KR101151108B1 - Thermoplastic resin and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition having excellent colorability and mechanical properties, and to a method for producing the same. More particularly, in the preparation of a rubbery polymer latex applied to an ABS resin, a seed having an average particle diameter of 500 to 1000 mm 3 and an average particle diameter To prepare a large-diameter rubber polymer having a high polymerization conversion rate of more than 95%, including a core of 2000 ~ 5000Å, 50 to 80% by weight of the large diameter rubber latex monomer mixture 20 to 50 weight percent of a monomer mixture composed of an aromatic vinyl compound and a vinyl cyan compound It relates to a method for producing a graft copolymer, characterized in that the graft copolymer is prepared by adding%. According to the present invention, not only can the graft ratio on the surface of the rubber polymer be maximized when the graft polymer is manufactured, but also the colorability, gloss, impact strength, and workability of the thermoplastic resin can be significantly improved.

ABS resin composition, rubbery polymer, seed, core, polymerization conversion rate, graft rate, conjugated diene compound, coloring property, impact resistance, tensile property, processability

Description

Thermoplastic resin and its manufacturing method {THERMOPLASTIC RESIN AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a thermoplastic resin composition having excellent colorability and mechanical properties, and to a method for producing the same. More particularly, in the preparation of a rubbery polymer latex applied to an ABS resin, a seed having an average particle diameter of 500 to 1000 mm 3 and an average particle diameter To prepare a large-diameter rubber polymer having a high polymerization conversion rate of more than 95%, including a core of 2000 ~ 5000Å, 50 to 80% by weight of the large diameter rubber latex monomer mixture 20 to 50 weight percent of a monomer mixture composed of an aromatic vinyl compound and a vinyl cyan compound The present invention relates to a method for preparing a graft copolymer, wherein the graft copolymer is prepared by continuously adding the monomer mixture in an emulsified state.

In general, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resins have relatively good physical properties such as impact resistance, mechanical strength, moldability, glossiness, and are widely used in electrical, electronic parts, office equipment, and automobile parts. In particular, since these products require a variety of colors to meet the needs of the consumer, the colorability becomes more important than anything else.

Accordingly, various methods for improving colorability of ABS resins have been proposed. The first method is to reduce the amount of graft ABS resin in the ABS resin by mixing rubbers with large rubber particle size. The second method is to minimize the use of additives such as emulsifiers in the emulsion graft polymerization. In order to minimize the difference in refractive index between the silver rubber graft polymer and the graft polymer, it is possible to increase the refractive index of the rubber polymer by using the monomer of the graft copolymer in the manufacture of the rubber polymer or to use the monomer having the low refractive index in the manufacture of the graft copolymer. This method minimizes the difference between the rubber polymer and the refractive index.

However, the first method may generate a large amount of coagulum during graft copolymerization, and the second method is not easy to apply due to inadequate conditions in the post-treatment process. The third method is not only improper in terms of impact resistance when the monomer of the graft copolymer is used in the manufacture of the rubber polymer, but also in the case of using the monomer which decreases the refractive index in the manufacture of the graft copolymer, the amount is not suitable for improving the colorability. There is this.

On the other hand, in the prior patent (Publication No. 2004-11905), the glass transition temperature (Tg) is at least 0 ℃, the inner layer having an average particle diameter of 2000 kPa, and the glass transition temperature is up to -20 ℃, the average particle diameter is 2500 ~ 5000 ℃ A method of preparing a rubber polymer including an outer layer to improve colorability and impact resistance, tensile properties, and processability of a resin has been proposed. However, when using the inner layer of 2000Å maximum, the rubber polymer having a conversion rate of 95% or more was not obtained during the polymerization time of 20 hours, and there was a problem that the colorability improvement of the ABS graft copolymer was not large.

In order to solve the problems of the prior art as described above, the present invention comprises a seed having an average particle diameter of 500 ~ 1000Å and a core having an average particle diameter of 2000 ~ 5000Å and producing a large diameter rubber latex having an average polymerization conversion of 95% or more graft air It is an object of the present invention to provide a thermoplastic resin which is remarkably improved in colorability and mechanical properties by preparing a copolymer and using the same for producing an ABS thermoplastic resin.

