METHOD FOR PREPARING THERMOPLASTIC RESIN, THERMOPLASTIC RESIN, AND THERMOPLASTIC RESIN COMPOSITION COMPRISING SAME

Detailed hereinafter the present invention are described as follows.

The present invention when tank number victims of the thermoplastic resin composition, a mixture when in vitro, without the deterioration of physical properties, the present invention significantly improved low temperature my all kinds of flowers characteristic based on making sure that it has been completed.

The present invention process for preparing thermoplastic resin by passing residual manufacturing method as follows.

The present invention is thermoplastic resin manufacturing method by consiting rubber, (meth) acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound selected from the group consisting 1 species comprising at least graft polymerisation; and said polymerized graft copolymer latex for agglomerating fine step; wherein, said graft polymerization, when said aggregation, or both in the case of graft copolymer 100 parts by weight of said hydrophobic silicon solution 0. 0001 0 but not more. 02 parts by weight to less than characterized in vitro. In this case said polymerization or aggregation (impeller) occur because of the agitation by said impeller when the air bubbles or froth hydrophobic silicon solutions which would then billion number and number, said hydrophobic really cone orgin mixture is but remain in the thermoplastic resin, the thermoplastic resin prepared by the number minimizes pore generating to prevent contraction at low temperatures, and an excellent effect my all kinds of flowers characteristic flow tides.

Example emulsion polymerization may be graft polymerization of said graft, said graft during emulsion polymerization method in vitro method and the addition of said monomer batch components, for continuously and sequentially using in vitro method can be all or part of a, preferably batch input continuous input method can be used together. Example said polymerization is 60 to 85 °C, or in 70 to 85 °C, time 1 to 8, or 3 to 8 hours can be embodiment.

Example emulsion number the emulsion polymerization, polymerization can be embodiment including disclosure number and number atmospheres, graft during emulsion polymerization can be used then a specially number is not one.

Example t - crystalline salts of dodecyl mercaptan said number is atmospheres, such as crystalline salts of dodecyl mercaptan type onethe mercaptan where also the Roh end will be burnt be.

Example said graft copolymer manufacturing method further comprises dehydrating and drying the agglomerated graft copolymer can be.

Said hydrophobic water molecules free affinity hydrophobic silicon solution, surface and fluorinated acrylate monomer units, unit made pushing water molecules at a surface thereof, a description of perceived conventional (hydrophobic) can be understood to exhibit hydrophobic or lipophilic.

For example hydrophobic silicon solution is said graft during emulsion polymerization can take on the role of vesicle number, this number in the bath by resin emulsion polymerization, polymerization and aggregation when the stirring impeller (impeller) due to the bubbles and foam can be a lipid vesicle comprising a number or number for the number of the graphics billion industry.

Said surface-modified silica (silica) hydrophobic silicon solution is for example a silicone compound can be, in this case made of a resin to prevent contraction at low temperatures in the air gap, and an excellent effect my all kinds of flowers characteristic flow tides.

0 example said said silica is hydrophobic silicon precursor solutions. 1 to 10% by weight, 0. 1 to 5% by weight, or 1 to 3% by weight and be included with the, mechanical properties and an excellent effect in low temperature within this range my all kinds of flowers characteristic flow tides.

Said silicone-based compounds are dialkyl polysiloxane and example, in specific embodiments be the dimethyl siloxanes.

Example may be said silica is solid, said dispersed hydrophobic silicon solution thereof can.

Said viscosity in hydrophobic silicon solution is 2,000 cps 25 °C hereinafter, 1,000 cps hereinafter, or may be 100 to 400 cps, prevent resin within this range rate in cold pore generating minimizes, and an excellent effect my all kinds of flowers characteristic flow tides.

Said system according to said hydrophobic silicon solution is silica, [thol[thol] Type, oxidized polyethylene, polyethylene - polypropylene glycol, positive number oil (petroleum) number for the positive number intermediate hydrotreated naphthenic oil (petroleum) and positive number selected from the group consisting of rear view mirror 1 be a mixture including at least one.

