolymer latex obtained was coagulated, aged, washed, dehydrated and dried to obtain graft copolymer powder B-4.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-4 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-4를 제조하였다.30 parts by weight of the graft copolymer powder B-4 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-4.
실시예Example 5 5
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 36 중량부(고형분 기준) 대신에 20 중량부(고형분 기준)를 투입하고, 대입경 부타디엔 고무질 중합체 라텍스 A-8 24 중량부(고형분 기준) 대신에 40 중량부를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-5를 제조하였다.20 parts by weight (based on solids) instead of 36 parts by weight (based on solids) butadiene rubbery polymer latex A-3 40 parts by weight instead of 24 parts by weight (based on solids) of butadiene rubbery polymer latex Graft copolymer powder B-5 was prepared in the same manner as in Example 1 except for the addition.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-5 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-5를 제조하였다.The thermoplastic resin composition C-5 was prepared by mixing 30 parts by weight of the graft copolymer powder B-5 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실시예Example 6 6
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
스티렌 30 중량부, 아크릴로니트릴 10 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.6 중량부, 유화제로 로진산 칼륨염 1.0 중량부, 분자량 조절제로 t-도데실 머캅탄 0.14 중량부와 α-메틸 스티렌 다이머 0.26 중량부 및 이온교환수 25 중량부를 포함하는 제1 혼합물을 준비하였다.30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.6 parts by weight of t-butyl hydroperoxide as an initiator, 1.0 parts by weight of potassium rosin acid as an emulsifier, 0.14 parts by weight of t-dodecyl mercaptan as a molecular weight modifier and α-methyl A first mixture including 0.26 parts by weight of styrene dimer and 25 parts by weight of ion-exchanged water was prepared.
또한, 덱스트로즈 0.027 중량부, 피로인산 나트륨 0.002 중량부 및 황산제1철 0.001 중량부를 포함하는 제2 혼합물을 준비하였다.In addition, a second mixture including 0.027 parts by weight of dextrose, 0.002 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate was prepared.
질소 치환된 반응기에 대입경 부타디엔 고무질 중합체 라텍스 A-3 20 중량부(고형분 기준), 대입경 부타디엔 고무질 중합체 라텍스 A-8 40 중량부(고형분 기준) 및 이온교환수 100 중량부를 투입하였다. 20 parts by weight of the large-diameter butadiene rubbery polymer latex A-3 (based on solids), 40 parts by weight of the large-diameter butadiene rubbery polymer latex A-8 (based on the solids), and 100 parts by weight of ion-exchanged water were added to the nitrogen-substituted reactor.
이어서, 상기 반응기에 상기 제1 혼합물과 제2 혼합물을 70 ℃에서 일정한 속도로 2시간 동안 연속 투입하면서 중합하였다.Subsequently, the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
이어서, 상기 반응기에 산화환원계 촉매로 덱스트로즈 0.05 중량부, 피로인산 나트륨 0.03 중량부 및 황산제1철 0.001 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.05 중량부를 일괄 투입하고, 80 ℃로 1 시간에 걸쳐 승온하면서 중합을 수행한 후, 중합을 종료하여, 그라프트 공중합체 라텍스를 제조하였다. 수득된 그라프트 공중합체 라텍스를 응집, 숙성, 세척, 탈수 및 건조하고 그라프트 공중합체 분말 B-6을 수득하였다.Subsequently, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide as an initiator were collectively added to the reactor at 80 ° C. After the polymerization was carried out while raising the temperature over 1 hour, the polymerization was terminated to prepare a graft copolymer latex. The graft copolymer latex obtained was coagulated, aged, washed, dehydrated and dried to obtain graft copolymer powder B-6.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-6 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-6을 제조하였다.30 parts by weight of the graft copolymer powder B-6 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-6.
실시예Example 7 7
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 대신에 대입경 부타디엔 고무질 중합체 라텍스 A-2를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-7을 제조하였다.Graft copolymer powder B-7 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-2 was added instead of the large particle butadiene rubber polymer latex A-3.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-7 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-7을 제조하였다.30 parts by weight of the graft copolymer powder B-7 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical Co., Ltd. were mixed to prepare a thermoplastic resin composition C-7.
