KR102007976B1

KR102007976B1 - Method for preparing thermoplastic resin, thermoplastic resin and thermoplastic resin composition comprising the resin

Info

Publication number: KR102007976B1
Application number: KR1020150168627A
Authority: KR
Inventors: 심형섭; 최정수; 유근훈; 이원석; 장석구; 이루다; 박상후; 김호훈
Original assignee: 주식회사 엘지화학
Priority date: 2015-11-30
Filing date: 2015-11-30
Publication date: 2019-08-06
Also published as: KR20170062888A

Abstract

The present invention relates to a thermoplastic resin manufacturing method, a thermoplastic resin and a thermoplastic resin composition comprising the same, and more particularly selected from the group consisting of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyan compound in a conjugated diene rubber. Graft polymerization comprising one or more species; And agglomerating the polymerized graft copolymer latex; wherein the hydrophobic silicone solution is added at least 0.0001 to 100 parts by weight of the graft copolymer during the graft polymerization, the agglomeration, or both. It relates to a thermoplastic resin manufacturing method, a thermoplastic resin, and a thermoplastic resin composition comprising the same, characterized in that it is added to less than 0.02 parts by weight.
According to the present invention, there is an effect of providing a thermoplastic resin manufacturing method, a thermoplastic resin and a thermoplastic resin composition comprising the same, while providing equivalent or more mechanical properties, excellent in permeability and transparency, and excellent in low-temperature whitening resistance.

Description

Manufacturing method of thermoplastic resin, thermoplastic resin, and thermoplastic resin composition comprising the same {METHOD FOR PREPARING THERMOPLASTIC RESIN, THERMOPLASTIC RESIN AND THERMOPLASTIC RESIN COMPOSITION COMPRISING THE RESIN}

The present invention relates to a method for producing a thermoplastic resin, a thermoplastic resin, and a thermoplastic resin composition comprising the same, and more particularly, to provide a thermoplastic resin having an equivalent or higher mechanical properties, and excellent in permeability and transparency, and excellent in low temperature whitening resistance. A method, a thermoplastic resin, and a thermoplastic resin composition comprising the same.

Transparent acrylonitrile-butadiene-styrene resins (hereinafter referred to as ABS resins) are well known as resins having extremely high light transmittance and excellent transparency. In addition, it has excellent impact resistance and processability, and is excellent in mechanical properties, and is used in the fields of electricity, electronics, OA equipment, miscellaneous goods, and construction materials. In particular, housings, electrical appliances, and electronics for home appliances including air conditioners, vacuum cleaners, and washing machines, etc. It is mainly used in the field of OA devices such as housings, such as facsimile machines, facsimile machines, computers and telephones, automobile parts, toy members, leisure goods, and interior decoration fields.

The said resin is generally manufactured by emulsion polymerization. In this emulsion polymerization, a large amount of emulsifier is used, and agitation by an impeller is essential in the polymerization and flocculation step, so that a large amount of bubbles and bubbles are generated from the emulsifier by the impeller. However, since bubbles and bubbles adversely affect the stability of the latex and the efficiency of the polymerization process, so far have been solved by introducing a silicone antifoaming agent to minimize the generation of bubbles and bubbles. However, the silicone antifoaming agent remains in the resin, and when exposed to a low temperature environment, there is a problem that adversely affects the physical properties of the resin, such as whitening phenomenon due to voids in the resin due to shrinkage of the silicone antifoaming agent. Therefore, research on a resin and a method of manufacturing the same that is excellent in transparency and at the same time reduce the whitening phenomenon at a low temperature is continuously required.

KR 0836572 B1

An object of the present invention is to provide a method for producing a thermoplastic resin which is excellent in permeability and transparency and excellent in low temperature whitening resistance while providing equivalent or more mechanical properties.

In addition, an object of the present invention is to provide a thermoplastic resin excellent in permeability and transparency and excellent in low temperature whitening resistance while providing equivalent or more mechanical properties.