Commercial hydrophobic silicone vesicles may be hydrophobic silicon solution said number, specific examples a number brush hemp cloth inventions (Solvay) high pressure liquid coolant, except the implementation being Rhodoline®962.

Example said graft copolymer 100 parts by weight of said hydrophobic silicon solution is 0. 0001 0 but not more. 02 parts by weight less than, 0. 001 0 but not more. 02 parts by weight of less than, or 0. 001 to 0. 015 parts by weight can be kiln, transparency and excellent effect in low temperature within this range my all kinds of flowers characteristic flow tides.

By the present invention consiting thermoplastic rubber, (meth) acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound selected from the group consisting 1 species comprising at least graft polymerized graft copolymer and silica characterized by including a.

10 to 70% by weight said graft copolymer is in one embodiment consiting rubber, 20 to 70% by weight (meth) acrylic acid alkyl ester, 0 to 20% by weight to 30% by weight aromatic vinyl compound 5 and vinyl cyan compound be said material by adhesion.

Said coupling arrangement arranged across one single double bonds consiting rubber consiting said material by a polymer or copolymer of a (conjugated diene) compound components, for example butadiene polymer, butadiene - styrene copolymer and butadiene - acrylonitrile copolymer 1 may be at least one selected from the group consisting of, said system according to said consiting rubber latex can be in the form of rubber consiting colloidal state is dispersed in water. Said 2,500 to 5,000 Å consiting rubber has an average particle diameter for example, 2,600 to 5,000 Å, or 2,600 to 4,000 Å in large-diameter consiting rubber may be, 60 to 99% by weight of gel content, or 70 to 95% by weight and can, 10 to 35 swelling quotient, or 12 and to Wednesday 30, and in this range having excellent impact strength, excellent effect in graft rate flow tides.

Said 10 to 70% by weight with respect to said graft copolymer example consiting rubber, 20 to 70% by weight, or 30 to 60% by weight and be included with the, mechanical properties and physical balance recorded X-grafting in graft polymerization within this range distance and an excellent effect flow tides.

Said (meth) acrylic acid alkyl ester (meth) acrylic acid methyl ester is for example, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2 - ethylhexyl ester, (meth) acrylic acid ester and (meth) acrylic acid esters selected from the group consisting at least one it will be burntit will soak be a 1.

Said (meth) acrylic acid alkyl ester is 20 to 70% by weight of said graft copolymer for example, 20 to 60 weight %, or 30 to 50% by weight and be included with the, with respect to the refractive index of the refractive index of the graft copolymer in this range consiting rubber having excellent transparency effect to the part flow tides.

Example said aromatic vinyl compound is styrene, α - methylstyrene, p - methylstyrene, o - methylstyrene, at least one selected from the group consisting styrene and vinyl toluene ethyl p - 1 be a.

5 to 30% by weight of said aromatic vinyl compounds are said graft copolymer for example, 7 to 30 weight %, or 7% by weight and 20 to be included with the, excellent fluid within this range which is excellent in processability, graft copolymer with respect to the refractive index of the refractive index of the part consiting rubber having excellent transparency effect flow tides.

In the event that said vinyl cyan compound thereby preventing any add, for example acrylonitrile, methacrylonitrile and with eta [khu[khu] reel with nitrile at least one selected from the group consisting 1 be a.

0 to 20% by weight of said vinyl cyan compound is said graft copolymer for example, 0 to 10% by weight, or 1 to 10% by weight and be included with the, yellowing phenomenon in resin composition within this range not guide natural color, solids (coagulum) generated have flat during graft sheath, part of the residual monomers is not detected effect and flow tides.

The weight average molecular weight of 80,000 to 300,000 g/mol said graft copolymer example, 85,000 to 200,000 g/mol, or 90,000 to 110,000 g/mol may be, excellent fluid within this range have excellent, impact strength and excellent chemical resistance effect flow tides.