실시예Example 8 8
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 대신에 대입경 부타디엔 고무질 중합체 라텍스 A-4를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-8을 제조하였다.Graft copolymer powder B-8 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-4 was added instead of the large particle butadiene rubber polymer latex A-3.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-8 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-8을 제조하였다.The thermoplastic resin composition C-8 was prepared by mixing 30 parts by weight of the graft copolymer powder B-8 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실시예Example 9 9
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-8 대신에 대입경 부타디엔 고무질 중합체 라텍스 A-7을 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-9를 제조하였다.Graft copolymer powder B-9 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-7 was added instead of the large particle butadiene rubber polymer latex A-8.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-9 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-9를 제조하였다.The thermoplastic resin composition C-9 was prepared by mixing 30 parts by weight of the graft copolymer powder B-9 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실시예Example 10 10
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-8 대신에 부타디엔 고무질 중합체 라텍스 A-9를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-10을 제조하였다.Graft copolymer powder B-10 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-9 was added instead of the large particle butadiene rubber polymer latex A-8.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-10 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-10을 제조하였다.A thermoplastic resin composition C-10 was prepared by mixing 30 parts by weight of the graft copolymer powder B-10 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실시예Example 11 11
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 대신에 대입경 고무질 중합체 라텍스 A-4를 투입하고, 대입경 부타디엔 고무질 중합체 A-8 대신에 대입경 부타디엔 고무질 중합체 A-9를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-11을 제조하였다.Except that the large-diameter rubbery polymer latex A-4 was added in place of the large-diameter butadiene rubbery polymer latex A-3, and the large-diameter butadiene rubbery polymer A-9 was added in place of the large-diameter butadiene rubbery polymer A-8. Graft copolymer powder B-11 was prepared in the same manner as in 1.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-11 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-11을 제조하였다.The thermoplastic resin composition C-11 was prepared by mixing 30 parts by weight of the graft copolymer powder B-11 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실시예Example 12 12
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 A-3 36 중량부(고형분 기준) 대신에 대입경 부타디엔 고무질 중합체 라텍스 A-4 40 중량부(고형분 기준)을 투입하고, 대입경 부타디엔 고무질 중합체 A-8 24 중량부(고형분 기준) 대신에 부타디엔 고무질 중합체 라텍스 A-9 20 중량부(고형분 기준)를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-12을 제조하였다.Butadiene rubber polymer A-3 40 parts by weight butadiene rubber polymer latex A-4 40 parts by weight (based on solids) instead of 36 parts by weight (based on solids), butadiene rubber polymer A-8 24 parts by weight (solids) Graft copolymer powder B-12 was prepared in the same manner as in Example 1, except that 20 parts by weight of butadiene rubbery polymer latex A-9 (based on solids) was added instead.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-12 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-12을 제조하였다.The thermoplastic resin composition C-12 was prepared by mixing 30 parts by weight of the graft copolymer powder B-12 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
비교예Comparative example 1 One
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
스티렌 30 중량부, 아크릴로니트릴 10 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.6 중량부, 유화제로 로진산 칼륨염 1.0 중량부, 분자량 조절제로 t-도데실 머캅탄 0.4 중량부 및 이온교환수 25 중량부를 포함하는 제1 혼합물을 준비하였다.30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.6 parts by weight of t-butyl hydroperoxide as initiator, 1.0 part by weight of potassium rosin salt as emulsifier, 0.4 part by weight of t-dodecyl mercaptan as molecular weight modifier and ion exchange water A first mixture comprising 25 parts by weight was prepared.
또한, 덱스트로즈 0.027 중량부, 피로인산 나트륨 0.002 중량부 및 황산제1철 0.001 중량부를 포함하는 제2 혼합물을 준비하였다.In addition, a second mixture including 0.027 parts by weight of dextrose, 0.002 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate was prepared.
질소 치환된 반응기에 대입경 부타디엔 고무질 중합체 라텍스 A-3 60 중량부(고형분 기준) 및 이온교환수 100 중량부를 투입하였다. 60 parts by weight of the large-diameter butadiene rubbery polymer latex A-3 (based on solids) and 100 parts by weight of ion-exchanged water were added to a nitrogen-substituted reactor.
이어서, 상기 반응기에 상기 제1 혼합물과 제2 혼합물을 70 ℃에서 일정한 속도로 2시간 동안 연속 투입하면서 중합하였다.Subsequently, the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
이어서, 상기 반응기에 산화환원계 촉매로 덱스트로즈 0.05 중량부, 피로인산 나트륨 0.03 중량부 및 황산제1철 0.001 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.05 중량부를 일괄 투입하고, 80 ℃로 1 시간에 걸쳐 승온하면서 중합을 수행한 후, 중합을 종료하여, 그라프트 공중합체 라텍스를 제조하였다. 수득된 그라프트 공중합체 라텍스를 응집, 숙성, 세척, 탈수 및 건조하고 그라프트 공중합체 분말 B-13을 수득하였다.Subsequently, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide as an initiator were collectively added to the reactor at 80 ° C. After the polymerization was carried out while raising the temperature over 1 hour, the polymerization was terminated to prepare a graft copolymer latex. The graft copolymer latex obtained was coagulated, aged, washed, dehydrated and dried to obtain graft copolymer powder B-13.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-13 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물을 제조하였다.The thermoplastic resin composition was prepared by mixing 30 parts by weight of the graft copolymer powder B-13 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
비교예Comparative example 2 2
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
스티렌 30 중량부, 아크릴로니트릴 10 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.6 중량부, 유화제로 로진산 칼륨염 1.0 중량부, 분자량 조절제로 α-메틸 스티렌 다이머 0.4 중량부 및 이온교환수 25 중량부를 포함하는 제1 혼합물을 준비하였다.30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.6 parts by weight of t-butyl hydroperoxide as initiator, 1.0 part by weight of potassium rosin salt as emulsifier, 0.4 part by weight of α-methyl styrene dimer as molecular weight modifier and 25 A first mixture including parts by weight was prepared.
또한, 덱스트로즈 0.027 중량부, 피로인산 나트륨 0.002 중량부 및 황산제1철 0.001 중량부를 포함하는 제2 혼합물을 준비하였다.In addition, a second mixture including 0.027 parts by weight of dextrose, 0.002 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate was prepared.
질소 치환된 반응기에 대입경 부타디엔 고무질 중합체 라텍스 A-3 60 중량부(고형분 기준) 및 이온교환수 100 중량부를 투입하였다. 60 parts by weight of the large-diameter butadiene rubbery polymer latex A-3 (based on solids) and 100 parts by weight of ion-exchanged water were added to a nitrogen-substituted reactor.
