KR102615706B1 - A methods for preparing vinylcyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, methods for thermoplastic resin compositin comprising the same, and thermoplastic resin composition - Google Patents

Abstract

The present invention relates to a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a method for producing a thermoplastic resin composition containing the same, and a thermoplastic resin composition, and more specifically, to the conjugated diene compound and molecular weight during polymerization. The gel content of the conjugated diene rubber is lowered by splitting the regulator and reducing the emulsifier content. After adding the electrolyte, the thickened conjugated diene rubber is thickened with an acid thickening agent. The full width at half maximum of the particle diameter is widened, improving glossiness, reflection haze, and fluidity. It has the effect of improving impact resistance and reducing residue during injection molding.

Description

Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, method for producing thermoplastic resin composition containing same, and thermoplastic resin composition {A METHODS FOR PREPARING VINYLCYAN COMPOUND-CONJUGATED DIENE RUBBER-AROMATIC VINYL COMPOUND GRAFT COPOLYMER, METHODS FOR THERMOPLASTIC RESIN COMPOSITIN COMPRISING THE SAME, AND THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a method for producing a thermoplastic resin composition containing the same, and a thermoplastic resin composition, and more specifically, to the conjugated diene compound and molecular weight during polymerization. The gel content of the conjugated diene rubber is lowered by splitting the regulator and reducing the emulsifier content. Then, a predetermined electrolyte is added and the thickened conjugated diene rubber is thickened with an acid thickening agent. The full width at half maximum of the particle size is widened, resulting in glossiness, reflection haze, and fluidity. and a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer with improved impact resistance and reduced injection residue during injection molding, a method for producing a thermoplastic resin composition containing the same, and a thermoplastic resin composition. .

Acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') copolymer has relatively good physical properties such as mechanical strength such as impact resistance as well as formability and gloss, making it suitable for use in electrical and electronic components. It is widely used in office equipment and automobile parts.

In general, when producing ABS copolymers by grafting styrene and acrylonitrile onto butadiene rubber latex through emulsion polymerization, it has the advantages of showing a good balance of physical properties and excellent gloss compared to ABS copolymers produced by bulk polymerization. ABS copolymers are mainly manufactured by emulsion polymerization.

Furthermore, the ABS copolymer prepared as above is mixed with a styrene-acrylonitrile (hereinafter referred to as 'SAN') copolymer and manufactured into a final product through a thermoforming process. The glossiness and impact resistance of the thermoplastic resin composition prepared in this way are It is affected by the gel content and particle size distribution of the dispersed rubber polymer. In addition, during the high-temperature injection process of the thermoplastic resin composition, the emulsifier remaining in the butadiene rubber remains as a residue in the injection mold. These residues can cause product defects and affect productivity as production must be temporarily stopped by a cleaning process to remove them.

Therefore, there is a need to develop a manufacturing method for ABS copolymers that can further improve the impact strength of ABS copolymers and improve productivity by reducing appearance qualities such as glossiness and residues during injection molding.

Korean Patent No. 0527095

In order to solve the problems of the prior art as described above, the present invention improves impact resistance while providing excellent fluidity, reflection haze, and gloss, and reduces residues in the mold during injection molding, so that impact resistance, gloss, and processability are all improved. The purpose of the present invention is to provide a method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, a method for producing a thermoplastic resin composition containing the same, and a thermoplastic resin composition that can be applied in high quality fields in need.

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

In order to achieve the above object, the present invention includes the steps of a) polymerizing 20 to 40 parts by weight of a total of 100 parts by weight of the conjugated diene compound, including 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator, and an electrolyte; b) after step a), adding the remaining conjugated diene compound and a molecular weight regulator to perform polymerization to obtain conjugated diene rubber latex; c) adding 0.05 to 0.2 parts by weight of electrolyte to 100 parts by weight (based on solid content) of the conjugated diene rubber latex; d) preparing hypertrophied conjugated diene rubber latex by adding 0.5 to 0.85 parts by weight of an acid thickening agent to 100 parts by weight (based on solid content) of the conjugated diene rubber latex; and e) 40 to 70% by weight (based on solid content) of the enlarged conjugated diene rubber latex, 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound, resulting in a graft polymerization reaction to produce a vinyl cyan compound-conjugate. Obtaining a diene rubber-aromatic vinyl compound graft copolymer, wherein the hypertrophied conjugated diene rubber latex obtained in step d) has an average particle diameter of 3,000 to 3,500 Å and a particle width at half maximum of 1,600 to 2,600 Å. A method for producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer is provided.

In addition, the present invention includes the steps of producing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the above production method; And adding 15 to 35 wt% of the prepared graft copolymer and 65 to 85 wt% of the aromatic vinyl compound-vinyl cyan compound copolymer into an extruder, melt-kneading the mixture, and then extruding the thermoplastic resin. A method for manufacturing the composition is provided.

In addition, the present invention includes 15 to 35% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and 65 to 85% by weight of an aromatic vinyl compound-vinylcyan compound copolymer, and the conjugated diene rubber has an average weight of A thermoplastic resin composition having a particle diameter of 3,000 to 3,500 Å, a full width at half maximum of 1,600 to 2,600 Å, and an Izod impact strength of 40 kgf·cm/cm or more as measured at a specimen thickness of 1/8" according to ASTM D256. to provide.

Additionally, the present invention provides a molded article comprising the thermoplastic resin composition.

According to the present invention, the gel content of the conjugated diene rubber is reduced and the full width at half maximum of the particle size is widened, so that the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer containing this has excellent fluidity, reflective haze and gloss, and is superior to the conventional one. It has excellent impact resistance compared to ABS resin and reduces residues in the mold during injection molding, resulting in excellent productivity and quality, making it a vinyl cyan compound-conjugated diene rubber-aromatic that can be applied at high quality in fields that require impact resistance, gloss, and processability. It has the effect of providing a method for producing a vinyl compound graft copolymer, a method for producing a thermoplastic resin composition containing the same, and a thermoplastic resin composition.

1 is a diagram for explaining the full width at half maximum of the particle diameter.

Hereinafter, the method for producing the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer of the present invention, the method for producing the thermoplastic resin composition containing the same, and the thermoplastic resin composition will be described in detail.

The present inventors found that when the method of adding the conjugated diene compound and the molecular weight regulator during polymerization was changed and the emulsifier content was reduced, the gel content of the conjugated diene rubber was reduced, and the hypertrophied conjugated diene rubber was thickened with an acid thickening agent after adding a predetermined electrolyte. The full width at half maximum of the particle diameter was widened, resulting in excellent reflective haze and gloss, significantly improving impact strength, and reducing residues in the mold during injection. Based on this, further research was conducted to complete the present invention.

The method for producing the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer of the present invention is a) adding 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator, and an electrolyte to 20 to 40 parts by weight out of a total of 100 parts by weight of the conjugated diene compound. polymerization step including; b) after step a), adding the remaining conjugated diene compound and a molecular weight regulator to perform polymerization to obtain conjugated diene rubber latex; c) adding 0.05 to 0.2 parts by weight of electrolyte to 100 parts by weight (based on solid content) of the conjugated diene rubber latex; d) preparing hypertrophied conjugated diene rubber latex by adding 0.5 to 0.85 parts by weight of an acid thickening agent to 100 parts by weight (based on solid content) of the conjugated diene rubber latex; and e) 40 to 70% by weight (based on solid content) of the enlarged conjugated diene rubber latex, 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound, resulting in a graft polymerization reaction to produce a vinyl cyan compound-conjugate. Obtaining a diene rubber-aromatic vinyl compound graft copolymer, wherein the hypertrophied conjugated diene rubber latex obtained in step d) has an average particle diameter of 3,000 to 3,500 Å and a particle width at half maximum of 1,600 to 2,600 Å. It is characterized by In this case, the fluidity, reflection haze, and gloss are excellent, while the impact resistance is greatly improved compared to the conventional ABS resin, and the residue during injection molding is significantly reduced.