These 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

a) preparing a seed having an average particle diameter of 500 to 1000 mm by batch administration of a mixture containing 100 parts by weight of an ethylenically unsaturated monomer and 0.1 to 10 parts by weight of a crosslinking agent in a reactor for 1 to 3 hours at a temperature of 60 to 90 ° C. ; And

In the reactor, in the presence of 0.1 to 3 parts by weight of the seed, 60 to 80 parts by weight of 100 parts by weight of the conjugated diene monomer, 1 to 3 parts by weight of an emulsifier, 0.1 to 3 parts by weight of a polymerization initiator, and 0.1 to 1 parts by weight of a molecular weight regulator. After the batch administration of the mixture and emulsion polymerization for 6 to 15 hours at 65 ~ 75 ℃,

20 to 40 parts by weight of the remaining conjugated diene monomer, 0.05 to 1 part by weight of the molecular weight regulator and 0.1 to 2 parts by weight of the seed are collectively added and polymerized at a temperature of 75 to 90 ° C. for 10 to 20 hours to obtain a core having an average particle diameter of 2000 to 5000 mm 3. Preparing to prepare a rubber polymer; And

b) graft copolymerizing a monomer mixture composed of an aromatic vinyl compound and a vinyl cyan compound in the rubber polymer prepared in step a).

Provided are methods for preparing the graft polymer.

In addition,

a) seeds having an average particle diameter of 500 to 1000 mm 3; And a graft polymer formed by graft polymerizing a monomer mixture comprising an aromatic vinyl compound and a vinyl cyan compound to a rubber polymer comprising a core having an average particle diameter of 2000 to 5000 mm 3; And

b) styrene-acrylonitrile (SAN) resins

It provides a resin composition.

As described above, according to the present invention, the monomer used in the graft polymerization is prevented from penetrating into the rubber polymer to maximize the graft ratio on the surface of the rubber polymer, thereby increasing the rubber content and improving thermoplastic efficiency. A resin can be obtained. In addition, the thermoplastic resin prepared according to the present invention has excellent colorability and mechanical properties.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the present invention, in preparing a graft copolymer applied to a thermoplastic resin, a large diameter rubber polymer including a seed having an average particle diameter of 500 to 1000 mm 3 and a core having an average particle diameter of 2000 to 5000 mm 3 and having a high polymerization conversion ratio of 95% or more on average To prepare a graft copolymer by adding 50 to 80% by weight of the monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound to 50 to 80% by weight of the large-diameter rubber latex.

In addition, when manufacturing the ABS resin containing the prepared ABS graft copolymer, it is possible to significantly improve the colorability, mechanical properties and the like.

The rubber polymer latex of the present invention can be prepared by the following method.

a) seed manufacturing

The seed is in the reactor i) 100 parts by weight of ethylenically unsaturated monomer, ii) 0.1 to 10 parts by weight of crosslinking agent, i) 4.5 to 10 parts by weight of emulsifier, i) 0.01 to 3 parts by weight of polymerization initiator and v) 300 to 450 weight of ion-exchanged water. It can be prepared by a method of batch administration of the part to react for 1 to 3 hours at a temperature of 60 ~ 90 ℃.

As the ethylenically unsaturated monomer, an aromatic vinyl compound, a vinyl cyan compound, an acrylic acid ester, and a methacrylic acid ester may be used alone or in combination of two or more thereof.

The crosslinking agent may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of an ethylenically unsaturated monomer, and examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and 1,3-butylene glycol dimethacrylate. , 1.4-butylene glycol dimethacrylate, aryl methacrylate, divinylbenzene and the like can be used.

The emulsifier may be used in an amount of 4.5 to 10 parts by weight based on 100 parts by weight of an ethylenically unsaturated monomer, and examples thereof include alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, or alkali salts of rosin acid. Etc.

The polymerization initiator may be used in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of an ethylenically unsaturated monomer, and examples thereof include a water-soluble persulfate, a peroxy compound, an oxidation-reduction system, and the like. Specifically, water-soluble persulfates, such as sodium or potassium persulfate; Fat-soluble polymerization initiators such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl peroxide; Mixtures of water-soluble radical initiators and oil-soluble radical initiators.

It is preferable that the average particle diameter of the emulsion-polymerized seed under the above conditions is 500 ~ 1000Å.

b) core production and large diameter rubber polymer production

I) in the presence of 0.1 to 3 parts by weight of the seed, ii) 60 to 80 parts by weight of 100 parts by weight of the conjugated diene monomer i) 1 to 3 parts by weight of emulsifier v) 0.1 to 3 parts by weight of polymerization initiator v) 0.1 to 3 parts by weight of molecular weight regulator 1 part by weight iv) 0.1 to 3 parts by weight of electrolyte iv) 40 to 80 parts by weight of ion-exchanged water in a batch to perform emulsion polymerization at 65 to 75 ° C. for 6 to 15 hours; And

20 to 40 parts by weight of the remaining conjugated diene monomer iii) to the reactant; And iii) 0.05 to 1 parts by weight of a molecular weight regulator; Iii) 0.1-2 parts by weight of the seed in a batch may be prepared by a method comprising the step of emulsion polymerization at a temperature of 75 ~ 90 ℃ for 10 to 20 hours.