Said (meth) acrylic acid alkyl esters for example, aromatic vinyl compound and vinyl cyan compound including at least one copolymer selected from the group consisting 1 and coherent light, the refractive index of the rubber consiting ± 0 said difference. 01 can be less than disclosed. Said transparent for imparting to said graft copolymer having a refractive index, said index of refraction of the graft copolymer of said transparency consiting rubber, which graft herein determined by the refractive index of the copolymer, copolymer can be controlled by a refractive index of between monomers in accordance. In addition, based on the refractive index of said consiting rubber, said (meth) acrylic acid alkyl esters, aromatic vinyl compound and vinyl cyan compound including a copolymer having a refractive index of said graft copolymer clarity of the absolute affecting other. I.e., graft copolymer is transparency in order to graft copolymer is used as an index of refraction of the seed consiting rubber, the refractive index of the entire monomer graft herein which difference ± 0. 01 preferably less than.

In another example, (meth) acrylic acid alkyl esters, aromatic vinyl compounds and reacting compounds including copolymer and coherent light, the refractive index of the rubber consiting ± 0 said difference. 008 hereinafter, or ± 0. 005 hereinafter may be, excellent effects in transparency within this range flow tides.

In specific embodiments, of the present invention in the embodiment having a refractive index of polybutadiene rubber used in 1. 518 and, said rubber grafted copolymers having a refractive index of each monomeric component consiting methyl methacrylate 1. 49, styrene 1. 59, acrylonitrile 1. 518 and, these monomer having a refractive index of each monomer can be adjustable in accordance including copolymer, said copolymer can be calculated by expressions (RI) is a refractive index of 1.

Said Wti % and weight of each monomer comprises a copolymer, the copolymer RIi within each refractive index monomers are disclosed.

Example methylation may be said silica is silica (methylated silica), dimethyl siloxane surface-modified silica (silica) said methylation silica is and which means, in this case made of a resin to prevent contraction at low temperatures in the air gap, and an excellent effect my all kinds of flowers characteristic flow tides.

By the present invention including a thermoplastic resin composition comprising said thermoplastic resin and acrylic copolymer characterized.

Said (meth) acrylic acid alkyl ester according to the acrylic copolymer, an aromatic vinyl compound and a compound comprising reacting said material by at least one selected from the group consisting 1 assemblies can be.

30 to 80% by weight (meth) acrylic acid alkyl ester example said acrylic copolymer, 10 to 40% by weight to 20% by weight of aromatic vinyl compound and a vinyl cyan compound assemblies can be said material by 0.

Said (meth) acrylic acid alkyl ester (meth) acrylic acid methyl ester is for example, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2 - ethylhexyl ester, (meth) acrylic acid ester and (meth) acrylic acid esters it will be burntit will soak 1 may be at least one selected from the group consisting, 30 to 80% by weight relative to said acrylic copolymer, 30 to 75% by weight, or 60 to 75% by weight and be included with the, excellent effects in impact strength and transparency within this range flow tides.

Example said aromatic vinyl compound is styrene, α - methylstyrene, p - methylstyrene, o - methylstyrene, selected from the group consisting styrene and vinyl toluene ethyl p - 1 may be at least one, 10 to 40% by weight relative to said acrylic copolymer, 15 to 40 weight %, or 15% by weight and 30 to be included with the, and an excellent effect in mechanical properties and physical balance within this range flow tides.

Said reacting compounds are for example acrylonitrile, methacrylonitrile and with eta [khu[khu] reel with nitrile may be at least one selected from the group consisting of 1, 0 to 20% by weight relative to said acrylic copolymer, 1 to 15% by weight, or 3 to 10% by weight can be included, without yellowing phenomenon in resin composition within this range, excellent effects in mechanical properties and transparency flow tides.

Weight average molecular weight of 80,000 to 300,000 g/mol example said acrylic copolymer, 80,000 to 200,000 g/mol, or 90,000 to 150,000 g/mol may be, and in this range having excellent impact strength, excellent processability and an excellent effect fluid flow tides.

In one embodiment said acrylic copolymer and coherent light, the refractive index of the thermoplastic resin said difference ± 0. 01 can be less than disclosed. For imparting said transparency to said thermoplastic resin composition having a refractive index, transparency is said thermoplastic resin and said thermoplastic resin composition, determined by the refractive index of the acrylic copolymer, having a refractive index of said acrylic copolymer can be controlled by the mixing ratio of monomers. In addition, based on the refractive index of said thermoplastic resin, said acrylic copolymer having a refractive index of said thermoplastic resin composition clarity of the absolute affecting other. I.e., thermoplastic resin and thermoplastic resin compositions in order to transparency, the refractive index of the acrylic copolymer difference ± 0. 01 preferably less than.

