WO2020122407A1 - Method for preparing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and thermoplastic resin composition comprising graft copolymer - Google Patents

Abstract

The present description relates to a method for preparing a graft copolymer and a thermoplastic resin composition comprising the graft copolymer and, more specifically, to a method for preparing a graft copolymer, comprising the step of adding an acid coagulant with respect to 100 parts by weight (based on the solid content) of a graft copolymer latex in which an aromatic vinyl compound and a vinyl cyan compound are graft polymerized with a conjugated diene rubber latex to cause coagulation, and then adding again a salt coagulant thereto to cause coagulation. According to the present description, when preparation is performed according to the above-described method, there are effects of excellent coagulation efficiency, a high degree of gloss, excellent color due to a low b value measured using a HunterLab colorimeter and a low b value measured after a retention time of 15 minutes at 250 °C, and excellent processing properties due to low heating loss and a long scorch time.

Description

Method for producing vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer and thermoplastic resin composition comprising the graft copolymer

(Mutual Citation with Application(s))

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0161808 filed on December 14, 2018 and Korean Patent Application No. 10-2019-0129090 filed again on October 17, 2019, All contents disclosed in the documents of the relevant Korean patent application are included as part of the present specification.

The present invention relates to a method for preparing a graft copolymer and a thermoplastic resin composition comprising the graft copolymer, and more specifically, to graft polymerization of an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubber latex. Agglomeration of the latex with an acid coagulant and then coagulation with a salt coagulant to produce a graft copolymer having excellent cohesion efficiency and excellent glossiness, color and processing properties, and thermoplastics containing the graft copolymer It relates to a resin composition.

Acrylonitrile-butadiene-styrene copolymers (hereinafter referred to as "ABS-based copolymers") represented by vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer are impact resistance, mechanical strength, moldability, gloss Due to its good physical properties such as degree, it is widely used in various fields such as electric parts, electronic parts, office equipment, and automobile parts.

In general, when an aromatic vinyl compound and a vinyl cyan compound monomer are grafted to a conjugated diene rubber latex by emulsion polymerization to produce an ABS-based copolymer, it exhibits a good physical property balance compared to an ABS-based copolymer produced by bulk polymerization and exhibits excellent gloss, etc. Since it has the advantage of having an ABS-based copolymer is mainly produced by emulsion polymerization.

In addition, the ABS-based copolymer latex produced by emulsion polymerization is preferably processed into a powder for the reduction of volume, various utilization and ease of handling, and usually, the ABS-based resin latex is agglomerated, aged, dehydrated and dried. An ABS resin powder can be obtained.

Aggregation of the ABS-based copolymer latex prepared by emulsion polymerization can chemically aggregate latex particles stabilized by the emulsifier used for emulsion polymerization using various flocculants, and the flocculant may use acid or metal salt. Can be. Aggregation of latex using an acid has a disadvantage that the thermal stability of the ABS-based resin is reduced by the residual acid, and the amount of gas generated during the thermoforming process is high, so that the yellowness of the resin is high. In addition, agglomeration of latex using a metal salt has a relatively low gas generation amount and yellowness, but has a problem of low productivity.

Therefore, it is necessary to develop a method for manufacturing an ABS-based copolymer having excellent color while effectively agglomerating the ABS-based copolymer latex.

〔Advanced technical literature〕

[Patent Document] (Patent Document 1) Korean Patent Registration No. 10-0463482

In order to solve the problems of the prior art as described above, the present invention is an acid flocculant 0.10 to 0.80 with respect to 100 parts by weight of graft copolymer latex (based on solid content) graft polymerized with an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber latex. A first agglomeration step of aggregating by adding a weight part; And a second agglomeration step in which 0.96 to 1.85 parts by weight of a salt flocculant is added after the first flocculation step to aggregate, and the total weight of the acid flocculant and salt flocculant is adjusted to 1.66 to 2.20 parts by weight, resulting in excellent cohesion efficiency and gloss High and low b value (b value) measured using a Hunter Lab color meter and b value (b value) measured after staying at an injection machine at 250°C for 15 minutes, excellent color, low heat loss, and long scorch time. It is an object to provide a method for producing a graft copolymer having excellent properties.

The above and other objects of the present description can be achieved by the present description described below.

In order to achieve the above object, the present invention is a graft polymerization of 20 to 40% by weight of an aromatic vinyl compound and 1 to 20% by weight of a vinyl cyan compound in 50 to 70% by weight of a conjugated diene rubber latex having a solid content of 30 to 65% by weight. Preparing a graft copolymer latex; A first agglomeration step in which 0.10 to 0.80 parts by weight of an acid coagulant is added to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second coagulation step in which 0.96 to 1.85 parts by weight of the salt coagulant is added after the first coagulation step to aggregate, and the total amount of the acid coagulant and the salt coagulant is 1.66 to 2.20 parts by weight. Provided is a method for preparing a compound-aromatic vinyl compound graft copolymer.

In addition, the present disclosure provides a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer prepared by the above production method.

In addition, the present description includes a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and an aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight according to the above production method It provides a thermoplastic resin composition characterized by.

