KR101089146B1 - Thermoplastic ABS resin composition - Google Patents

Abstract

The present invention (a) 10 to 25% by weight ABS graft copolymer grafted aromatic vinyl compound and vinyl cyan compound to the conjugated diene rubber polymer; (b) 40 to 75 wt% of a copolymer of an aromatic vinyl compound and a vinyl cyan compound; (c) 10 to 40% by weight of a terpolymer having a weight average molecular weight of 80,000 to 130,000 of the (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound, and the vinyl cyan compound; And (d) a thermoplastic ABS resin composition comprising 0 to 20% by weight of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and a maleic anhydride polymer, which does not undergo a coating process after injection molding and has scratch resistance, impact strength and gloss. Degree has an excellent effect.

Thermoplastic ABS resin, conjugated diene graft copolymer, acrylic resin, SAN resin, unpainted resin, scratch resistance, impact strength, gloss

Description

Thermoplastic ABS resin composition {Thermoplasitc ABS resin composition}

The present invention relates to a thermoplastic ABS resin composition having excellent scratch resistance, impact strength and gloss, and more particularly, to a thermoplastic ABS resin composition and a manufacturing method which can be commercialized immediately without coating and plating after injection molding. will be.

ABS resin composed of acrylonitrile-butadiene-styrene is a typical resin that combines functionality and versatility, and has excellent properties such as impact strength, tensile strength, elastic modulus and flame retardancy. It is widely used. However, ABS resin is vulnerable in terms of weather resistance because the double bond of butadiene rubber used for impact reinforcement is decomposed by oxygen, ozone, light, etc. in the air when it is exposed to ultraviolet rays for a certain period of time. There is a problem that the quality is poor and the strength is also weakened a lot and can easily be broken. For this reason, in many cases, efforts have been made to compensate for the disadvantages of the ABS resin and improve appearance quality through a painting process.

In particular, in the case of home appliances, there is a tendency to demand not only functions of home appliances themselves but also functions such as interior goods, and demand for appearance quality is increasing. However, the coating or plating process applied to improve the appearance quality is not environmentally friendly and has a disadvantage that cannot be recycled when disposing of the product, and should be avoided as it is regulated according to the recent EU and EU electrical and electronic waste directive (WEEE). I think it's a process. In this sense, not only electrical and electronic products, but also automobile fields, etc., are actively developed for resin compositions for excluding coating processes and for reinforcing weather resistance. In addition, in order to remove the coating process, the scratch resistance of the resin must be raised and the glossiness must be improved.

Republic of Korea Patent Publication No. 2008-0062083 discloses a resin composition that can increase the physical properties such as wear resistance and stiffness by adding inorganic particles in the polymer resin and a manufacturing method thereof. However, the present patent has a disadvantage in that fluidity and processability are low by applying PMMA as a matrix resin, and impact strength and gloss may be reduced due to the addition of inorganic particles.

In US Pat. No. 6,048617, a curable resin, which is a mixture of an acrylic resin having an molecular weight of 2,000 to 30,000, an organic metal compound, and a silicone compound, is surfaced by heating or photo-irradiation. The method of apply | coating and hardening to this is disclosed. It is claimed that this method can improve the weather resistance, scratch resistance and thermal stability of plastic products. However, processes such as application and curing after injection of the product should be added. It has a disadvantage.

Therefore, there is a need for a thermoplastic ABS resin composition excellent in scratch resistance, impact strength, and glossiness, and a manufacturing method thereof.

The present invention is to solve the various problems of the prior art in the production of the ABS-based thermoplastic resin composition.

An object of the present invention is to provide a thermoplastic ABS resin composition excellent in scratch resistance, impact strength and gloss.

In the present invention, (a) a conjugated diene-based rubber polymer is an ABS graft copolymer grafted with an aromatic vinyl compound and a vinyl cyan compound, (b) a copolymer of an aromatic vinyl compound and a vinyl cyan compound, (c) a specific molecular weight After injection molding by containing a polymer of a satisfactory (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and a vinyl cyan compound terpolymer, and (d) a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and maleic anhydride It is possible to produce a thermoplastic ABS resin composition having excellent scratch resistance, impact strength and gloss without going through a painting process.

The thermoplastic ABS resin composition according to the present invention has excellent scratch resistance, impact strength and gloss, and is economical and recyclable because it is not coated.

In order to achieve the above object, the thermoplastic ABS resin composition of the present invention comprises: (a) 10 to 25% by weight of an ABS graft copolymer in which an aromatic vinyl compound and a vinyl cyan compound are grafted to a conjugated diene rubber polymer; (b) 40 to 75 wt% of a copolymer of an aromatic vinyl compound and a vinyl cyan compound; (c) 10 to 40% by weight of a terpolymer having a weight average molecular weight of 80,000 to 130,000 of the (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound, and the vinyl cyan compound; And (d) 0 to 20% by weight of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound, and a maleic anhydride polymer.

