KR102136339B1 - Thermoplastic resine, thermoplastic resine composition comprising the same, method for preparing thermoplastic resine and method for preparing thermoplastic resine composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin, a thermoplastic resin composition and a method for manufacturing the same, and more specifically, in polymerizing a diene rubber polymer, an aromatic vinyl compound and a vinyl cyan compound, an alkylene oxide copolymer is applied to form a latex resin. Provides a thermoplastic resin capable of reducing the coagulum content and improving latex stability, and a method for manufacturing the same, and the thermoplastic resin according to the present invention is mixed with an aromatic vinyl compound-vinyl cyan compound copolymer to provide excellent impact resistance and chemical resistance. And it has the effect of providing a thermoplastic resin composition with improved organic solvent resistance.

Description

Thermoplastic resins, thermoplastic resin compositions comprising the same, and methods of manufacturing the same

The present invention relates to a thermoplastic resin, a thermoplastic resin composition, and a method for manufacturing the same, including an alkylene oxide copolymer when producing a thermoplastic resin, while having excellent impact resistance and processability while improving chemical and chemical resistance, including a thermoplastic resin and the same. A thermoplastic resin composition can be provided.

Acrylonitrile-butadiene-styrene (ABS) copolymer resins have relatively good physical properties such as impact resistance, moldability and gloss, as well as mechanical strength, such as impact resistance, so electrical components, electronic components, office equipment, or automobiles It is widely used for interior and exterior materials.

In general, when an ABS resin is prepared by grafting an aromatic vinyl compound and a vinyl cyan compound monomer on a conjugated diene rubber latex by an emulsion polymerization method, it exhibits a good physical property balance compared to that produced by a bulk polymerization method and has excellent gloss, etc. Due to its advantages, ABS resins are mainly produced by emulsion polymerization.

In addition, ABS-based resins produced by emulsion polymerization are widely used in fields where heat resistance and impact resistance are required by kneading with heat resistant resins such as SAN to improve heat resistance.

On the other hand, ABS resins used in special materials such as interior and exterior materials for automobiles often go through post-processing processes such as plating or painting, and when affinity between the resin and the coating solvent is poor, pin holes are formed after painting. When the chemical resistance of the resin was weak, there was a problem in that coating cracks and the like resulted in defective coating appearance.

Accordingly, in order to supplement the chemical resistance and chemical resistance of the ABS-based resin, a method of increasing the content of the vinyl cyan compound in the manufacture of the ABS-based graft resin has been proposed, but in this case, the compatibility between the ABS-based resin and the heat-resistant resin such as SAN is poor. There was a problem, and there was a problem in that the quality of the resin deteriorated due to yellowing of the resin and a decrease in fluidity. In addition, although a technique for kneading ABS resin with a high molecular weight SAN resin has been proposed, in this case, there is a disadvantage in that fluidity decreases and physical properties such as impact strength decrease.

Therefore, there is still a need for a technique for simultaneously improving the mechanical strength and flow resistance of ABS-based resins and chemical resistance.

Korean Patent Publication No. 2016-0055799

In order to solve the problems of the prior art as described above, the present invention is to provide a thermoplastic resin, a thermoplastic resin composition and a method of manufacturing the same, having a proper flow index, excellent physical properties such as impact strength, and improved chemical and chemical resistance. The purpose.

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 is a diene-based rubber polymer, an aromatic vinyl compound and a vinyl cyanide compound total of 100 parts by weight of alkylene oxide copolymer 0.05 to 3 parts by weight, emulsifier 0.1 to 5 parts by weight, polymerization initiator 0.001 It provides a method for producing a thermoplastic resin, characterized in that it comprises a step of graft polymerization, including from 3 parts by weight.

In addition, the present invention is based on 100 parts by weight of the monomer mixture containing 30 to 70% by weight of the diene-based rubber polymer, 15 to 60% by weight of the aromatic vinyl compound and 5 to 35% by weight of the vinyl cyan compound, (a) diene-based rubber polymer 30 Graphs including 70 to 70 parts by weight, 5 to 20 parts by weight of an aromatic vinyl compound, 1 to 10 parts by weight of a vinyl cyan compound, 0.05 to 3 parts by weight of an alkylene oxide copolymer, 0.05 to 1 parts by weight of an emulsifier, and 0.01 to 0.5 parts by weight of an initiator Polymerization first step of polymerization; (b) A second polymerization step of graft polymerization including 10 to 30 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyan compound, 0.1 to 1.5 parts by weight of an emulsifier, and 0.05 to 1 parts by weight of an initiator; It provides a method for producing a thermoplastic resin.