According to the present disclosure, the graft copolymer latex obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubber latex is agglomerated with 0.10 to 0.80 parts by weight of an acid coagulant, and then agglomerated with 0.96 to 1.85 parts by weight of a salt flocculant When the total amount of the acid flocculant and the salt flocculant is 1.66 to 2.20 parts by weight, the gloss is high while the cohesive efficiency is high, and the b value measured using a HunterLab color meter and the b value measured after staying at 250°C for 15 minutes are low. This has excellent effect, low heating loss and long scorch time, so it has the effect of excellent processing characteristics.

The present inventors agglomerated the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex with an acid coagulant, and then agglomerated with a salt coagulant. The effect of excellent color and processing characteristics was confirmed, and based on this, more research was conducted to complete the present invention.

The method for producing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer according to the present disclosure will be described in detail as follows.

The method for producing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is 20 to 40% by weight of the aromatic vinyl compound and 50 to 70% by weight of the conjugated diene rubber latex having a solid content of 30 to 65% by weight, and vinyl Graft polymerization of 1 to 20% by weight of the cyan compound to prepare a graft copolymer latex; A first agglomeration step in which 0.10 to 0.80 parts by weight of an acid coagulant is added to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And a second coagulation step in which 0.96 to 1.85 parts by weight of a salt coagulant is added and then coagulated after the first coagulation step, wherein the sum of the weights of the acid coagulant and the salt coagulant is 1.66 to 2.20 parts by weight, in this case Excellent cohesive efficiency, excellent b-value measured using HunterLab color meter and low b-value measured after staying at 250°C for 15 minutes and high gloss It works.

The manufacturing method of the present description will be described step by step as follows.

Preparation of conjugated diene rubber latex

The manufacturing method of the conjugated diene rubber latex is, for example, 100 parts by weight of a conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, and 0.1 to 0.5 parts by weight of a molecular weight modifier, and It may include the step of preparing 0.1 to 1 part by weight of the initiator and polymerizing to form a conjugated diene rubber latex, and in this case, there is an excellent impact resistance effect.

As another example, the method for preparing the conjugated diene rubber latex is 100 parts by weight of a conjugated diene compound, 40 to 70 parts by weight of ion-exchanged water, 1 to 2.5 parts by weight of an emulsifier, 0.05 to 0.3 parts by weight of an electrolyte, and 0.2 to 0.4 parts by weight of a molecular weight modifier. And adding 0.3 to 0.8 parts by weight of the initiator and polymerizing to prepare a conjugated diene rubber latex, in which case there is an excellent impact resistance effect.

As a specific example, the manufacturing method of the conjugated diene rubber latex is 30 to 100 parts by weight of ion-exchanged water, 0.3 to 2 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, and a molecular weight modifier 0.1 to 0.5 parts by weight of the initiator and 0.05 to 0.5 parts by weight of the initiator and primary polymerization; After the first polymerization step, the polymerization conversion rate of 35 to 45% at the time of adding 0.05 to 0.5 parts by weight of the initiator, 10 to 25 parts by weight of the conjugated diene compound continuously, and secondary polymerization; After the second polymerization step, the polymerization conversion rate is 70 to 80%, and 0.2 to 1 part by weight of an emulsifier is added, followed by tertiary polymerization; And terminating the polymerization at a polymerization conversion rate of 93 to 99% by weight after the third polymerization step. In this case, impact resistance is excellent.

In the present description, the polymerization conversion rate may be defined as the weight percentage of the monomer converted to the polymer until measurement based on 100% of the total weight of the monomers input until the end of polymerization, and the method for measuring the polymerization conversion rate is measured according to this definition. In the case of the polymerization conversion rate measurement method, it is not particularly limited, and after 1.5 g of the latex prepared in a specific example is dried in a 150° C. hot air dryer for 15 minutes, the weight is measured to calculate the total solid content (Total Solid Content; TSC). It can be obtained and calculated using Equation 2 below. Equation 2 is based on the total weight of the injected monomer is 100 parts by weight.

[Equation 1]

Total solids content (TSC; %) = (Weight after drying / Weight before drying) × 100

[Equation 2]

Polymerization conversion rate (%) = [Total solids content (TSC) × (total weight of the added monomers, ion-exchanged water and auxiliary materials) / 100]-(weight of added sub-materials other than monomer and ion-exchanged water)

In Equation 2, the auxiliary material refers to an initiator, an emulsifier, an electrolyte, and a molecular weight modifier.

The injected monomer refers to a conjugated diene compound.

The conjugated diene compound is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and isoprene. It may be abnormal.

The emulsifier may be, for example, one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acids.

The electrolyte is, for example, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ and Na ₂ HPO ₄ .

The initiator may be, for example, a water-soluble persulfate polymerization initiator, a fat-soluble polymerization initiator, or an oxidation-reduction catalyst system, and the like, and the water-soluble persulfate polymerization initiator may include, for example, potassium persulfate, sodium persulfate, and ammonium persulfate. It may be at least one selected from, and the fat-soluble polymerization initiator is, for example, cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, t-butyl hydroperoxide, paramethane hydroperoxide and benzoyl It may be at least one selected from the group consisting of peroxides, and examples of the oxidation-reduction catalyst system include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and ah. It may be one or more selected from the group consisting of sodium sulfate.