Hereinafter, the present invention will be described in more detail.

(A) ABS graft copolymer in which aromatic vinyl compound and vinyl cyan compound are grafted to conjugated diene rubber polymer

In the present invention, the conjugated diene graft copolymer is prepared by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on a conjugated diene rubber polymer. The conjugated diene-based rubbery polymer is prepared by using a method of preparing a large-diameter rubbery polymer having a relatively large average particle diameter by first preparing a small-diameter rubbery polymer having a relatively small average particle diameter and fusion using an acid.

The particle size and gel content of the conjugated diene-based rubbery polymer used in the preparation of the conjugated diene-based graft copolymer have a great influence on the impact strength and processability of the resin. That is, in general, the smaller the particle size of the rubbery polymer, the lower the impact strength and processability, and the larger the particle size, the larger the impact strength. Impact strength is improved. However, the higher the content of the rubbery polymer and the larger the particle size, there is a problem that the graft rate is lowered. The graft rate greatly affects the physical properties of the conjugated diene-based graft copolymer. However, when the graft rate drops, there are many ungrafted rubbery polymers.

Therefore, it is important to prepare a conjugated diene rubber polymer having an appropriate particle diameter and gel content, and it is important to have an appropriate graft ratio when grafting an aromatic vinyl compound and a vinyl cyan compound to the conjugated diene rubber polymer.

Hereinafter, a method for preparing a conjugated diene graft copolymer used in the present invention is prepared by (i) preparing a small diameter conjugated diene rubber polymer, (ii) preparing a large diameter conjugated diene rubber polymer, and (iii) graft polymerization. It will be described in detail by dividing into three steps of the preparation of the conjugated diene-based graft copolymer.

(i) Preparation of small diameter conjugated diene rubber polymer

The small-diameter conjugated diene-based rubber polymer of the present invention can be prepared by mixing and emulsion-polymerizing a conjugated diene monomer, an emulsifier, a polymerization initiator, an electrolyte material, a molecular weight regulator and water.

The conjugated diene monomer is preferably at least one selected from the group consisting of butadiene, isoprene, and chloroisoprene, and more preferably butadiene.

In addition, the emulsifier is preferably one or more selected from the group consisting of alkyl aryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters, fatty acid soaps and rosin acid alkali salts, and the amount of the emulsifier is 100% by weight of the conjugated diene monomer. It is preferable that it is 1-4 weight part with respect to a part.

In addition, the polymerization initiator can use a water-soluble persulfate or a peroxy compound, and an oxidation-reduction system can also be used. The most preferred water soluble persulfates are sodium and potassium persulfates and the fat soluble polymerization initiators are cumene hydroperoxide, diisopropylbenzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, para-methane hydroperoxide and benzoyl At least one selected from the group consisting of peroxides is preferable, and the amount thereof is preferably 0.1 to 0.6 parts by weight based on 100 parts by weight of the conjugated diene monomer.

In addition, the electrolyte material is KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , Na ₂ HPO _{4 At} least one selected from the group consisting of, the amount is preferably 0.1 to 1 parts by weight based on 100 parts by weight of the conjugated diene monomer.

In addition, the molecular weight modifier is preferably t-dodecyl mercaptan or n-octyl mercaptan, the amount of use is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the conjugated diene monomer.

In addition, the water is preferably ion-exchanged water, the amount is preferably 90 to 130 parts by weight based on 100 parts by weight of the conjugated diene monomer.

The conjugated diene monomer and the polymerization additive are collectively added to the reactor for the first polymerization at 50 to 65 ° C. for 7 to 12 hours, and 0.05 to 1.2 parts by weight of a molecular weight modifier is further added for 55 to 5 hours to 15 hours. By polymerizing at 70 ℃ can be prepared a small diameter conjugated diene rubber polymer.

It is preferable that the small-diameter conjugated diene-based rubber polymer prepared as described above has an average particle diameter of 600 to 1500 kPa. If the average particle diameter is less than 600 mm 3, the mechanical properties and thermal stability, such as impact strength and tensile strength, are poor, and if the average particle diameter is more than 1500 mm, colorability is deteriorated.

 (ii) Preparation of large diameter conjugated diene rubber polymer

When the small diameter conjugated diene rubber polymer is fused with an acid component, a large diameter conjugated diene rubber polymer can be prepared.

Specifically, 2.5 to 4.5 parts by weight of an aqueous acetic acid solution is slowly administered to 100 parts by weight of the small-diameter conjugated diene-based rubbery polymer for 1 hour to cause fusion of the small-diameter conjugated diene-based rubbery polymer particles. After the process is performed for about 1 hour, the stirring is stopped and the predetermined period of time is retained to enlarge the rubbery polymer, thereby preparing a large-diameter conjugated diene-based rubbery polymer having an average particle size of 2500 kPa to 5000 kPa.

