KR102183091B1 - Odorless thermoplastic resin composition having good transparency and method for preparing the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition and a method for producing the same, and more particularly, (A) (a1) 20 to 70% by weight of a conjugated diene rubber polymer (a2) an alkyl methacrylate compound or an alkyl acrylate compound 20 (A5) quinone based on 100 parts by weight of the total amount of the (a3) aromatic vinyl compound 7 to 30% by weight, (a4) vinylcyan compound 1 to 10% by weight, and (a1) to (a4) 20 to 80% by weight of a copolymerized graft copolymer including 0.01 parts by weight or more to less than 0.7 parts by weight of the compound; And (B) (b1) 50 to 80% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (b2) 15 to 45% by weight of an aromatic vinyl compound and (b3) 1 to 10% by weight of a vinyl cyan compound, and the ( Characterized in that it comprises a styrenic copolymer of 20 to 80% by weight, including 0.01 parts by weight or more to less than 0.7 parts by weight of the quinone compound, based on 100 parts by weight of the total amount of b1) to (b3). It relates to a thermoplastic resin composition and a method for producing the same.
According to the present invention, there is an effect of providing a thermoplastic resin composition that is excellent in transparency and processability, and can be used for toys and interior decoration, etc., which require odorlessness by solving the characteristic odor problem of the existing resin.

Description

Odorless transparent thermoplastic resin composition and its manufacturing method {ODORLESS THERMOPLASTIC RESIN COMPOSITION HAVING GOOD TRANSPARENCY AND METHOD FOR PREPARING THE SAME}

The present invention relates to a thermoplastic resin composition and a method for manufacturing the same, and more particularly, it has excellent transparency and processability, and solves the peculiar odor problem of the existing resin, and can be used for toys and interior decoration that requires odorlessness. It relates to a resin composition and a method of manufacturing the same.

In general, transparent ABS resin has extremely high light transmittance and excellent transparency, and is applied to electronic fields, OA equipment, and general goods. That is, the housing of home appliances including air conditioners, vacuum cleaners, washing machines, and OA equipment fields of electric, electronic, facsimile, computer, and telephone housings, automobile parts, toys, leisure goods, and interior decoration fields. .

In a recent society, it is desirable that devices and products installed in places used by a large number of people are made of materials that do not have a characteristic odor in the material itself. Existing methods for removing odors from odorous rubbers have been known as a method of masking a molecular weight modifier having an odor during processing and a method of using an odorless molecular weight modifier in the polymerization process.

The masking method is a method of additionally adding only a masking agent as a processing additive.It is easy to apply, but the actual odor improvement effect is not great, and the masking agent and the odor of the rubber itself are mixed, resulting in a unique strong odor. Because it is expensive and is expensive, there is a problem that it is not easy to apply in the actual application process.

The odor-improving method in the polymerization process using the odorless molecular weight modifier has excellent odor-improving properties, but has a problem of lowering impact strength and chemical resistance, and an odorless styrene-based thermoplastic resin composition and odorless using an odorless molecular weight modifier There are many patents related to the manufacturing method of ABS thermoplastic resin, but research on the odorless transparent thermoplastic resin composition is insufficient.

Accordingly, there is a need to develop a thermoplastic resin composition that satisfies the mechanical properties required for the thermoplastic resin composition and at the same time improves the characteristic odor problem of the existing resin.

Korean Patent Registration No. 10-0497406

In order to solve the problems of the prior art as described above, the present invention has excellent transparency and processability, and solves the peculiar odor problem of the existing resin, and can be used for toys and interior decoration, etc. It aims to provide a manufacturing method.

All of 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 provides (A) (a1) 20 to 70% by weight of a conjugated diene rubber polymer, (a2) 20 to 60% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (a3 )Aromatic vinyl compound 7 to 30% by weight, (a4) vinylcyan compound 1 to 10% by weight, and (a1) to (a4) based on 100 parts by weight of the total amount of (a5) quinone compound 0.01 parts by weight or more to 0.7 20 to 80% by weight of the copolymerized graft copolymer including less than parts by weight; And (B) (b1) 50 to 80% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (b2) 15 to 45% by weight of an aromatic vinyl compound and (b3) 1 to 10% by weight of a vinyl cyan compound, and the ( Characterized in that it comprises: (b4) 20 to 80% by weight of a copolymerized styrenic copolymer including 0.01 parts by weight or more to less than 0.7 parts by weight of the quinone compound based on 100 parts by weight of the sum total of b1) to (b3). It provides a thermoplastic resin composition and a method for producing the same.