In the case of preparing the conjugated diene rubber latex, it may be most preferably potassium persulfate.

The molecular weight modifier may be, for example, a mercaptan-based molecular weight modifier, and a tertiary dodecyl mercaptan is particularly preferable.

The conjugated diene rubber latex of the present base material may have, for example, an average particle diameter of 1,800 to 5,000 mm 2, preferably 2,000 to 4,000 mm 2, more preferably 2,500 to 3,500 mm 2, and has excellent impact resistance within this range.

In this description, the average particle diameter of the conjugated diene rubber latex is diluted to less than 0.1% of the total solids content (TSC) to prepare a sample, and then the Nicomp ^TM 380 instrument (USA, PSS, Nicomp) is used by dynamic laser light skating. Can be measured.

Graft copolymer latex manufacturing steps

In the step of preparing the graft copolymer latex, for example, 20 to 40 wt% of aromatic vinyl compounds and 1 to 20 wt% of vinyl cyan compounds are grafted to 50 to 70 wt% of conjugated diene rubber latex having a solid content of 30 to 65 wt%. Can be polymerized, preferably 25 to 35% by weight of aromatic vinyl compounds and 5 to 15% by weight of vinyl cyan compounds can be graft polymerized to 55 to 65% by weight of conjugated diene rubber latex having a solid content of 30 to 65% by weight. There is an effect excellent in impact resistance, mechanical strength and moldability within this range.

In the present description, the solid content is defined as the content of the active ingredient remaining when all the moisture in the latex is evaporated, and after measuring 2.5g of latex on a balance with an aluminum dish, heat it for 5 minutes with heat at 150℃ to evaporate all the moisture. It can be obtained by measuring the weight by the following equation (3).

[Equation 3]

Solid content (% by weight) = 100-[(Weight of latex before moisture drying (g)-Weight of powder remaining after moisture drying (g))/Weight of latex before moisture drying]

The step of preparing the graft copolymer latex is, for example, 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound, 70 to 200 parts by weight of ion-exchanged water, 0.1 to 2 parts by weight of an initiator, and 0.1 to 2 parts by weight of an emulsifier. After the polymerization reaction by adding 2 parts by weight and 0.05 to 1.5 parts by weight of the molecular weight regulator, the polymerization reaction may be terminated at a polymerization conversion rate of 93 to 99% by weight.

In this step, the polymerization conversion rate follows the definition and measurement method of the polymerization conversion rate described above in the preparation step of the conjugated diene rubber latex, but the injected monomer means the conjugated diene compound, the aromatic vinyl compound, and the vinyl cyan compound contained in the rubber latex.

As another example, the step of preparing the graft copolymer latex includes 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound, 100 to 170 parts by weight of ion-exchanged water, 0.3 to 1 parts by weight of an initiator, and an emulsifier. After the polymerization reaction by adding 0.5 to 1.5 parts by weight and 0.1 to 1.0 parts by weight of the molecular weight modifier, the polymerization reaction may be terminated at a polymerization conversion rate of 95 to 98% by weight.

In a specific example, the step of preparing the graft copolymer latex comprises 50 to 70% by weight of conjugated diene rubber latex and 30 to 65% by weight of solid content based on 100 parts by weight of the conjugated diene rubber, aromatic vinyl compound, and vinyl cyan compound. 60 to 150 parts by weight of exchanged water, 20 to 40% by weight of an aromatic vinyl compound mixed in a separate mixing device, 1 to 20% by weight of a vinyl cyan compound, 10 to 50 parts by weight of ion-exchanged water, 0.09 to 1.5 parts by weight of an initiator, A mixed solution containing 0.1 to 2 parts by weight of the emulsifier and 0.05 to 1.5 parts by weight of the molecular weight modifier was added at 65 to 75°C for 2 to 4 hours, and then 0.01 to 0.5 parts by weight of the initiator was added, and 75 to 80 over 30 to 90 minutes. After raising the temperature to ℃, the polymerization conversion rate can be terminated by the graft polymerization at 93 to 99% by weight, in this case, there is an effect of excellent impact resistance, mechanical strength and moldability.

The conjugated diene rubber latex may have, for example, a solid content of 30 to 65% by weight, preferably 40 to 60% by weight, more preferably 55 to 60% by weight, and in this case, the polymerization reaction proceeds uniformly There is.

The aromatic vinyl compound is, for example, styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ-bro It may be one or more selected from the group consisting of parent styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene and vinyl naphthalene.

The vinyl cyan compound may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof.

The emulsifier, initiator and molecular weight modifier may be used, for example, within the range used in the preparation of the conjugated diene rubber latex.

Other additives, such as electrolytes, etc., which are not specifically mentioned in the present description, may be appropriately selected as needed, and are particularly limited in the range generally applicable to the production of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer latex. Does not work.

Other reaction conditions, such as reaction time, reaction temperature, pressure, reactant input time, etc. in the method for preparing a graft copolymer other than the above-described substrates, are not particularly limited if they are within the range commonly used in the technical field to which the present invention pertains. It can be carried out by appropriately selecting according to.