As the conjugated diene monomer, 1,3-butadiene, isoprene, chloroprene, pyrrylene, or comonomers thereof may be used.

As the monomer copolymerizable with the conjugated diene monomer, an aromatic vinyl compound such as styrene or α-methylstyrene, or a vinyl cyan compound such as acrylonitrile may be used, and the content thereof may be used within 20 parts by weight of the total monomer mixture. desirable.

The emulsifier and the polymerization initiator may be the same as those used in the production of the seed.

As the molecular weight regulator, mercaptans are mainly used, and tertiary dodecyl mercaptan is particularly preferable.

In the present invention, it is preferable that the monomer is emulsion-polymerized by batch administration of a part of the core, and then the emulsion is polymerized by batch or continuous administration of the remainder to the reaction product. When the entire amount of the monomer is administered in a batch, a phenomenon in which a perfect core is not formed on the surface of the seed, that is, a phenomenon in which the average particle diameter of the rubber polymer is much smaller than the desired average particle diameter occurs.

The average particle diameter of the rubber polymer including the seed and the core prepared according to the present invention is preferably 2000 to 5000 mm 3.

c) graft copolymer preparation

~) 50 to 80% by weight of a large diameter rubber latex is added to the nitrogen-substituted polymerization reactor, and ii) 20 to 50% by weight of a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound is prepared to prepare a graft copolymer. The monomer mixture is graft copolymerized by continuous dosing in an emulsified state. In this case, it is preferable to prepare by graft copolymerization by adding 0.2 to 2 parts by weight of the emulsifier, i) 0.1 to 0.5 parts by weight of the molecular weight modifier, and 0.1 to 0.5 parts by weight of the polymerization initiator.

At this time, the polymerization temperature is suitable 45 ~ 80 ℃, the polymerization time is suitable 3 to 6 hours.

Styrene, α-methylstyrene, vinyl toluene, etc. may be used as the aromatic vinyl compound, and acrylonitrile or methacrylonitrile may be used as the vinyl cyan compound.

The emulsifiers include alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acids, and the like, and these may be used alone or as mixtures of two or more thereof. It is very important to select an emulsifier to secure the latex stability when preparing a graft copolymer having a high rubber content.

As the molecular weight regulator, mercaptans are mainly used, and tertiary dodecyl mercaptan is particularly preferable.

The polymerization initiators include peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, persulfate, sodium formaldehyde succilate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, Oxidation-reduction catalyst systems made of a mixture with a reducing agent such as sodium sulfite and the like can be used.

The polymerization conversion rate of the latex obtained after completion of the polymerization is 98% or more.

Stability of the graft copolymer latex prepared above was determined by measuring the solidified solid content (%) as shown in Equation 1 below.

Equation 1

Solid coagulation (%) = {weight of coagulum produced in the reactor (g) / weight of total rubber and monomers (g)} x 100

When the solidified solid content is 0.7% or more, latex stability is extremely low and a large amount of coagulated material makes it difficult to obtain a graft polymer suitable for the present invention.

In addition, the graft ratio of the said graft polymer is measured as follows. The graft polymer latex is coagulated, washed, and dried to obtain a powder form, 2 g of this powder is placed in 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 ungrafted portion, which is dried and weighed. From these weights, the graft ratio is calculated according to the following equation.

Equation 2

Graft Rate (%) = Weight of Grafted Monomer (g) / Rubber Weight (g) x 100

If the graft ratio is 25% or less, glossiness is lowered, which is not preferable.

In addition, an antioxidant and a stabilizer may be administered to the ABS graft polymer having a multilayer structure prepared as described above, aggregated into an aqueous sulfuric acid solution at a temperature of 90 ° C. or higher, and then dehydrated and dried to obtain a powdered ABS graft polymer. .

The rubber polymer including the seed and the core of the present invention has the effect of maximizing the graft rate on the surface of the rubber polymer by inhibiting the penetration of the monomer used in the graft polymerization into the rubber polymer when manufacturing the ABS graft polymer having a multilayer structure. There is.

d) ABS resin composition

The present invention provides an ABS resin composition prepared by mixing the prepared ABS graft copolymer with a styrene-acrylonitrile (SAN) resin.