According to the present invention, there is an effect of providing a thermoplastic resin composition that is excellent in transparency and processability, and can be used for toys and interior decoration, etc., which require odorlessness by solving the characteristic odor problem of the existing resin.

Hereinafter, the odorless transparent thermoplastic resin composition of the present disclosure and a method of manufacturing the same will be described in detail.

The thermoplastic resin composition of the present invention comprises (A) (a1) 20 to 70% by weight of a conjugated diene-based rubber polymer, (a2) 20 to 60% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, and (a3) an aromatic vinyl compound. From 7 to 30% by weight, (a4) from 1 to 10% by weight of the vinyl cyan compound, and from 0.01 to less than 0.7 parts by weight of the (a5) quinone compound based on 100 parts by weight of the total amount of the (a1) to (a4) 20 to 80% by weight of the copolymerized graft copolymer including; And (B) (b1) 50 to 80% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (b2) 15 to 45% by weight of an aromatic vinyl compound and (b3) 1 to 10% by weight of a vinyl cyan compound, and the ( Characterized in that it comprises: (b4) 20 to 80% by weight of a copolymerized styrenic copolymer including 0.01 parts by weight or more to less than 0.7 parts by weight of the quinone compound based on 100 parts by weight of the sum total of b1) to (b3). do.

As described above, the thermoplastic resin composition according to the present invention has excellent transparency and processability, and solves the peculiar odor problem of the existing resin, and can be used for toys and interior decoration requiring odorlessness.

Hereinafter, each component constituting the thermoplastic resin composition of the present invention will be described in detail.

(A) Graft Copolymer

The graft copolymer is, for example, (a1) 20 to 70% by weight of a conjugated diene rubber polymer, (a2) 20 to 60% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, and (a3) an aromatic vinyl compound 7 Graft copolymerization of 1 to 10% by weight of (a4) vinylcyan compound, but 0.01 parts by weight or more to less than 0.7 parts by weight of a quinone compound based on the total 100 parts by weight of the (a1) to (a4) They can be used together to produce graft copolymerization.

The conjugated diene-based rubber polymer may have an average particle diameter of 600 to 5,000 Å, or 700 to 4,500 Å, preferably 800 to 3,200 Å, and has excellent mechanical properties such as transparency and impact strength within the above range. have.

The graft copolymer is, for example, a graft copolymer comprising a conjugated diene rubber polymer having an average particle diameter of 2,600 to 5,000 Å (hereinafter referred to as "large diameter conjugated diene rubber polymer) and a conjugated diene having an average particle diameter of 600 to 1,500 Å. It may include one or more of the graft copolymers including the rubber-based polymer (hereinafter "small diameter conjugated diene rubber polymer).

The large-diameter conjugated diene-based rubber polymer may be, for example, an average particle diameter of 2,600 to 5,000 Å, or 2,800 to 4,500 Å, preferably 2,800 to 3,200 Å, and has excellent transparency and impact strength within the above range.

As another example, the small-diameter conjugated diene-based rubber polymer may have an average particle diameter of 600 to 1,500 Å, or 700 to 1,300 Å, preferably 800 to 1,200 Å, and has excellent transparency and impact strength within the above range. .

In the present description, the average particle diameter may be measured by, for example, a device capable of measuring the average particle diameter of a rubbery polymer such as Nicomp 380.

The graft copolymer is, for example, a weight ratio of the graft copolymer including the large diameter conjugated diene-based rubber polymer to the graft copolymer including the small-diameter conjugated diene-based rubber polymer is 3: 1 to 1: 8, or It may be 2: 1 to 1: 5, and there is an excellent effect of transparency and impact strength within the above range.

The conjugated diene rubber is a polymer of a conjugated diene compound having a structure in which a double bond and a single bond are arranged across one, and may further include a comonomer if necessary.