이어서, 상기 반응기에 상기 제1 혼합물과 제2 혼합물을 70 ℃에서 일정한 속도로 2시간 동안 연속 투입하면서 중합하였다.Subsequently, the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
이어서, 상기 반응기에 산화환원계 촉매로 덱스트로즈 0.05 중량부, 피로인산 나트륨 0.03 중량부 및 황산제1철 0.001 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.05 중량부를 일괄 투입하고, 80 ℃로 1 시간에 걸쳐 승온하면서 중합을 수행한 후, 중합을 종료하여, 그라프트 공중합체 라텍스를 제조하였다. 수득된 그라프트 공중합체 라텍스를 응집, 숙성, 세척, 탈수 및 건조하고 그라프트 공중합체 분말 B-14를 수득하였다.Subsequently, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide as an initiator were collectively added to the reactor at 80 ° C. After the polymerization was carried out while raising the temperature over 1 hour, the polymerization was terminated to prepare a graft copolymer latex. The graft copolymer latex obtained was coagulated, aged, washed, dehydrated and dried to obtain graft copolymer powder B-14.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-14 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)을 70 중량부를 혼합하여 열가소성 수지 조성물 C-14을 제조하였다.The thermoplastic resin composition C-14 was prepared by mixing 30 parts by weight of the graft copolymer powder B-14 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
비교예Comparative example 3 3
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
스티렌 30 중량부, 아크릴로니트릴 10 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.6 중량부, 유화제로 로진산 칼륨염 1.0 중량부, 분자량 조절제로 t-도데실 머캅탄 0.4 중량부 및 이온교환수 25 중량부를 포함하는 제1 혼합물을 준비하였다.30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.6 parts by weight of t-butyl hydroperoxide as initiator, 1.0 part by weight of potassium rosin salt as emulsifier, 0.4 part by weight of t-dodecyl mercaptan as molecular weight modifier and ion exchange water A first mixture comprising 25 parts by weight was prepared.
또한, 덱스트로즈 0.027 중량부, 피로인산 나트륨 0.002 중량부 및 황산제1철 0.001 중량부를 포함하는 제2 혼합물을 준비하였다.In addition, a second mixture including 0.027 parts by weight of dextrose, 0.002 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate was prepared.
질소 치환된 반응기에 대입경 부타디엔 고무질 중합체 라텍스 A-8 60 중량부(고형분 기준) 및 이온교환수 100 중량부를 투입하였다. 60 parts by weight of the large-diameter butadiene rubbery polymer latex A-8 (based on solids) and 100 parts by weight of ion-exchanged water were added to a nitrogen-substituted reactor.
이어서, 상기 반응기에 상기 제1 혼합물과 제2 혼합물을 70 ℃에서 일정한 속도로 2시간 동안 연속 투입하면서 중합하였다.Subsequently, the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
이어서, 상기 반응기에 산화환원계 촉매로 덱스트로즈 0.05 중량부, 피로인산 나트륨 0.03 중량부 및 황산제1철 0.001 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.05 중량부를 일괄 투입하고, 80 ℃로 1 시간에 걸쳐 승온하면서 중합을 수행한 후, 중합을 종료하여, 그라프트 공중합체 라텍스를 제조하였다. 수득된 그라프트 공중합체 라텍스를 응집, 숙성, 세척, 탈수 및 건조하고 그라프트 공중합체 분말 B-15를 수득하였다.Subsequently, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide as an initiator were collectively added to the reactor at 80 ° C. After the polymerization was carried out while raising the temperature over 1 hour, the polymerization was terminated to prepare a graft copolymer latex. The graft copolymer latex obtained was coagulated, aged, washed, dehydrated and dried to obtain graft copolymer powder B-15.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-15 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-15을 제조하였다.The thermoplastic resin composition C-15 was prepared by mixing 30 parts by weight of the graft copolymer powder B-15 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
비교예Comparative example 4 4
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
스티렌 30 중량부, 아크릴로니트릴 10 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.6 중량부, 유화제로 로진산 칼륨염 1.0 중량부, 분자량 조절제로 α-메틸 스티렌 다이머 0.4 중량부 및 이온교환수 25 중량부를 포함하는 제1 혼합물을 준비하였다.30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.6 parts by weight of t-butyl hydroperoxide as initiator, 1.0 part by weight of potassium rosin salt as emulsifier, 0.4 part by weight of α-methyl styrene dimer as molecular weight modifier and 25 A first mixture including parts by weight was prepared.
또한, 덱스트로즈 0.027 중량부, 피로인산 나트륨 0.002 중량부 및 황산제1철 0.001 중량부를 포함하는 제2 혼합물을 준비하였다.In addition, a second mixture including 0.027 parts by weight of dextrose, 0.002 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate was prepared.
질소 치환된 반응기에 대입경 부타디엔 고무질 중합체 라텍스 A-8 60 중량부(고형분 기준) 및 이온교환수 100 중량부를 투입하였다. 60 parts by weight of the large-diameter butadiene rubbery polymer latex A-8 (based on solids) and 100 parts by weight of ion-exchanged water were added to the reactor substituted with nitrogen.
이어서, 상기 반응기에 상기 제1 혼합물과 제2 혼합물을 70 ℃에서 일정한 속도로 2시간 동안 연속 투입하면서 중합하였다.Subsequently, the first and second mixtures were polymerized into the reactor while continuously input at 70 ° C. for 2 hours at a constant rate.
이어서, 상기 반응기에 산화환원계 촉매로 덱스트로즈 0.05 중량부, 피로인산 나트륨 0.03 중량부 및 황산제1철 0.001 중량부, 개시제로 t-부틸 하이드로퍼옥사이드 0.05 중량부를 일괄 투입하고, 80 ℃로 1 시간에 걸쳐 승온하면서 중합을 수행한 후, 중합을 종료하여, 그라프트 공중합체 라텍스를 제조하였다. 수득된 그라프트 공중합체 라텍스를 응집, 숙성, 세척, 탈수 및 건조하고 그라프트 공중합체 분말 B-16을 수득하였다.Subsequently, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrophosphate and 0.001 part by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide as an initiator were collectively added to the reactor at 80 ° C. After the polymerization was carried out while raising the temperature over 1 hour, the polymerization was terminated to prepare a graft copolymer latex. The graft copolymer latex obtained was coagulated, aged, washed, dehydrated and dried to obtain graft copolymer powder B-16.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-16 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-16을 제조하였다.The thermoplastic resin composition C-16 was prepared by mixing 30 parts by weight of the graft copolymer powder B-16 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
비교예Comparative example 5 5
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 대신에 대입경 부타디엔 고무질 중합체 라텍스 A-1를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-17을 제조하였다.Graft copolymer powder B-17 was prepared in the same manner as in Example 1 except that the large particle butadiene rubber polymer latex A-1 was added instead of the large particle butadiene rubber polymer latex A-3.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-17 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-17을 제조하였다.30 parts by weight of the graft copolymer powder B-17 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-17.