The particle size of the large-diameter conjugated diene-based rubbery polymer is very important in order to impart impact strength to the thermoplastic resin, and in order to satisfy the physical properties required by the present invention, the average particle diameter is preferably 2500 to 5000 mm. If the average particle diameter of the large-diameter conjugated diene-based rubbery polymer is less than 2500 kPa, mechanical properties such as impact strength and tensile strength may be lowered, and if it exceeds 5000 kPa, gloss may be lowered, fluidity may be lowered, and graft rate may be lowered.

(iii) Preparation of conjugated diene graft copolymer by graft polymerization

A graft copolymer is prepared by adding an aromatic vinyl compound and a vinyl cyan compound to the prepared large-diameter conjugated diene-based rubber polymer. At this time, the reaction is emulsion polymerization by adding an emulsifier, a molecular weight regulator, a polymerization initiator and water.

The aromatic vinyl compound is preferably one or more selected from the group consisting of styrene, α-methylstyrene, para-methyl styrene, ο-ethylstyrene, para-ethylstyrene and vinyltoluene, and more preferably styrene. It is preferable that the usage-amount of the said aromatic vinyl compound is 60 weight part which is 30-weight part with respect to 100 weight part of said large diameter rubbery polymers. If the amount of the aromatic vinyl compound is less than 30 parts by weight, there is a problem of yellowing, and if the amount of the aromatic vinyl compound exceeds 60 parts by weight, there is a problem such as a decrease in compatibility between the copolymer of the aromatic vinyl compound and the vinyl cyan compound (SAN). Not.

In addition, the vinyl cyan compound is preferably at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, more preferably acrylonitrile. The amount of the vinyl cyan compound used is preferably 10 to 30 parts by weight based on 100 parts by weight of the large-diameter rubbery polymer. If the amount of the vinyl cyan compound used is less than 10 parts by weight, there is a problem such as a decrease in compatibility with the matrix SAN, and if it exceeds 30 parts by weight, there is a problem of yellowing.

The emulsifier used in the emulsion polymerization is preferably at least one selected from the group consisting of alkylaryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and rosin acid alkali salts, and the amount of the emulsifier used is the large diameter conjugated diene. It is preferable that it is 0.2-1 weight part with respect to 100 weight part of type rubbery polymers.

In addition, the molecular weight modifier is preferably t-dodecyl mercaptan or n-octyl mercaptan, the amount of the amount is preferably 0.2 to 0.6 parts by weight based on 100 parts by weight of the large diameter conjugated diene rubber polymer.

In addition, the polymerization initiator is a peroxide and sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrroline acid, including cumene hydroperoxide, diisopropylbenzene hydroperoxide or persulfate It is preferable that it is an oxidation-reduction catalyst system composed of a mixture of a reducing agent containing sodium or sodium sulfite, and the amount thereof is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the large-diameter conjugated diene rubber polymer.

In addition, it is preferable that the water is ion-exchanged water, and the amount thereof is preferably 80 to 150 parts by weight based on 100 parts by weight of the large-diameter conjugated diene rubber polymer.

When the reaction mixture and the polymerization additives are added to the reactor, it is preferable to administer in multiple stages or continuously in order to improve the graft rate and minimize the formation of coagulum.

The condition of the emulsion polymerization for producing the conjugated diene-based graft copolymer is preferably performed for 3 to 5 hours at a temperature of 45 to 80 ℃.

After completion of the emulsion polymerization, the polymerization conversion rate of the obtained conjugated diene-based graft copolymer latex is preferably 95% or more, and the antioxidant and ultraviolet stabilizer are added to the conjugated diene-based graft copolymer latex to a temperature of 80 ° C. or higher. After condensation with an aqueous solution of sulfuric acid in the dehydration and dried to obtain a conjugated diene graft copolymer powder.

The polymerization stability of the prepared conjugated diene graft copolymer latex can be determined by measuring the solidified solid content (%) by the following equation (1).

Solid coagulation (%) = (weight of product coagulum in the reactor (g) / total weight of the rubber polymer and monomer) × 100

When the solidified solid content is 0.7% or more, latex stability is extremely low, and a large amount of coagulated product makes it difficult to obtain a conjugated diene graft copolymer suitable for the present invention. Therefore, it is preferable that the said solidified content is less than 0.7%.

In addition, the graft ratio of the conjugated diene graft copolymer is measured as follows. That is, the conjugated diene graft copolymer latex is coagulated, washed and dried to obtain a powder form, and 2 g of the powder is added to 300 ml of acetone and stirred for 24 hours. The solution is separated using an ultracentrifuge, and then the separated acetone solution is dropped in methanol to obtain an grafted portion, which is dried and weighed. From these weights, the graft ratio is calculated by the following equation.

Graft Rate (%) = (weight of grafted monomer / total weight of rubber) × 100

In the present invention, the graft ratio of the conjugated diene graft copolymer is preferably 26 to 60%. If the graft ratio is less than 26%, the thermal stability is lowered. If the graft ratio is higher than 60%, the mechanical properties are lowered, which is not preferable.