The conjugated diene-based rubbery polymer may be, for example, at least one selected from butadiene polymer, butadiene-styrene copolymer (SBR), butadiene-acrylonitrile copolymer (NBR), and ethylene-propylene copolymer (EPDM).

The conjugated diene-based rubber polymer may be, for example, 20 to 70% by weight, or 40 to 65% by weight, preferably 45 to 55% by weight of the graft copolymer (A), and impact strength within the above range. And there is an effect excellent in transparency.

The conjugated diene-based rubbery polymer may have a gel content of 70 to 97% by weight, or 80 to 97% by weight, preferably 85 to 97% by weight, for example, and has excellent transparency within the above range.

The conjugated diene-based rubbery polymer may have a swelling index of 12 to 30, or 5 to 25, for example, and has excellent transparency within the above range.

The gel content and swelling index of the present description are as an example, after coagulating rubber latex with a dilute acid or metal salt, washing, drying for 24 hours in a vacuum oven at 60°C, and then cutting the obtained rubber mass finely with scissors and 1 g of The rubber piece was put in 100 g of toluene and stored in a dark room at room temperature for 48 hours, and then separated into a sol and a gel, which can be measured by Equations 1 and 2 below.

[Equation 1]

Gel content (%) = weight of insoluble matter (gel) / weight of sample * 100

[Equation 2]

Swelling index = weight of swollen gel / weight of gel

The manufacturing method of the conjugated diene-based rubber polymer is not particularly limited in the case of a conventional conjugated diene-based rubber polymer manufacturing method, for example, a conjugated diene-based compound, ion-exchanged water, an emulsifier, a polymerization initiator, an electrolyte, and a molecular weight modifier if necessary. It may be a method of emulsion polymerization after adding the same additive.

The methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound is, for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) One or more selected from acrylic acid decyl ester and (meth) acrylic acid lauryl ester may be used, and methyl methacrylate may be preferably used.

The methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound may be, for example, 20 to 60% by weight, or 25 to 50% by weight, preferably 30 to 40% by weight of the graft copolymer (A), Within the above range, the difference between the refractive index of the graft polymer and the refractive index of the conjugated diene rubbery polymer is small, so that the transparency is excellent.

As an example, the aromatic vinyl compound may be one or more selected from styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene, and styrene may be preferably used.

The aromatic vinyl compound may be, for example, 7 to 30% by weight, or 10 to 20% by weight, preferably 10 to 15% by weight of the graft copolymer (A), and within the range of the thermoplastic resin composition There is an effect of improving transparency.

The vinyl cyan compound may be, for example, a saturated nitrile such as acrylonitrile and one or more selected from unsaturated nitrile such as methacrylonitrile and ethacrylonitrile, preferably acrylonitrile or methacrylonitrile. Acrylonitrile can be used.

The vinyl cyan compound may be, for example, 1 to 10% by weight, or 1 to 7% by weight, preferably 1 to 5% by weight of the graft copolymer (A), and within the range of the thermoplastic resin composition There is an effect of improving the impact strength.

The graft copolymer may be, for example, 0.01 parts by weight or more to less than 0.7 parts by weight, or 0.1 to 0.6 parts by weight, preferably 0.1 to 0.5 parts by weight of the quinone compound during polymerization, and within the above range, It improves stability and has excellent impact strength.

The present invention uses a quinone compound in place of the dodecyl mercaptans modifier that causes the characteristic odor of the thermoplastic resin during polymerization of the graft copolymer, thereby controlling the molecular weight of the graft copolymer and the characteristic odor of the existing thermoplastic resin. Problems can be improved.

The quinone compound is, for example, 1,2-benzoquinone (1,2-Benzoquinone), 1,4-benzoquinone (1,4-Benzoquinone), 1,2-naphthoquinone (1,2-Naphthoquinone), 1,4-Naphthoquinone, 2,3-naphthoquinone, 2,6-Naphthoquinone, 9,10-anthra Quinone (9,10-Anthraquinone), tetrachloro-1,4-benzoquinone, 2-hydroxy-1,4-naphthoquinone (2-hydroxy-1,4-naphthoquinone) ) And 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone) may be one or more selected from the group consisting of , Preferably, 1,4-Naphthoquinone may be used.