비교예Comparative example 6 6
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-3 대신에 부타디엔 고무질 중합체 라텍스 A-5를 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-18을 제조하였다.Graft copolymer powder B-18 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-5 was added instead of the large particle butadiene rubber polymer latex A-3.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-18 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-18을 제조하였다.The thermoplastic resin composition C-18 was prepared by mixing 30 parts by weight of the graft copolymer powder B-18 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
비교예Comparative example 7 7
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
대입경 부타디엔 고무질 중합체 라텍스 A-8 대신에 부타디엔 고무질 중합체 라텍스 A-6을 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-19를 제조하였다.Graft copolymer powder B-19 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-6 was added instead of the large particle butadiene rubber polymer latex A-8.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-19 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-19를 제조하였다.30 parts by weight of the graft copolymer powder B-19 and 92 parts by weight of LG Chem (styrene / acrylonitrile copolymer) were mixed to prepare a thermoplastic resin composition C-19.
비교예Comparative example 8 8
<그라프트 공중합체 분말의 제조><Production of Graft Copolymer Powder>
부타디엔 고무질 중합체 라텍스 A-8 대신에 부타디엔 고무질 중합체 라텍스 A-10을 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 그라프트 공중합체 분말 B-20을 제조하였다.Graft copolymer powder B-20 was prepared in the same manner as in Example 1 except that butadiene rubber polymer latex A-10 was added instead of butadiene rubber polymer latex A-8.
<열가소성 수지 조성물><Thermoplastic Resin Composition>
상기 그라프트 공중합체 분말 B-20 30 중량부 및 엘지화학 社의 92HR(스티렌/아크릴로니트릴 공중합체)를 70 중량부를 혼합하여 열가소성 수지 조성물 C-20을 제조하였다.The thermoplastic resin composition C-20 was prepared by mixing 30 parts by weight of the graft copolymer powder B-20 and 70 parts by weight of 92HR (styrene / acrylonitrile copolymer) manufactured by LG Chemical.
실험예Experimental Example 1 One
실시예 및 비교예의 그라프트 공중합체의 중합전환율, 그라프트율 및 중량평균분자량을 측정하고 하기 [표 2] 내지 [표 5]에 기재하였다.The polymerization conversion rate, the graft rate and the weight average molecular weight of the graft copolymers of Examples and Comparative Examples were measured and described in the following [Table 2] to [Table 5].
(1) 중합전환율(%): 그라프트 공중합체 라텍스 2g을 150 ℃의 열풍 건조기 내에서 15분 동안 건조 후, 무게를 측정하여 총 고형분 함량(TSC)을 구하고 하기 식을 이용하여 산출하였다.(1) Polymerization Conversion Rate (%): After graft copolymer latex was dried in a hot air dryer at 150 ° C. for 15 minutes, the weight was measured to obtain a total solid content (TSC) and calculated using the following equation.
중합전환율(%) = [총 고형분 함량(TSC) × (투입된 단량체 및 부원료 중량부) / 100] - (단량체 외 투입된 부원료 중량부)Polymerization Conversion Rate (%) = [Total Solids Content (TSC) × (parts of monomers and subsidiary materials added) / 100]-(parts of subsidiary materials added to the monomer)
(2) 그라프트율(%): 그라프트 공중합체 분말 2 g을 아세톤 300 ㎖에 넣고 24 시간 동안 교반하였다. 이 용액을 초원심분리기에 투입한 후, 상등액을 분리한 뒤, 상등액에 메탄올에 떨어뜨려 그라프트되지 않은 부분을 수득하고, 이를 85 ℃에서 건조시켜 건조물의 수득한 후, 건조물의 함량을 측정한 뒤, 하기 식에 따라 그라프트율을 산출하였다.(2) Graft ratio (%): 2 g of the graft copolymer powder was added to 300 ml of acetone and stirred for 24 hours. After the solution was put into an ultracentrifuge, the supernatant was separated, and the supernatant was dropped in methanol to obtain an grafted portion, which was dried at 85 ° C. to obtain a dried product, and then the content of the dried product was measured. Then, the graft ratio was computed according to the following formula.
그라프트율(%) = [(그라프트된 SAN 공중합체의 함량) / (대입경 부타디엔 고무질 중합체의 함량의 합)] × 100Graft rate (%) = [(content of grafted SAN copolymer) / (sum of content of large particle butadiene rubbery polymer)] × 100
* 그라프트된 SAN 공중합체의 함량 = (수득된 건조물의 함량) - (대입경 부타디엔 고무질 중합체의 함량의 합)* Content of grafted SAN copolymer = (content of dry matter obtained)-(sum of content of large particle butadiene rubbery polymer)
* 대입경 부타디엔 고무질 중합체의 함량의 합: 이론상 투입된 대입경 부타디엔 고무질 중합체의 고형분 함량* Sum of content of large particle butadiene rubber polymer: Solid content of theoretically added large particle butadiene rubber polymer
(3)쉘의 중량평균분자량(g/mol): 그라프트율 측정 방법에서 수득된 상등액을 50 ℃의 열풍 오븐에 건조하였다. 그 후, 건조물을 THF에 녹여 용액(농도: 0.1 중량%)을 제조하고, 이를 0.1 ㎛ 필터를 통해 걸려낸 뒤 최종적으로 GPC를 이용하여 측정하였다.(3) Weight average molecular weight (g / mol) of the shell: The supernatant obtained by the graft ratio measuring method was dried in a hot air oven at 50 ° C. Thereafter, the dried product was dissolved in THF to prepare a solution (concentration: 0.1% by weight), which was hung through a 0.1 μm filter and finally measured using GPC.