The conjugated diene graft copolymer is preferably contained in 10 to 25% by weight of the thermoplastic ABS resin composition of the present invention, when less than 10% by weight has a problem that the impact strength is significantly lowered, if it exceeds 25% by weight Scratch resistance and gloss are inferior, which is undesirable.

(b) Copolymer of Aromatic Vinyl Compound and Vinyl Cyan Compound (SAN Resin)

The SAN-based resin may be a resin prepared using the conditions commonly used in the art, preferably 30 to 90% by weight of the aromatic vinyl compound and 10 to 70% by weight of the vinyl cyan compound may be a method of continuous bulk polymerization. SAN-based resins prepared using can be used.

The aromatic vinyl compound is preferably at least one selected from the group consisting of styrene, α-methylstyrene, para-methyl styrene, ο-ethylstyrene, para-ethylstyrene, and vinyltoluene, and more preferably styrene.

In addition, the vinyl cyan compound is preferably at least one member selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, more preferably acrylonitrile.

The amount of the SAN-based resin is preferably 40 to 75% by weight of the total thermoplastic ABS resin composition. When the amount of the SAN-based resin is more than 75% by weight, there is a problem that the weather resistance and impact strength is weak, and when less than 40% by weight is added, there is a problem that the scratch resistance and workability are poor.

(c) Terpolymers of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds and vinyl cyan compounds

The terpolymer according to the present invention can be prepared by bulk polymerization of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyan compound.

It is preferable that the composition ratio of the reaction mixture used for the said polymer is 40 to 70 weight% of the (meth) acrylic-acid alkylester compound, 10 to 30 weight% of an aromatic vinyl compound, and 3 to 30 weight% of a vinyl cyan compound.

It is preferable that the (meth) acrylic acid alkyl ester compound is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. Preferably methyl methacrylate. It is preferable that the usage-amount of the (meth) acrylic-acid alkylester compound is 40 to 70 weight% in the whole reaction mixture. If the amount is less than 40% by weight, there is a problem that the refractive index is increased and the haze is increased. If the amount is more than 70% by weight, the viscosity of the reactant is increased so that polymerization does not proceed uniformly. not.

In addition, the aromatic vinyl compound is one or more selected from the group consisting of styrene, α-methyl styrene, para-methyl styrene, styrene benzene optionally substituted with one or more hydrogen of C ₁ to C ₅ alkyl group or halogen. Preferred, more preferably styrene. It is preferable that the usage-amount of the said aromatic vinyl compound is 10-30 weight% with respect to the whole reaction mixture. If the amount is less than 10% by weight, there is a problem that the viscosity of the reactant is high and the processability and fluidity of the produced product are deteriorated. If the amount is more than 30% by weight, the refractive index becomes large and the transparency is lowered, which is not preferable.

In addition, the vinyl cyan compound is preferably at least one member selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, more preferably acrylonitrile. The amount of the vinyl cyan compound used is preferably 3 to 30% by weight based on the total reaction mixture. If the amount is less than 3% by weight, there is a problem that the chemical resistance is remarkably inferior, and if it exceeds 30% by weight, there is a problem that the heat discoloration occurs badly, which is not preferable.

The reaction lubricant is preferably an aromatic hydrocarbon compound optionally substituted with a C ₁ to C ₃ alkyl group or a halogen, more preferably at least one compound selected from the group consisting of ethylbenzene, toluene and xylene. It is preferable that the usage-amount of the said reaction lubricant is 20-30 weight part with respect to 100 weight part of all reaction monomers. If the amount is less than 20 parts by weight, there is a problem that the viscosity of the reactant is increased rapidly, and if it exceeds 30 parts by weight, the molecular weight is low and the yield is low, which is not preferable.

In the production of the terpolymer, the polymerization reaction may be optionally performed by adding an antioxidant, a molecular weight regulator and an organic peroxide initiator.

The antioxidant may be a hindered phenolic antioxidant alone or mixed with the hindered phenolic antioxidant and phosphite antioxidant in a predetermined composition to suppress yellowing in a high temperature volatilization tank 100 It is preferable to use 0.01-1 weight part with respect to a weight part. If the amount is less than 0.01 parts by weight, the effect of suppressing yellowing due to thermal history in a high temperature volatilization tank is small, and if it exceeds 1 part by weight, there is a problem that the refractive index increases due to a decrease in conversion rate, which is not preferable.

Among the antioxidants, phenolic antioxidants are tetrakis methylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate methane, 1,3,5-tris- (4-t-butyl -3-hydroxy-2,6-dimethyl benzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and 1,3,5-tris It is preferably one kind selected from the group consisting of-(3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione The phosphite antioxidant is preferably one selected from the group consisting of tris (2,4-t-butyl phenyl) phosphite and tris- (nonylphenyl) phosphite.