The weight average molecular weight of the graft polymer may be, for example, 50,000 to 150,000 g/mol, or 85,000 to 150,000 g/mol, preferably 90,000 to 120,000 g/mol, and the impact strength of the thermoplastic resin composition within this range Is excellent, and the fluidity is improved, so that the processability is excellent.

The weight average molecular weight of the present substrate may be measured using, for example, Gel Permeation Chromatography (GPC).

The transparency of the (A) graft resin of the present disclosure is determined by the refractive index of the rubber used and the refractive index of the polymer to be grafted thereto, and the refractive index of the grafted polymer is controlled by the mixing ratio of the monomers. That is, since the refractive index of the conjugated diene rubber latex and the refractive index of the rest of the components must be matched, the mixing ratio of the monomer is very important. In the end, in order to have transparency, the refractive index of the conjugated diene compound used as a seed or core for grafting and the refractive index of the entire component to be grafted must be similar, and preferably, the refractive index of the conjugated diene compound and the entire grafted component. It is good that the refractive indices match.

In total, the difference between the refractive index of the conjugated diene rubber latex and the refractive index of the entire compound grafted thereto may be, for example, less than 0.01, or less than 0.007, preferably less than 0.005, and there is an effect of excellent transparency within the above range.

In the present description, the polymer refractive index of the monomers included in the thermoplastic transparent resin is 1.518 butadiene, 1.49 methyl methacrylate, 1.592 styrene, and 1.52 acrylonitrile.

The refractive index of the present disclosure may be calculated by Equation 3 below.

[Equation 3]

RI = ∑ Wti * RIi

Wti = weight fraction of each component in the copolymer (%)

RIi = refractive index of the polymer of each component of the copolymer

The graft polymerization method is not particularly limited in the case of a conventional graft polymerization method, for example, as an emulsion graft polymerization method, a (meth)acrylic acid alkyl ester compound, a vinyl cyan compound, and an aromatic vinyl compound are added to the conjugated diene rubber latex. , An emulsifier, a polymerization initiator, and, if necessary, a molecular weight control agent, etc., all or one of them before or after the initiation of polymerization in a batch, or a whole or part of the polymerization process by divided, continuous or drop by drop administration. have.

Examples of emulsifiers used in the emulsion polymerization reaction include alkylaryl sulfonate salts, alkalimethylalkyl sulfate salts, sulfonated alkyl ester salts, alkyl (alkenyl) carboxylates, alkyl (alkenyl) succinates, rosin There are acid salts, oleate salts, paty salts, and toll oil fatty acid salts, and these can be used alone or in combination of two or more.

The graft copolymer in an emulsified state after the emulsion polymerization is, for example, a coagulant using one or two or more salt coagulants such as magnesium sulfate, calcium chloride, and sodium chloride as a coagulant or an acid coagulant such as sulfuric acid, hydrochloric acid, formic acid, and acetic acid. After aggregation, it is dehydrated and dried to form a powder.

(B) Styrene-based copolymer

Styrene-based copolymer (B) is, for example, (b1) 50 to 80% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (b2) 15 to 45% by weight of an aromatic vinyl compound, and (b3) a vinyl cyan compound 1 It may be prepared by copolymerization using 0.01 parts by weight or more to less than 0.7 parts by weight of the (b4) quinone compound based on 100 parts by weight of the sum of the (b1) to (b3) to 10% by weight.

In another example, a styrene-based copolymer (b1) 60 to 75% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (b2) 20 to 30% by weight of an aromatic vinyl compound, and (b3) 2 to 7% by weight of a vinylcyan compound % And 0.1 to 0.5 parts by weight of the (b4) quinone compound based on 100 parts by weight of the total amount of the (b1) to (b3) combined.

In another example, a styrenic copolymer (b1) 67 to 73% by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (b2) 23 to 27% by weight of an aromatic vinyl compound, and (b3) 3 to 6 vinylcyanic compounds It may be prepared by copolymerization using 0.1 to 0.3 parts by weight of the (b4) quinone compound based on weight% and 100 parts by weight of the total amount of the (b1) to (b3).