Hereinafter, the method for producing the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer of the present invention will be described in detail step by step.

a) polymerizing 20 to 40 parts by weight of a total of 100 parts by weight of the conjugated diene compound, including 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator, and an electrolyte.

In step a), the emulsifier may be preferably 0.3 to 1.7 parts by weight, more preferably 0.5 to 1.5 parts by weight, and even more preferably 0.7 to 1.3 parts by weight. Within this range, impact resistance is improved and it can be used during injection molding. Residues are reduced, resulting in excellent productivity and appearance quality.

Conventionally, when polymerizing conjugated diene rubber latex, an emulsifier is added in an amount of 3 parts by weight or more based on 100 parts by weight of the conjugated diene compound to ensure a smooth polymerization reaction. In this case, the residual emulsifier volatilized at high temperature during injection molding leaves a residue in the mold. There is a problem of decreased productivity and defects in product appearance due to excessive adhesion. In the present invention, the conjugated diene compound and the molecular weight regulator are separately added at the start of the reaction and after the polymerization reaction is performed at 50 to 60°C for 50 to 70 minutes to improve impact resistance, fluidity, and reflection even when the emulsifier content is greatly reduced. It has excellent haze and gloss, and has the effect of significantly reducing injection mold residue during injection molding.

In step a), the emulsifier is, for example, at least one selected from the group consisting of docusate sodium, allyl aryl sulfonate, alkali methyl alkyl sulfonate, sulfonate alkyl ester, fatty acid soap, and alkali salt of rosin acid. It may be, preferably fatty acid soap, and in this case, impact resistance is improved and residues are reduced during injection molding, resulting in excellent productivity and appearance quality.

In step a), the molecular weight regulator may be, for example, 0.05 to 0.3 parts by weight, preferably 0.1 to 0.25 parts by weight, more preferably 0.13 to 0.2 parts by weight, and within this range, the gel content is reduced to improve impact resistance. There is an effect.

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

In step a), the electrolyte may be, for example, one or more selected from the group consisting of K ₂ CO ₃ , Na ₂ SO ₄ , Na ₃ PO ₄ , NaH ₂ PO ₄ and Na ₂ HPO ₄ , and is preferably K ₂ CO It may be ₃ , and in this case, the gel content is reduced and the full width at half maximum of the particle size of the hypertrophied conjugated diene rubber is widened, thereby significantly increasing impact resistance and providing excellent fluidity, reflective haze, and gloss.

In step a), the electrolyte may be, for example, 0.1 to 0.5 parts by weight, preferably 0.2 to 0.4 parts by weight, and within this range, the gel content is reduced and the full width at half maximum of the particle diameter of the enlarged conjugated diene rubber is widened, thereby improving impact resistance. The significant increase results in excellent fluidity, reflective haze, and glossiness.

In step a), for example, the polymerization reaction may be performed at 50 to 60°C for 50 to 70 minutes, and preferably, the polymerization reaction may be performed at 53 to 57°C for 55 to 65 minutes. In this case, the gel content is The full width at half maximum of the particle size of the reduced and enlarged conjugated diene rubber is widened, resulting in a significant increase in impact resistance, resulting in excellent fluidity, reflection haze, and gloss.

In step a), for example, a polymerization reaction may be carried out including 0.01 to 0.5 parts by weight of an oxidation-reduction catalyst, 0.01 to 0.7 parts by weight of an oil-soluble polymerization initiator, and 80 to 120 parts by weight of ion-exchanged water, preferably an oxidation-reduction system. The polymerization reaction can be carried out by including 0.05 to 0.3 parts by weight of a catalyst, 0.1 to 0.5 parts by weight of an oil-soluble polymerization initiator, and 90 to 110 parts by weight of ion-exchanged water, and the unreacted monomer is reduced within this range to form a vinyl cyan compound-conjugated diene rubber- This has the effect of increasing the productivity of the aromatic vinyl compound graft copolymer as well as improving the gloss and reflective haze of the copolymer.

For example, the redox catalyst may include one or more selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrole phosphate, and sodium sulfite. , within this range, the unreacted monomers are reduced, thereby increasing the productivity of the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer, as well as improving the gloss and reflective haze of the copolymer.

The oil-soluble polymerization initiator may be, for example, one or more selected from the group consisting of alkyl peroxide, aryl peroxide, and azonitrile, and specifically cumenehydroperoxide, diisopropyl benzene hydroperoxide, and azobis isobutyl. One or more types selected from the group consisting of nitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl peroxide can be used, and tertiary butyl hydroperoxide is preferred.

b) After step a), adding the remaining conjugated diene compound and a molecular weight regulator to perform polymerization to obtain conjugated diene rubber latex.

In step b), preferably, after step a), the remaining conjugated diene compound and molecular weight regulator are continuously added for 9 to 11 hours, and the temperature is raised to 73 to 83° C. over 8 to 10 hours and then maintained. More preferably, the remaining conjugated diene compound and the molecular weight regulator are continuously added for 9.5 to 10.5 hours and the temperature is raised to 75 to 80°C over 8.5 to 9.5 hours and then maintained. In this case, the gel content and coagulation are maintained. The water content is reduced and the full width at half maximum of the particle size of the enlarged conjugated diene rubber is widened, greatly increasing impact resistance and providing excellent fluidity, reflection haze, and gloss.

In this description, 'continuous injection' means not 'batch injection', for example, drop by drop for more than 10 minutes, more than 30 minutes, more than 1 hour, preferably more than 2 hours within the polymerization reaction time range. This refers to input by drop, little by little, step by step, or continuous flow.

In step b), more preferably, b-1) the remaining conjugated diene compound and molecular weight regulator are continuously added for 9 to 11 hours, the temperature is raised to 73 to 83 ° C. over 8 to 10 hours, and the polymerization reaction is maintained. ordering step; b-2) adding 0.05 to 0.2 parts by weight of a water-soluble initiator and 0.05 to 0.3 parts by weight of an emulsifier at a polymerization conversion rate of 30 to 40% by weight and conducting a polymerization reaction; and b-3) terminating the polymerization reaction at a polymerization conversion rate of 93 to 99% by weight.

In step b), the molecular weight regulator may be, for example, 0.05 to 0.5 parts by weight, preferably 0.1 to 0.45 parts by weight, more preferably 0.2 to 0.4 parts by weight, and within this range, the coagulated product of the conjugated diene rubber latex As the content decreases, the full width at half maximum of the particle size widens, resulting in excellent impact strength and fluidity.

The molecular weight regulator used in step b) may be within the same category as that used in step a).

In the present invention, by dividing the conjugated diene compound and the molecular weight regulator into steps a) and b), the polymerization reaction of the conjugated diene rubber latex is smooth even when the emulsifier content is reduced, thereby reducing the gel content and coagulant content and enlarging it. Conjugated diene rubber latex has a wide particle size at half width, resulting in excellent impact resistance.