In addition, the present invention is a thermoplastic resin characterized in that it comprises the step of extruding and then extruding and kneading the thermoplastic resin 10 to 50% by weight and the aromatic vinyl compound-vinyl cyan compound copolymer 50 to 90% by weight according to the above production method. It provides a method for producing a resin composition.

In addition, the present invention is a diene-based rubber polymer 30 to 70% by weight, 15 to 60% by weight of an aromatic vinyl compound and 5 to 35% by weight of a vinyl cyan compound graft polymerized graft resin 100 parts by weight and ethylene oxide-propylene oxide It provides a thermoplastic resin, characterized in that it comprises 0.05 to 3 parts by weight of the copolymer.

In addition, the present invention provides a thermoplastic resin composition comprising 10 to 50% by weight of the thermoplastic resin and 50 to 90% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer.

According to the present invention, while maintaining the inherent mechanical properties of the ABS-based resin, there is an effect of providing a thermoplastic resin and a thermoplastic resin composition having excellent latex stability, chemical resistance, and organic solvent resistance.

Specifically, the thermoplastic resin prepared according to the present invention has an effect of improving the productivity of the resin powder by excellent stability of the resin latex with a coagulant content of 0.04% by weight or less, and mixing the thermoplastic resin with a heat-resistant resin such as SAN. The resin composition produced by the Izod has an impact strength of 18 kgcm/cm or more and a falling impact strength of 4,000 N or more, but has an appropriate flow index, so it has excellent moldability and workability, and has an environmental stress cracking characteristic (ESCR) and It has the advantage of excellent organic solvent resistance.

Hereinafter, a method of manufacturing the thermoplastic resin of the present substrate will be described in detail.

The present inventors introduced an alkylene oxide copolymer upon graft polymerization of an aromatic vinyl compound and a vinyl cyan compound in a diene rubber polymer to prepare an ABS-based graft resin, such as chemical resistance, latex stability, etc., compared to conventional ABS-based resins. It was confirmed that the improvement was made, and based on this, it was further sold out to complete the present invention.

The thermoplastic resin manufacturing method of the present invention is 0.05 to 3 parts by weight of an alkylene oxide copolymer, 0.1 to 5 parts by weight of an emulsifier, and 0.001 to 1 of a polymerization initiator based on 100 parts by weight of a mixture of a diene rubber polymer, an aromatic vinyl compound, and a vinyl cyan compound. It may be characterized in that it comprises a step of graft polymerization including 3 parts by weight.

The mixture of the diene-based rubber polymer, the aromatic vinyl compound, and the vinyl cyan compound may include, for example, 30 to 70% by weight of the diene-based rubber polymer, 15 to 60% by weight of the aromatic vinyl compound, and 5 to 35% by weight of the vinyl cyan compound. Within this range, there is an advantage in that the balance of processability and physical properties of the final resin is excellent.

As another example, the mixture of the diene-based rubber polymer, the aromatic vinyl compound, and the vinyl cyan compound may include 40 to 70% by weight of the diene-based rubber polymer, 15 to 35% by weight of the aromatic vinyl compound, and 5 to 25% by weight of the vinyl cyan compound. In this range, the fluidity of the final resin is appropriate within this range, and thus the processability is excellent and the physical property balance is excellent.

The diene-based rubber polymer may be at least one selected from the group consisting of butadiene-based polymers, butadiene-aromatic vinyl compound copolymers, butadiene-vinyl cyan compound copolymers, ethylene-propylene copolymers, or polymers derived therefrom, preferably Can be a butadiene-based polymer or a butadiene-aromatic vinyl compound copolymer.

The polymer derived from the present description means a polymer prepared by polymerization of a polymer or a derivative of a conjugated compound or other monomer compound or polymer not included in the polymer.

In the present description, a derivative means a compound in which the hydrogen atom or atomic group of the original compound is substituted with another atom, such as halogen or atomic group, such as an alkyl group.

The diene-based rubber polymer may have an average particle diameter of 200 to 450 nm, 250 to 400 nm, or 280 to 370 nm as an example, and has an advantage of excellent impact strength of the final resin within this range. The average particle diameter of the rubber polymer in this substrate can be measured using Nicomp 370HPL by the dynamic light scattering method.

Unless otherwise specified in the present description, the aromatic vinyl compound may be at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, or vinyltoluene, of which styrene or α-methylstyrene may be preferred. have.