Coagulation step of graft copolymer latex

The graft copolymer latex prepared above is aggregated by a flocculant to form a graft copolymer slurry.

The agglomeration step is a first agglomeration step to agglomerate by adding 0.10 to 0.80 parts by weight of an acid coagulant with respect to 100 parts by weight of the graft copolymer latex prepared as an example (based on solid content); And a second agglomeration step in which 0.96 to 1.85 parts by weight of a salt flocculant is added after the first flocculation step to aggregate, and the sum of the acid flocculant and the salt flocculant may be 1.66 to 2.20 parts by weight, The gloss is high and the b value measured using a Hunter Lab color meter and the b value measured after staying at 250° C. for 15 minutes have low color, excellent heating, low scorch time, and excellent processing characteristics.

The first coagulation step may be, for example, an acid flocculant added to the graft copolymer latex at 75 to 85° C., and then a temperature of 5 to 10° C. from 5 to 35° C. may be increased. After the flocculant is added at 78 to 82° C., it may be a step of raising the temperature over a period of 10 to 30 minutes by 6 to 8° C. In this case, coagulation is uniformly performed and coagulation efficiency is excellent.

In the second coagulation step, for example, a salt coagulant is introduced at 80 to 95° C., from which it can be heated over 5 to 35 minutes by 5 to 10° C., preferably a salt coagulant is added at 84 to 90° C. , From this, the temperature can be increased over a period of 10 to 30 minutes by 6 to 8°C, and in this case, there is an effect that aggregation is uniformly performed, and aggregation efficiency is excellent and aged.

As a specific example, the temperature at which the first agglomeration step ends and the temperature at which the second agglomeration step starts may be the same.

The first agglomeration step and the second agglomeration step may be performed under conditions of, for example, agitation speeds of 5 to 450 rpm, or 10 to 400 rpm, preferably 30 to 300 rpm, more preferably 30 to 100 rpm. , But is not limited thereto. Productivity is excellent within the stirring speed range, and cohesion efficiency is high, and there is an effect of excellent physical property balance.

The acid flocculant is, for example, 0.10 to 0.80 parts by weight, preferably 0.15 to 0.75 parts by weight, more preferably 0.20 to 0.70 parts by weight, even more preferably 100 parts by weight of the graft copolymer latex (based on solid content) 0.20 to 0.50 parts by weight, or 0.50 to 0.70 parts by weight can be agglomerated, excellent cohesive efficiency within this range, high gloss, and a b value measured using a HunterLab color meter and 250°C for 15 minutes It is excellent in color, low color loss, long scorch time, and excellent processing characteristics.

The salt coagulant is, for example, 0.96 to 1.85 parts by weight, or 0.96 to 1.80 parts by weight, preferably 1.00 to 1.80 parts by weight, more preferably 1.25 to 1.80 parts by weight based on 100 parts by weight of the graft copolymer latex (based on solid content). Part, more preferably, it can be agglomerated by including 1.30 to 1.50 parts by weight, within this range is excellent glossiness, low heating loss and long scorch time, there is an effect of excellent processing characteristics.

The total amount of the acid coagulant and the salt coagulant is, for example, 1.66 to 2.20 parts by weight, or 1.70 to 2.10 parts by weight, preferably 1.70 to 2.00 parts by weight, more preferably 100 parts by weight of the graft copolymer latex (based on solid content). Can be added 1.75 to 2.00 parts by weight, excellent cohesive efficiency within this range, gloss is high, the b value measured using a HunterLab color meter and the b value measured after staying at 250° C. for 15 minutes is low This has excellent effect, low heating loss and long scorch time, so it has the effect of excellent processing characteristics.

The acid coagulant may be, for example, one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, and acetic acid, preferably sulfuric acid, in this case at a b value and 250° C. measured using a HunterLab colorimeter. The b-value measured after 15 minutes of residence has an excellent effect.

The salt coagulant may be, for example, one or more selected from the group consisting of magnesium sulfate, calcium sulfate, aluminum sulfate, magnesium chloride, calcium chloride, and aluminum chloride, preferably magnesium sulfate, and in this case, aggregation efficiency is good. It has an excellent glossiness effect.

When the acid coagulant and the salt coagulant contain a solvent such as water, their weight means the weight excluding the solvent.

The agglomeration step may further include, for example, antioxidants, stabilizers, or a mixture thereof, and in this case, there is an excellent effect in physical properties balance after extrusion.

The agglomerated graft copolymer latex may be dehydrated and dried to obtain a graft copolymer powder.

In the present description, a powder refers to an object in a state in which a large number of solid particles are aggregated. For example, an object having an average particle diameter in a state in which a large number of solid particles are aggregated may be 1 to 10,000 μm or 10 to 2,000 μm. have.

In the present description, the average particle diameter of the powder can be measured by a DP caking test. The DP caking test specifically compresses 10 g of powder with a weight of 20 kg for 10 minutes, and then stacks layers from #8 mesh (2380 μm) to #625 mesh (20 μm) on a sieve vibrator (Analysette 3) of Fritsch, Germany. After installing a stainless steel container capable of collecting powder that passes through 625 mesh at the bottom of #625 mesh, apply vibration to the sieve vibrator for 20 minutes, check the particle size distribution of the powder remaining in the mesh, and accumulate in the particle size distribution. The diameter of particles passing through 50% by weight is taken as the average particle size of the powder.