In the present disclosure, the polymerization conversion rate can be defined as the weight percent of the monomer converted to polymer until measurement based on 100% by weight of the total weight of monomers added until the end of polymerization, and the method for measuring the polymerization conversion rate is measured according to this definition. The method of measuring the polymerization conversion rate is not particularly limited, and as a specific example, 1.5 g of the prepared latex is dried in a hot air dryer at 150°C for 15 minutes, then weighed, and the total solid content (TSC) is calculated using Equation 1 below. can be obtained and calculated using Equation 2 below. This equation 2 is based on the total weight of the monomers added being 100 parts by weight.

[Equation 1]

[Equation 2]

Polymerization conversion rate (%) = [Total solid content (TSC)

In Equation 2 above, auxiliary materials refer to initiators, emulsifiers, electrolytes, and molecular weight regulators.

In the case of conjugated diene rubber latex polymerization, the added monomer refers to a conjugated diene compound, and in the case of vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer latex polymerization, it refers to a conjugated diene compound, a vinyl cyan compound, and an aromatic vinyl compound. refers to

In step b-2), the water-soluble initiator may preferably be 0.07 to 0.15 parts by weight, and the productivity of the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer can be increased by reducing unreacted monomers within this range. Of course, there is an effect of improving the gloss and reflection haze of the copolymer.

In step b-2), the water-soluble initiator may be, for example, one or more selected from the group consisting of hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate, and is preferably potassium persulfate.

In step b-2), the emulsifier may preferably be 0.1 to 0.25 parts by weight, more preferably 0.1 to 0.2 parts by weight, and within this range, the gel content is reduced to improve impact resistance and reduce residue during injection molding. It has a reducing effect.

The emulsifier used in step b-2) may be within the same category as that used in step a).

For example, the conjugated diene rubber latex obtained in step b) may have a gel content of 80% by weight or less, preferably 78% by weight or less, more preferably 76% by weight or less, and even more preferably 70 to 76% by weight. Within this range, the gel content is reduced and the full width at half maximum of the particle diameter of the enlarged conjugated diene rubber is widened, thereby significantly increasing impact resistance and providing excellent fluidity, reflective haze, and gloss.

In this material, the gel content is determined by coagulating the rubber latex using dilute acid or metal salt, washing it, drying it in a vacuum oven at 60°C for 24 hours, cutting the obtained rubber lump into small pieces with scissors, and dissolving 1 g of rubber pieces in toluene. Add 100 g and store in the dark at room temperature for 48 hours, separate into sol and gel, and measure the gel content according to Equation 3 below.

[Equation 3]

Gel content (% by weight) = [Weight of insoluble matter (gel) / Weight of sample] x 100

The conjugated diene rubber latex obtained in step b) may have an average particle diameter of, for example, 700 to 1,500 Å, preferably 800 to 1,400 Å, and more preferably 1,000 to 1,200 Å, and the gel content decreases within this range. The full width at half maximum of the particle diameter of the enlarged conjugated diene rubber is widened, greatly increasing impact resistance, and providing excellent fluidity, reflection haze, and glossiness.

In this material, the average particle diameter can be measured using dynamic light scattering, and in detail, the intensity can be measured in Gaussian mode using a particle meter (product name: Nicomp 380, manufacturer: PSS). ) is measured by the value. As a specific measurement example, the sample was prepared by diluting 0.1g of latex (TSC 35-50wt%) 1,000-5,000 times with deionized water or distilled water, that is, diluting appropriately so as not to deviate significantly from the Intensity Setpoint 300kHz, placing it in a glass tube, and measuring. The method is auto-dilution and measurement using a flow cell, and the measurement mode is dynamic light scattering/Intensity 300KHz/Intensity-weight Gaussian Analysis, and the setting values are temperature 23℃, measurement wavelength 632.8nm, and channel width. It can be measured at 10μsec.

For example, the conjugated diene rubber latex obtained in step b) may have a coagulant content of 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.05 to 0.35% by weight, and can be injection molded within this range. It has the effect of reducing residues.

In this material, the coagulant content in the latex is determined by filtering the polymerized latex through a 100 mesh stainless steel net, drying the unfiltered coagulant at 80°C for 24 hours, measuring its weight, and then calculating its content as a percentage of the total solid content. Calculated as a percentage.

c) Adding 0.05 to 0.2 parts by weight of electrolyte to 100 parts by weight (based on solid content) of the conjugated diene rubber latex.

In step c), preferably 0.07 to 0.2 parts by weight, more preferably 0.07 to 0.15 parts by weight, of electrolyte may be added to 100 parts by weight (based on solid content) of the conjugated diene rubber latex, and within this range, the conjugated diene rubber latex There is an advantage that the coagulant content is reduced by uniformly thickening and reducing the content of the acid thickening agent.

In step c), the electrolyte may be added to the conjugated diene rubber latex at, for example, 30 to 65°C and stirred for 10 to 30 minutes at a stirring speed of 45 to 70 rpm, preferably at 35 to 60°C. It can be stirred for 10 to 20 minutes at a stirring speed of 50 to 65 rpm, and within this range, there is an advantage that the conjugated diene rubber latex is uniformly enlarged and the coagulum content is reduced.

For convenience, 100 parts by weight (based on solid content) of the conjugated diene rubber latex may be calculated as the weight of the total conjugated diene compound added when manufacturing the conjugated diene rubber latex.

In step c), the electrolyte may be, for example, one or more selected from the group consisting of K ₂ CO ₃ , CaCO ₃ , Na ₂ SO ₄ , Na ₃ PO ₄ , NaH ₂ PO ₄ and Na ₂ HPO ₄ , preferably It may be Na ₂ SO ₄ , Na ₂ HPO ₄ , or a mixture thereof, and in this case, the conjugated diene rubber latex is uniformly enlarged and the content of the acid enlargement agent is reduced, thereby broadening the full width at half maximum of the particle size and reducing the coagulant content. There is.

d) Preparing thickened conjugated diene rubber latex by thickening it by adding 0.5 to 0.85 parts by weight of an acid thickening agent to 100 parts by weight (based on solid content) of the conjugated diene rubber latex.

In step d), preferably 0.6 to 0.85 parts by weight, more preferably 0.65 to 0.8 parts by weight, more preferably 0.65 to 0.75 parts by weight of the acid thickening agent per 100 parts by weight (based on solid content) of the conjugated diene rubber latex. There is an advantage that within this range, the conjugated diene rubber latex is uniformly enlarged, the coagulum content is reduced, and the impact resistance is improved.

For example, the acid thickening agent may be one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, and acetic acid, and is preferably acetic acid. In this case, the acid thickening agent has the effect of uniformly thickening, good coagulation efficiency, and reducing the coagulant content. There is.

The hypertrophied conjugated diene rubber latex obtained in step d) preferably has an average particle diameter of 3,100 to 3,400 Å and a full width at half maximum of the particle size of 1,600 to 2,500 Å, more preferably an average particle diameter of 3,200 to 3,400 Å and a full width at half maximum of the particle size. 1,700 to 2,500 Å, more preferably, the average particle diameter may be 3,300 to 3,400 Å and the full width at half maximum of the particle size may be 2,000 to 2,500 Å. Within this range, impact resistance is significantly improved and fluidity, reflection haze and gloss are excellent. This has the effect of reducing injection mold residue during injection molding.

In this description, the full width at half maximum of the particle size means the difference between the particle sizes corresponding to 1/2 of the maximum particle diameter in the particle size distribution chart, and the larger the difference, that is, the larger the full width at half maximum, the more uniform the rubber particle size is. In Figure 1 below, f _max is the maximum particle size, 1/2 of the maximum particle size is f _max/2 , the corresponding particle sizes are X ₁ and X ₂ respectively, and the range from X ₁ to X ₂ , that is, FWHM is The particle diameter becomes the full width at half-maximum.