Unless otherwise specified in the present description, the vinyl cyan compound may be at least one selected from the group consisting of acrylonitrile and methacrylonitrile, and acrylonitrile may be preferred.

The alkylene oxide copolymer may be an ethylene oxide-propylene oxide copolymer, which may improve the chemical resistance and latex stability of the resin, thereby making it possible to manufacture an excellent quality resin.

The alkylene oxide copolymer may preferably include 0.05 to 3 parts by weight, 0.1 to 2.5 parts by weight, and 0.3 to 2 parts by weight based on 100 parts by weight of the diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound, More preferably, it is 0.1 to 1.5 parts by weight or 0.5 to 1.2 parts by weight. Within the above range, there is an excellent effect of stability of the resin latex and chemical resistance of the resin.

The alkylene oxide copolymer may preferably contain 15 to 95 mol% of ethylene oxide, more preferably 30 to 90 mol%, and even more preferably 50 to 90 mol% or 60 to It is 85 mol%. Within the above range, there is an advantage that the chemical resistance of the resin is excellent, the affinity with the organic solvent is appropriate, and the mechanical strength such as impact strength is excellent.

As a more specific example, the ethylene oxide-propylene oxide copolymer may include 15 to 95 mol% of ethylene oxide and 5 to 85 mol% of propylene oxide, and within this range, the chemical resistance of the resin is excellent, such as impact strength It has excellent mechanical properties.

As another specific example, the ethylene oxide-propylene oxide copolymer may include 50 to 95 mol% of ethylene oxide and 5 to 50 mol% of propylene oxide, and in this range, the chemical resistance of the resin is particularly excellent, but the stability of the resin latex There is an advantage of excellent productivity by improvement.

In the present invention, the alkylene oxide copolymer may preferably have a number average molecular weight of 1,000 to 25,000 g/mol, 2,000 to 20,000 g/mol, 2,500 to 15,000 g/mol, or 2,800 to 10,000 g/mol, and within this range In the stability of the resin latex is excellent and the chemical resistance and impact resistance of the resin is excellent.

In the present description, the number average molecular weight of the alkylene oxide copolymer is quantitatively analyzed by the nuclear magnetic resonance method for the amount of the functional group (-OH) at the end of the alkylene oxide copolymer, and the weight of the alkylene oxide copolymer is terminated. It can be calculated by dividing by the number of functional groups.

The emulsifiers include, for example, alkylaryl sulfonate salts, alkali methyl alkyl sulfate salts, sulfonated alkyl ester salts, alkyl (alkenyl) carboxylate salts, alkyl (alkenyl) succinate salts, fatty acid metal salts, rosin acid gold salts, It may be one or more selected from the group consisting of oleic acid metal salts, but is not limited thereto.

The emulsifier may be preferably 0.1 to 5 parts by weight, 0.3 to 3 parts by weight, 0.5 to 2 parts by weight, or 0.5 to 1 part by weight based on 100 parts by weight of the diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound, Within this range, the stability of the polymerization reaction and the graft rate are excellent, and a resin having a desired weight average molecular weight can be easily produced.

The polymerization initiator is, for example, sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, di-t-butyl peroxide , t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, 3,5,5-trimethylhexanol peroxide, t-butyl Peroxidation initiators such as peroxy isobutylate and azo systems such as azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobis isobutyrate (butyl acid) methyl It may be one or more selected from the initiator, but is not limited thereto.

The polymerization initiator may be used, for example, 0.001 to 3 parts by weight, 0.01 to 2 parts by weight, or 0.1 to 1 part by weight based on 100 parts by weight of the diene-based rubber polymer, aromatic vinyl compound, and vinyl cyan compound, and within this range It does not cause overreaction and it may be possible to prepare a polymer of a desired size.

The graft polymerization may further include a molecular weight modifier or an oxidation-reduction catalyst as needed.

The molecular weight modifier is, for example, tertiary dodecyl mercaptan, n-octyl mercaptan, sec-octyl mercaptan, n-nonyl mercaptan, n-decylmercaptan, n-dodecylmercaptan, and n-octadecylmercaptan. It may be one or more selected from the group, preferably tertiary dodecyl mercaptan.

The molecular weight modifier may be used as an example, 0.05 to 1 part by weight, 0.1 to 1 part by weight, or 0.3 to 0.8 part by weight based on 100 parts by weight of the diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound, and within this range A resin having excellent stability of latex but having a desired weight average molecular weight can be easily prepared.