In another example, acrylic copolymer and coherent light, the refractive index of the thermoplastic resin said difference ± 0. 008 hereinafter, or ± 0. 005 hereinafter may be, within this range is excellent in transparency in effects, said acrylic copolymer having a refractive index of said 1 can be calculated by a mathematical equation.

Polymerization of the acrylic copolymer is polymerized acrylic copolymer said method can be particularly number but not one back method, suspension polymerization or bulk polymerization can be polymerization example, preferably continuous bulk polymerization can be polymerization, in this case number bath can be reduced cost-number flow tides excellent effects in diameter.

In one embodiment including said acrylic copolymer of the polymerization is controlled molecular weight number can be, but not one specifically then a number can be used, in particular specific embodiments t - crystalline salts of dodecyl mercaptan, such as crystalline salts of dodecyl mercaptan type onethe mercaptan where also the Roh end will be burnt be.

10 to 50% by weight said thermoplastic resin composition comprising said thermoplastic resin for example, 15 to 50% by weight, or 20 to 40% by weight and comprise, 50 to 90% by weight of said acrylic copolymer, 50 to 85% by weight, or 60 to 80% by weight can be comprising, excellent effects in impact strength and transparency within this range flow tides.

Example 10 to 40% by weight of a thermoplastic resin composition containing said end rubber content, or 10 to 25% by weight may be, in this range which is excellent in processability, flow mark are carved surface having excellent transparency effect between flow tides.

Said (meth) acrylic acid alkyl ester monomer content to a thermoplastic resin composition containing 20% by weight final example 65, or 40 to 65% by weight and comprise, 10 to 30% by weight of an aromatic vinyl compound, or 15 to 25% by weight can be comprising, in said rubber and refractive index differences within this range to very TCEs, excellent effects in transparency flow tides.

Example 5 weight % vinyl cyan compound to a thermoplastic resin composition comprising said end monomer content of 0, or 1 to 5% by weight and comprise, in vinyl cyan compound monomer will remain within this range not excellent effect mechanical properties and physical balance flow tides.

Said thermoplastic resin composition containing a low temperature my all kinds of flowers characteristic example (Δ Haze, -50 °C) is 0. 5 less than, 0. 1 to 0. 4, or 0. 2 to 0. Wednesday 4 2000.

Example said thermoplastic resin composition comprising a melt index (220 °C, 10 kg) is 24. 2 g/10 min or more, 24. 2 to 30 g/10 min, or 24. 3 to 25 g/10 min implementation being.

The physical properties of said thermoplastic resin composition comprising components without impairing stable within a range that the number depending on the objective, pigment, dye, reinforcing number, ultraviolet absorbing number, anti-oxidation number, colored number, release number, bow number, number and at least one plasticizer selected from the group consisting 1 addition of antistatic number can be a number.

Hereinafter, a preferred embodiment of the present invention to aid in the understanding at one number, in the embodiment of the present invention is to in various angular positions in the present invention is exemplified ephemeral range feature category and vertical to it is apparent that changes and modifications in which conventional, these modified and modifying natural also belonging to claim of relay are disclosed.

[In the embodiment]

In the embodiment 1

Large number of polybutadiene rubber latex bath

Nitrogen substituted polymerization reactor applied 65 parts by weight of ion (auto clay strobe), 70 parts by weight of 1, 3 - butadiene monomer, of the potassium salt of rosin acid into emulsion number 1. 5 parts by weight, potassium 0 contact angle. 8 parts by weight, potassium carbonate electrolyte (K₂ CO₃ ) 2 parts by weight, of boron atoms to class 3 atmospheres (TDDM) thread mercaptan number 0. 2 parts by weight, to with sulfuric acid potassium disclosure number (K₂ S₂ O₈ ) 0. 3 parts by weight of 30 to 40% by reacting collectively charged into a polymerization conversion rate in up until that point, with sulfuric acid potassium (K₂ S₂ O₈ ) 0. 1 parts by weight of 1, 3 - butadiene 20 parts by weight of ethylene-vinyl acetate polymer which can be 70 °C up until that point with respect to the 60% conversion in a batch reaction. Then, 10 parts by weight of 1, 3 - butadiene to the temperature which can be collectively after 80 °C, 22 in response to his terminate start reaction has been completed. In this case, polymerization of the polybutadiene rubber latex obtained was 97% conversion rate, average diameter to the web is 3,000 Å, 89% by weight of the gel fluorescence, this been swelling quotient 20.