In this article, the full width at half maximum of the particle size is measured by CHDF (Capillary Hydrodynamic Fractionation) using MATEC CHDF 400.

For example, the hypertrophied conjugated diene rubber latex obtained in step d) has a coagulant content of 1.2% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less, and even more preferably 0.01 to 0.07% by weight. %, and within this range, impact resistance is improved and injection mold residue is reduced during injection molding.

e) 40 to 70% by weight (based on solid content) of the enlarged conjugated diene rubber latex, 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound, followed by graft polymerization to produce a vinyl cyan compound-conjugated diene. Obtaining a rubber-aromatic vinyl compound graft copolymer

The step e) of obtaining the graft copolymer preferably includes 45 to 65% by weight (based on solid content) of the hypertrophied conjugated diene rubber latex, 20 to 40% by weight of the aromatic vinyl compound, and 10 to 20% by weight of the vinyl cyan compound. It can be subjected to graft polymerization, and more preferably includes 50 to 60% by weight (based on solid content) of hypertrophied conjugated diene rubber latex, 25 to 35% by weight of aromatic vinyl compound, and 12 to 17% by weight of vinyl cyan compound. It can be subjected to graft polymerization, and within this range, it has excellent fluidity, reflective haze, gloss, and impact resistance, and has the effect of reducing residue in the injection mold during injection molding.

In step e), preferably, e-1) 40 to 70 parts by weight of the enlarged conjugated diene rubber latex, based on a total of 100 parts by weight of the conjugated diene rubber latex (based on solid content), aromatic vinyl compound, and vinyl cyan compound. (based on solid content) and 80 to 120 parts by weight of ion-exchanged water, 15 to 45 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyan compound, 10 to 30 parts by weight of ion-exchanged water, 0.01 to 2 parts by weight of an emulsifier and molecular weight. First graft polymerization in which a mixed solution containing 0.01 to 2 parts by weight of a regulator, 0.01 to 2 parts by weight of a fat-soluble polymerization initiator, and 0.001 to 0.4 parts by weight of an oxidation-reduction catalyst are continuously added at 65 to 75° C. for 2 to 4 hours to react. step; e-2) After the first graft polymerization step, adding 0.001 to 0.6 parts by weight of a redox catalyst and 0.001 to 0.5 parts by weight of an oil-soluble polymerization initiator; e-3) A second graft polymerization step of reacting by adding a redox catalyst and an oil-soluble polymerization initiator and then raising the temperature to 75 to 85° C. for 50 to 70 minutes; and e-4) terminating the polymerization reaction at the point where the conversion rate of the polymerization reaction is 90 to 99%. In this case, the fluidity, reflection haze, gloss, and impact resistance are all excellent and the injection molding effect is excellent. It has the effect of reducing residue in the mold.

In step e-1), the emulsifier may be, for example, 0.01 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight, and even more preferably 0.2 to 0.7 parts by weight. Within this range, latex stability is excellent and the coagulant content is reduced.

In step e-1), the emulsifier may be, for example, a multimer acid of an unsaturated fatty acid or a metal salt thereof, and in this case, latex stability is excellent and the coagulant content is reduced.

For example, the unsaturated fatty acid may be a straight-chain, branched, or cyclic unsaturated fatty acid having 8 to 22 carbon atoms. In this case, it has the effect of reducing coagulation of latex and reducing residue in the injection mold during injection molding.

In step e-1), the molecular weight regulator may be preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight, and even more preferably 0.2 to 0.7 parts by weight.

In step e-1), the oxidation-reduction catalyst may be preferably 0.001 to 0.3 parts by weight, more preferably 0.005 to 0.1 parts by weight.

In step e-1), the reaction may be carried out by continuously adding the mixture at 67 to 73°C for 2.5 to 3.5 hours. Within this range, the grafting efficiency is excellent and latex coagulation is reduced.

In step e-2), the oxidation-reduction catalyst may be preferably 0.001 to 0.6 parts by weight, more preferably 0.01 to 0.3 parts by weight.

In step e-2), the molecular weight regulator may be preferably 0.01 to 0.3 parts by weight, more preferably 0.03 to 0.1 parts by weight.

In step e-3), the reaction may be preferably carried out by raising the temperature to 77 to 82°C for 55 to 65 minutes, and within this range, the reaction efficiency is excellent and the coagulant content is reduced.

In step e-4), the polymerization reaction may preferably be terminated at a polymerization conversion rate of 93 to 97%.

The latex of the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer obtained in step e-4) can be obtained in powder form through conventional processes such as coagulation, washing, and drying.

The coagulation can be performed, for example, by adding 0.1 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight, of the acid coagulant based on 100 parts by weight (based on solid content) of the graft copolymer latex.

For example, the acid coagulant may be one or more selected from the group consisting of sulfuric acid, hydrochloric acid, formic acid, and acetic acid, and is preferably sulfuric acid. In this case, it has good coagulation efficiency and excellent gloss.

For example, the vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer obtained in step e) has a coagulant content of 0.1% by weight or less, preferably 0.06% by weight or less, more preferably 0.01 to 0.03% by weight. %, and within this range, impact resistance is improved and residues in the injection mold are reduced during injection molding.

In the present description, when the electrolyte, acid thickening agent, or coagulant includes a solvent such as water, their weight refers to the weight excluding the solvent.

Method for producing thermoplastic resin composition

The method for producing a thermoplastic resin composition of the present invention includes preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the above production method; And in this case, adding 15 to 35% by weight of the prepared graft copolymer and 65 to 85% by weight of the aromatic vinyl compound-vinylcyan compound copolymer into an extruder, melt-kneading, and then extruding. It has excellent fluidity, reflective haze, and gloss, and in particular, has excellent impact resistance and has the effect of reducing residue in the injection mold during injection molding.

Preferably, the method for producing the thermoplastic resin composition includes preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the above production method; And in this case, adding 20 to 30% by weight of the prepared graft copolymer and 70 to 80% by weight of the aromatic vinyl compound-vinylcyan compound copolymer into an extruder, melt-kneading, and then extruding. It has excellent fluidity, reflective haze, and gloss, and in particular, has excellent impact resistance and has the effect of reducing residue in the injection mold during injection molding.

The melt kneading and extrusion steps are carried out within a barrel temperature of, for example, 200 to 330°C, preferably 210 to 300°C, more preferably 210 to 280°C, and even more preferably 220 to 250°C. In this case, sufficient melt-kneading can be achieved while the throughput per unit time is appropriate, and there is an effect of not causing problems such as thermal decomposition of the resin component.

In the melt kneading and extrusion steps, for example, the screw rotation speed is 100 to 500 rpm, preferably 150 to 400 rpm, more preferably 100 to 350 rpm, even more preferably 200 to 310 rpm, and most preferably 250 to 350 rpm. It can be performed under rpm conditions, and in this case, the throughput per unit time is appropriate, which has the effect of suppressing excessive cutting while providing excellent process efficiency.