When the antioxidant is used in combination, the composition ratio of the phenolic antioxidant to the phosphite antioxidant is preferably 9: 1 to 1: 5, more preferably 5: 1 to 1: 3, most preferably. Preferably 2: 1 to 1: 2. Phenolic antioxidant: When the composition ratio of phosphite-based antioxidant is more than 1: 5, the amount of phosphite-based compound is vulnerable to thermal history during polymerization, and the amount of phosphite-based compound is less than 9: 1. In the volatilization and processing there is a problem vulnerable to thermal history.

In addition, the molecular weight regulator serves to appropriately adjust the molecular weight of the acrylic resin in order to prevent the viscosity rises rapidly during bulk polymerization, the amount of the amount is preferably 0.01 to 1 parts by weight based on 100 parts by weight of the reaction mixture. Do. If the amount is less than 0.01 parts by weight, there is a problem in that the operation is difficult due to the high viscosity, and if it exceeds 1 parts by weight, the molecular weight is low, there is a problem of low impact strength. The molecular weight modifier is preferably at least one member selected from the group consisting of t-dodecyl mercaptan and n-octyl mercaptan.

In addition, the organic peroxide initiator serves to initiate the polymerization of the acrylic copolymer, the amount is preferably 0.01 to 0.1 parts by weight based on 100 parts by weight of the reaction mixture. If the amount is less than 0.01 parts by weight, the amount of production is low and there is a problem that a lot of thermal discoloration occurs due to the difference in the composition ratio in the polymer, and when it exceeds 0.1 parts by weight, the polymerization reaction occurs rapidly, which makes it difficult to control the reaction pressure and the heat of reaction. There is a problem that the viscosity of the reactants is rapidly increased by the gel effect. The organic peroxide initiators include 1,1-bis (t-butyl peroxy) -3,3,5-trimethyl cyclohexane and 1,1-bis (t-butyl peroxy) cyclohexane and 1,1-bis (t It is preferably one or more selected from the group consisting of -butyl peroxy) 2-methyl cyclohexane.

The addition of the additives to the reaction mixture does not necessarily have to be added after the monomers have been mixed but may be added to the reactor at the same time and the present invention is not limited by the order thereof.

The terpolymer is polymerized at a temperature of 120 to 140 ° C. for 2 to 4 hours in a first step, and then at 130 to 150 ° C. in a second step, while introducing the reaction mixture and an additive mixture into a reactor. It is prepared by carrying out the polymerization continuously for 2 to 4 hours.

In the first stage of polymerization, the reaction temperature is preferably 120 to 140 ° C. If the reaction temperature is less than 120 ° C, the initiator efficiency is low, and the conversion rate is low. If the reaction temperature is higher than 140 ° C, the molecular weight is lowered. In the first step polymerization, the polymerization time is preferably 2 to 4 hours. If the polymerization time is less than 2 hours, there is a problem that the conversion rate is low, and if it exceeds 4 hours, there is a problem that the operation is difficult due to the high viscosity.

In the second stage of polymerization, the reaction temperature is preferably 130 to 150 ° C. If the reaction temperature is less than 130 ℃ there is a problem that the conversion rate is low to reduce the production, and if it exceeds 150 ℃ there is a problem that the molecular weight is lowered. In the second step polymerization, the polymerization time is preferably 2 to 4 hours. If the polymerization time is less than 2 hours, there is a problem that the conversion rate is low to increase the refractive index, and if it exceeds 4 hours, there is a problem that the impact strength is lowered because the molecular weight is low.

When polymerization proceeds as described above and the polymerization conversion rate is about 60% or more, an acrylic transparent resin having excellent chemical resistance, fluidity and color tone is pelleted by removing unreacted monomer and reaction lubricant at a temperature of 200 to 240 ° C. in a volatilization tank. It can be prepared as.

The weight average molecular weight of the terpolymer obtained by the polymerization proceeds as described above is 80,000 to 130,000, when the molecular weight is less than 80,000, there is a problem that the impact strength is lowered, if it exceeds 130,000 there is a problem of poor workability is not preferred.

In the present invention, the amount of the terpolymer is preferably 10 to 40% by weight in the total thermoplastic ABS resin composition. If the amount is less than 10% by weight, there is a problem that it is difficult to obtain sufficient scratch resistance and glossiness, and when it exceeds 40% by weight, the impact strength is lowered and the price is expensive, which is not preferable.

(d) Polymers of (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds, and maleic anhydride (maleic acid acrylic resins)

On the other hand, the thermoplastic ABS resin composition according to the present invention optionally comprises (d) (meth) acrylic acid alkyl ester compounds, aromatic vinyl compounds, and terpolymers of maleic anhydride (hereinafter referred to as "maleic acid acrylic resin") as a whole resin. It may further comprise within 20% by weight of the composition.

Maleic acid acrylic resin can manufacture a (meth) acrylic-acid alkylester compound, an aromatic vinyl compound, and maleic anhydride by continuous block polymerization.