실험예Experimental Example 2 2
실시예 및 비교예의 열가소성 수지 조성물을 210 ℃로 설정된 이축 압출기에 투입하고 압출하여 펠렛을 제조하였다. 상기 펠렛의 물성을 하기와 같은 방법으로 측정하였고, 그 결과를 하기 [표 2] 내지 [표 5]에 기재하였다.The thermoplastic resin composition of the Example and the comparative example was put into the twin screw extruder set to 210 degreeC, and extruded, and the pellet was manufactured. The physical properties of the pellets were measured in the following manner, and the results are shown in the following [Table 2] to [Table 5].
(1) 유동지수(g/10min): ASTM D1238에 의거하여 측정하였다.(1) Flow index (g / 10min): Measured according to ASTM D1238.
(2) 휘발성 유기 화합물의 잔류량(ppm): 가스 크로마토그라피 설비(상품명: GC, 제조사: Agilent)를 이용하여 휘발성 유기 화합물의 잔류량을 측정하였다.(2) Residual amount of volatile organic compounds (ppm): The residual amount of volatile organic compounds was measured using a gas chromatography equipment (trade name: GC, manufacturer: Agilent).
실험예Experimental Example 3 3
실험예 1에서 제조한 펠렛을 사출하여 시편을 제조하고, 그 물성을 하기와 같은 방법으로 측정하였고, 그 결과를 하기 [표 2] 내지 [표 5]에 기재하였다.The pellet prepared in Experimental Example 1 was injected to prepare a specimen, and the physical properties thereof were measured in the following manner, and the results are shown in the following [Table 2] to [Table 5].
(1) 표면돌기 개수: 시편을 필름 시트로 제조하여 1㎡ 당 시트 내 돌기크기가 0.3 ㎛ 이상인 것만 셌다.(1) Number of surface protrusions: The specimens were made of a film sheet, and only the protrusion size in the sheet per 1 m 2 was 0.3 µm or more.
(2) 낙구 충격강도(N): ASTM D3763에 의거하여 측정하였다.(2) Falling ball impact strength (N): Measured according to ASTM D3763.
(3) 노치드 아이조드 충격강도(Notched Izod Impact Strength, ㎏f·㎝/㎝): 1/4 In의 시편을 이용하여 ASTM D256에 의거하여 측정하였다.(3) Notched Izod Impact Strength (kgf · cm / cm): Measured according to ASTM D256 using a 1/4 In specimen.
구분division 실시예Example
1One 22 33 44 55 66
대입경부타디엔 고무질 중합체(중량부)Large particle butadiene rubbery polymer (part by weight) A-1A-1 -- -- -- -- -- --
A-2A-2 -- -- -- -- -- --
A-3A-3 3636 4040 4545 4040 2020 2020
A-4A-4 -- -- -- -- -- --
A-5A-5 -- -- -- -- -- --
A-6A-6 -- -- -- -- -- --
A-7A-7 -- -- -- -- -- --
A-8A-8 2424 2020 1515 2020 4040 4040
A-9A-9 -- -- -- -- -- --
A-10A-10 -- -- -- -- -- --
스티렌(중량부)Styrene (part by weight) 3030 3030 3030 3030 3030 3030
아크릴로니트릴(중량부)Acrylonitrile (parts by weight) 1010 1010 1010 1010 1010 1010
분자량 조절제(중량부)Molecular weight regulator (part by weight) t-도데실 머캅탄t-dodecyl mercaptan 0.260.26 0.260.26 0.260.26 0.140.14 0.260.26 0.140.14
α-메틸 스티렌 다이머α-methyl styrene dimer 0.140.14 0.140.14 0.140.14 0.260.26 0.140.14 0.260.26
중합전환율Polymerization conversion rate 9595 9797 9696 9595 9696 9494
그라프트율Graft rate 3939 4848 3838 4040 3737 4141
쉘의 중량평균분자량Shell weight average molecular weight 88,00088,000 75,00075,000 84,00084,000 85,00085,000 100,000100,000 80,00080,000
유동지수Flow index 7.27.2 7.57.5 7.07.0 6.86.8 6.56.5 6.96.9
휘발성 유기 화합물의 잔류량Residual amount of volatile organic compounds 820820 700700 800800 850850 900900 900900
표면돌기 개수Number of surface protrusions 66 33 77 66 77 55
낙구 충격강도Falling Impact Strength 3,9003,900 4,3004,300 3,8003,800 3,8003,800 4,4004,400 4,0004,000
노치드 아이조드 충격강도Notched Izod Impact Strength 3131 3333 3030 3232 3131 3030
구분division 실시예Example
77 88 99 1010 1111 1212
대입경부타디엔 고무질 중합체(중량부)Large particle butadiene rubbery polymer (part by weight) A-1A-1 -- -- -- -- --
A-2A-2 3636 -- -- -- --
A-3A-3 -- -- 3636 3636 -- --
A-4A-4 -- 3636 -- 3636 4040
A-5A-5 -- -- -- -- --
A-6A-6 -- -- -- -- --
A-7A-7 -- -- 2424 -- -- --
A-8A-8 2424 2424 -- -- -- --
A-9A-9 -- -- -- 2424 2424 2020
A-10A-10 -- -- -- -- -- --
스티렌(중량부)Styrene (part by weight) 3030 3030 3030 3030 3030 3030
아크릴로니트릴(중량부)Acrylonitrile (parts by weight) 1010 1010 1010 1010 1010 1010
분자량 조절제(중량부)Molecular weight regulator (part by weight) t-도데실 머캅탄t-dodecyl mercaptan 0.260.26 0.260.26 0.260.26 0.260.26 0.260.26 0.260.26
α-메틸 스티렌 다이머α-methyl styrene dimer 0.140.14 0.140.14 0.140.14 0.140.14 0.140.14 0.140.14
중합전환율Polymerization conversion rate 9696 9696 9696 9696 9696 9696
그라프트율Graft rate 3939 4040 4141 4040 4040 4343
쉘의 중량평균분자량Shell weight average molecular weight 83,00083,000 84,00084,000 82,00082,000 85,00085,000 85,00085,000 77,00077,000
유동지수Flow index 7.27.2 7.27.2 7.37.3 7.07.0 7.17.1 7.37.3