Moreover, an object of this invention is to provide the thermoplastic resin composition containing the said thermoplastic resin.

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

In order to achieve the above object, the present invention comprises the steps of graft polymerization on conjugated diene rubber, including at least one selected from the group consisting of (meth) acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyan compound; And agglomerating the polymerized graft copolymer latex; wherein the hydrophobic silicone solution is added at least 0.0001 to 100 parts by weight of the graft copolymer during the graft polymerization, the agglomeration, or both. To provide a thermoplastic resin production method to be added to less than 0.02 parts by weight.

In addition, the present invention is a thermoplastic resin comprising a graft copolymer and silica graft polymerized in a conjugated diene rubber, including one or more selected from the group consisting of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds and vinyl cyan compounds To provide.

In another aspect, the present invention provides a thermoplastic resin composition comprising the thermoplastic resin and the acrylic copolymer.

According to the present invention, there is an effect of providing a method for producing a thermoplastic resin having excellent permeability and transparency, excellent low temperature whitening resistance, a thermoplastic resin, and a thermoplastic resin composition comprising the same while providing equivalent or more mechanical properties.

Hereinafter, the present invention will be described in detail.

The present inventors have completed the present invention by confirming that the low-temperature whitening resistance is remarkably improved when a specific mixture is added when preparing a thermoplastic resin, without deteriorating physical properties.

Looking at the manufacturing method of the thermoplastic resin according to the present invention in detail.

The thermoplastic resin manufacturing method according to the present invention comprises the steps of graft polymerization on a conjugated diene rubber, including one or more selected from the group consisting of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds and vinyl cyan compounds; And agglomerating the polymerized graft copolymer latex; wherein the hydrophobic silicone solution is added at least 0.0001 to 100 parts by weight of the graft copolymer during the graft polymerization, the agglomeration, or both. To less than 0.02 parts by weight. In this case, bubbles and bubbles generated due to stirring by the impeller during the polymerization or aggregation are suppressed and removed by the hydrophobic silicone solution, and the hydrophobic silocon-based mixture remains in the thermoplastic resin, but at low temperature. By preventing the shrinkage of the thermoplastic resin produced by minimizing the generation of voids, there is an effect of excellent whitening resistance.

The graft polymerization may be, for example, graft emulsion polymerization, and the method of adding monomers in the graft emulsion polymerization may include a method of collectively adding the respective components, and a method of continuously or sequentially adding all or part of the components. Preferably, a batch feeding and a continuous feeding method can be used together. For example, the polymerization may be performed at 60 to 85 ° C., or 70 to 85 ° C. for 1 to 8 hours or 3 to 8 hours.

The emulsion polymerization may be carried out, for example, including an emulsifier, a polymerization initiator and a molecular weight regulator, and is not particularly limited as long as it can be used in the graft emulsion polymerization.

The molecular weight modifier may be, for example, dodecyl mercaptans such as t-dodecyl mercaptan, normal dodecyl mercaptan and the like.

The graft copolymer production method may further include, for example, dehydrating and drying the aggregated graft copolymer.

The hydrophobicity of the hydrophobic silicone solution has no affinity for water molecules, the surface does not dissolve in water, and pushes water molecules off the surface, and it is understood that the hydrophobic or lipophilic recognized by a person skilled in the art. Can be.

The hydrophobic silicone solution may serve as an antifoaming agent in the graft emulsion polymerization, for example, which is used to prepare bubbles and bubbles generated by stirring by an impeller during polymerization and agglomeration in resin production by emulsion polymerization. It may mean an antifoaming agent for inhibiting or eliminating.

The hydrophobic silicone solution may include, for example, silica (silica) whose surface is modified with a silicon-based compound. In this case, the shrinkage at low temperature is minimized to minimize the occurrence of voids in the resin, thereby having excellent whitening resistance.