It is preferable that the (meth) acrylic acid alkyl ester compound is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. Preferably methyl methacrylate. It is preferable that the usage-amount of the said (meth) acrylic-acid alkylester compound is 50-70 weight% in the whole reaction mixture. If the amount is less than 50% by weight, there is a problem that the refractive index is increased and the haze is increased. If the amount is more than 70% by weight, the viscosity of the reactant is rapidly increased so that the polymerization does not proceed uniformly. not.

In addition, the aromatic vinyl compound is one or more selected from the group consisting of styrene, α-methyl styrene, para-methyl styrene, styrene benzene optionally substituted with one or more hydrogen of C ₁ to C ₅ alkyl group or halogen. Preferred, more preferably styrene. The amount of the aromatic vinyl compound is preferably 10 to 30% by weight of the total reaction mixture. If the amount is less than 10% by weight, there is a problem that the viscosity of the reactant is high and the processability and fluidity of the produced product are deteriorated. If the amount is more than 30% by weight, the refractive index becomes large and the transparency is lowered, which is not preferable.

In addition, the amount of maleic anhydride used is preferably 3 to 20% by weight of the total reaction mixture. If the amount is less than 3% by weight, there is a problem that the heat resistance is lowered, and if the amount is more than 20% by weight, the workability and impact strength is lowered, the refractive index is increased, the transparency is lowered, which is not preferable.

The amount of the maleic acid acrylic resin may be included in less than 20% by weight of the total resin composition, if it exceeds 20% by weight is not preferable because there is a problem of poor workability and weak impact strength.

The thermoplastic resin of the present invention composed of the above components may be prepared by further adding a lubricant, an antioxidant, an antistatic agent, a mold releasing agent or a UV stabilizer which are commonly used according to the use.

The lubricant may be ethylene bis stearamide, polyethylene oxide wax, magnesium stearate or a combination thereof, and the amount of the lubricant is preferably 0.1 to 5 parts by weight, more preferably 100 parts by weight of the thermoplastic ABS resin composition. 0.5 to 2 parts by weight.

In addition, the antioxidant may be used, such as IR1076 which is a phenolic antioxidant, the amount is preferably 0.5 to 2 parts by weight based on 100 parts by weight of the thermoplastic ABS resin composition.

In addition, the UV stabilizer may be used, such as TINUVIN 327, an ultraviolet absorber, the amount is preferably 0.05 to 3 parts by weight, more preferably 0.2 to 1 part by weight based on 100 parts by weight of the thermoplastic ABS resin composition.

The thermoplastic ABS resin composition of the present invention as described above is excellent in scratch resistance, impact strength and gloss, and can be immediately commercialized without coating and plating treatment after injection molding.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Synthesis Example 1 (a) Preparation of conjugated diene graft copolymer

(i) Preparation of Small Diameter Rubbery Polymers

In a nitrogen-substituted polymerization reactor (autoclave), 100 parts by weight of 1,3-butadiene, 1.2 parts by weight of potassium rosin acid salt and 1.5 parts by weight of potassium oleate salt, 0.1 part by weight of sodium carbonate (Na ₂ CO ₃ ) and potassium hydrogencarbonate (KHCO ₃ ) 0.5 parts by weight, 0.3 parts by weight of t-dodecyl mercaptan and 100 parts by weight of ion-exchanged water were collectively administered, the reaction temperature was raised to 55 ° C, and 0.3 parts by weight of potassium persulfate was collectively administered to initiate the reaction. After reacting for 10 hours, 0.05 parts by weight of t-dodecyl mercaptan was further administered, and reacted at 65 ° C. for 8 hours to terminate the reaction to prepare a small diameter rubbery polymer. The gel content of the prepared small-diameter rubbery polymer was 90%, the swelling index was 18, and the particle diameter was about 1000 mm 3.

(ii) Preparation of Large Diameter Rubbery Polymers

100 parts by weight of the prepared small-diameter rubbery polymer was added to the reactor, the stirring speed was adjusted to 10 rpm, and the temperature was adjusted to 30 ° C., and then 3.0 parts by weight of 7% acetic acid aqueous solution was gradually added for 1 hour, and then the stirring was stopped and 30 Large diameter butadiene rubber polymers were prepared by fusing a small diameter rubbery polymer by standing for minutes. The large diameter rubbery polymer prepared by the fusion process was analyzed in the same manner as the small diameter rubbery polymer. The rubber polymer obtained at this time had a particle diameter of 3100 mm 3, and a gel content of 90%.

(iii) Preparation of conjugated diene graft copolymer

65 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium rosinate, 0.1 part by weight of sodium ethylenediaminetetraacetate, 0.005 part by weight of ferrous sulfate, and sodium formaldehyde 0.23 parts by weight of sulfoxylate was dosed in a reactor and the temperature was raised to 70 ° C. A mixture of 40 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium rosinate, 32.0 parts by weight of styrene, 13.7 parts by weight of acrylonitrile, 0.3 parts by weight of t-dodecyl mercaptan, and 0.3 parts by weight of diisopropylene hydroperoxide was added for 2 hours. After the continuous dosing, 10 parts by weight of ion-exchanged water, 0.1 parts by weight of potassium rosinate, 16.0 parts by weight of styrene, 5.0 parts by weight of acrylonitrile, 0.1 parts by weight of t-dodecyl mercaptan and diisopropylene hydroper 0.1 parts by weight of a mixed solution of oxide was continuously added for 1 hour, and then heated to 80 ° C, and aged for 1 hour to terminate the reaction.