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

During the 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 are added to 100 parts by weight of the thermoplastic resin composition (vinyl cyan compound) -Conjugated diene rubber-aromatic vinyl compound graft copolymer + aromatic vinyl compound-vinylcyan compound copolymer) can be added within the range of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

The aromatic vinyl compound-vinyl cyan compound copolymer is, for example, 65 to 85% by weight of an aromatic vinyl compound and 15 to 35% by weight of a vinyl cyan compound, preferably 70 to 80% by weight of an aromatic vinyl compound and 20 to 30% by weight of a vinyl cyan compound. % may be included, and within this range, fluidity is appropriate, resulting in excellent processability and excellent impact resistance.

For example, the aromatic vinyl compound-vinylcyan compound copolymer may have a weight average molecular weight of 120,000 to 200,000 g/mol, preferably 140,000 to 180,000 g/mol, and within this range, the fluidity is appropriate, so the processability is excellent and the resistance is excellent. It has excellent impact resistance.

In this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze). As a specific example, using THF (tetrahydrofuran) as an eluent, GPC (Gel Permeation Chromatography, waters breeze) ) can be measured as a relative value to a standard PS (standard polystyrene) sample. As a specific measurement example, the solvent is THF, the column temperature is 40℃, the flow rate is 0.3 ml/min, the sample concentration is 20 mg/ml, the injection volume is 5㎕, and the column model is 1xPLgel 10㎛ MiniMix-B (250x4.6mm ) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), measuring device is Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature is 35℃, data Treatment can be measured using Agilent ChemStation S/W, and test methods (Mn, Mw, and PDI) can be measured under OECD TG 118 conditions.

In this description, a polymer comprising a certain compound refers to a polymer polymerized including that compound, and the units in the polymerized polymer are derived from the compound.

The aromatic vinyl compound-vinyl cyan compound copolymer may be prepared, for example, by solution polymerization or bulk polymerization, and preferably bulk polymerization, and in this case, it has excellent heat resistance and fluidity.

The solution polymerization and bulk polymerization are not particularly limited as long as the solution polymerization and bulk polymerization methods are respectively commonly practiced in the technical field to which the present invention pertains.

In the present disclosure, the conjugated diene compound is, for example, selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene. There may be one or more types, preferably 1,3-butadiene.

Examples of aromatic vinyl compounds in the present disclosure include styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobostyrene, ρ - It may be one or more selected from the group consisting of bromo styrene, m-bromo styrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyl toluene, vinyl xylene, fluorostyrene, and vinyl naphthalene, Preferably, it may be at least one selected from the group consisting of styrene and α-methyl styrene, more preferably styrene. In this case, it has appropriate fluidity, excellent processability, and has excellent mechanical properties such as impact resistance.

In the present disclosure, the vinyl cyan compound may be, for example, one or more selected from the group consisting of acrylonitrile, metanitronitrile, ethyl acrylonitrile, and isopropylacrylonitrile, and is preferably acrylonitrile.

Thermoplastic resin composition

The thermoplastic resin composition of the present invention includes 15 to 35% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and 65 to 85% by weight of an aromatic vinyl compound-vinylcyan compound copolymer, and the conjugated diene rubber has an average particle diameter of 3,000 to 3,500 Å, a full width at half maximum of 1,600 to 2,600 Å, and an Izod impact strength measured with a specimen thickness of 1/8" at room temperature (23°C) according to ASTM D256 of 40 kgf·cm/cm or more. In this case, impact resistance is greatly increased, and fluidity, reflective haze, and gloss are all excellent, and residues in the injection mold are reduced during injection molding.

The conjugated diene rubber preferably has an average particle diameter of 3,100 to 3,400 Å and a full width at half maximum of the particle size of 1,600 to 2,500 Å, more preferably an average particle diameter of 3,200 to 3,400 Å and a full width at half maximum of the particle size of 1,700 to 2,500 Å, and even more preferably The average particle diameter may be 3,300 to 3,400 Å and the full width at half maximum of the particle size may be 2,000 to 2,500 Å. Within this range, impact resistance is significantly improved while fluidity, reflective haze and gloss are excellent, and injection mold residue is reduced during injection molding. There is an effect.

The thermoplastic resin composition preferably has an Izod impact strength of 42 kgf·cm/cm or more, more preferably 42 to 50 kgf·cm, as measured at room temperature (23°C) with a specimen thickness of 1/8" according to ASTM D256. /cm, more preferably 45 to 48 kgf·cm/cm, and within this range, excellent physical property balance is achieved.

For example, the thermoplastic resin composition has an Izod impact strength of 25 kgf·cm/cm or more, preferably 26 kgf·cm/cm or more, as measured at room temperature (23°C) with a specimen thickness of 1/4" according to ASTM D256, More preferably, it may be 26 to 31 kgf·cm/cm, and even more preferably 27 to 30 kgf·cm/cm, and within this range, excellent balance of physical properties is achieved.

For example, the thermoplastic resin composition has a flow index of 24 g/10 min or more, preferably 24 to 30 g/10 min, more preferably 24.5 to 27 g, as measured at 220°C for 10 minutes under a load of 10 kg according to ASTM D1238. /10min, and within this range, it has excellent fluidity and has the advantage of being easy to mold into various shapes.

For example, the thermoplastic resin composition has a reflection haze of 1.1 or less, preferably 0.5 to 1.1, more preferably 0.5 to 1.1, as measured according to ASTM E430 with a RhopointQ instrument manufactured by Rhopoint Instruments. may be 0.6 to 1.1, and within this range, excellent balance of physical properties and excellent surface clarity are achieved.

For example, the thermoplastic resin composition has a gloss of 97 or more, preferably 97 to 110, more preferably 100 to 107, as measured at a 45° angle with a gloss meter according to ASTM D258. Preferably, it may be 101 to 105, and within this range, the physical property balance is excellent and the surface appearance is excellent.

The thermoplastic resin composition is, for example, injected 100 kg of resin in a 30-second cycle at a cylinder temperature of 230°C and a mold temperature of 25°C using an injection machine (ENGEL, clamp force 150 tons), and then the injection mold residue remaining on the plate. It may be 93 mg or less, preferably 92 mg or less, more preferably 83 to 92 mg, and even more preferably 85 to 90 mg, and within this range, the product has excellent physical property balance, excellent productivity, and excellent appearance quality. It works.

It takes 30 seconds for a pellet to melt in an injection machine cylinder at a temperature of 220℃, eject into a mold at 30℃, and harden, which is considered one cycle.

The thermoplastic resin composition optionally contains at least one selected from the group consisting of antioxidants, UV stabilizers, dyes, pigments, flame retardants and inorganic fillers, if necessary, in 100 parts by weight of the thermoplastic resin composition (vinyl cyan compound-conjugated diene rubber-aromatic vinyl) 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, even more preferably 0.5, based on the compound graft copolymer + aromatic vinyl compound-vinylcyan compound copolymer). It may further be included in an amount of from 1 part by weight, and within this range, the necessary physical properties are effectively implemented without deteriorating the original physical properties of the thermoplastic resin composition of the present base.

The thermoplastic resin composition shares all technical features of the method for producing the thermoplastic resin composition described above. Therefore, description of overlapping parts will be omitted.

molded product

The molded article of the present base is characterized in that it contains the thermoplastic resin composition, and in this case, it has excellent fluidity, reflective haze, and gloss, while its impact resistance is greatly improved compared to the conventional ABS resin and the residue during injection molding is significantly reduced, thereby increasing productivity. and has excellent product appearance.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the attached patent claims.