The manufacturing method of the styrene-based copolymer (B) is not particularly limited if it is a manufacturing method commonly used in this technical field, but as an example, it may be manufactured by suspension polymerization or block polymerization, and the continuous block polymerization method is used in manufacturing cost and heat. It can be excellent in terms of stability and transparency.

The weight average molecular weight of the styrenic copolymer may be, for example, 50,000 to 150,000 g/mol, or 80,000 to 140,000 g/mol, preferably 90,000 to 130,000 g/mol, and the impact of the thermoplastic resin composition within this range It has excellent strength, improved fluidity, and excellent processability.

The present invention uses a quinone compound in place of the dodecyl mercaptans modifier that causes the characteristic odor of the thermoplastic resin during polymerization of the styrenic copolymer, thereby controlling the molecular weight of the graft copolymer and the characteristic odor of the existing thermoplastic resin. Problems can be improved.

The quinone compound is, for example, 1,2-benzoquinone (1,2-Benzoquinone), 1,4-benzoquinone (1,4-Benzoquinone), 1,2-naphthoquinone (1,2-Naphthoquinone), 1,4-Naphthoquinone, 2,3-naphthoquinone, 2,6-Naphthoquinone, 9,10-anthra Quinone (9,10-Anthraquinone), tetrachloro-1,4-benzoquinone, 2-hydroxy-1,4-naphthoquinone (2-hydroxy-1,4-naphthoquinone) ) And 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone) may be one or more selected from the group consisting of , Preferably, 1,4-Naphthoquinone may be used.

The difference between the refractive index of the graft copolymer (A) and the refractive index of the styrenic copolymer (B) may be, for example, less than 0.01, or less than 0.01, less than 0.001 or less than 0.001, and has excellent transparency within the above range.

The thermoplastic resin composition may be included as an example, 20 to 80% by weight of the graft copolymer (A) and 20 to 80% by weight of the styrene-based copolymer (B).

In another example, the thermoplastic resin composition may be included in 25 to 75% by weight of the graft copolymer (A) and 25 to 75% by weight of the styrenic copolymer (B), and has excellent impact strength and transparency within the above range. There is.

In another example, the thermoplastic resin composition may be included in 30 to 60% by weight of the graft copolymer (A) and 40 to 70% by weight of the styrenic copolymer (B), and has excellent impact strength and transparency within the above range. It works.

The method for preparing the thermoplastic resin composition of the present invention includes 20 to 70% by weight of a conjugated diene rubber polymer (a1), 20 to 60% by weight of an alkyl methacrylic ester compound or an alkyl acrylate compound (a2), and an aromatic vinyl compound (a3). 0.01 parts by weight of a quinone compound (a4) based on 7 to 30% by weight, 1 to 10% by weight of a vinyl cyanide compound (a4) and 100 parts by weight of the sum of (a1), (a2), (a3) and (a4) More than or less than 0.7 parts by weight of the rubber-modified graft copolymer (A) and (alkyl methacrylate compound or alkyl acrylate compound (b1) 50 to 80% by weight, aromatic vinyl compound (b2) 15 to 45% by weight) % And vinylcyan compound (b3) 1 to 10% by weight, and the quinone compound (b4) 0.01 parts by weight or more to less than 0.7 parts by weight based on a total of 100 parts by weight of the (b1), (b2) and (b3) It is characterized in that it comprises the step of melt-kneading and extruding the styrenic copolymer (B).

The melt kneading and extrusion may be carried out under 200 to 350 rpm and 180 to 250 ℃ conditions, for example.

The thermoplastic resin composition, for example, further comprises one or more additives selected from the group consisting of anti-drip agents, flame retardants, antibacterial agents, antistatic agents, stabilizers, heat stabilizers, inorganic additives, antioxidants, light stabilizers, pigments, dyes and inorganic fillers can do.

The additive may be included in an amount of 0.01 to 5 parts by weight, 0.01 to 3 parts by weight, or 0.5 to 1 parts by weight based on a total of 100 parts by weight of the graft copolymer (A) and the styrenic copolymer (B), for example, , Within this range, there is an effect of expressing the natural properties of the additive without affecting the physical properties of the thermoplastic transparent resin.