The silica may be included, for example, 0.1 to 10% by weight, 0.1 to 5% by weight, or 1 to 3% by weight with respect to the hydrophobic silicon solution, there is an excellent mechanical properties and low temperature whitening resistance within this range.

The silicon-based compound may be, for example, dialkyl siloxane, and in detail, may be dimethyl siloxane.

The silica may be solid, for example, and may be dispersed in the hydrophobic silicone solution.

The hydrophobic silicone solution may have a viscosity at 25 ° C. of 2,000 cps or less, 1,000 cps or less, or 100 to 400 cps, and prevent shrinkage at low temperatures within this range to minimize the occurrence of voids in the resin, thereby preventing whitening resistance. Excellent effect.

The hydrophobic silicone solution may be, for example, at least one selected from the group consisting of silica, tall oil, oxidized polyethylene, polyethylene-polypropylene glycol, hydrogenated intermediate refined oil (petroleum), and solvent refined light naphthenic refined oil (petroleum). It may be a mixture containing.

The hydrophobic silicone solution may be a commercially available hydrophobic silicone antifoaming agent, and a specific example may be trade name Rhodoline® 962 manufactured by Solvay.

For example, the hydrophobic silicone solution may be added in an amount of 0.0001 to less than 0.02 parts by weight, 0.001 to less than 0.02 parts by weight, or 0.001 to 0.015 parts by weight, based on 100 parts by weight of the graft copolymer. It is effective in low temperature whitening resistance.

The thermoplastic resin according to the present invention includes a graft copolymer and silica graft polymerized in a conjugated diene rubber, including one or more selected from the group consisting of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds and vinyl cyan compounds. Characterized in that.

The graft copolymer includes, for example, 10 to 70% by weight of conjugated diene rubber, 20 to 70% by weight of (meth) acrylic acid alkyl ester compound, 5 to 30% by weight of aromatic vinyl compound, and 0 to 20% by weight of vinyl cyan compound. It may be polymerized.

The conjugated diene rubber refers to a polymer or copolymer polymerized including a conjugated diene-based compound having a structure in which a double bond and a single bond are arranged across one another. For example, butadiene polymer, butadiene-styrene copolymer and It may be at least one selected from the group consisting of butadiene-acrylonitrile copolymer, and the conjugated diene rubber may be in the form of a latex in which the conjugated diene rubber is dispersed in water in a colloidal state. The conjugated diene rubber may be, for example, a large diameter conjugated diene rubber having an average particle diameter of 2,500 to 5,000 mm 3, 2,600 to 5,000 mm 3, or 2,600 to 4,000 mm 3, and having a gel content of 60 to 99% by weight, or 70 to 95% by weight. It may be, the swelling index may be 10 to 35, or 12 to 30, the impact strength is excellent within this range, the graft ratio is excellent.

The conjugated diene rubber may be included, for example, 10 to 70% by weight, 20 to 70% by weight, or 30 to 60% by weight with respect to the graft copolymer, the graft proceeds intact during graft polymerization within this range. The mechanical and physical property balance is excellent effect.

Examples of the (meth) acrylic acid alkyl ester compound include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, and ( It may be at least one selected from the group consisting of meth) acrylic acid lauryl ester.

The (meth) acrylic acid alkyl ester compound may be included in an example of 20 to 70% by weight, 20 to 60% by weight, or 30 to 50% by weight with respect to the graft copolymer, within the range of the graft copolymer The refractive index is maintained at an appropriate level with respect to the refractive index of the conjugated diene rubber has an excellent transparency effect.

The aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-ethylstyrene, and vinyltoluene.

For example, the aromatic vinyl compound may be included in an amount of 5 to 30% by weight, 7 to 30% by weight, or 7 to 20% by weight based on the graft copolymer, having excellent fluidity and excellent workability within this range. The refractive index of the copolymer is maintained at an appropriate level with respect to the refractive index of the conjugated diene rubber has an excellent transparency effect.