The oxidation-reduction catalyst may be one or more selected from the group consisting of sodium pyrrolate, dextrose, ferrous sulfate, sodium sulfite, sodium formaldehyde sulfoxylate, and sodium ethylenediamine tetraacetate. Can be used in combination with sodium pyrrolate, dextrose and ferrous sulfate.

The oxidation-reduction catalyst may be used in an amount of 0.0001 to 1 part by weight, 0.01 to 0.8 part by weight, or 0.1 to 0.5 part by weight based on 100 parts by weight of the diene rubber polymer, aromatic vinyl compound, and vinyl cyan compound.

In the present invention, the graft polymerization may be performed at a temperature of 60 to 95°C or 65 to 85°C for 0.5 to 7 hours or 1 to 5 hours, and within this range, the graft rate is high and has a desired weight average molecular weight There is an advantage that the resin can be easily produced.

In a specific example, the thermoplastic resin manufacturing method of the present invention is based on 100 parts by weight of a monomer mixture comprising 30 to 70% by weight of a diene rubber polymer, 15 to 60% by weight of an aromatic vinyl compound and 5 to 35% by weight of a vinyl cyan compound, (a) 30 to 70 parts by weight of a diene rubber polymer, 5 to 20 parts by weight of an aromatic vinyl compound, 1 to 10 parts by weight of a vinyl cyan compound, 0.05 to 3 parts by weight of an alkylene oxide copolymer, 0.05 to 1 parts by weight of an emulsifier, initiator A first polymerization step of graft polymerization including 0.01 to 0.5 parts by weight; And (b) a second polymerization step of graft polymerization including 10 to 30 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyan compound, 0.1 to 1.5 parts by weight of an emulsifier, and 0.05 to 1 part by weight of an initiator. have.

The first polymerization step may be performed at 60 to 80°C or 65 to 75°C for 0.5 to 3 hours, for example, and the second polymerization step may be, for example, 70 to 95°C or 80 to 90°C (first polymerization step It can be carried out for 1 to 4 hours at a higher than the reaction temperature of, there is an excellent effect in the polymerization conversion rate and graft rate within this range.

The first polymerization step may optionally be carried out further comprising 0.05 to 1 part by weight of a molecular weight modifier or 0.05 to 1 part by weight of an oxidation-reduction catalyst.

In the second polymerization step, it may be desirable to continuously inject the monomers (aromatic vinyl compound and vinyl cyan compound) in an emulsified state, and in this case, a resin having excellent polymerization conversion rate and graft rate but having uniform physical properties may be prepared.

The second polymerization step may optionally be carried out further comprising 0.1 to 1 part by weight of a molecular weight modifier.

In addition, when the polymerization is carried out in two steps as described above, the stability of the latex is excellent, but the polymerization conversion rate and the graft rate are excellent.

The thermoplastic resin latex prepared according to the method for producing a thermoplastic resin of the present invention may preferably have a polymerization conversion ratio of 95% or more or 97% or more, and a graft rate of 45% or more, 55% or more, or 45 to 65% as an example. There is an advantage in that the mechanical properties and physical properties balance is excellent within this range.

The thermoplastic resin latex according to the above manufacturing method may be characterized in that the content of coagulation is 0.04% by weight or less, 0.01% by weight or less, 0.008% by weight or less or 0.005% by weight or less, and the productivity of the resin within this range is excellent. There is an advantage.

The thermoplastic resin produced according to the production method of the present invention is, for example, graft polymerized graft containing 30 to 70% by weight of a diene rubber polymer, 15 to 60% by weight of an aromatic vinyl compound and 5 to 35% by weight of a vinyl cyan compound The resin may contain 100 parts by weight of the resin and 0.05 to 3 parts by weight of the ethylene oxide-propylene oxide copolymer, and have excellent effects in chemical resistance and organic solvent resistance, while having excellent processability and mechanical strength within this range.

The thermoplastic resin latex according to the above manufacturing method may preferably have a weight average molecular weight of 50,000 to 100,000 g/mol, 60,000 to 80,000 g/mol, 62,000 to 70,000 g/mol, or 63,000 to 68,000 g/mol, within this range. In the resin has the advantage of excellent processability and formability and excellent physical property balance. In the present description, the weight average molecular weight can be measured by gel permeation chromatography by dissolving the powdery resin in a solvent.

Other conditions not explicitly described in addition to the above-described description, for example, reaction pressure, polymerization water, etc., are not particularly limited when they are within the range that is generally practiced in the technical field to which the present invention belongs, and are appropriately selected and executed as necessary State that you can.