After mixing the graft copolymer (A) and the styrenic copolymer (B), for example, it is uniformly dispersed and extruded using a single screw extruder, a twin screw extruder, or a Banbury mixer, and then the extrudate is passed through a water bath, and this It can be cut to prepare a thermoplastic transparent resin in the form of a pellet.

As an example, the thermoplastic resin composition may have a Haze value (%) of less than 2.0, or less than 1.7, preferably 0.7 to 1.6, measured according to the method of ASTM D1003.

The thermoplastic resin composition may have a flowability (Melt Index) of 5 to 30g/10min, or 5 to 22g/10min, measured under 220°C and 10kg according to ASTM D1238.

The thermoplastic resin composition is for example, according to ASTM D256, the impact strength measured using a 1/4 specimen is 4 to 13kgf·cm/cm ² , or 5 to 12kgf·cm/cm ² Preferably it may be 5.9 to 11.1kgf·cm/cm ² .

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It is natural that such modifications and modifications fall within the appended claims.

[Production Example]

Preparation of the graft copolymer (A) and the styrenic copolymer (B) was performed as follows.

Manufacturing example A-1

50 parts by weight of large-diameter butadiene rubber latex with an average particle diameter of 3000 Å as a seed, 100 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium oleate emulsifier, 0.2 parts by weight of acetic acid, 34 parts by weight of methyl methacrylate, 13 parts by weight of styrene, acrylo Nitrile 3 parts by weight, 1,4-naphthoquinone (Quinoexter QE-2014) 0.3 parts by weight (C) as a molecular weight modifier, sodium pyrophosphate 0.048 parts by weight, dextrose 0.012 parts by weight, ferrous sulfide 0.001 parts by weight, cumene 0.04 parts by weight of hydroperoxide was continuously administered and reacted at 75° C. for 4 hours. After the reaction, the temperature was raised to 78° C., aged for 1 hour, and the reaction was terminated. The obtained rubber-modified graft copolymer had a refractive index of 1.5157, and a weight average molecular weight of 114,125 g/mol.

Then, the latex was agglomerated with an aqueous calcium chloride solution and washed to obtain a powder.

Manufacturing example A-2

In Preparation Example A-1, instead of using 50 parts by weight of a large-diameter butadiene rubber latex having an average particle diameter of 3000 Å, except that 50 parts by weight of a small-diameter butadiene rubber latex having an average particle diameter of 1000 Å was used. It was prepared in the same way. At this time, the obtained rubber-modified graft copolymer had a refractive index of 1.5154 and a weight average molecular weight of 96,164 g/mol.

Manufacturing example A-3

It was prepared in the same manner as in Preparation Example A-1, except that 1.0 part by weight of 1,4-naphthoquinone (Quinoexter QE-2014) was used in Preparation Example A-1.

Manufacturing example A-4

It was prepared in the same manner as in Preparation Example A-2, except that 1.0 part by weight of 1,4-naphthoquinone (Quinoexter QE-2014) was used in Preparation Example A-2.

Manufacturing example A-5

In Preparation Example A-1, 1,4-naphthoquinone (Quinoexter QE-2014) was prepared in the same manner as in Preparation Example A-1, except that 0.3 parts by weight of a dodecyl mercaptan molecular weight modifier was used.

Manufacturing example A-6

In Preparation Example A-2, 1,4-naphthoquinone (Quinoexter QE-2014) was prepared in the same manner as in Preparation Example A-2, except that 0.3 parts by weight of a dodecyl mercaptan molecular weight modifier was used.

Manufacturing example A-7

It was prepared in the same manner as in Preparation Example A-1, except that 0.7 parts by weight of 1,4-naphthoquinone (Quinoexter QE-2014) was used in Preparation Example A-1.