The vinyl cyan compound may be added as needed, for example, may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile.

The vinyl cyan compound may be included, for example, in an amount of 0 to 20 wt%, 0 to 10 wt%, or 1 to 10 wt% with respect to the graft copolymer, and does not occur yellowing phenomenon of the resin composition within this range. It is possible to implement color, minimizing the generation of coagulum during graft polymerization, and there is no harm to human body because residual monomer is not detected.

The graft copolymer may have, for example, a weight average molecular weight of 80,000 to 300,000 g / mol, 85,000 to 200,000 g / mol, or 90,000 to 110,000 g / mol, and excellent flowability within this range to provide excellent workability and impact. The effect is excellent in strength and chemical resistance.

For example, the difference between the refractive index of the copolymer including at least one selected from the group consisting of the (meth) acrylic acid alkyl ester, the aromatic vinyl compound, and the vinyl cyan compound and the conjugated diene rubber may be less than ± 0.01. The refractive index is to impart transparency to the graft copolymer, and the transparency of the graft copolymer is determined by the refractive index of the conjugated diene rubber and the refractive index of the copolymer grafted thereto, and the refractive index of the copolymer Silver can be adjusted by the mixing ratio of the monomers. Also, based on the refractive index of the conjugated diene rubber, the refractive index of the copolymer including the (meth) acrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound absolutely affects the transparency of the graft copolymer. That is, in order for a graft copolymer to have transparency, it is preferable that the difference of the refractive index of the conjugated diene rubber used as a seed of a graft copolymer, and the refractive index of the whole monomer grafted here is less than +/- 0.01.

As another example, the difference between the refractive index of the copolymer comprising a (meth) acrylic acid alkyl ester, an aromatic vinyl compound, and a vinyl cyan compound, and the refractive index of the conjugated diene rubber may be ± 0.008 or less, or ± 0.005 or less, within this range The transparency is excellent effect.

As a specific example, the refractive index of the polybutadiene rubber used in the embodiment of the present invention is 1.518, and the refractive index of each monomer component of the copolymer grafted to the conjugated diene rubber is 1.49 methyl methacrylate, 1.59 styrene, 1.518 acrylonitrile 1.518. The refractive index of the copolymer including these monomers may be adjusted according to the mixing ratio of each monomer, and the refractive index (RI) of the copolymer may be calculated by Equation 1 below.

Wti is the weight percent of each monomer in the copolymer, and RIi is the refractive index of each monomer in the copolymer.

The silica may be, for example, methylated silica, and the methylated silica refers to silica whose surface is modified with dimethyl siloxane, in this case, to prevent shrinkage at low temperatures to minimize the occurrence of voids in the resin. It is effective in whitening resistance.

The thermoplastic resin composition according to the present invention is characterized by comprising the thermoplastic resin and the acrylic copolymer.

The acrylic copolymer may be polymerized, including at least one selected from the group consisting of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds, and vinyl cyan compounds.

The acrylic copolymer may be polymerized, including, for example, 30 to 80 wt% of (meth) acrylic acid alkyl ester compound, 10 to 40 wt% of aromatic vinyl compound, and 0 to 20 wt% of vinyl cyan compound.

Examples of the (meth) acrylic acid alkyl ester compound include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, and ( It may be at least one selected from the group consisting of meth) acrylic acid lauryl ester, it may be included in 30 to 80% by weight, 30 to 75% by weight, or 60 to 75% by weight relative to the acrylic copolymer, within this range Impact strength and transparency is excellent effect.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-ethylstyrene, and vinyltoluene, for example, from 10 to 10 with respect to the acrylic copolymer. It may be included in 40% by weight, 15 to 40% by weight, or 15 to 30% by weight, there is an excellent effect of mechanical and physical properties balance within this range.

The vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, for example, 0 to 20 wt%, 1 to 15 wt%, or It may be included in 3 to 10% by weight, there is no yellowing phenomenon of the resin composition within this range, there is an effect excellent in mechanical properties and transparency.

The acrylic copolymer may have, for example, a weight average molecular weight of 80,000 to 300,000 g / mol, 80,000 to 200,000 g / mol, or 90,000 to 150,000 g / mol, and within this range, excellent impact strength and excellent fluidity and workability. This has an excellent effect.

For example, the difference between the refractive index of the acrylic copolymer and the refractive index of the thermoplastic resin may be less than ± 0.01. The refractive index is to impart transparency to the thermoplastic resin composition, and the transparency of the thermoplastic resin composition is determined by the refractive index of the thermoplastic resin and the refractive index of the acrylic copolymer, and the refractive index of the acrylic copolymer is determined by the mixing ratio of the monomers. Can be adjusted. In addition, based on the refractive index of the thermoplastic resin, the refractive index of the acrylic copolymer absolutely affects the transparency of the thermoplastic resin composition. That is, in order for a thermoplastic resin composition to have transparency, it is preferable that the difference of the refractive index of a thermoplastic resin and the refractive index of an acryl-type copolymer is less than +/- 0.01.

As another example, the difference between the refractive index of the acrylic copolymer and the refractive index of the thermoplastic resin may be ± 0.008 or less, or ± 0.005 or less, and has excellent transparency within this range, and the refractive index of the acrylic copolymer is It can be calculated by Equation 1.

The polymerization method of the acrylic copolymer is not particularly limited as long as it is a method capable of polymerizing the acrylic copolymer, but may be polymerized by suspension polymerization or bulk polymerization, for example, and may be polymerized by continuous bulk polymerization. The manufacturing cost can be lowered and the economic efficiency is excellent.

Polymerization of the acrylic copolymer may be carried out including, for example, a molecular weight regulator, and is not particularly limited as long as it can be used, but may be dodecyl mercaptans such as t-dodecyl mercaptan, normal dodecyl mercaptan, etc. have.

The thermoplastic resin composition may include, for example, 10 to 50 wt%, 15 to 50 wt%, or 20 to 40 wt% of the thermoplastic resin, and 50 to 90 wt% and 50 to 85 wt% of the acrylic copolymer. %, Or 60 to 80% by weight, and within this range there is an excellent impact strength and transparency.

For example, the thermoplastic resin composition may have a final rubber content of 10 to 40% by weight, or 10 to 25% by weight, and have excellent workability within this range, and do not form a flow mark on the surface, thereby having excellent transparency. .

The thermoplastic resin composition may include, for example, 20 to 65% by weight of the (meth) acrylic acid alkyl ester compound, or 40 to 65% by weight, and 10 to 30% by weight of the aromatic vinyl compound, or 15 to the final monomer content. It may be included in 25% by weight, the difference between the rubber and the refractive index is very small within this range, there is an excellent transparency effect.

The thermoplastic resin composition may include, for example, a vinyl cyan compound in an amount of 0 to 5% by weight, or 1 to 5% by weight as a final monomer content, and the vinyl cyan compound monomer does not remain within this range so that mechanical and physical properties balance Has an excellent effect.

For example, the thermoplastic resin composition may have a low temperature whitening resistance (ΔHaze, −50 ° C.) of less than 0.5, 0.1 to 0.4, or 0.2 to 0.4.

For example, the thermoplastic resin composition may have a melt index (220 ° C., 10 kg) of 24.2 g / 10 min or more, 24.2 to 30 g / 10 min, or 24.3 to 25 g / 10 min.

The thermoplastic resin composition is one selected from the group consisting of stabilizers, pigments, dyes, reinforcing agents, ultraviolet absorbers, antioxidants, colorants, mold release agents, lubricants, antistatic agents and plasticizers according to the purpose within the range of not impairing the physical properties of each component. The above additive may be included.