Furthermore, the thermoplastic resin latex manufactured according to the method for manufacturing a thermoplastic resin of the present base material may be obtained in powder form through conventional processes such as agglomeration, washing, and drying. For example, the thermoplastic resin latex is an acid or metal salt such as sulfuric acid. After the addition and agglomeration, the thermoplastic resin powder may be obtained through washing, dehydrating and drying processes.

In addition, the thermoplastic resin powder may be prepared with a thermoplastic resin composition by mixing with an aromatic vinyl monomer-vinyl cyan monomer copolymer, and the method of manufacturing the thermoplastic resin composition of the present disclosure will be described below.

The manufacturing method of the thermoplastic resin composition is, for example, 10 to 50% by weight of the thermoplastic resin and 50 to 90% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer according to the manufacturing method, kneaded and extruded, and then extruding it It may be characterized by including.

In another example, the thermoplastic resin composition comprises kneading and extruding 20 to 40% by weight of the thermoplastic resin and 60 to 80% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer according to the manufacturing method, and then extruding it. Can be manufactured. Within the above range, there is an advantage that the mechanical strength, formability, and physical property balance of the resin composition are excellent.

The extrusion may be performed under conditions of, for example, 220 to 270°C and 200 to 280 rpm, or 220 to 250°C and 200 to 280 rpm, and the moldability of the resin composition within this range is excellent.

The injection may be performed under conditions of 200 to 270°C and 70 to 100 bar, or 220 to 250°C and 80 to 100 bar, for example, and the moldability of the resin composition within this range is excellent, and the desired physical properties are obtained. Can have

The thermoplastic resin composition prepared according to the above-described manufacturing method has an Izod impact strength of 18 kgcm/cm or more or 19 kgcm/cm, and a falling impact strength of 4,000 N or more or 4,200 N, which has excellent impact resistance. In the present description, the Izod impact strength is measured according to ASTM D256, and the drop impact strength is measured according to D3763.

In addition, the thermoplastic resin composition prepared according to the present disclosure may be characterized in that the flow index is 5 to 6 g/10min, and within this range, the processability of the resin composition is excellent. The flow index in this description can be measured according to ASTM D1238.

In addition, the thermoplastic resin composition prepared according to the present disclosure may be characterized in that the water contact angle is 60 to 90° or 65 to 80°, and in this case, it has excellent chemical resistance and organic solvent resistance, and affinity with an organic solvent. This is appropriate and the defect rate in post-processing such as painting can be reduced.

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

[Example] Preparation of thermoplastic ABS resin

Example One

In a nitrogen-filled polymerization reactor, 100 parts by weight of ion-exchanged water, 50 parts by weight of a rubbery polymer, 10 parts by weight of styrene as a monomer, 5 parts by weight of acrylonitrile, 0.3 parts by weight of a fatty acid potassium salt as an emulsifier, Pluronic PE 6800 (PEO-PPO air Copolymer, PEO 80%, Mv 8,000 g/mol, BASF) 1.0 part by weight, 0.1 part by weight of tertiary decyl mercaptan as a molecular weight regulator, 0.05 part by weight of hydroperoxide as an initiator and dextrose as an oxidation-reduction catalyst 0.15 Weight part, 0.1 part by weight of sodium pyrrolate, and 0.001 part by weight of ferrous sulfate were collectively administered and heated at 70° C. for one hour to perform polymerization. After polymerization for one hour, 25 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.5 parts by weight of fatty acid potassium salt, 0.3 parts by weight of tertiary dodecylmercaptan, and 0.1 parts by weight of hydroperoxide are continuously administered in an emulsified monomer. The reaction was terminated after heating to 80° C. for about three hours. After completion of the reaction, the latex was aggregated with 2 parts by weight of an aqueous magnesium sulfate solution, dehydrated and dried to obtain a thermoplastic ABS resin powder.

Example 2

In the same manner as in Example 1, except that Pluronic PE 6800 (PEO-PPO copolymer, PEO 80 mol%, Mv 8,000 g/mol, BASF Co.) in Example 1 was added in 0.1 parts by weight instead of 1.0 parts by weight. It was carried out.

Example 3

In the same manner as in Example 1, except that Pluronic PE 6800 (PEO-PPO copolymer, PEO 80 mol%, Mv 8,000 g/mol, BASF, Inc.) in Example 1 was added in 0.5 parts by weight instead of 1.0 parts by weight. It was carried out.