휘발성 유기 화합물의 잔류량Residual amount of volatile organic compounds 800800 810810 790790 820820 790790 750750
표면돌기 개수Number of surface protrusions 44 55 44 44 55 44
낙구 충격강도Falling Impact Strength 3,8503,850 3,9503,950 4,0004,000 3,8003,800 3,9503,950 4,2004,200
노치드 아이조드 충격강도Notched Izod Impact Strength 3333 3434 3535 3232 3232 3232
구분division 비교예Comparative example
1One 22 33 44
대입경부타디엔 고무질 중합체(중량부)Large particle butadiene rubbery polymer (part by weight) A-1A-1 -- -- -- --
A-2A-2 -- -- -- --
A-3A-3 6060 6060 -- --
A-4A-4 -- -- -- --
A-5A-5 -- -- -- --
A-6A-6 -- -- -- --
A-7A-7 -- -- -- --
A-8A-8 -- -- 6060 6060
A-9A-9 -- -- -- --
A-10A-10 -- -- -- --
스티렌(중량부)Styrene (part by weight) 3030 3030 3030 3030
아크릴로니트릴(중량부)Acrylonitrile (parts by weight) 1010 1010 1010 1010
분자량 조절제(중량부)Molecular weight regulator (part by weight) t-도데실 머캅탄t-dodecyl mercaptan 0.40.4 -- 0.40.4 --
α-메틸 스티렌 다이머α-methyl styrene dimer -- 0.40.4 -- 0.40.4
중합전환율Polymerization conversion rate 9898 9494 97.597.5 9494
그라프트율Graft rate 3838 3535 3737 3333
쉘의 중량평균분자량Shell weight average molecular weight 60,00060,000 95,00095,000 65,00065,000 105,000105,000
유동지수Flow index 7.87.8 6.66.6 7.67.6 6.76.7
휘발성 유기 화합물의 잔류량Residual amount of volatile organic compounds 1,2001,200 1,3001,300 1,3501,350 1,1501,150
표면돌기 개수Number of surface protrusions 2525 2828 3030 3535
낙구 충격강도Falling Impact Strength 3,7003,700 3,5003,500 3,9003,900 3,6003,600
노치드 아이조드 충격강도Notched Izod Impact Strength 2828 2929 2727 2828
구분division 비교예Comparative example
55 66 77 88
대입경부타디엔 고무질 중합체(중량부)Large particle butadiene rubbery polymer (part by weight) A-1A-1 3636 -- -- --
A-2A-2 -- -- -- --
A-3A-3 -- -- 3636 3636
A-4A-4 -- -- -- --
A-5A-5 -- 3636 -- --
A-6A-6 -- -- 2424 --
A-7A-7 -- -- -- --
A-8A-8 2424 2424 -- --
A-9A-9 -- -- -- --
A-10A-10 -- -- -- 2424
스티렌(중량부)Styrene (part by weight) 3030 3030 3030 3030
아크릴로니트릴(중량부)Acrylonitrile (parts by weight) 1010 1010 1010 1010
분자량 조절제(중량부)Molecular weight regulator (part by weight) t-도데실 머캅탄t-dodecyl mercaptan 0.260.26 0.260.26 0.260.26 0.260.26
α-메틸 스티렌 다이머α-methyl styrene dimer 0.140.14 0.140.14 0.140.14 0.140.14
중합전환율Polymerization conversion rate 9696 95.595.5 9696 9696
그라프트율Graft rate 3535 3434 3434 3535
쉘의 중량평균분자량Shell weight average molecular weight 83,00083,000 92,00092,000 85,00085,000 83,00083,000
유동지수Flow index 6.86.8 6.56.5 6.76.7 6.86.8
휘발성 유기 화합물의 잔류량Residual amount of volatile organic compounds 1,2501,250 1,4001,400 1,3801,380 1,3401,340
표면돌기 개수Number of surface protrusions 3333 3434 3232 3333
낙구 충격강도Falling Impact Strength 3,8003,800 3,6003,600 3,5003,500 3,7003,700
노치드 아이조드 충격강도Notched Izod Impact Strength 2929 2727 2626 2727
표 2 내지 5를 참조하면, 입도분포가 0.35 내지 0.4인 대입경 부타디엔 고무질 중합체와 입도분포가 0.2 내지 0.4인 대입경 부타디엔 고무질 중합체로 제조된 실시예 1 내지 12의 그라프트 공중합체는 그라프트율이 37% 이상이고, 쉘의 중량평균분자량이 75,000 g/mol 이상인 것을 확인할 수 있었다. 하지만, 비교예 1 내지 12의 그라프트 공중합체는 그라프트율이 37% 이상이면, 쉘의 중량평균분자량이 65,000 g/mol 이하이고, 그라프트율이 37% 미만이면, 중량평균분자량이 75,000 g/mol 이상인 것을 확인할 수 있었다.또한, 실시예 1 내지 12의 열가소성 수지 조성물은 휘발성 유기 화합물의 잔류량이 적으므로, 냄새 특성이 우수하고, 표면돌기 개수가 적으므로 표면 특성이 우수한 것을 확인할 수 있었다. 낙구 충격강도 및 노치드 아이조드 충격강도가 우수하므로 기계적 특성도 우수한 것을 확인할 수 있었다. Referring to Tables 2 to 5, the graft copolymers of Examples 1 to 12 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.35 to 0.4 and a large particle butadiene rubber polymer having a particle size distribution of 0.2 to 0.4 have a graft ratio of 37. It was confirmed that it was% or more and the weight average molecular weight of the shell was 75,000 g / mol or more. However, in the graft copolymers of Comparative Examples 1 to 12, when the graft ratio is 37% or more, the weight average molecular weight of the shell is 65,000 g / mol or less, and when the graft ratio is less than 37%, the weight average molecular weight is 75,000 g / mol or more. In addition, the thermoplastic resin compositions of Examples 1 to 12 had a small amount of residual volatile organic compounds, so that the odor characteristics were excellent, and the number of surface protrusions was small, indicating that the surface characteristics were excellent. It was found that the falling ball impact strength and notched Izod impact strength were also excellent in mechanical properties.