At this time, the polymerization conversion rate was 97.5 parts by weight, the solidification content was 0.2%, and the graft rate was 37%.

The prepared ABS graft copolymer latex was coagulated with an aqueous sulfuric acid solution, washed, and dried to obtain a powder.

Synthesis Example 2 (b) Copolymer of Aromatic Vinyl Compound and Vinyl Cyan Compound (SAN Resin)

The copolymer resin was made through continuous bulk polymerization using a catalyst, and a copolymer of an aromatic vinyl compound and a vinyl cyan compound (product name 92HRC) manufactured by LG Chem was used as it was without purification.

Synthesis Example 3 (c) Terpolymer of (meth) acrylic acid alkyl ester compound, aromatic vinyl compound, and vinyl cyan compound

20 parts by weight of toluene, 1,1-bis (t-butylperoxy) -3,3 in 100 parts by weight of the reaction mixture containing 25% by weight of styrene, 40% by weight of methyl methacrylate and 15% by weight of acrylonitrile. 0.02 parts by weight of 5-trimethyl cyclohexane, 0.08 parts by weight of n-dodecyl mercaptan, and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3 A polymerization reaction mixture containing 0.1 parts by weight of, 5-triazine-2,4,6- (1H, 3H, 5H) -trione was added to a 26L reactor at a rate of 14L / hr, at a temperature of 140 ° C in the first reactor. Polymerization and polymerization at 150 ° C. in the second reactor resulted in removal of unreacted monomer and reaction medium at a temperature of 215 ° C. in a volatilizer to prepare a transparent copolymer in pellet form.

The weight average molecular weight of the terpolymer of the (meth) acrylic-acid alkylester compound, aromatic vinyl compound, and vinyl cyan compound which were prepared above was 100,000.

Synthesis Example 3-1 Ternary copolymer-1 of (c) (meth) acrylic acid alkyl ester compound, aromatic vinyl compound, and vinyl cyan compound

Except for including 1.5 parts by weight of n-dodecyl mercaptan in Synthesis Example 3 was prepared in the same composition and conditions and the weight average molecular weight was 50,000.

Synthesis Example 4 (d) Preparation of Maleic Acid Acrylic Resin

The maleic acid acrylic resin was used without purification as the XT580 resin manufactured by LG Chem. The composition of the acrylic acid maleic resin is 65% by weight of methyl methacrylate, 30% by weight of an aromatic vinyl compound, and 5% by weight of maleic anhydride.

Example 1 Preparation of Thermoplastic ABS Resin Compositions

EBA 2.0 weight as a lubricant based on 100 parts by weight of the base resin comprising (a) 20% by weight of the conjugated diene graft copolymer, (b) 65% by weight of the SAN-based resin (c) 15% by weight of the terpolymer. To add 0.5 parts by weight of antioxidant IR1076 to prepare a thermoplastic ABS resin composition. The composition was prepared in pellet form at 230 ° C. using a twin screw extruder.

Example 2

20% by weight of the (a) ABS graft copolymer prepared in the synthesis example, (b) 50% by weight of the SAN-based resin, (c) 20% by weight of the terpolymer copolymer, and (d) 10% by weight of the maleic acid acrylic resin A thermoplastic ABS resin composition and pellets were prepared in the same manner as in Example 1 except for the one described above.

Example 3

20% by weight of the (a) ABS graft copolymer prepared in the synthesis example, (b) 40% by weight of the SAN-based resin, (c) 30% by weight of the terpolymer copolymer, and (d) 10% by weight of the maleic acid acrylic resin A thermoplastic ABS resin composition and pellets were prepared in the same manner as in Example 1 except for the one described above.

Comparative Example 1

A thermoplastic ABS resin composition and pellets were prepared in the same manner as in Example 1, except that (a) 20 wt% of the ABS graft copolymer prepared in the synthesis example and (b) 80 wt% of the SAN-based resin were used.

Comparative Example 2

A thermoplastic ABS resin composition and pellets were prepared in the same manner as in Example 1, except that 27% by weight of the (a) ABS graft copolymer prepared in Synthesis Example and 73% by weight of the (c) terpolymer copolymer resin were added. Prepared.

Comparative Example 3

(A) 20 wt% ABS graft copolymer prepared in Synthesis Example, (b) 40 wt% SAN resin and (c) terpolymer having a weight average molecular weight of 50,000 (synthesis example 3-1) 30 A thermoplastic ABS resin composition and pellets were prepared in the same manner as in Example 1, except that 10% by weight and (d) 10% by weight of the maleic acid acrylic resin were added.