[Example]

Example 1

<Manufacture of conjugated diene rubber latex>

In a nitrogen-substituted polymerization reactor (autoclave), 90 parts by weight of ion-exchanged water, 30 parts by weight of a total of 100 parts by weight of 1,3-butadiene as a conjugated diene compound, 1 part by weight of fatty acid saponification as an emulsifier, and K ₂ CO ₃ as an electrolyte. 0.3 parts by weight, 0.15 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.15 parts by weight of tertiary butyl hydroperoxide as a fat-soluble initiator, 0.06 parts by weight of dextrose as a redox catalyst, and 0.005 parts by weight of sodium pyrrolate. parts by weight and 0.0025 parts by weight of ferrous sulfate were administered in batches and maintained at a reaction temperature of 55°C for 1 hour. Afterwards, 70 parts by weight of the remaining 1,3-butadiene and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator were continuously added for 10 hours, and the temperature was raised to 78°C over 9 hours and maintained. After reacting to a polymerization conversion rate of 30 to 40%, 0.1 parts by weight of potassium persulfate and 0.15 parts by weight of rosin acid emulsifier were added as a water-soluble initiator. The reaction was terminated at a polymerization conversion rate of 95%, and at this time, the average particle diameter of the conjugated diene rubber latex was 1180 Å.

<Conjugated diene rubber latex thickening>

0.1 parts by weight of potassium carbonate (K ₂ CO ₃ ) as an electrolyte was added to 100 parts by weight (based on solid content) of the conjugated diene rubber latex prepared above, stirred for 10 minutes at a stirring speed of 45 to 70 rpm, and then 0.82 parts by weight of acetic acid as an acid thickening agent. It was enlarged by adding an aqueous solution containing one part by weight, and at this time, the average particle diameter of the enlarged conjugated diene rubber latex was 3,270 Å.

< Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer polymerization >

In a nitrogen-substituted polymerization reactor, 55 parts by weight (based on solid content) of the hypertrophied conjugated diene rubber latex prepared above and 100 parts by weight of ion-exchanged water were mixed in a separate mixing device, 15 parts by weight of acrylonitrile, 30 parts by weight of styrene, A mixed solution consisting of 20 parts by weight of ion-exchanged water, 0.4 parts by weight of saponified dimer acid, and 0.35 parts by weight of tertiary dodecyl mercaptan, 0.12 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, and 0.004 parts by weight of sodium pyrrolate. parts and 0.002 parts by weight of ferrous sulfate were added continuously at 70°C for 3 hours. After the above addition, 0.05 part by weight of dextrose, 0.03 part by weight of sodium pyrrolate, 0.001 part by weight of ferrous sulfate, and 0.05 part by weight of t-butyl hydroperoxide were added to the polymerization reactor in batches, and the temperature was raised to 80°C for 1 hour. The temperature was raised over , and then the reaction was terminated to prepare acrylonitrile-butadiene-styrene (hereinafter referred to as 'ABS') latex.

Based on 100 parts by weight (based on solid content) of the prepared ABS latex, 1 part by weight of MgSO ₄ was added and coagulated, and then washed and dried to obtain ABS powder.

<Manufacture of thermoplastic resin composition>

Pellets were prepared by mixing and extruding 25 parts by weight of the ABS powder obtained above and 75 parts by weight of SAN resin (LG Chemical, weight average molecular weight 120,000 g/mol, acrylonitrile content 27 wt%) at 210°C. The melt index was measured with the prepared pellets. In addition, the manufactured pellets were injected at a molding temperature of 220°C to produce specimens for measuring physical properties.

Example 2

In <Conjugated diene rubber latex thickening> of Example 1, 0.1 part by weight of sodium sulfate (Na ₂ SO ₄ ) was added instead of 0.1 part by weight of potassium carbonate (K ₂ CO ₃ ) as the electrolyte, stirred, and then an aqueous solution containing 0.7 parts by weight of acetic acid was added. It was carried out in the same manner as in Example 1 except for one thing.

Example 3

In <Conjugated diene rubber latex thickening> of Example 1, 0.1 part by weight of sodium phosphate (Na ₃ PO ₄ ) was added instead of 0.1 part by weight of potassium carbonate (K ₂ CO ₃ ) as the electrolyte, stirred, and then an aqueous solution containing 0.7 parts by weight of acetic acid was added. It was carried out in the same manner as Example 1 except that it was added.

Example 4

In <Conjugated diene rubber latex thickening> of Example 1, 0.1 part by weight of sodium monohydrogen phosphate (Na ₂ HPO ₄ ) was added instead of 0.1 part by weight of potassium carbonate (K ₂ CO ₃ ) as an electrolyte, stirred, and then added to a solution containing 0.7 part by weight of acetic acid. The same procedure as Example 1 was performed except that an aqueous solution was added.

Example 5

In <Conjugated diene rubber latex thickening> of Example 1, 0.1 part by weight of sodium dihydrogen phosphate (NaH ₂ PO ₄ ) was added instead of 0.1 part by weight of potassium carbonate (K ₂ CO ₃ ) as an electrolyte, stirred, and then mixed with 0.8 part by weight of acetic acid. The same procedure as Example 1 was performed except that an aqueous solution was added.

Comparative Example 1

<Manufacture of conjugated diene rubber latex>

In a nitrogen-substituted polymerization reactor (autoclave), 75 parts by weight of ion-exchanged water, 90 parts by weight of a total of 100 parts by weight of 1,3-butadiene as a monomer, 3 parts by weight of dimer acid saponification as an emulsifier, and potassium carbonate (K _{2 )} as an electrolyte. CO ₃ ) 0.1 part by weight, 0.1 part by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.15 part by weight of tertiary butyl hydroperoxide as an initiator, 0.06 part by weight of dextrose, 0.005 part by weight of sodium pyrrolate, and sulfuric acid. After adding 0.0025 parts by weight of ferrous iron in batches and reacting at a reaction temperature of 55°C to a polymerization conversion rate of 30 to 40%, 0.3 mass% of potassium persulfate was added in batches, the temperature was raised to 72°C, and the remainder was added at a polymerization conversion rate of 60 to 70%. 10 parts by weight of 1,3-butadiene was added in batches, and the reaction was terminated at a polymerization conversion rate of 95%. The average particle diameter of the conjugated diene rubber latex obtained at this time was 1155 Å.

<Conjugated diene rubber latex thickening>

100 parts by weight (based on solid content) of the conjugated diene rubber latex prepared above was thickened by adding an aqueous solution containing 1.5 parts by weight of acetic acid as an acid thickening agent. At this time, the average particle diameter of the thickened conjugated diene rubber latex was 3272 Å.

< Vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer polymerization >

It was carried out in the same manner as <vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer polymerization> of Example 1.

<Manufacture of thermoplastic resin composition>

It was carried out in the same manner as <Preparation of thermoplastic resin composition> in Example 1 above.

Comparative Example 2

In Comparative Example 1, <Conjugated diene rubber latex thickening>, before adding the acid thickening agent, 0.1 part by weight of sodium sulfate was added, and then an aqueous solution containing 1.37 parts by weight of acetic acid as an acid thickening agent was added to thicken, and at this time, the thickened conjugated diene was added. The average particle diameter of rubber latex was 3300 Å.

Comparative Example 3

In Example 1, <Conjugated diene rubber latex thickening>, the same procedure as Example 1 was performed, except that 0.1 part by weight of potassium carbonate (K ₂ CO ₃ ) was not added as an electrolyte.

Comparative Example 4

In <Conjugated diene rubber latex thickening> of Example 1, 0.1 parts by weight of sodium chloride (NaCl) was added instead of 0.1 parts by weight of potassium carbonate (K ₂ CO ₃ ) as an electrolyte, and then an aqueous solution containing 0.9 parts by weight of acetic acid was added as an acid thickening agent. It was carried out in the same manner as in Example 1 except that it was enlarged.