Hereinafter, preferred examples are provided to aid in understanding the present invention, but the following examples are merely for exemplifying the present invention, and various changes and modifications within the scope and spirit of the present invention are apparent to those skilled in the art. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example 1

Manufacture of large diameter polybutadiene rubber latex

In a nitrogen-substituted polymerization reactor (autoclave) 65 parts by weight of ion-exchanged water, 70 parts by weight of 1,3-butadiene as monomer, 1.5 parts by weight of potassium rosin salt as emulsifier, 0.8 parts by weight of potassium oleate, potassium carbonate as electrolyte ₂ CO ₃ ) 2 parts by weight, 0.2 parts by weight of tertiary dodecyl mercaptan (TDDM) as the molecular weight regulator, 0.3 parts by weight of potassium persulfate (K ₂ S ₂ O ₈ ) as the initiator and a polymerization conversion of 30 to 40% After the reaction to the time point, 0.1 part by weight of potassium persulfate (K ₂ S ₂ O ₈ ) and 20 parts by weight of 1,3-butadiene were collectively added, and the reaction was carried out at 70 ° C. until the time of polymerization conversion was 60%. Subsequently, 10 weight part of 1, 3- butadienes were thrown in batch, and it heated up to 80 degreeC, and reaction was complete | finished 22 hours after the start of reaction. At this time, the polymerization conversion rate of the obtained polybutadiene rubber latex was 97%, the average particle diameter was 3,000 kPa, the gel content was 89% by weight, the swelling index was 20.

Thermoplastic resin manufacturing

100 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium oleate, 0.2 parts by weight of acetic acid, 34 parts by weight of methyl methacrylate, 13 parts by weight of styrene, and 50 parts by weight of the obtained polybutadiene rubber latex (based on solids). Nitrile 3 parts by weight, tertiary dodecyl mercaptan 0.45 parts by weight, sodium pyrophosphate 0.048 parts by weight, dextrose 0.012 parts by weight, ferrous sulfide 0.001 parts by weight, cumene hydroperoxide 0.04 parts by weight and an antifoaming agent with a hydrophobic silicone solution ( Solvay, trade name Rhodoiline® 962, viscosity (25 ℃) 100 to 400 cps) 0.01 parts by weight was continuously added at 75 ℃ for 4 hours and reacted. Thereafter, the mixture was warmed to 78 ° C. and aged for 1 hour to complete the reaction. At this time, the polymerization conversion was 98.8%, the solid coagulation content was 0.1% by weight, the refractive index of the obtained graft copolymer was 1.516, and the weight average molecular weight was 100,000 g / mol. Thereafter, the mixture was agglomerated using 40 parts by weight of a 5% by weight aqueous potassium chloride solution, washed, dehydrated and dried to obtain an acryl-based graft copolymer.

Acrylic Copolymer Preparation

70.4 parts by weight of methyl methacrylate, 24.6 parts by weight of styrene, 5 parts by weight of acrylonitrile, 30 parts by weight of toluene as a solvent, and 0.15 parts by weight of t-dodecyl mercaptan as the molecular weight regulator were mixed. Continuously added to the reaction tank so that the reaction temperature was maintained at 148 ℃. The polymerization liquid discharged from the reactor was heated in a preheating bath and volatilized unreacted monomer in a volatilization bath. Subsequently, an acrylic copolymer in pellet form was prepared using a polymer transfer pump extrusion machine at a temperature of 210 ° C. At this time, the refractive index of the obtained acrylic copolymer was 1.516, and the weight average molecular weight was 120,000 g / mol.

Manufacture of thermoplastic resin composition

30 parts by weight of the thermoplastic resin and 70 parts by weight of the acrylic copolymer were mixed, 1 part by weight of lubricant and 0.4 part by weight of antioxidant were prepared to prepare a thermoplastic resin composition in pellet form using a twin screw extruder at a cylinder temperature of 220 ° C. Injecting the same, a specimen for measuring physical properties was produced.