Example 4

In Example 1, Pluronic PE 8100 (PEO-PPO copolymer, PEO 10 mol%, Mv 2,600) instead of 1.0 part by weight of Pluronic PE 6800 (PEO-PPO copolymer, PEO 80 mol%, Mv 8,000 g/mol, BASF) g/mol, BASF) was carried out in the same manner as in Example 1, except that 1.0 part by weight.

Example 5

In Example 1, Pluronic PE 10100 (PEO-PPO copolymer, PEO 10 mol%, Mv 3,500) instead of 1.0 parts by weight of Pluronic PE 6800 (PEO-PPO copolymer, PEO 80% mol, Mv 8,000 g/mol, BASF) g/mol, BASF) was carried out in the same manner as in Example 1, except that 1.0 part by weight.

Comparative example One

In Example 1, except for omitting the Pluronic PE 6800 (PEO-PPO copolymer, PEO 80 mol%, Mv 8,000 g/mol, BASF), it was carried out in the same manner as in Example 1.

Comparative example 2

It was carried out in the same manner as in Comparative Example 1, except that the tertiary dodecyl mercaptan (molecular weight modifier) additionally added in Comparative Example 1 was used as 0.1 parts by weight instead of 0.3 parts by weight.

Comparative example 3

It was carried out in the same manner as in Comparative Example 1, except that 20 parts by weight of styrene and 15 parts by weight of acrylonitrile were used instead of 25 parts by weight of styrene and 10 parts by weight of acrylonitrile as the monomer to be added in Comparative Example 1.

Comparative example 4

In the same manner as in Example 1, except that Pluronic PE 6800 (PEO-PPO copolymer, PEO 80 mol%, Mv 8,000 g/mol, BASF Co.) in Example 1 was added in 5.0 parts by weight instead of 1.0 parts by weight. It was carried out. The ABS resin latex prepared according to Comparative Example 4 had a low polymerization conversion rate and poor latex stability, so it was not prepared as a specimen for measuring physical properties.

[Example of use] Preparation of thermoplastic ABS resin composition

Usage example One

30 parts by weight of ABS resin powder obtained in Example 1 and 70 parts by weight of alphamethylstyrene-acrylonitrile copolymer (100 UH, heat-resistant ABS grade, LG Chemical) were kneaded and extruded in a kneading extruder under conditions of 250 rpm and 240°C. After the pellets were prepared, the specimens were prepared by injection (injection temperature: 250°C) using an injection molding machine.

Usage example 2 to 8

Using the ABS resin powders obtained in Examples 2 to 5 and Comparative Examples 1 to 3, specimens were prepared in the same manner as in Example 1.

[Reference Example] Preparation of thermoplastic ABS resin composition

30 parts by weight of ABS resin powder, alphamethylstyrene-acrylonitrile copolymer (100 UH, heat-resistant ABS grade, LG Chemical) 70 parts by weight and Pluronic PE 6800 (PEO-PPO copolymer, PEO) 80 mol%, Mv 8,000 g/mol, BASF) 1.0 parts by weight was kneaded and extruded in a kneading extruder under conditions of 250 rpm and 240° C. to produce pellets, and then injected using an injection molding machine (injection temperature: 250° C.) Specimens were prepared.

[Test Example]

Test example 1: Measurement of physical properties of thermoplastic ABS resin

The properties of the ABS resins prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 1 below.

1. Polymerization conversion rate (%)

2 g of the ABS resin latex was dried in a 150° C. hot air dryer for 15 minutes, and then weighed to obtain a total solids content (TSC), and then the polymerization conversion rate was calculated by Equation 1 below.

[Equation 1]

Polymerization conversion rate (%) = [(total solids content)* (total weight of rubber polymer, monomers and auxiliary ingredients used in the reaction)/100]-weight of auxiliary ingredients

2. Coagulum content (%)

After filtering the ABS resin latex through a 100 mesh wire mesh filter, the coagulum filtered over the wire mesh was dried in a 100° C. hot air dryer for 1 hour, and then the coagulum content was calculated by Equation 2 below.

[Equation 2]

Coagulant content (%) = weight of coagulant in latex/total weight of rubber polymer and monomer used for reaction

3. Graft rate (%)

10 g of ABS resin powder was dried in an oven at 60° C. to remove moisture, and then the weight (A) was measured. After adding it to 100 ml of acetone and stirring for 24 hours, the sol and the gel were separated under a condition of 10,000 rpm using a centrifuge. After drying the residue not dissolved in acetone on an oven, the weight (B) was measured, and the graft ratio was calculated by the following equation (3).