The dehydration and drying step is not particularly limited when it is a method generally used in the art.

The slurry obtained after the agglomeration can be dehydrated using a centrifugal dehydrator, a press-type dehydrator, for example, to obtain a wet powder graft copolymer.

The dehydration may be preferably performed at least once, preferably 1 to 3 times, more preferably 2 to 3 times as an example, and in this case, the residual emulsifier content is reduced to improve surface properties such as glossiness. It has the effect.

The graft copolymer in the wet powder state obtained after the dehydration has a water content of, for example, 40% by weight or less, preferably 10 to 40% by weight, more preferably 10 to 35% by weight or 10 to 30% by weight. %, in this case, there is an advantage in that productivity is increased by increasing efficiency in a drying step, which is a post-process.

The drying is not particularly limited in the case of a known drying process that is commonly practiced in the technical field to which the present invention pertains. For example, an air using a graft copolymer in a wet powder state is used as a fluidized bed dryer. After supplying and drying, a graft copolymer powder can be obtained.

In addition, the graft copolymer powder obtained by drying the wet powder-type graft copolymer may have a water content of, for example, 2% by weight or less, preferably 0.1 to 2% by weight, and more preferably 0.1 to 1% by weight. There is an advantage in that the productivity of the copolymer is excellent within this range, and the physical properties such as mechanical strength, heat resistance and surface gloss are excellent.

In the present description, the water content can be measured using a moisture analyzer, specifically, it can be measured with a moisture analyzer from METTLER TOLEDO of Switzerland.

The graft copolymer powder can be extruded after melt-kneading with an aromatic vinyl compound-vinyl cyan compound copolymer as an example, and in this case, has excellent impact resistance, chemical resistance, moldability, etc., excellent glossiness, and Hunter wrap color. The b-value measured using a meter and the b-value measured after staying at 250° C. for 15 minutes can be low to produce a beautifully colored thermoplastic resin composition.

The melt kneading and extrusion steps may be performed under 220 to 240° C. and 250 to 400 rpm, for example, 225 to 235° C. and 300 to 400 rpm, for example, but are not limited thereto.

The melt-kneading may be performed using, for example, a Banbari mixer, a single screw extruder, a twin screw extruder, a kneader, etc., and is not particularly limited.

When melt-kneading, for example, one or more additives selected from the group consisting of colorants, heat stabilizers, light stabilizers, reinforcing agents, fillers, flame retardants, lubricants, plasticizers, antistatic agents and processing aids, 0.1 to 10 parts by weight or 0.1 to 5 parts by weight It can be injected within the sub-range.

In addition, the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer of the present disclosure is characterized by being manufactured by the above manufacturing method, and in this case, a b value and 250 measured using a HunterLab colorimeter. After staying at ℃ for 15 minutes, the measured b value is low and the gloss is high, so the color is excellent. It works.

In addition, the thermoplastic resin composition of the present disclosure is 20 to 40% by weight of the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer, preferably 25 to 35% by weight, and aromatic vinyl compound-vinyl cyan compound copolymer 60 It characterized in that it contains 80 to 80% by weight, preferably 65 to 75% by weight, in this case it is excellent in impact resistance, chemical resistance, moldability and gloss, b value measured using a Hunter Lab color meter and After staying at 250°C for 15 minutes, the measured b-value is low, so the color has a beautiful effect.

The thermoplastic resin composition is, for example, a glossiness of a specimen having a thickness of 1/8 inch (3.2 mm) measured at a 45° angle with a gloss meter in accordance with ASTM D523. It may be from 110 to 110, preferably from 92 to 102, more preferably from 96 to 100, and within this range, physical properties and color are excellent.

For example, the thermoplastic resin composition may have a b value of 3.6 or less, preferably 3.0 to 3.6, more preferably 3.2 to 3.5, measured using a HunterLab color meter, and excellent in physical property balance and color within this range. It works.

For example, the thermoplastic resin composition has a b value of 9 or less, preferably 3 to 9, more preferably 5 to 9, and more preferably 5 to 9, measured using a HunterLab colorimeter after 15 minutes of residence at 250°C, for example. It may be 8, and within this range, the physical properties balance and color are excellent.

The thermoplastic resin composition may have, for example, a scorch time by a scorch test at 190° C. for 60 minutes or more, or 80 minutes or more, preferably 80 to 180 minutes, more preferably 80 to 150 minutes. There is an effect of excellent processing properties and physical properties balance within this range.

In the present description, the scorch time is the time when the flow stops in the mold and the rubber starts to ripen. If the scorch time is short, the unvulcanized compound is vulcanized during molding at a high temperature, thereby increasing the frequency of molding failure.

In the present description, the scorch time is a scorch time by placing the thermoplastic resin composition powder having a water content of 1% by weight or less in an aluminum foil in a state where it can be contacted with oxygen in the air, leaving it in a hot air oven at 190°C and measuring the time at which carbonization starts. . The longer the scorch time, the better the thermal stability.