한편, 실시예 2 및 4와, 실시예 5 및 6을 비교하면, t-도데실 머캅탄의 함량이 높을수록, 낙구 충격강도가 개선되는 것을 확인할 수 있었다.On the other hand, comparing Examples 2 and 4 with Examples 5 and 6, the higher the content of t-dodecyl mercaptan, it was confirmed that the falling ball impact strength is improved.
또한, 실시예 1, 7, 8, 비교예 5 및 6을 비교하면, 입도분포가 0.35 내지 0.4인 대입경 부타디엔 고무질 중합체와 입도분포가 0.23인 대입경 부타디엔 고무질 중합체로 제조된 실시예 1, 7 및 8이, 입도분포가 0.34인 대입경 부타디엔 고무질 중합체와 입도분포가 0.23인 대입경 부타디엔 고무질 중합체로 제조된 비교예 5 대비 휘발성 유기 화합물의 잔류량이 현저하게 낮고, 표면돌기 개수도 현저하게 적으며, 낙구 충격강도 및 노치드 아이조드 충격강도가 우수하여 기계적 특성이 우수한 것을 확인할 수 있었다. 또한, 실시예 1, 7 및 8이 입도분포가 0.41인 대입경 부타디엔 고무질 중합체와 입도분포가 0.23인 대입경 부타디엔 고무질 중합체로 제조된 비교예 6 대비 휘발성 유기 화합물의 잔류량이 현저하게 낮고, 표면돌기 개수도 현저하게 적으며, 낙구 충격강도 및 노치드 아이조드 충격강도가 우수하여 기계적 특성이 우수한 것을 확인할 수 있었다. In addition, when comparing Examples 1, 7, 8, Comparative Examples 5 and 6, Examples 1, 7 made of a large particle butadiene rubber polymer having a particle size distribution of 0.35 to 0.4 and a large particle butadiene rubber polymer having a particle size distribution of 0.23 And 8, the residual amount of volatile organic compounds is significantly lower than that of Comparative Example 5 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.34 and a large particle butadiene rubber polymer having a particle size distribution of 0.23, and the number of surface protrusions is markedly low. , Falling ball impact strength and notched Izod impact strength were excellent mechanical properties. In addition, Examples 1, 7 and 8 have a significantly lower residual amount of volatile organic compounds than Comparative Example 6 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.41 and a large particle butadiene rubber polymer having a particle size distribution of 0.23, and having a surface protrusion. In addition, the number was remarkably small, and the fall impact strength and the notched Izod impact strength were excellent.
또한, 실시예 1, 9, 10, 비교예 7 및 8을 비교하면, 입도분포가 0.37인 대입경 부타디엔 고무질 중합체와 입도분포가 0.2 내지 0.3인 대입경 부타디엔 고무질 중합체로 제조된 실시예 1, 9, 및 10이, 입도분포가 0.37인 대입경 부타디엔 고무질 중합체와 입도분포가 0.19인 대입경 부타디엔 고무질 중합체로 제조된 비교예 7 대비 휘발성 유기 화합물의 잔류량이 현저하게 낮고, 표면돌기 개수도 현저하게 적으며, 낙구 충격강도 및 노치드 아이조드 충격강도가 우수하여 기계적 특성이 우수한 것을 확인할 수 있었다. 또한, 실시예 1, 9, 및 10이 입도분포가 0.37인 대입경 부타디엔 고무질 중합체와 입도분포가 0.31인 대입경 부타디엔 고무질 중합체로 제조된 비교예 8 대비 휘발성 유기 화합물의 잔류량이 현저하게 낮고, 표면돌기 개수도 현저하게 적으며, 낙구 충격강도 및 노치드 아이조드 충격강도가 우수하여 기계적 특성이 우수한 것을 확인할 수 있었다.In addition, when comparing Examples 1, 9, 10, Comparative Examples 7 and 8, Examples 1, 9 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.37 and a large particle butadiene rubber polymer having a particle size distribution of 0.2 to 0.3 , And 10 have a significantly lower residual amount of volatile organic compounds and a significantly smaller number of surface protrusions than Comparative Example 7 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.37 and a large particle butadiene rubber polymer having a particle size distribution of 0.19. In addition, it was confirmed that the falling ball impact strength and notched Izod impact strength excellent mechanical properties. In addition, Examples 1, 9, and 10 had a significantly lower residual amount of volatile organic compounds compared to Comparative Example 8 prepared from a large particle butadiene rubber polymer having a particle size distribution of 0.37 and a large particle butadiene rubber polymer having a particle size distribution of 0.31. In addition, the number of protrusions was remarkably small, and it was confirmed that the falling ball impact strength and the notched Izod impact strength were excellent.