Manufacturing example B-1

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 (C) of 1,4-naphthoquinone (Quinoexter QE-2014) as a molecular weight modifier The mixed raw materials were continuously added to the reaction tank so that the average reaction time was 3 hours, and the reaction temperature was maintained at 148°C. The polymerization liquid discharged from the reaction tank was heated in a preheating tank, unreacted monomers were volatilized in the volatilization tank, and the temperature of the polymer was maintained at 210°C, and the copolymer resin was processed into pellets using a polymer transfer pump extruder. The weight average molecular weight of the prepared copolymer resin was 120,000 g/mol, and the final refractive index of the obtained pellet was 1.5153.

Manufacturing example B-2

It was prepared in the same manner as in Preparation Example B-1, except that the weight average molecular weight of the copolymer resin prepared in Preparation Example B-1 was 40,000 g/mol.

[Example]

Example 1 to 4 and Comparative example 1 to 8

The graft copolymer (A) and the styrenic copolymer (B) prepared in the above Preparation Example were mixed as in [Table 1], and 1 part by weight of a lubricant and 0.4 parts by weight of an antioxidant were added to the cylinder temperature of 220°C. Was prepared in the form of pellets using a twin-screw extrusion kneader. A specimen was prepared by injection into the pellets, and the physical properties were measured by the following method, and are shown in Table 2.

[Test Example]

The pellets prepared in Examples and Comparative Examples were injected to measure transmittance, transparency, odorlessness, impact strength and fluidity in the following manner, and the results are shown in Table 2 below.

-Transmittance (Tt): measured according to ASTM D1003.

-Transparency (Haze): Haze value (%) was measured according to ASTM D1003.

-Odorless: 10 panelists were evaluated by direct sense of smell, ◎ for odorless, X for odor, and sensory evaluation.

-Notched Izod Impact Strength (kgf·cm/cm ² ): According to ASTM D256, a 1/4” specimen was used to measure the Notched Izod Impact Strength.

-Flowability (Melt Index) (g/10min): In accordance with ASTM D-1238, the flowability of the extruded pellets at 220° C. and 10 kg was measured.

division Graft Copolymer (A) Copolymer (B) A-1 A-2 A-3 A-4 A-5 A-6 A-7 B-1 B-2 Example 1 30 - - - - - - 70 - Example 2 - 60 - - - - - 40 - Example 3 20 10 - - - - - 70 - Example 4 10 50 - - - - - 40 - Comparative Example 1 - - 30 - - - - 70 - Comparative Example 2 - - - 60 - - - 40 - Comparative Example 3 - - - - 30 - - 70 - Comparative Example 4 - - - - - 60 - 40 - Comparative Example 5 - - - - - - 30 70 - Comparative Example 6 - - - - - - 60 40 - Comparative Example 7 30 - - - - - - - 70 Comparative Example 8 70 - - - - - - - 40

Tt Haze smell Impact strength liquidity Example 1 90.5 1.6 ◎ 11.1 18.4 Example 2 91.5 0.7 ◎ 5.9 5.7 Example 3 90.7 1.5 ◎ 10.7 21.6 Example 4 90.1 1.0 ◎ 8.09 8.41 Comparative Example 1 91.2 1.3 ◎ 5.74 63.11 Comparative Example 2 93.0 0.8 ◎ 2.6 28.4 Comparative Example 3 90.5 1.7 X 11.6 18.9 Comparative Example 4 91.6 0.7 X 6.0 5.4 Comparative Example 5 91.3 1.3 ◎ 5.92 55.0 Comparative Example 6 92.8 0.8 ◎ 2.8 26.9 Comparative Example 7 90.1 1.6 ◎ 3.8 69.8 Comparative Example 8 91.4 0.8 ◎ 2.5 31.0

As shown in Table 2, it was confirmed that Examples 1 to 4 carried out according to the present invention maintained an impact strength equal to or higher than the same, had excellent transparency and workability, and had no odor.

On the other hand, in the case of Comparative Example 1, Comparative Example 2, Comparative Example 5, Comparative Example 6, Comparative Example 7 and Comparative Example 8, where an excessive amount of the molecular weight modifier was used, it was confirmed that the impact strength was decreased and the fluidity was increased.

In addition, in the case of Comparative Examples 3 and 4, the use of dodecyl mercaptan in the polymerization process, compared to Examples 1 to 4, it was confirmed that the smell peculiar to the resin remains.