Thermoplastic resin number bath

50 parts by weight of polybutadiene rubber latex obtained said ion applied 100 parts by weight (solids reference), Lactobacillus to emulsion number potassium 0. 35 parts by weight, acetic acid 0. 2 parts by weight, 34 parts by weight of methyl methacrylate, 13 parts by weight of styrene, acrylonitrile 3 parts by weight, of boron atoms thread mercaptan class 3 0. 45 parts by weight, sodium pyrophosphate 0. 048 parts by weight, dextrose 0. 012 parts by weight, number 1 sulfide iron 0. 001 parts by weight, queue the high draw ladling oxide which it carries on shoulder 0. 04 parts by weight of hydrophobic silicon solution to parcel number (brush hemp cloth yarn number bath, hanger Rhodoiline®962, viscosity (25 °C) 100 to 400 cps) 0. 01 parts by weight with respect to the reaction which can be continuously while 75 °C 4 in time. Then, the reaction was heated above the 78 °C after steaming time 1 terminate. In this case, polymerization conversion rate is 98. Fluorescence is 8%, a light solid coagulation 0. 1% by weight to the web is, obtained graft copolymer having a refractive index of 1. 516 is fluorescence, weight average molecular weight is 100,000 g/mol been. Then, 40 parts by weight of 5% by weight aqueous potassium chloride using aggregation, cleaning, dewatering and drying powder on acrylic graft copolymer obtained.

Acrylic copolymer number bath

Methyl methacrylate 70. 4 parts by weight, styrene 24. 6 parts by weight, 5 parts by weight of acrylonitrile, number t - crystalline salts of dodecyl mercaptan 0 to 30 parts by weight of toluene solvent atmospheres. 15 parts by weight of a raw material is put in the bath time controlled to an average reaction time won 3 148 °C reaction temperature was continuously maintained. Pre-heating the tank exiting the polymerization solution with respect to the unreacted monomers is volatilized for bath heating in volatile bath. Then 210 °C utilizing the acrylic copolymer pellets polymer transfer pump extrusion temperature of high pressure liquid coolant his number. At this time, obtained acrylic copolymer having a refractive index of 1. 516 is fluorescence, weight average molecular weights in this been 120,000 g/mol.

Thermoplastic resin composition number bath

30 parts by weight of an acrylic copolymer 70 parts by weight of said thermoplastic resin obtained by mixing, bow number 1 parts by weight, anti-oxidation number 0. 4 parts by weight of pellets in a cylinder temperature of 220 °C followed by extrusion using thermoplastic resin composition number soul [lyen[lyen] it will raise axis when the high pressure liquid coolant, and extruded to measure the property number-gate for small specimen.

In the embodiment 2

Thermoplastic resin number bath in said in the embodiment 1, vesicle number instead of adding hydrophobic silicon in solution polymerization, the reaction when added thereto after said in the embodiment 1 and the same method embodiment under the outside aggregation number to him.

In the embodiment 3

Thermoplastic resin number bath in said in the embodiment 1, vesicle number in hydrophobic silicon solution 0. 01 parts by weight instead of 0. 001 parts by weight of the same number and a charging method was the embodiment under the outside said in the embodiment 1.

Comparison example 1

Thermoplastic resin number bath in said in the embodiment 1, vesicle number is not the number adding hydrophobic silicon solution in said in the embodiment 1 and the embodiment under the outside was the same method.