Example 2

In preparing the thermoplastic resin of Example 1, instead of adding the hydrophobic silicone solution as an antifoaming agent during polymerization, the same method as in Example 1 was performed except that the hydrophobic silicone solution was added after aggregation.

Example 3

The thermoplastic resin of Example 1 was prepared in the same manner as in Example 1, except that 0.001 parts by weight of the hydrophobic silicone solution as an antifoaming agent was added instead of 0.01 parts by weight.

Comparative Example 1

The thermoplastic resin of Example 1 was prepared in the same manner as in Example 1, except that the hydrophobic silicone solution as an antifoaming agent was not added.

Comparative Example 2

When preparing the thermoplastic resin of Example 1, except that the same amount of particulate antifoaming agent (SILOX manufactured by Dow Corning Korea, trade name SILOX, viscosity (25 ° C) 2,300 cps) was added instead of the hydrophobic silicone solution as the antifoaming agent. It carried out in the same way.

Comparative Example 3

When preparing the thermoplastic resin of Example 1, except that the hydrophobic silicone solution as the antifoaming agent was not added during polymerization, and 0.01 parts by weight of the particulate antifoaming agent (trade name Silox, manufactured by Dow Corning Korea Co., Ltd.) was added at the time of aggregation after the reaction was completed. It carried out by the same method as Example 1.

Comparative Example 4

The thermoplastic resin of Example 1 was prepared in the same manner as in Example 1, except that 0.02 parts by weight of the hydrophobic silicone solution, which is an antifoaming agent, was added instead of 0.01 parts by weight.

[Test Example]

The physical properties of the acrylic resin composition specimens obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Table 1 below.

How to measure

* Average particle diameter (Å): Measured by the dynamic laser light scattering method using a Nicomp 380 instrument of Nicomp.

* Gel content and swelling index: The polybutadiene rubber latex is coagulated with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C. for 24 hours, and the resulting rubber mass is chopped with scissors and then 1 g of rubber sections To 100 g of toluene was stored in a dark room at room temperature for 48 hours, separated into sol and gel and dried, respectively, the gel content by the following formula 2, the swelling index was measured by the following formula (3).

* Solid coagulant (%): The weight of the coagulum produced in the reaction tank, the weight of the total rubber and the monomer weight were measured, and the coagulum content was calculated by the following Equation 4.

* Refractive index: After thinning to a thickness of about 0.2 mm using a specimen, it was measured by using an Abbe refractometer at 25 ℃.

* Weight average molecular weight (Mw, g / mol): After gel chromatography (GPC) using a polymethylmethacrylate (PMMA) standard calibration, the weight average molecular weight was measured.

* Silicon (Si) residual amount (ppm): 3 g of the sample is combusted at 600 ° C. to ash and then silicon in the resin using an energy-dispersive X-ray spectroscopy (EDS). The residual amount was measured.

Transparency and Transmittance (Haze, Tt): The haze value and the transmittance (Tt) of the 3 mm sheet were respectively measured according to the standard measurement ASTM D1003 using the specimen.

* Low temperature bleaching (△ Haze): Using a specimen stored at -50 ℃ for 2 hours, the haze value of the 3 mm sheet was measured according to the standard measurement ASTM D1003, and compared with the transparency of the specimen before cold storage. Thus, the difference value is shown. Lower ΔHaze indicates better low-temperature whitening resistance.

* Notched Izod Impact Strength (kgcm / cm): Measured according to standard measurement ASTM D256 using a 1/4 "specimen.