[Equation 3]

Graft rate (%) = (B-A*% by weight of rubber used for graft polymerization)/(A*% by weight of rubber used for graft polymerization) X 100

4. Weight average molecular weight (Mw, g/mol)

After dissolving the ABS resin powder in THF, it was measured by gel permeation chromatography.

5. Latex stability test

After transferring 300 g of the polymerized latex to a 600 ml beaker, measure the time until stability is destroyed (time when the ampere (A) value of the mixer changes) by mixing the latex at 120,000 rpm using a homomixer from PRIMX. Did.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PEO-PPO*
Parts by weight 1.0 0.1 0.5 1.0 1.0 - - - 5.0 PEO content*
(mole%) 80 80 80 10 10 - - - 80 AN ^*
Parts by weight 30 30 30 30 30 30 40 30 30 TDDM ^*
Parts by weight 0.4 0.4 0.4 0.4 0.4 0.4 0.2 0.4 0.4 Conversion rate (%) 97.9 98.1 98.0 97.8 97.8 97.7 97.5 97.3 93.2 Clot
content(%) 0.003 0.01 0.008 0.004 0.004 0.05 0.05 0.07 1.5 Graft rate (%) 58 57 57 58 58 55 62 53 - Mw (g/mol) 65,000 67,000 66,000 65,000 64,000 67,000 85,000 70,000 - Stability (min.) 80 55 65 78 77 40 45 41 -

(PEO-PPO means ethylene oxide-propylene oxide copolymer, PEO content means content of ethylene oxide component in PEO-PPO copolymer, AN is acrylonitrile, TDDM is molecular weight regulator tertiary dodecylmercaptan Means.)

As shown in Table 1, it can be seen that Examples 1 to 5 according to the present disclosure had a small amount of coagulum and excellent latex stability compared to Comparative Examples 1 to 4 not according to the present description. In addition, Examples 1 to 5 according to the present disclosure was confirmed to have a higher graft rate than the comparative example using the same amount of monomers and auxiliary materials.

Test example 2: Measurement of physical properties of the thermoplastic ABS resin composition

The properties of the ABS resin compositions prepared in Examples 1 to 9 were measured by the following method, and the results are shown in Table 2 below.

1. Izod Impact Strength (IMP)

Izod impact strength was measured according to the ASTM D256 method with a specimen thickness of 1/4", and the unit is kgcm/cm.

2. Current Index (Melt Index, MI)

According to ASTM D1238, the specimen was held in a 220° C. cylinder for 5 minutes, and then the flow index was measured under a 10 kg load, and the unit is g/10 minutes.

3. Impact impact

The impact strength was measured according to ASTM D3763 using a 3.2 mm thick specimen, and the unit is N.

4. Environmental Stress Cracking Resistance (ESCR)

According to ASTM D1693, after placing a specimen prepared through injection on a 1.0% jig, 1 mg of thinner was dropped in the center of each specimen, and the time until fracture occurred was measured.

5. Measurement of water contact angle

The contact angle meter THETA Lite 101-attention was used to measure the number of contact angles of the specimen.

IMP
(kgcm/cm) MI
(g/10min) Falling
Impact strength (N) ESCR (sec) Water contact angle (°) Example 1 Example 1 19 5.5 4,300 100 68 Example 2 Example 2 18 5.2 4,300 30 75 Example 3 Example 3 19 5.3 4,300 60 73 Example 4 Example 4 19 5.4 4,200 60 73 Example 5 Example 5 19 5.4 4,200 80 72 Example 6 Comparative Example 1 18 5.0 4,200 15 79 Example 7 Comparative Example 2 19 4.0 4,200 30 79 Example 8 Comparative Example 3 15 4.8 3,800 25 76 Reference example - 15 5.3 2,200 110 69

As shown in Table 2, Examples 1 to 5 according to the present disclosure have excellent Izod impact strength and falling impact strength compared to Examples 6 to 8 that do not conform to the present description, and have an appropriate flow index while being chemically resistant (ESCR). This improvement was confirmed.

In addition, referring to the results of Examples 1, 4, and 5, it was confirmed that chemical resistance of Example 1 using a PEO-PPO copolymer having a high PEO content in the PEO-PPO copolymer was more excellent.

In addition, referring to the results of Examples 1 to 3, it can be seen that chemical resistance properties are further improved as the amount of the PEO-PPO copolymer increases.