It is preferable that the graft polymer is included in an amount of 20 to 50% by weight, and the SAN resin is included in an amount of 50 to 80% by weight based on 100 parts by weight of the ABS resin composition.

The resin composition prepared in this way has the effect which is excellent in coloring property and a mechanical characteristic.

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

[Example]

Examples 1-2, Comparative Example 1 <Preparation of seeds>

Example 1

300 parts by weight of ion-exchanged water, 100 parts by weight of styrene as an ethylenically unsaturated monomer, 3 parts by weight of aryl methacrylate as a crosslinking agent, 6 parts by weight of fatty acid soap as an emulsifier, potassium persulfate as an initiator in a nitrogen-substituted polymerization reactor (autoclave) K ₂ S ₂ O ₈ ) 0.1 parts by weight of the batch and polymerization was carried out for 2 hours at a reaction temperature of 75 ℃ to prepare a seed, the conversion was 97%. The glass transition temperature of the prepared seeds and the average particle diameter of the seeds are shown in Table 1 below.

Example 2

Except that 100 parts by weight of styrene instead of 100 parts by weight of styrene and 25 parts by weight of acrylonitrile was prepared in the same manner as in Example 1 to prepare a seed, the glass transition temperature of the prepared seed and The average particle diameter of the seeds is shown in Table 1 below.

Comparative Example 1

Except for using 4 parts by weight instead of 6 parts by weight of fatty acid soap in Example 1, the seed was prepared in the same manner as in Example 1, the glass transition temperature and the average particle diameter of the seed of the prepared seed 1 is shown.

The glass transition temperature and the particle diameter were measured using the seeds prepared in Examples 1 and 2 and Comparative Example 1 as described below, and the results are shown in Table 1 below.

A) Glass transition temperature (DSC)-11 mg of the powder obtained by solidifying the prepared seed with sulfuric acid was heated to 150 ° C on DSC, cooled to -40 ° C to 150 ° C / min to remove the thermal history, and then to 10 ° C. The glass transition temperature was measured by raising the temperature to / min.

B) Particle size and particle size distribution—Measured by using Nicomp 370HPL by dynamic laser light scattering method.

Table 1 Preparation of Seeds

division Example 1 Example 2 Comparative Example 1 Ion exchange water 300 300 300 Monomer Styrene 100 75 100 Acrylonitrile - 25 - Crosslinking agent Aryl methacrylate 3 3 3 Emulsifier Fatty acid soap 6 6 4 Polymerization initiator Potassium persulfate 0.1 0.1 0.1 Glass transition temperature (Tg) (℃) 105 107 105 Average particle size of seed 700 650 1200

As described in Table 1, according to the present invention, it can be seen that the average particle diameter of the prepared seeds falls within the range of 500 to 1000 mm 3.

Examples 3-4, Comparative Examples 2-5 <Core and Rubber Polymer Preparation>

Example 3

1.5 parts by weight of the seed prepared in Example 1 in a nitrogen-substituted polymerization reactor, 73.5 parts by weight of 1,3-butadiene as a conjugated diene monomer, 1.6 parts by weight of fatty acid soap, 0.3 parts by weight of potassium persulfate as a polymerization initiator, molecular weight control 0.2 parts by weight of zero tertiary dodecyl mercaptan, 1.2 parts by weight of sodium carbonate and 60 parts by weight of ion-exchanged water as an electrolyte were emulsified and polymerized at 70 ° C. for 10 hours. Thereafter, 1 part by weight of the seed, 25 parts by weight of 1,3-butadiene monomer, and 0.1 parts by weight of the molecular weight modifier tertiary dodecylmercaptan were collectively administered and reacted at a temperature of 80 ° C. for 10 hours. A polymer was prepared, in which the polymerization conversion was 95%, the average particle diameter of the rubber polymer was 3100 mm 3, and the gel content was 86%.

1 shows the distribution of seeds in the large diameter rubber latex of Example 3 through the TEM image.

Example 4

A rubber polymer was prepared in the same manner as in Example 3, except that 1.5 parts by weight of the seed of Example 2 was used instead of 1.5 parts by weight of the seed of Example 1, and polymerization of the prepared rubber polymer was performed. Conversion rate, average particle diameter and gel content are shown in Table 2 below.

Comparative Example 2

In Example 3, 5 parts by weight of the seed of Example 1, 55 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene, and no seed in the second step, 1,3-butadiene 20 Except for administering parts by weight, a rubber polymer was prepared in the same manner as in Example 3, and the polymerization conversion rate, average particle size, and gel content of the rubber polymer were shown in Table 2 below.