In the present description, the water content can be measured using a moisture analyzer, specifically, it can be measured with a moisture analyzer from METTLER TOLEDO of Switzerland.

For example, the thermoplastic resin composition may have a heating loss of 0.8% by weight or less, or 0.1 to 0.8% by weight, preferably 0.1 to 0.6% by weight, more preferably 0.4 to 0.6% by weight, and processing characteristics within this range. And it has the effect of excellent physical properties balance.

In the present description, the reduction in heating is a decrease in weight generated during heating of a substance under certain conditions, and is heated under a nitrogen atmosphere at a heating rate of 20° C./min from 80° C. to 250° C., and then maintained under 250° C. for 60 minutes. By measuring the weight of the resin before and after heating, it can be obtained by the following equation (4). The weight before and after heating can be determined by measuring by thermogravimetric analysis (TGA). The lower the heating loss, the better the processing characteristics.

[Equation 4]

Heating loss (% by weight) = {(Weight before heating-Weight after heating)/Weight before heating}×100

Hereinafter, a preferred embodiment is provided to help understanding of the present description, but the following examples are merely illustrative of the present description, and it is apparent to those skilled in the art that various changes and modifications are possible within the scope and technical thought scope of the present description, It is no wonder that such variations and modifications fall within the scope of the appended claims.

[Example]

The components used in the following Examples and Comparative Examples are as follows.

* Acid coagulant: sulfuric acid

* Salt flocculant: magnesium sulfate

<Production of conjugated diene rubber latex>

55 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 85 parts by weight of 100 parts by weight of 1,3-butadiene as a monomer, 1.5 parts by weight of a fatty acid metal salt of C16 to C18 as an emulsifier, potassium carbonate as an electrolyte (K ₂ CO ₃ ) 0.15 parts by weight, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and 0.3 parts by weight of potassium persulfate as an initiator were collectively administered and polymerized at a reaction temperature of 70°C. At a polymerization conversion rate of 35 to 45%, 0.3 parts by weight of potassium persulfate was added in batch, and the remaining amount of 1,3-butadiene was continuously injected to react. After reacting to the polymerization conversion rate of 70 to 80%, 0.3 parts by weight of rosin acid saponified product was reacted, and then the reaction was terminated at a conversion rate of 93% to prepare a conjugated diene rubber latex.

The prepared conjugated diene rubber latex had an average particle diameter of 3,000 Å and a solid content of 55 to 60% by weight.

<Production of vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer (hereinafter referred to as "ABS graft copolymer")>

In a nitrogen-substituted polymerization reactor, 60 parts by weight of conjugated diene rubber latex having a solid content of 55 to 60% by weight and 100 parts by weight of ion-exchanged water, 10 parts by weight of acrylonitrile mixed in a separate mixing device, and styrene 30 5 parts by weight, 25 parts by weight of ion-exchanged water, 0.12 parts by weight of t-butyl hydroperoxide, 0.9 parts by weight of potassium rosin and 0.35 parts by weight of tertiary dodecyl mercaptan, 0.054 parts by weight of dextrose, sodium pyrrophosphate 0.004 part by weight and 0.002 part by weight of ferrous sulfate were added together at 70° C. for 3 hours. After the addition, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrophosphate, 0.001 part by weight of ferrous sulfate and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the polymerization reactor, and the temperature was raised to 80°C. After heating over 1 hour, the reaction was terminated to prepare an ABS graft copolymer latex. At this time, the polymerization conversion rate was 97%.

Example 1

After adding 0.20 part by weight of sulfuric acid at 80°C to 100 parts by weight of the ABS graft copolymer latex prepared above (based on solid content) and then heating it up to 87°C over 20 minutes to aggregate (first coagulation step), at 87°C After adding 1.80 parts by weight of magnesium sulfate, the mixture was heated to 93° C. over 15 minutes to aggregate (second aggregation step). The agglomerated ABS graft copolymer was dehydrated and dried to prepare an ABS graft copolymer powder. 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed in a mixer, melt-kneaded at 210°C using an extruder, and pelletized, This was used to prepare a specimen for measuring physical properties using an injection machine.

Examples 2 to 6

In Example 1, the contents of sulfuric acid and magnesium sulfate were changed in the same manner as in Example 1, except that the contents of Table 1 were changed.

Comparative Example 1

After adding 2.0 parts by weight of sulfuric acid to 100 parts by weight of the ABS graft copolymer latex prepared above (based on solid content) at 80° C., heating to 93° C. over 30 minutes to aggregate and age, and then flocculated and aged ABS graft air The coalescence was dehydrated and dried to prepare an ABS graft copolymer powder. 27 parts by weight of the prepared ABS graft copolymer powder and 73 parts by weight of acrylonitrile-styrene copolymer (LG Chemical, 92HR) were mixed in a mixer, melt-kneaded at 210°C using an extruder, and pelletized, This was used to prepare a specimen for measuring physical properties using an injection machine.

Comparative Example 2

In Comparative Example 1, it was carried out in the same manner as in Comparative Example 1, except that 2 parts by weight of magnesium sulfate was added instead of 2 parts by weight of sulfuric acid.