* Melt Index (Melt Index, g / 10 min): Measured according to the standard measurement ASTM D1238 (220 ℃, 10 kg conditions) using the specimen.

division Example Comparative example One 2 3 One 2 3 4 Silicon residue 21.9 21.8 3.2 - 22.1 22.0 40.7 transparency
(Haze) 1.7 1.6 1.7 1.6 1.9 1.9 1.6 Transmittance
(Tt) 90.8 90.8 90.9 91 90.8 90.9 90.9 Low temperature whitening
(△ Haze) 0.3 0.4 0.4 0.5 1.2 1.0 0.8 Impact strength 6.93 6.89 6.69 6.68 7.23 7.27 7.02 Melt index 24.52 24.47 24.1 24.15 23.46 24.11 24.63

As shown in Table 1, in Examples 1 to 3 prepared according to the present invention, compared to Comparative Example 1 without the addition of the antifoaming agent, while maintaining the physical properties at the same level, it can be confirmed that low-temperature whitening resistance is improved there was.

On the other hand, in the case of Comparative Examples 2 and 3 to which a high viscosity SILOX antifoaming agent was added, it was confirmed that the melt index was slightly lowered and the low-temperature whitening resistance was poor. In addition, in the case of Comparative Example 1 in which the antifoaming agent was not added, it was confirmed that a lot of bubbles that hinder the manufacturing process itself due to stirring by an impeller in the polymerization and agglomeration processes. In addition, in the case of Comparative Example 4 in which an excessive amount of hydrophobic silicone solution as an antifoaming agent was added, it was confirmed that low-temperature whitening resistance was poor.

From this, the present inventors include a specific antifoaming agent, thereby reducing bubbles generated in the polymerization and agglomeration process to improve productivity and economical efficiency, and at the same time, significantly reducing low temperature whitening resistance without deteriorating physical properties, and a thermoplastic resin composition comprising the same. We can see that we can implement

Claims

Graft polymerizing a conjugated diene rubber including one or more selected from the group consisting of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds, and vinyl cyan compounds; And agglomerating the polymerized graft copolymer latex; wherein the hydrophobic silicone solution is added in an amount of 0.010 to 100 parts by weight based on 100 parts by weight of the graft copolymer. In an amount of 0.015 parts by weight,
The hydrophobic silicone solution is a thermoplastic resin manufacturing method comprising a methylated silica (methylated silica) surface is modified with dimethyl siloxane.

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The method of claim 1,
The silica is a thermoplastic resin manufacturing method, characterized in that contained in 0.1 to 10% by weight relative to the hydrophobic silicone solution.

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The method of claim 1,
The hydrophobic silicone solution is a thermoplastic resin manufacturing method, characterized in that the viscosity at 25 ℃ 2,000 cps or less.

Conjugated diene rubbers include graft polymerized graft copolymers and methylated silica, including one or more selected from the group consisting of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds and vinyl cyan compounds,
The methylated silica is a thermoplastic resin, characterized in that the silica surface modified with dimethyl siloxane.

The method of claim 6,
The graft copolymer is a thermoplastic resin, characterized in that the weight average molecular weight of 80,000 to 300,000 g / mol.

The method of claim 6,
The difference between the refractive index of the copolymer comprising at least one selected from the group consisting of the (meth) acrylic acid alkyl ester, the aromatic vinyl compound and the vinyl cyan compound, and the refractive index of the conjugated diene rubber is less than ± 0.01. .

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A thermoplastic resin and an acrylic copolymer according to any one of claims 6 to 8, wherein the low-temperature whitening resistance (ΔHaze, -50 ° C) is less than 0.5, and the melt index (220 ° C, 10 kg) is 24.2. g / 10 min or more.

The method of claim 10,
The acrylic copolymer is a thermoplastic resin composition, characterized in that the polymerization including at least one selected from the group consisting of (meth) acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyan compound.

The method of claim 10,
The acrylic copolymer has a weight average molecular weight of 80,000 to 300,000 g / mol thermoplastic resin composition.

The method of claim 10,
The difference between the refractive index of the acrylic copolymer and the refractive index of the thermoplastic resin is less than ± 0.01, the thermoplastic resin composition.

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