Comparative Example 3

A rubber polymer was prepared in the same manner as in Comparative Example 2, except that 1.5 parts by weight of the seed 5 of Example 1 was used instead of 1.5 parts by weight of the seed of Example 1, to prepare a rubber polymer. Polymerization conversion, average particle diameter and gel content are shown in Table 2 below.

Comparative Example 4

In Example 3, 10 parts by weight of the seed of Comparative Example 1 was used instead of 1.5 parts by weight of the seed of Example 1, 55 parts by weight of ion-exchanged water and 70 parts by weight of 1,3-butadiene were administered, and the first step was a batch. 12 hours after the start of the administration reaction, 20 parts by weight of 1,3-butadiene was administered, except that the seed was not administered in the second step, the same procedure as in Example 3 was carried out to prepare a rubber polymer. The polymerization conversion, average particle diameter, and gel content of are shown in Table 2 below.

Comparative Example 5

In Example 3, 85 parts by weight of 1,3-butadiene was used without administering a seed in the first step, and 15 parts by weight of 1,3-butadiene was administered 12 hours after the start of the first batch reaction. Except not administering a seed, a rubber polymer was prepared in the same manner as in Example 3, and the polymerization conversion rate, average particle diameter, and gel content of the rubber polymer prepared are shown in Table 2 below.

TABLE 2 Core and Rubber Polymer Preparation

division Example 3 Example 4 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Stage 1



Seed 1.5 parts by weight of the seed of Example 1 1.5 parts by weight of the seed of Example 2 5 parts by weight of the seed of Example 1 5 parts by weight of the seed of Example 2 10 parts by weight of seed of Comparative Example 1 ? Ion exchange water 60 60 55 55 55 60 1,3-butadiene 73.5 73.5 75 75 70 85 Fatty acid soap 1.6 1.6 1.6 1.6 1.6 1.6 Dosing method 10 hours after the start of the batch administration reaction 10 hours after the start of the batch administration reaction 10 hours after the start of the batch administration reaction 10 hours after the start of the batch administration reaction 12 hours after the start of the batch administration reaction 12 hours after the start of the batch administration reaction Tier 2
Seed One One - - - - 1,3-butadiene 25 25 20 20 20 15 Polymerization Conversion Rate (%) 95.0 95.5 96 96.5 90.0 87.5 Average particle size 3100 3070 2700 2650 3200 3050 Gel content (%) 86 87 90 92 82 78

Looking at the Table 2, it can be seen that the polymerization conversion rate is higher than in Comparative Example 5, in which the seed was administered in one step and two steps in forming the core, the seed was not added only in one step. In addition, when the seed is added only in one step, it can be seen that the average particle diameter is smaller than the case where the seed is added by dividing into one and two steps.

When the seeds of Examples 1 and 2 were used within the ranges described in the present invention, it was found that the polymerization conversion was higher than that of the seeds of Comparative Example 1, and the gel content was also good.

The analysis method of the rubber latex is as follows.

A) gel content

The rubber latex was coagulated with dilute acid or metal salt and washed, dried in a vacuum oven at 60 ° C. for 24 hours, and the resulting rubber mass was chopped with scissors, and then 1 g of rubber fragments was put in 100 g of toluene for 48 hours. After storage in the dark, it is separated into sol and gel and the gel content is measured by the following formula.

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

B) particle size and particle size distribution

It was measured using a Nicomp 370HPL instrument (Nicomp, USA) by the dynamic laser light scattering method.

Examples 5-6, Comparative Examples 6-9 <Preparation of ABS Graft Polymer>

Example 5

60 parts by weight of the large-diameter rubber latex obtained in Example 3 was added to the polymerization reactor, and 10 parts by weight of acrylonitrile, 30 parts by weight of styrene, 10 parts by weight of ion-exchanged water, and 0.12 parts by weight of t-butyl hydroperoxide in a separate mixing device. , 1 part by weight of fatty acid soap, 0.3 parts by weight of tertiary dodecyl mercaptan was added to the polymerization reactor continuously at 70 ℃ for 3 hours. At this time, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrolate, and 0.002 parts by weight of ferrous sulfate are continuously added together.

After the addition of the monomer emulsion, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrolate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the reactor, and then the temperature was 80 ° C. The temperature was raised over 1 hour and then the reaction was terminated.

The polymerization conversion rate of the obtained graft polymer was 98%, the graft rate was 42%, and the resulting coagulant content was about 0.2%.