Comparative Example 3

In Comparative Example 1, it was carried out in the same manner as in Comparative Example 1, except that 1 part by weight of sulfuric acid and 1 part by weight of magnesium sulfate were mixed instead of 2 parts by weight of sulfuric acid.

Comparative Examples 4 to 7

In Comparative Example 1, it was carried out in the same manner as in Comparative Example 1, except that sulfuric acid and magnesium sulfate were mixed and added in the contents shown in Table 2 below.

Comparative Examples 8 to 17

In Example 1, it was carried out in the same manner as in Example 1, except that the input order and content of sulfuric acid and magnesium sulfate were changed and input as shown in Table 3 below.

[Test Example]

The properties of the specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 17 were measured by the following method, and the results are shown in Tables 1 to 3 below.

How to measure

* Glossiness: The glossiness of the specimen having a thickness of 1/8 inch (3.2mm) was measured at an angle of 45° according to ASTM D523.

* b value: b value was measured using a HunterLab color meter.

* B value after residence: b value was measured using a HunterLab color meter after staying in the injection machine at 250°C for 15 minutes.

* Scorch test (min.): A powder of a thermoplastic resin composition having a water content of 1% by weight or less was put in an aluminum foil in a state where it can be contacted with oxygen in the air, and a time at which a hot air oven at 190°C was left to stand and carbonization was measured was measured.

* Heating loss (% by weight): Under a nitrogen atmosphere, the temperature rises from 80°C to 250°C at a rate of 20°C/min, and then heats under conditions maintained at 250°C for 60 minutes to analyze the weight of the resin before and after heating by thermal gravimetric analysis (TGA It was measured by) and calculated by the following equation (4).

[Equation 4]

Heating loss (% by weight)={(Weight before heating-Weight after heating)/Weight before heating}Х100

division	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
Coagulant input method	After adding the first coagulant, adding the second coagulant
First flocculant (parts by weight)	H 2 SO 4 0.2	H 2 SO 4 0.3	H 2 SO 4 0.5	H 2 SO 4 0.7	H 2 SO 4 0.7	H 2 SO 4 0.45
Second flocculant (parts by weight)	MgSO 4 1.8	MgSO 4 1.7	MgSO 4 1.5	MgSO 4 1.3	MgSO 4 1.0	MgSO 4 1.4
Total flocculant (parts by weight)	2.0	2.0	2.0	2.0	1.7	1.85
b value	3.2	3.2	3.2	3.2	3.3	3.2
B value after stay	9	9	8	8	8	8
Glossiness	97	97	97	97	96	97
Scorch time (min.)	80 minutes or more	80 minutes or more	80 minutes or more	80 minutes or more	80 minutes or more	80 minutes or more
Heating loss (% by weight)	0.4	0.4	0.5	0.4	0.6	0.5

division	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6	Comparative Example 7
Coagulant input method	Mixing the first flocculant and the second flocculant
First flocculant (parts by weight)	H 2 SO 4 2.0	-	H 2 SO 4 1.0	H 2 SO 4 0.5	H 2 SO 4 0.5	H 2 SO 4 0.2	H 2 SO 4 1.0
Second flocculant (parts by weight)	-	MgSO 4 2.0	MgSO 4 1.0	MgSO 4 1.5	MgSO 4 1.0	MgSO 4 1.0	MgSO 4 0.2
Total flocculant (parts by weight)	2	2	2	2	1.5	1.2	1.2
b value	6.2	3.2	4.8	3.9	4.5	3.3	4.9
B value after stay	8	14	11	13	13	14	9
Glossiness	85	95	90	93	90	93	89
Scorch time (min.)	80 minutes or more	15	25	20	24	17	70
Heating loss (% by weight)	3.2	0.2	1.8	0.9	1.1	0.5	2.9

division	Comparative example
	8	9	10	11	12	13	14	15	16	17
Coagulant input method	After adding the first coagulant, adding the second coagulant
First flocculant (parts by weight)	MgSO 4 0.2	MgSO 4 1.3	MgSO 4 1.8	MgSO 4 1.0	MgSO 4 0.2	H 2 SO 4 0.7	H 2 SO 4 0.2	H 2 SO 4 0.2	H 2 SO 4 0.7	H 2 SO 4 1.3
Second flocculant (parts by weight)	H 2 SO 4 1.8	H 2 SO 4 0.7	H 2 SO 4 0.2	H 2 SO 4 0.2	H 2 SO 4 1.0	MgSO 4 0.9	MgSO 4 1.9	MgSO 4 1.0	MgSO 4 1.8	MgSO 4 0.7
Total flocculant (parts by weight)	2.0	2.0	2.0	1.2	1.2	1.6	2.1	1.2	2.5	2.0
b value	5.9	3.3	3.3	3.4	4.7	3.7	3.3	3.3	3.7	4.7
B value after stay	9	11	12	11	9	8	12	12	9	8
Glossiness	86	90	93	91	88	89	94	92	89	91
Scorch time (min.)	80 minutes or more	55	25	33	70	80 minutes or more	40	45	58	80
Heating loss (% by weight)	3	1.0	0.4	0.5	2.2	0.9	0.4	0.4	0.9	1.6

As shown in Tables 1 to 3, Examples 1 to 6 according to the present invention have high gloss, and a b value measured using a HunterLab color meter and a b value measured after a 15 minute stay at 250° C. Not only was the color excellent, but the scorch time was long and the heating loss was low, so the processing characteristics were excellent.