(Performance test)

The compositions of the above Examples and Comparative Examples are summarized in Table 1 below, and the prepared pellets were injected to measure impact strength, flowability, pencil hardness, and glossiness in the following manner, and the results are shown in Table 2 below. Indicated.

Impact strength (IMP): measured according to ASTM D256

-Fluidity (MI): measured under the condition of 220 ℃, 10 kg load and g / 10 min in accordance with ASTM D1238, to determine whether the processability is easy.

-Pencil Hardness: After fixing the pencil with a load of 0.5kg and an angle of 45˚, it was determined whether the surface of the specimen was scratched by the naked eye by the pencil hardness.

Gloss (Gloss) was measured at a 45 degree angle with a gloss meter.

Composition (% by weight) Example Comparative example One 2 3 One 2 3 (a) ABS graft copolymer 20 20 20 20 27 20 (b) SAN-based resin 50 50 40 80 0 40 (c) terpolymers 30 20 30 0 73 0 (c) Terpolymer Copolymer-1 0 0 0 0 0 30 (d) Maleic acid acrylic resin 0 10 10 0 0 10

Properties Example Comparative example One 2 3 One 2 3 Impact Strength (1/4 ") 18 16.9 17.2 19.1 19.6 12.4 Fluidity (220 ℃ / 10kg) 34.6 33.8 34.1 33.5 32 42.3 Pencil hardness B B HB 3B 2B 4B Glossiness (45 degrees) 99 100 101 95 93 97

As can be seen through Table 1, Example 1 according to the present invention can be confirmed that the scratch resistance (pencil hardness) and gloss is excellent compared to Comparative Example 1 does not include a terpolymer. In addition, it can be seen that in Examples 2 to 3 further comprising maleic acid acrylic resin, scratch resistance and glossiness are improved.

In addition, when comparing the Example 2 and Comparative Example 2, even though the rubber content of the ABS graft copolymer of Comparative Example 2 is increased, the impact strength decreases due to the deviation of the content range of the terpolymer, it can be confirmed that the scratch resistance and It can be seen that the gloss is also degraded.

In addition, when comparing Example 3 and Comparative Example 3 according to the present invention, it can be seen that the impact strength and scratch resistance is lowered as the molecular weight of the terpolymer-1 of Comparative Example 3 is lowered to 50,000.

Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, it is natural that such variations and modifications belong to the appended claims. .

Claims (13)

(a) 10 to 25% by weight ABS graft copolymer comprising less than 0.7% solid coagulant in which the conjugated diene-based rubber polymer is 20 to 60% grafted with an aromatic vinyl compound and a vinyl cyan compound; (b) 40 to 75 wt% of a copolymer of an aromatic vinyl compound and a vinyl cyan compound; (c) 10 to 40% by weight of a terpolymer having a weight average molecular weight of 80,000 to 130,000 of the (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound, and the vinyl cyan compound; And (d) A thermoplastic ABS resin composition for injection molding comprising 0.01 to 20% by weight of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a maleic anhydride terpolymer. The thermoplastic ABS resin composition for injection molding according to claim 1, wherein the conjugated diene rubber polymer (a) is a large-diameter polymer having an average particle size of 2500 to 5000 Pa. According to claim 2, wherein the (a) conjugated diene rubber polymer is injection molding thermoplastic, characterized in that at least one selected from the group consisting of butadiene rubber polymer, isoprene rubber polymer, chloroisoprene rubber polymer and any mixture thereof. ABS resin composition. delete delete The thermoplastic vinyl compound for injection molding according to claim 1, wherein the aromatic vinyl compound of (a), (b), and (c) is at least one member selected from the group consisting of styrene, alpha methyl styrene, and para methyl styrene. Resin composition. The injection molding method according to claim 1, wherein the vinyl cyan compound of (a), (b), and (c) is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. Thermoplastic ABS resin composition for molding. According to claim 1, wherein the ABS graft copolymer of (a) is 30 to 60 parts by weight of the aromatic vinyl compound with respect to 100 parts by weight of the conjugated diene rubber polymer; And 10 to 30 parts by weight of the vinyl cyan compound, injection molding thermoplastic ABS resin composition. The method of claim 1, wherein the (meth) acrylic acid alkyl ester compound is one selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. Thermoplastic ABS resin composition for injection molding, characterized in that above. delete The terpolymer of the (d) (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound, and maleic anhydride is 50 to 70% by weight of the (meth) acrylic acid alkyl ester compound, and 10 to 30% by weight of the aromatic vinyl compound. %, And 3 to 20% by weight of maleic anhydride, the thermoplastic ABS resin composition for injection molding. delete The injection molding thermoplastic ABS resin composition according to claim 1, wherein the composition further comprises at least one additive selected from the group consisting of a lubricant, an antioxidant, an antistatic agent, a mold release agent and an ultraviolet stabilizer.