Example 6

A graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the large-diameter rubbery latex obtained in Example 4 was used instead of the large-diameter rubbery latex obtained in Example 3 in Example 5. The polymerization conversion rate of the graft copolymer was 98.1%, the graft rate was 43%, and the resultant coagulant content was 0.25%.

Comparative Example 6

A graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the large diameter rubber latex obtained in Comparative Example 2 was used instead of the large diameter rubber latex obtained in Example 3 in Example 5. The polymerization conversion rate of the graft copolymer was 98.5%, the graft rate was 44%, and the product coagulant content was 0.40%.

Comparative Example 7

A graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the large diameter rubber latex obtained in Comparative Example 3 was used instead of the large diameter rubber latex obtained in Example 3 in Example 5. The polymerization conversion rate of the graft copolymer was 98.6%, the graft rate was 45%, and the resultant coagulant content was 0.42%.

Comparative Example 8

A graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the large-diameter rubbery latex obtained in Comparative Example 4 was used instead of the large-diameter rubbery latex obtained in Example 3 in Example 5. The polymerization conversion rate of the graft copolymer was 97.2%, the graft rate was 36%, and the resultant coagulant content was 0.45%.

Comparative Example 9

A graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the large diameter rubber latex obtained in Comparative Example 5 was used instead of the large diameter rubber latex obtained in Example 3 to Example 5. The polymerization conversion rate of the graft copolymer was 97.5%, the graft rate was 35%, and the product coagulant content was 0.41%.

Example 7

70 parts by weight of the large-diameter rubber latex obtained in Example 3 was added to the polymerization reactor, and 9 parts by weight of acrylonitrile, 30 parts by weight of styrene, 10 parts by weight of ion-exchanged water, and 0.12 parts by weight of t-butyl hydroperoxide in a separate mixing device. , 1 part by weight of fatty acid soap, 0.3 parts by weight of tertiary dodecyl mercaptan was added to the polymerization reactor continuously at 70 ℃ for 3 hours. At this time, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrolate, and 0.002 parts by weight of ferrous sulfate are continuously added together.

After the addition of the monomer emulsion, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrolate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide were collectively added to the reactor, and then the temperature was 80 ° C. The temperature was raised over 1 hour until the reaction was terminated.

The polymerization conversion rate of the obtained graft polymer was 98.3%, the graft rate was 43%, and the product coagulant content was 0.33%.

Example 8

The same procedure as in Example 7 was carried out except that 70 parts by weight of the large-diameter rubber latex obtained in Example 4 was added instead of the large-diameter rubber latex obtained in Example 3.

The polymerization conversion rate of the prepared graft copolymer was 98.5%, the graft rate was 43%, the product coagulant content was 0.29%.

Comparative Example 10

The same procedure as in Example 7 was carried out except that 70 parts by weight of the large-diameter rubbery latex obtained in Comparative Example 5 was added instead of the large-diameter rubbery latex obtained in Example 3.

The polymerization conversion rate of the prepared graft copolymer was 97.6%, the graft rate was 37%, and the product coagulant content was 0.35%.

Examples 9-12, Comparative Examples 11-15 <ABS resin manufacture>

Example 9

The graft copolymer latex obtained in Example 5 was coagulated by washing with an aqueous sulfuric acid solution, washed, and then made into a powder, and 27.5 parts by weight of the powder and SAN resin (LG chemical product, product name: 92HR) prepared to have a rubber content of 16.5%. ) After mixing 72.5 parts by weight, adjust the amount of red pigment to have similar L, a, and b values in order to determine the degree of colorability improvement, put it into the mixer, mix it, and pelletize it using an extruder, and then use an injection machine. The physical properties of the specimens were obtained, and the physical properties thereof were shown in Table 3 below.

Example 10

Except for using the graft copolymer latex obtained in Example 6 instead of the graft copolymer latex obtained in Example 5 to Example 9 was carried out in the same manner as in Example 9, the physical properties measured for this Is shown in Table 3 below.

Comparative Example 11

Except for using the graft copolymer latex obtained in Comparative Example 6 instead of the graft copolymer latex obtained in Example 9 to Example 9 was carried out in the same manner as in Example 9, the physical properties measured for this Is shown in Table 4 below.

Comparative Example 12

Example 9 was carried out in the same manner as in Example 9, except that the graft copolymer latex obtained in Comparative Example 7 was used instead of the graft copolymer latex obtained in Example 5, and the physical properties measured for this Is shown in Table 4 below.