On the other hand, Comparative Examples 1 and 2 containing the acid flocculant or the salt flocculant alone and the acid flocculant and the salt flocculant were mixed in batches, and Comparative Examples 3 to 7 were measured for gloss and b values measured using a HunterLab color meter. After staying at 250°C for 15 minutes, the measured b value, scorch time, and heating loss were poor.

Further, Comparative Examples 8 to 12 in which the acid coagulant was added after the salt coagulant was agglomerated and the glossiness, the b value measured using a Hunter Lab color meter, and the b value measured after 15 minutes of residence at 50° C. and scorch time. Or the heating loss was poor.

In addition, after the acid coagulant was added, a salt coagulant was added to agglomerate, but the total amount of the coagulant was small or excessive. And Comparative Example 14 in which the salt coagulant was excessive, the glossiness, the b value measured using a HunterLab color meter, the b value measured after 15 minutes of residence at 250° C., the scorch time or the heating loss was poor.

In addition, in Comparative Example 17 in which the acid coagulant was included in excess, the b value and the heating loss measured using a Hunter Lab color meter were poor.

Claims (13)

1. Preparing a graft copolymer latex by graft polymerization of 20 to 40 wt% of an aromatic vinyl compound and 1 to 20 wt% of a vinyl cyan compound in 50 to 70 wt% of a conjugated diene rubber latex having a solid content of 30 to 65 wt%;

   A first agglomeration step in which 0.10 to 0.80 parts by weight of an acid coagulant is added to 100 parts by weight of the prepared graft copolymer latex (based on solid content); And

   After the first coagulation step, a second coagulation step to agglomerate by adding 0.96 to 1.85 parts by weight of salt coagulant;

   The sum of the acid coagulant and salt coagulant is characterized in that 1.66 to 2.20 parts by weight

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
2. According to claim 1,

   The acid coagulant is characterized in that at least one selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid and acetic acid

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
3. According to claim 1,

   The salt coagulant is characterized in that at least one member selected from the group consisting of magnesium sulfate, calcium sulfate, aluminum sulfate, magnesium chloride, calcium chloride and aluminum chloride.

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
4. According to claim 1,

   The first coagulation step is characterized in that the acid coagulant is introduced at 75 to 85° C., and the temperature is increased by 5 to 10° C. over 5 to 35 minutes.

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
5. According to claim 1,

   The second coagulation step is characterized in that the salt coagulant is introduced at 80 to 95° C., and the temperature is increased by 5 to 10° C. over 5 to 35 minutes.

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
6. According to claim 1,

   The step of preparing the graft copolymer latex includes 100 parts by weight of a conjugated diene rubber latex, an aromatic vinyl compound, and a vinyl cyan compound, 70 to 200 parts by weight of ion-exchanged water, 0.1 to 2 parts by weight of an initiator, and 0.1 to 2 parts by weight of an emulsifier. Characterized in that the polymerization reaction is terminated at a polymerization conversion rate of 93 to 99% by weight after polymerization by adding 0.05 to 1.5 parts by weight of a part and a molecular weight modifier.

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
7. According to claim 1,

   The step of preparing the graft copolymer latex includes 100 parts by weight of a conjugated diene compound, 30 to 100 parts by weight of ion-exchanged water, 0.5 to 3 parts by weight of an emulsifier, 0.01 to 0.5 parts by weight of an electrolyte, and 0.1 to 0.5 parts by weight of a molecular weight modifier, and Characterized in that it comprises the step of preparing 0.1 to 1 parts by weight of the initiator and polymerizing to form a conjugated diene rubber latex

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
8. According to claim 1,

   The method for producing the vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer comprises a dehydration and drying step after the agglomeration step.

   A method for producing a vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
9. It characterized in that it is manufactured by the manufacturing method according to any one of claims 1 to 8

   Vinyl cyan compound-conjugated diene compound-aromatic vinyl compound graft copolymer.
10. It characterized in that it comprises a vinyl cyan compound of claim 9-conjugated diene compound-aromatic vinyl compound graft copolymer 20 to 40% by weight and aromatic vinyl compound-vinyl cyan compound copolymer 60 to 80% by weight

    Thermoplastic resin composition.
11. The method of claim 10,

    The thermoplastic resin composition is characterized in that the b value (b value) measured after staying at 250°C for 15 minutes using a HunterLab color meter is 9 or less.

    Thermoplastic resin composition.
12. The method of claim 10,

    The thermoplastic resin composition is characterized in that the glossiness measured at an angle of 45° with a gloss meter according to ASTM D523 is 90 or more.

    Thermoplastic resin composition.
13. The method of claim 10,

    The thermoplastic resin composition contains a thermoplastic resin composition powder having a water content of 1% by weight or less in an aluminum foil in a state in which it can be contacted with oxygen in the air, left in a hot air oven at 190°C, and scorch time by a scorch test to measure the time at which carbonization starts. (scorch time) is characterized in that more than 60 minutes

    Thermoplastic resin composition.