Comparative Example 5

In <Conjugated diene rubber latex thickening> of Example 1, 0.1 parts by weight of sodium sulfate was added as an electrolyte, and then 1.4 parts by weight of acetic acid was added.

Comparative Example 6

In <Manufacture of conjugated diene rubber latex> of Example 1, 70 parts by weight of the remaining 1,3-butadiene and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator were continuously added for 10 hours to obtain the remaining 1,3-butadiene. Silver was added continuously for 10 hours, and 0.15 parts by weight of tertiary dodecyl mercaptan (TDDM) was added at 5 and 10 hours, respectively. It was the same as <Manufacture of conjugated diene rubber latex> in Example 1 above. It was carried out properly.

<Conjugated diene rubber latex thickening>

100 parts by weight (based on solid content) of the conjugated diene rubber latex prepared above was thickened by adding an aqueous solution containing 0.8 parts by weight of acetic acid as an acid thickening agent. At this time, the average particle diameter of the thickened conjugated diene rubber latex was 3,239 Å.

Comparative Example 7

In <Conjugated diene rubber latex thickening> of Example 1, the same procedure as Example 1 was carried out, except that an aqueous solution containing 0.1 part by weight of potassium carbonate as an electrolyte and 0.82 parts by weight of acetic acid as an acid thickening agent was mixed and added.

Comparative Example 8

In Example 1, <Manufacture of conjugated diene rubber latex>, the same procedure as Example 1 was carried out, except that 3 parts by weight of the emulsifier was added.

[Test example]

The properties of the pellets and specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 8 were measured by the following method, and the results are shown in Tables 1 to 2 below.

* Average particle diameter (Å): Measured using dynamic light scattering. Specifically, intensity was measured in Gaussian mode using a particle meter (product name: Nicomp 380, manufacturer: PSS). It was measured by value.

* Particle diameter full width at half maximum (Å): CHDF (Capillary Hydrodynamic Fractionation) was measured using MATEC CHDF 400.

* Gel content (% by weight): After coagulating the rubber latex using diluted acid or metal salt, washing and drying in a vacuum oven at 60℃ for 24 hours, the resulting rubber lump is cut into small pieces with scissors, and then 1 g of rubber is added. The section was placed in 100 g of toluene and stored in the dark at room temperature for 48 hours, then separated into sol and gel, and the gel content was measured according to Equation 3 below.

[Equation 3]

Gel content (% by weight) = [Weight of insoluble matter (gel) / Weight of sample] x 100

* Coagulant content (% by weight): After filtering the polymerized latex through a 100 mesh stainless steel net, the unfiltered coagulant was dried at 80°C for 24 hours, then weighed, and its content was compared to the total solid content. Calculated as a percentage.

* Melt index (g/10min): The manufactured pellets were measured by the ASTM D1238 method under the conditions of 220°C and 10 kg.

* Izod impact strength (IMP; kgf·cm/cm): Izod impact strength was measured at room temperature (23°C) at room temperature (23°C) at 1/4" and 1/8" thickness of the specimen, respectively, according to ASTM D256.

* Glossiness: Measured at 45° according to ASTM D528.

* Reflection Haze: Measured by adding gloss values between 17 to 19° and 21 to 23° according to ASTM E430 with a RhopointQ instrument from Rhopoint instruments. The lower the reflection haze, the better the surface quality.

* Injection mold residue (mold deposit; mg): Remains on the plate after injecting 100 kg of resin in a 30-second cycle at a cylinder temperature of 230℃ and a mold temperature of 25℃ using an injection machine (ENGEL, mold clamping force of 150 tons). The weight of the injection residue was measured.

division Example 1 Example 2 Example 3 Example 4 Example 5 Conjugated diene
rubber
latex Electrolyte (parts by weight) K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 emulsifier 1.0 1.0 1.0 1.0 1.0 average particle size 1180 1180 1180 1180 1180 coagulum content 0.32 0.32 0.32 0.32 0.32 Gel content (% by weight) 75 75 75 75 75 bloated
Conjugated diene
rubber
latex Electrolyte (parts by weight) K ₂ CO ₃
0.1 Na ₂ SO ₄
0.1 _{Na3PO4 _}
0.1 _{Na2HPO4 _}
0.1 _{NaH2PO4 _}
0.1 Acetic acid (parts by weight) 0.82 0.7 0.7 0.7 0.8 coagulum content 0.06 0.05 1.12 0.04 0.05 average particle size 3270 3320 3392 3310 3265 Full width at half width 1650 2420 2202 2380 1720 ABS resin coagulum content 0.05 0.03 0.03 0.03 0.09 thermoplastic
profit
composition 1/4" impact strength 26.4 28.7 27.4 28.9 26.6 1/8" impact strength 42.2 46.8 44.1 46.3 42.7 liquid index 24.7 25.2 24.3 24.9 25.3 reflective haze 1.1 0.9 1.0 1.1 0.9 Glossiness 97 102 101 103 101 Injection mold residue 92 88 93 90 92

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 conjugate
Dien
rubber
latex electrolyte
(part by weight) K ₂ CO ₃
0.1 K ₂ CO ₃
0.1 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 K ₂ CO ₃
0.3 emulsifier
(part by weight) 3 3 1.0 1.0 1.0 1.0 1.0 3 average particle size 1155 1155 1180 1180 1090 1130 1180 1110 coagulum content 0.31 0.31 0.32 0.32 0.32 0.33 0.32 0.28 gel content
(weight%) 90 90 75 75 76 86 75 77 bloated
conjugate
Dien
rubber
latex electrolyte
(part by weight) - Na ₂ SO ₄
0.1 - NaCl
0.1 Na ₂ SO ₄
0.1 - K ₂ CO ₃
0.1
+
acetic acid
0.82 K ₂ CO ₃
0.1 acetic acid
(part by weight) 1.5 1.37 0.82 0.9 1.4 0.9 1.0 coagulum content 0.06 0.07 0.04 0.06 0.06 0.04 0.12 0.11 average particle size 3272 3300 3200 3218 3195 3239 3273 3320 Particle diameter half width 620 2256 582 585 2156 621 1282 1210 ABS resin coagulum content 0.04 0.06 0.03 0.1 0.07 0.03 0.08 0.07 fever
firing
profit
composition 1/4"
impact strength 23 24.1 25.3 24.9 22.5 24.6 24.3 24.1 1/8"
impact strength 34.2 38.3 35.8 35.2 32.6 35.5 36.6 38.8 liquid index 23.2 23.6 25.1 25.0 23.7 24.1 24.1 24.0 reflective haze 1.5 1.6 1.0 1.0 1.3 1.1 1.3 1.2 Glossiness 98 100 96 100 102 96 98 97 injection mold
residue 148 149 96 97 148 102 142 140

As shown in Tables 1 to 2, the thermoplastic resin composition according to the present invention (Examples 1 to 5) has excellent fluidity, reflection haze and gloss compared to Comparative Examples 1 to 8, and has a specimen thickness of 1/4" and It was confirmed that the impact strength was significantly increased at 1/8" and the injection mold residue was reduced.

As a notable result, Examples 1 to 5 in which K ₂ CO ₃ , Na ₂ SO ₄ , Na ₃ PO ₄ or NaH ₂ PO ₄ were added as an electrolyte before thickening the conjugated diene rubber latex had a particle size of the thickened conjugated diene rubber latex. The full width at half maximum was widened, and the impact strength, especially at a thickness of 1/8", was greatly increased compared to Comparative Example 1 manufactured using the conventional technology.