Comparative Example 13

In Example 9, except that the graft copolymer latex obtained in Comparative Example 8 was used instead of the graft copolymer latex obtained in Example 5, and was carried out in the same manner as in Example 9, the physical properties measured for this Is shown in Table 4 below.

Comparative Example 14

In Example 9, except that the graft copolymer latex obtained in Comparative Example 9 was used instead of the graft copolymer latex obtained in Example 5, it was carried out in the same manner as in Example 9, the physical properties measurement for this The values are shown in Table 4 below.

Example 11

In order to contain the same rubber content (16.5%), 23.57 parts by weight of powder prepared in Example 7, SAN resin (LG Chemical, product name: 92HR) Except for adding 76.43 parts by weight, it was carried out in the same manner as in Example 9, the physical properties measured for this are shown in Table 3 below.

Example 12

In order to contain the same rubber content (16.5%), 23.57 parts by weight of the powder prepared in Example 8, 76.43 parts by weight of SAN resin (LG Chemicals, product name: 92HR) was added, except that It was carried out by the method, the physical properties for this is shown in Table 3 below.

Comparative Example 15

The same method as in Example 9, except that 23.57 parts by weight of the powder prepared in Comparative Example 10 and 76.43 parts by weight of the SAN resin (LG Chemicals, product name: 92HR) were added to contain the same rubber content (16.5%). It carried out as, the physical properties measured for this is shown in Table 4 below.

The physical properties of the ABS specimens prepared in Examples 9 to 12 and Comparative Examples 11 to 15 were measured in the following manner.

A) Izod impact strength-The thickness of the specimen was measured in accordance with ASTM 256 method with 1 / 4˝.

B) Melt Flow Index (MI)-measured by ASTM D1238 under the condition of 220 ° C / 10 kg.

C) Tensile strength-measured by ASTM D638 method.

D) Surface gloss-measured by ASTM D528 method at 45˚ angle.

I) Colorability-The color level (SUGA color computer) was used to measure the degree of coloring based on the red color sensitive to the human eye and expressed as L, a value. At this time, it was assumed that the lower the L value and the higher the a value, the better the red value was. Coloring experiments were performed to vary the amounts of colorants to have similar values.

TABLE 3 ABS-based resin composition production

division Example 9 Example 10 Example 11 Example 12 ABS graft latex Example 5
Graft latex Example 6
Graft latex Example 7
Graft latex Example 8
Graft latex % Conversion 97.9 98.1 98.3 98.5 Graft Rate (%) 42 43 43 43 Izod impact strength
(kg? cm / cm) 32 33 31.5 32 Fluidity (g / 10min) 22 21 21 20.5 Tensile Strength (㎏ / ㎠) 445 443 447 445 Surface gloss (%) 101 100 101.5 101 Colorant Usage 0.06 0.06 0.06 0.06 Coloring L 33 33.2 33.4 33.5 Coloring a 43.5 43.8 43.8 44

TABLE 4 ABS resin composition

division Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 ABS graft
Latex Of Comparative Example 6
Graft
Latex Of Comparative Example 7
Graft
Latex Of Comparative Example 8
Graft
Latex Graft of Comparative Example 9
Latex Of Comparative Example 10
Graft
Latex % Conversion 98 .5 98.6 97.2 97.5 97.6 Graft Rate (%) 44 45 36 35 37 Izod
Impact strength
(kg? cm / cm) 26 26 29 35 36 Fluidity (g / 10min) 18 17 20 16 16.5 Tensile Strength (㎏ / ㎠) 455 460 447 430 432 Surface gloss (%) 102 101 101 97 98 Colorant Usage 0.05 0.05 0.06 0.1 0.1 Coloring L 32.6 32.9 33.4 33.3 33.5 Coloring a 43.0 43.3 43.4 42.1 42.1

As described in Tables 3 and 4, the ABS resins of Examples 9 to 12 prepared according to the present invention have similar colorability to the ABS resins of Comparative Examples 11 to 13, but have excellent mechanical properties, Compared with the ABS resins of Comparative Examples 14 to 15, it was confirmed that it had similar physical properties but excellent colorability and processability.

Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and modifications fall within the scope of the appended claims. It is also natural.

1 is a photograph showing the distribution of seeds in the large diameter rubber latex of Example 3 in a TEM image.