Claims (13)

(A) (a1) 20 to 70 parts by weight of a conjugated diene rubber polymer (a2) 20 to 60 parts by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (a3) 7 to 30 parts by weight of an aromatic vinyl compound, ( a4) Copolymerized graph including (a5) 0.1 parts by weight to 0.5 parts by weight of 1,4-naphthoquinone based on 1 to 10 parts by weight of vinylcyan compound and 100 parts by weight of the total amount of (a1) to (a4) 30 to 60% by weight of the copolymer; And
(B) (b1) 50 to 80 parts by weight of an alkyl methacrylate compound or an alkyl acrylate compound, (b2) 15 to 45 parts by weight of an aromatic vinyl compound, and (b3) 1 to 10 parts by weight of a vinyl cyan compound and the above (b1) ) To (b3), based on 100 parts by weight of the total amount of (b4) 1,4-naphthoquinone 40 to 70% by weight of a copolymerized styrenic copolymer including 0.1 to 0.5 parts by weight; Including,
The flowability measured under 220° C. and 10 kg according to ASTM D1238 is 5 to 22 g/min,
The styrenic copolymer (B) has a weight average molecular weight of 90,000 to 130,000 g/mol.
Thermoplastic resin composition. The method of claim 1,
Characterized in that the average particle diameter of the conjugated diene-based rubber polymer is 600 to 5,000Å
Thermoplastic resin composition. The method of claim 1,
The graft copolymer (A) is a graft copolymer comprising a conjugated diene-based rubber polymer having an average particle diameter of 2,600 to 5,000 Å and a graft copolymer comprising a conjugated diene-based rubber polymer having an average particle diameter of 600 to 1,500 Å. Characterized in that it contains at least one of
Thermoplastic resin composition. The method of claim 1,
The conjugated diene-based rubber polymer is characterized in that at least one selected from the group consisting of a butadiene polymer, a butadiene-styrene copolymer (SBR), and a butadiene-acrylonitrile copolymer (NBR).
Thermoplastic resin composition. The method of claim 1,
The graft copolymer (A) has a weight average molecular weight of 50,000 to 150,000 g/mol.
Thermoplastic resin composition. delete The method of claim 1,
Characterized in that the difference in refractive index between the graft copolymer (A) and the styrene-based copolymer (B) is less than 0.01
Thermoplastic resin composition. The method of claim 1,
The methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound is (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 (meth) acrylic acid lauryl ester, characterized in that at least one selected from the group consisting of
Thermoplastic resin composition. The method of claim 1,
The aromatic vinyl compound is characterized in that at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene.
Thermoplastic resin composition. The method of claim 1,
The vinyl cyan compound is characterized in that at least one selected from the group consisting of acrylonitrile and methacrylonitrile
Thermoplastic resin composition. delete The method of claim 1,
The thermoplastic resin composition is characterized in that the haze value measured by ASTM D1003 is 0.5 to 2.0
Thermoplastic resin composition. Conjugated diene rubber polymer (a1) 20 to 70 parts by weight, methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound (a2) 20 to 60 parts by weight, aromatic vinyl compound (a3) 7 to 30 parts by weight, vinyl cyan compound ( a4) 1 to 10 parts by weight and 0.1 to 0.5 parts by weight of 1,4-naphthoquinone (a5) based on a total of 100 parts by weight of (a1), (a2), (a3) and (a4) Thereby preparing a rubber-modified graft copolymer (A); And
50 to 80 parts by weight of an alkyl methacrylate compound or an alkyl acrylate compound (b1), 15 to 45 parts by weight of an aromatic vinyl compound (b2) and 1 to 10 parts by weight of a vinyl cyan compound (b3), and the above (b1), (b2) and (b3) adding 0.1 parts by weight to 0.5 parts by weight of 1,4-naphthoquinone (b4) based on 100 parts by weight of the total to prepare a styrenic copolymer (B); Including,
The flowability measured under 220° C. and 10 kg according to ASTM D1238 is 5 to 22 g/min,
The styrenic copolymer (B) has a weight average molecular weight of 90,000 to 130,000 g/mol.
Method for producing a thermoplastic resin composition.