In addition, in the case of the use examples 1 to 5 according to the present disclosure, it was confirmed that the chemical resistance is excellent and the water contact angle is 68 to 75°, so that the affinity with the organic solvent is appropriate.

On the other hand, in the case of the reference example in which the PEO-PPO copolymer was applied in the kneading process of the ABS-based resin and the SAN resin rather than the ABS-based resin manufacturing process, it was confirmed that the chemical resistance was very good but the impact strength was poor.

Claims (19)

Graft polymerization comprising 100 parts by weight of a mixture of diene rubber polymer, aromatic vinyl compound and vinyl cyan compound, 0.05 to 3 parts by weight of an alkylene oxide copolymer, 0.1 to 5 parts by weight of an emulsifier and 0.001 to 3 parts by weight of a polymerization initiator Including the steps,
The alkylene oxide copolymer is a method for producing a thermoplastic resin, characterized in that the number average molecular weight of 1,000 to 25,000 g / mol According to claim 1,
The alkylene oxide copolymer is a method for producing a thermoplastic resin, characterized in that the ethylene oxide-propylene oxide copolymer. According to claim 1,
The alkylene oxide copolymer is a method of manufacturing a thermoplastic resin comprising 15 to 95 mol% of ethylene oxide. delete According to claim 1,
The mixture of the diene-based rubber polymer, the aromatic vinyl compound and the vinyl cyan compound comprises 30 to 70% by weight of the diene-based rubber polymer, 15 to 60% by weight of the aromatic vinyl compound, and 5 to 35% by weight of the vinyl cyan compound. Method of manufacturing a thermoplastic resin. According to claim 1,
The graft polymerization step is a method for producing a thermoplastic resin, characterized in that it further comprises 0.05 to 1 part by weight of a molecular weight modifier. According to claim 1,
The step of the graft polymerization is a method of producing a thermoplastic resin, characterized in that it further comprises 0.0001 to 1 part by weight of an oxidation-reduction catalyst. According to claim 1,
The method of producing a thermoplastic resin, characterized in that the step of graft polymerization is carried out at 60 to 95 ℃. According to claim 1,
The thermoplastic resin latex produced by the graft polymerization is a method of manufacturing a thermoplastic resin, characterized in that the coagulant content is 0.04% by weight or less. According to claim 1,
The thermoplastic resin produced by the graft polymerization is a method of manufacturing a thermoplastic resin, characterized in that the graft rate is 45% or more. According to claim 1,
The thermoplastic resin produced by the graft polymerization is a method for producing a thermoplastic resin, characterized in that the weight average molecular weight is 50,000 to 100,000 g/mol. Based on 100 parts by weight of the monomer mixture containing 30 to 70% by weight of the diene rubber polymer, 15 to 60% by weight of the aromatic vinyl compound and 5 to 35% by weight of the vinyl cyan compound, (a) 30 to 70 parts by weight of the diene rubber polymer , Aromatic vinyl compound 5 to 20 parts by weight, vinyl cyan compound 1 to 10 parts by weight, alkylene oxide copolymers 0.05 to 3 parts by weight, emulsifiers 0.05 to 1 parts by weight, initiators containing 0.01 to 0.5 parts by weight of graft polymerization agent 1 polymerization step; (b) A second polymerization step of graft polymerization including 10 to 30 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyan compound, 0.1 to 1.5 parts by weight of an emulsifier, and 0.05 to 1 parts by weight of an initiator; Method for producing a thermoplastic resin. 10 to 50% by weight of a thermoplastic resin and 50 to 90% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer according to the method of any one of claims 1 to 3, 5 to 12, kneaded and extruded. After, the method of manufacturing a thermoplastic resin composition comprising the step of injecting it. 30 to 70% by weight of diene rubber polymer, 15 to 60% by weight of aromatic vinyl compound and 5 to 35% by weight of vinyl cyan compound, 100 parts by weight of graft polymerized graft resin and 0.05 to ethylene oxide-propylene oxide copolymer Thermoplastic resin comprising 3 parts by weight. A thermoplastic resin composition comprising 10 to 50% by weight of a thermoplastic resin according to claim 14 and 50 to 90% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer. The method of claim 15,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the Izod impact strength is 18 kgcm/cm or more. The method of claim 15,
The thermoplastic resin composition is a thermoplastic resin composition characterized in that the falling impact strength is 4,000N or more. The method of claim 15,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the flow index is 5 to 6 g/10min. The method of claim 15,
The thermoplastic resin composition is a thermoplastic resin composition, characterized in that the water contact angle (water contact angle) is 60 to 90 °.