한편, 한 종류의 대입경 부타디엔 고무질 중합체로만 제조된 비교예 1 내지 4의 경우, 실시예 대비 휘발성 유기 화합물의 잔류량이 많으므로 냄새 특성이 우수하지 못하고, 표면돌기 개수가 많으므로 표면특성이 우수하지 못하고, 낙구 충격강도 및 충격강도가 저하된 것을 확인할 수 있었다. On the other hand, in Comparative Examples 1 to 4 made of only one type of large-diameter butadiene rubbery polymer, the amount of residual volatile organic compounds compared to the examples is not good because the odor characteristics are not good, and the number of surface projections is large, the surface properties are not good It could not be confirmed that falling ball impact strength and impact strength were reduced.

Claims (12)

  1. 제1 공액 디엔계 중합체, 제2 공액 디엔계 중합체, 방향족 비닐계 단량체 및 비닐 시안계 단량체를 중합하는 단계를 포함하며,Polymerizing a first conjugated diene polymer, a second conjugated diene polymer, an aromatic vinyl monomer, and a vinyl cyan monomer,
    상기 제1 공액 디엔계 중합체는 입도분포가 0.346 내지 0.404이고,The first conjugated diene polymer has a particle size distribution of 0.346 to 0.404,
    상기 제2 공액 디엔계 중합체는 입도분포가 0.196 내지 0.304인 그라프트 공중합체의 제조방법.The second conjugated diene-based polymer has a particle size distribution of 0.196 to 0.304 method for producing a graft copolymer.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 공액 디엔계 중합체 및 제2 공액 디엔계 중합체는 각각 평균입경이 0.2 내지 0.4 ㎛인 그라프트 공중합체의 제조방법.The first conjugated diene-based polymer and the second conjugated diene-based polymer have a mean particle size of 0.2 to 0.4 ㎛ respectively.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 공액 디엔계 중합체는 입도분포가 0.35 내지 0.4인 것인 그라프트 공중합체의 제조방법.The first conjugated diene-based polymer has a particle size distribution of 0.35 to 0.4 method of producing a graft copolymer.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 및 제2 공액 디엔계 중합체는 각각The first and second conjugated diene-based polymers, respectively
    공액 디엔계 단량체를 중합하여 소입경 공액 디엔계 중합체를 제조한 후, 상기 소입경 공액 디엔계 중합체를 비대화하여 제조하는 방법으로 제조하는 것인 그라프트 공중합체의 제조방법.A method for producing a graft copolymer, which is prepared by polymerizing a conjugated diene monomer to prepare a small particle conjugated diene polymer and then enlarging the small particle conjugated diene polymer.
  5. 청구항 4에 있어서,The method according to claim 4,
    상기 소입경 디엔계 고무질 중합체는 겔 함량이 90 % 이상인 것인 그라프트 공중합체의 제조방법.The small particle diene rubber polymer is a graft copolymer manufacturing method of 90% or more gel content.
  6. 청구항 1에 있어서,The method according to claim 1,
    상기 제2 공액 디엔계 중합체는 입도분포가 0.2 내지 0.3인 것인 그라프트 공중합체의 제조방법.The second conjugated diene-based polymer has a particle size distribution of 0.2 to 0.3 method of producing a graft copolymer.
  7. 청구항 1에 있어서,The method according to claim 1,
    상기 제1 공액 디엔계 중합체와 제2 공액 디엔계 중합체의 중량비는 30:70 내지 80:20인 것인 그라프트 공중합체의 제조방법.The weight ratio of the first conjugated diene-based polymer and the second conjugated diene-based polymer is 30:70 to 80:20 method of producing a graft copolymer.
  8. 청구항 1에 있어서,The method according to claim 1,
    상기 방향족 비닐계 단량체와 비닐 시안계 단량체의 중량비는 80:20 내지 65:35인 것인 그라프트 공중합체의 제조방법.The weight ratio of the aromatic vinyl monomer and the vinyl cyan monomer is 80:20 to 65:35 method of producing a graft copolymer.
  9. 청구항 1에 있어서,The method according to claim 1,
    상기 중합 시 머캅탄계 화합물 및 방향족 비닐계 다이머를 더 투입하는 것인 그라프트 공중합체의 제조방법.Method of producing a graft copolymer is further added to the mercaptan compound and aromatic vinyl dimer during the polymerization.
  10. 청구항 9에 있어서,The method according to claim 9,
    상기 머캅탄계 화합물 및 방향족 비닐계 다이머를 60:40 내지 70:30의 중량비로 투입하는 것인 그라프트 공중합체의 제조방법.Method for producing a graft copolymer is a mercaptan compound and an aromatic vinyl dimer is added in a weight ratio of 60:40 to 70:30.
  11. 청구항 1에 따른 제조방법으로 제조되고,Manufactured by a manufacturing method according to claim 1,
    그라프트율이 37% 이상이고, 쉘의 중량평균분자량이 75,000 g/mol 이상인 그라프트 공중합체.A graft copolymer having a graft ratio of at least 37% and a weight average molecular weight of the shell of at least 75,000 g / mol.
  12. 청구항 11에 따른 그라프트 공중합체; 및Graft copolymers according to claim 11; And
    방향족 비닐계 단량체 유래 단위 및 비닐 시안계 단량체 유래 단위를 포함하는 공중합체를 포함하는 열가소성 수지 조성물로 제조되고,It is made of a thermoplastic resin composition comprising a copolymer comprising an aromatic vinyl monomer derived unit and a vinyl cyan monomer derived unit,
    휘발성 유기 화합물의 잔류량이 1,000 ppm 이하인 열가소성 수지 성형품.A thermoplastic resin molded article having a residual amount of volatile organic compound of 1,000 ppm or less.
PCT/KR2019/001304 2018-02-02 2019-01-30 Preparation method of graft copolymer, graft copolymer, and thermoplastic resin molded article WO2019151776A1 (en)

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