Comparison example 2

Thermoplastic resin number bath in said in the embodiment 1, vesicle number instead of hydrophobic silicon solution to fine-grained vesicle number (Korean dow Corning yarn number bath, hanger SILOX, viscosity (25 °C) 2,300 cps) and the same method embodiment in the number equal to replacement added thereto under the outside was said in the embodiment 1.

Comparison example 3

Thermoplastic resin number bath in said in the embodiment 1, vesicle number in polymerization without adding hydrophobic silicon solution, when fine-grained vesicle number after aggregation reaction (Korean dow Corning yarn number bath, hanger Silox) 0. 01 parts by weight of said in the embodiment 1 and the embodiment under the outside number added thereto was the same method.

Comparison example 4

Thermoplastic resin number bath in said in the embodiment 1, vesicle number in hydrophobic silicon solution 0. 01 parts by weight instead of 0. 02 parts by weight of said in the embodiment 1 and the embodiment method was equal to the number under the outside to charging.

[Test example]

Said in the embodiment 1 to 3 and comparison example 1 to 4 obtained in the center of the acrylic resin composition of the following properties by measuring method, 1 have shown the result of the following table.

Measuring method

Average particle diameter (Å) *: device for laser light skeins to American Nicomp yarn Nicomp 380 is dynamically [thu[thu] the ring law were measured.

* Gel content and swelling index: polybutadiene rubber latex a dilute acid or metal salts after 24 hours then heated in an oven to dry the surface of vacuum 60 °C solidifies by rubber mass obtained after 48 hours 1 g 100 g toluene scissors got to chop up the rubber fragments is placed in room temperature and drying the sol after completion measured region of each separating gel, gel content to a mathematical equation 2, that they have in index expressions 3 for a long time.

To make solid polymer (%) *: reactor that are produced in the coagulation of weight, and the weight of the total rubber weight and the monomer, solidifies to equations 4 content the bill.

* Refractive index: using a sample of 0. More preferably piece after thickness of 2 mm, using from step 25 °C readings were measured.

A weight average molecular weight (Mw, g/mol) *: gel chromatography (GPC) PMMA (polymethylmethacrylate) through using Standard after calibration, weight average molecular weight were measured.

Silicon (Si)* float (ppm): 3 g (ash) in a combustion material after which a sample 600 °C, energy dispersion X - ray device using at least one silicon resin units (EDS, Energy non-dispersive X-a ray spectroscopy) were measured.

* Transparency and transmission (Haze, Tt): ASTM D1003 haze value of 3 mm sheet using a sample of standard measuring (haze value) and transmission (Tt) based on each were measured.

Low temperature whitening (Δ Haze) *: -50 °C 2 in time from the cell compartment using a sample of standard measuring 3 mm sheet based on ASTM D1003 haze value of measuring (haze value), as compared to the center of the cold storage before same transparency, values shown. Δ Haze can comprise low temperature my all kinds of flowers characteristic exhibits low or an.

(Notched Izod Impact Strength, kgcm/cm)* impact strength: 1/4 " of specimen were measured according to the ASTM D256 using standard measuring.

Melt index * (Melt Index, g/10 min): using a sample of standard measuring ASTM D1238 (220 °C, 10 kg conditions) were measured based on.

As shown in said table 1, in the case of number 3 in the embodiment 1 according to the present invention produced therewith, vesicle number but as compared to the comparison example 1, equivalent properties less, improving low temperature my all kinds of flowers characteristic were confirmed.

While, in the case of comparison example 2 and adding high viscosity SILOX vesicle number 3, a melt index of from somewhat lowered, poor low temperature my all kinds of flowers characteristic were confirmed. In addition, in the case of example 1 compared to the vesicle number but, due to the running wheel (impeller) stirring polymerization and aggregation process, process for preparing itself is encoded number limited verify bubbles were. In addition, in the case of comparison example 4 vesicle number input in excess hydrophobic silicon solution, poor low temperature my all kinds of flowers characteristic were confirmed.

The present invention therefrom by including particular victims of the vesicle number, polymerization and aggregation by reducing bubbles generated in the productivity and the mirror number-beam, without the deterioration of physical properties, including low temperature my all kinds of flowers characteristic remarkably improved thermoplastic resin and thermoplastic resin composition were confirm it can be implemented.