Claims (20)

a) seeds with an average particle diameter of 500-1000 mm 3 in the reactor; And preparing a rubber polymer comprising a core having an average particle diameter of 2000 ~ 5000Å; And b) graft copolymerizing a monomer mixture comprising an aromatic vinyl compound and a vinyl cyan compound in the rubber polymer of step a), The core is In the presence of 0.1 to 3 parts by weight of the seed in the reactor of a), 60 to 80 parts by weight, 1 to 3 parts by weight of emulsifier, 0.1 to 3 parts by weight of polymerization initiator, 0.1 to 1 weight of molecular weight regulator in 100 parts by weight of the conjugated diene monomer Emulsion-polymerizing the monomer mixture containing parts in a batch for 6 to 15 hours at 65 to 75 ° C; And 20 to 40 parts by weight of the remainder of the conjugated diene monomer, 0.05 to 1 parts by weight of the molecular weight regulator and 0.1 to 2 parts by weight of the seed in the reactor of a) to polymerize for 10 to 20 hours at a temperature of 75 ~ 90 ℃; includes Characterized in that the manufacturing method Process for preparing graft polymer The method of claim 1, Step b) is characterized in that the graft copolymerization is made by adding 20 to 50% by weight of the monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound to 50 to 80% by weight of the rubber polymer Process for preparing graft polymer The method according to claim 1 or 2, Graft polymerization by continuously administering the monomer mixture in an emulsified state Process for preparing graft polymer The method of claim 1, The seed It is prepared by reacting for 1 to 3 hours at a temperature of 60 ~ 90 ℃ by batch administration of a mixture containing 0.1 to 10 parts by weight of crosslinking agent and 4.5 to 10 parts by weight of emulsifier in 100 parts by weight of the ethylenically unsaturated monomer in the reactor Process for preparing graft polymer delete The method of claim 4, wherein The ethylenically unsaturated monomer is at least one member selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, acrylic esters and methacrylic acid esters Process for preparing graft polymer The method of claim 4, wherein The crosslinking agent is composed of ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1.4-butylene glycol dimethacrylate, aryl methacrylate and divinylbenzene At least one member selected from the group Process for preparing graft polymer The method of claim 1, The conjugated diene monomer is at least one member selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, pyrrylene, aromatic vinyl compound and vinyl cyan compound Process for preparing graft polymer a) seeds having an average particle diameter of 500 to 1000 mm 3; And rubber polymer comprising a core having an average particle diameter of 2000 ~ 5000Å; And b) graft polymerization of the monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound in the a) rubber polymer, The core is In the presence of 0.1 to 3 parts by weight of the seed of a), 60 to 80 parts by weight, 1 to 3 parts by weight of an emulsifier, 0.1 to 3 parts by weight of a polymerization initiator, 0.1 to 1 parts by weight of a molecular weight modifier, 65 to 100 parts by weight of the conjugated diene monomer. Emulsified and polymerized at 75 ° C. for 6 to 15 hours, followed by polymerization of 20 to 40 parts by weight of the remaining conjugated diene monomer, 0.05 to 1 part by weight of the molecular weight regulator, and 0.1 to 2 parts by weight of the seed at a temperature of 75 to 90 ° C. for 10 to 20 hours. Characterized in that obtained Graft polymer The method of claim 9, 50 to 80% by weight of the rubber polymer; And 20 to 50% by weight of a monomer mixture selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and mixtures thereof. Graft polymer The method of claim 9, The seed is prepared by polymerizing a mixture containing 0.1 to 10 parts by weight of a crosslinking agent, 4.5 to 10 parts by weight of an emulsifier, and 0.01 to 3 parts by weight of a polymerization initiator in 100 parts by weight of an ethylenically unsaturated monomer. Graft polymer delete 11. The method according to claim 9 or 10, The aromatic vinyl compound is at least one member selected from the group consisting of styrene, α-methylstyrene and vinyl toluene Graft polymer 11. The method according to claim 9 or 10, The vinyl cyan compound is characterized in that acrylonitrile or methacrylonitrile Graft polymer The method of claim 11, The ethylenically unsaturated monomer is at least one member selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, acrylic esters and methacrylic acid esters Graft polymer The method of claim 11, The crosslinking agent is composed of ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1.4-butylene glycol dimethacrylate, aryl methacrylate and divinylbenzene At least one member selected from the group Graft polymer The method of claim 11, The emulsifier is at least one member selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids and alkali salts of rosin acid. Graft polymer The method of claim 11, The polymerization initiator is at least one member selected from the group consisting of water-soluble persulfate, peroxy compound and redox-based compound Graft polymer  20 to 50% by weight of the graft polymer of claim 9; And 50 to 80% by weight of styrene-acrylonitrile resin. Resin composition delete

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