In addition, as in the past, Comparative Examples 1 and 2, which included 3 parts by weight of an emulsifier during polymerization of conjugated diene rubber latex, had a very narrow particle size full width at half maximum, poor impact strength, reflective haze and gloss, and a sharp increase in injection mold residue.

In addition, Comparative Examples 1, 3, and 6, in which electrolyte was not added before adding the acid thickening agent, had a very narrow particle size full width at half maximum, poor impact strength, reflection haze, and gloss, and a sharp increase in injection mold residue.

In addition, in Comparative Example 4, in which 0.1 part by weight of NaCl was added as an electrolyte before adding the acid thickening agent and the full width at half maximum of the particle size was only 585 Å, the coagulant content of the ABS resin increased and the injection mold residue also increased.

In addition, Comparative Example 5, in which 1.4 parts by weight of the acid thickening agent was added, had poor impact strength, reflective haze, and gloss, and injection mold residue also rapidly increased.

In addition, in <Conjugated diene rubber latex thickening>, Comparative Example 7, in which electrolyte and acid thickening agent were mixed, had a narrow particle size full width at half maximum, poor impact strength, reflection haze, and gloss, and increased injection mold residue.

In addition, in <Conjugated diene rubber latex production>, Comparative Example 8, in which the emulsifier was used beyond the scope of the present invention, had a narrow particle size full width at half maximum, poor impact strength, reflection haze, and gloss, and increased injection mold residue.

Claims (15)

a) polymerizing 20 to 40 parts by weight of a total of 100 parts by weight of the conjugated diene compound, including 0.1 to 2 parts by weight of an emulsifier, a molecular weight regulator, and an electrolyte;
b) after step a), adding the remaining conjugated diene compound and a molecular weight regulator to perform polymerization to obtain conjugated diene rubber latex;
c) adding 0.05 to 0.2 parts by weight of electrolyte to 100 parts by weight (based on solid content) of the conjugated diene rubber latex;
d) preparing hypertrophied conjugated diene rubber latex by adding 0.5 to 0.85 parts by weight of an acid thickening agent to 100 parts by weight (based on solid content) of the conjugated diene rubber latex; and
e) 40 to 70% by weight (based on solid content) of the enlarged conjugated diene rubber latex, 15 to 45% by weight of an aromatic vinyl compound, and 5 to 25% by weight of a vinyl cyan compound, followed by graft polymerization to produce a vinyl cyan compound-conjugated diene. Obtaining a rubber-aromatic vinyl compound graft copolymer;
The hypertrophied conjugated diene rubber latex obtained in step d) has an average particle diameter of 3,000 to 3,500 Å and a particle width at half maximum of 1,600 to 2,600 Å.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
In steps a) and c), the electrolyte is one or more selected from the group consisting of K ₂ CO ₃ , Na ₂ SO ₄ , Na ₃ PO ₄ , NaH ₂ PO ₄ and Na ₂ HPO ₄
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
In steps a) and b), the molecular weight regulator is 0.05 to 0.3 parts by weight, and 0.1 to 0.5 parts by weight, respectively.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
Step a) is characterized in that the polymerization reaction takes place at 50 to 60 ° C. for 50 to 70 minutes.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
Step a) is characterized in that the polymerization reaction includes 0.01 to 0.5 parts by weight of an oxidation-reduction catalyst, 0.01 to 0.7 parts by weight of an oil-soluble polymerization initiator, and 80 to 120 parts by weight of ion-exchanged water.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
In step b), the remaining conjugated diene compound and molecular weight regulator are continuously added for 9 to 11 hours, and the temperature is raised to 73 to 83 ° C. over 8 to 10 hours and then maintained.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
Step b) includes continuously adding the remaining conjugated diene compound and molecular weight regulator b-1) for 9 to 11 hours, raising the temperature to 73 to 83°C over 8 to 10 hours, and then maintaining the polymerization reaction; b-2) adding 0.05 to 0.2 parts by weight of an initiator and 0.05 to 0.3 parts by weight of an emulsifier and performing a polymerization reaction at a polymerization conversion rate of 30 to 40% by weight; and b-3) terminating the polymerization reaction at a polymerization conversion rate of 93 to 99% by weight.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
The conjugated diene rubber latex obtained in step b) is characterized in that the gel content is 80% by weight or less.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
According to paragraph 1,
In step e), based on a total of 100 parts by weight of the conjugated diene rubber latex (based on solid content), aromatic vinyl compound, and vinyl cyan compound, e-1) 40 to 70 parts by weight of the enlarged conjugated diene rubber latex (based on solid content) ) and 80 to 120 parts by weight of ion-exchanged water, 15 to 45 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyan compound, 10 to 30 parts by weight of ion-exchanged water, 0.01 to 2 parts by weight of an emulsifier, and 0.01 to 0.01 to 200 parts by weight of a molecular weight regulator. A first graft polymerization step of continuously adding and reacting a mixed solution containing 2 parts by weight, 0.01 to 2 parts by weight of an oil-soluble polymerization initiator, and 0.001 to 0.4 parts by weight of a redox catalyst at 65 to 75° C. for 2 to 4 hours; e-2) After the first graft polymerization step, adding 0.001 to 0.6 parts by weight of a redox catalyst and 0.001 to 0.5 parts by weight of an oil-soluble polymerization initiator; e-3) A second graft polymerization step of reacting by adding a redox catalyst and an oil-soluble polymerization initiator and then raising the temperature to 75 to 85° C. for 50 to 70 minutes; and e-4) terminating the polymerization reaction at a conversion rate of 90 to 99% of the polymerization reaction.
Method for producing vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer.
Preparing a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer according to the production method of any one of claims 1 to 9; and
Injecting 15 to 35% by weight of the prepared graft copolymer and 65 to 85% by weight of the aromatic vinyl compound-vinylcyan compound copolymer into an extruder, melt-kneading, and then extruding;
Method for producing a thermoplastic resin composition.
Comprising 15 to 35% by weight of a vinyl cyan compound-conjugated diene rubber-aromatic vinyl compound graft copolymer and 65 to 85% by weight of an aromatic vinyl compound-vinylcyan compound copolymer,
The conjugated diene rubber has an average particle diameter of 3,000 to 3,500 Å and a full width at half maximum of the particle size of 1,600 to 2,600 Å,
Characterized by an Izod impact strength of 40 kgf·cm/cm or more, measured at a specimen thickness of 1/8" according to ASTM D256.
Thermoplastic resin composition.
According to clause 11,
The thermoplastic resin composition is characterized in that it has a reflection haze of 1.1 or less as measured according to ASTM E430 with a RhopointQ instrument manufactured by Rhopoint Instruments.
Thermoplastic resin composition.
According to clause 11,
The thermoplastic resin composition is characterized in that it has a gloss of 97 or more as measured at 45° according to ASTM D528.
Thermoplastic resin composition.
According to clause 11,
The thermoplastic resin composition was manufactured by injecting 100 kg of resin in a 30-second cycle at a cylinder temperature of 230°C and a mold temperature of 25°C using an injection machine (ENGEL, clamp force 150 tons), and the injection mold residue remaining on the plate was 95%. Characterized by being less than mg
Thermoplastic resin composition.
Characterized by comprising the thermoplastic resin composition of any one of claims 11 to 14.
Molded product.