KR20030037440A - Odorless acrylonitrile-butadiene-styrene resin composition and method for preparing thereof - Google Patents

Abstract

PURPOSE: Provided are an odorless acrylonitrile-butadiene-styrene resin composition, which effectively removes inherent odor of resin while retaining inherent property of resin, and a method for preparing the same. CONSTITUTION: The resin composition comprises (a) 0.1-5.0 parts by weight of cyclo oligosaccharide-based compound; and (b) 0.05-0.5 parts by weight of mercaptan-based molecular weight controller. Alternatively, the composition comprises (a) 0.1-5 parts by weight of cyclo oligosaccharide-based compound; (b) 0.05-0.2 parts by weight of mercaptan-based molecular weight controller; (c) 100 parts by weight of resin component comprising (i) 40-80 parts by weight of a mixture of one or two rubber latex of diene or alkyl acrylate component having rubber particle diameter of 2500-3500 angstrom and gel content of 65-95%, and (ii) 60-20 parts by weight of at least two monomers selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a maleic anhydride monomer; and (d) 0.1-2.0 parts by weight of reactive emulsifier.

Description

Odorless acrylonitrile-butadiene-styrene resin composition and preparation method thereof {ODORLESS ACRYLONITRILE-BUTADIENE-STYRENE RESIN COMPOSITION AND METHOD FOR PREPARING THEREOF}

The present invention relates to an odorless acrylonitrile-butadiene-styrene resin composition containing a cyclo oligosaccharide compound and a mercaptan-based molecular weight regulator in an acrylonitrile-butadiene-styrene resin composition, and a method for producing the same.

Acrylonitrile-butadiene-styrene copolymer resin has excellent impact resistance, chemical resistance, processability, and surface gloss, so that it can be used in places such as monitor housing, game console housing, home appliances, office equipment, automobile interior materials, etc. It is being used, and its usage is also increasing year by year. However, in using it, in particular, when used as an interior material of an enclosed space such as a refrigerator and a car, it may cause discomfort during use due to the smell of the resin itself, and also due to odor during processing such as extrusion and injection. There is a problem that can interfere with the operation of.

In order to improve the malodorous resin, generally, a method of masking a malodorous molecular weight regulator during processing and a method of using an odorless molecular weight regulator in a polymerization process have been widely known. The first method is to add only the masking aid as a processing additive to the conventional polymerization component, there is a problem that the effect of improving the smell is not large, the second method is easy to remove the odor itself, but the impact strength, chemical resistance However, it is difficult to apply it directly to mass production, such as changing the intrinsic properties of resin such as thermal stability.

Therefore, there is a need for a study on a resin capable of effectively removing odors while maintaining its inherent properties and a method of manufacturing the same.

In order to solve the above problems, an object of the present invention is to provide an acrylonitrile-butadiene-styrene resin composition which effectively removes the dendritic odor while maintaining the intrinsic properties of the resin.

Another object of the present invention is to provide a method for producing an acrylonitrile-butadiene-styrene resin which can effectively remove the smell of the resin.

In order to achieve the above object, the present invention is acrylonitrile-butadiene-styrene resin composition, based on 100 parts by weight of the resin component

a) 0.1 to 5.0 parts by weight of a cyclo oligosaccharide compound; And

b) 0.05 to 0.5 parts by weight of a mercaptan-based molecular weight regulator

It provides an acrylonitrile-butadiene-styrene resin composition comprising a.

In addition, the present invention is a method for producing an acrylonitrile-butadiene-styrene resin, polymerization is carried out by adding 0.1 to 5.0 parts by weight of a cyclo oligosaccharide compound and 0.05 to 0.5 parts by weight of a mercaptan-based molecular weight regulator with respect to 100 parts by weight of the resin component. It provides a method for producing an odorless acrylonitrile-butadiene-styrene resin comprising the step of.

Hereinafter, the present invention will be described in detail.

While the present inventors are studying a method of removing the odor of acrylonitrile-butadiene-styrene resin, the use of a cyclo oligosaccharide compound minimizes the amount of mercaptan-based molecular weight regulator that acts as a major factor of the resin odor. As a result, it was confirmed that there is an excellent effect on the odor removal of the final resin, the present invention was completed based on this.

Acrylonitrile-butadiene-styrene resin of the present invention

a) 0.1 to 5 parts by weight of a cyclo oligosaccharide compound;

d) 0.05 to 0.2 parts by weight of a mercaptan-based molecular weight modifier;

c) iii) diene type with different rubber content of rubber from 2500 to 3500 겔 and gel content of 65 to 95%;

Or a mixture of 1 to 2 rubber latexes of an alkyl acrylate component

40 to 80 parts by weight of the mixture; And

Ii) aromatic vinyl monomers, vinyl cyan monomers, and maleic anhydride monomers;

60 to 20 parts by weight of at least two monomers selected from the group consisting of

100 parts by weight of a resin component comprising a; And

d) 0.1 to 2.0 parts by weight of a reactive emulsifier

It includes.

The cyclo oligosaccharide-based compound of a) used in the present invention has a hydrophobic cavity as a polymer organic compound, and α-, β-, γ-cyclodextrin, or cyclodextrin derivatives, cycloinurohexarose, cyclo Inuroheptatose, cycloinurooctose, or calissaren may be used. The cyclo oligosaccharide-based compound is preferably included in 0.1 to 5 parts by weight. In this case, the entire amount may be added in a batch or in a continuous dose, and preferably a complex and a molecular weight modifier are added before the graft reaction.

The saccharide compound having the hydrophobic cavities forms a complex with a strong hydrophobic property and a molecular weight modifier to facilitate the polymerization reaction during emulsion polymerization. In addition, it forms a complex with the molecular weight regulator in the molecular weight control to facilitate effective molecular weight control even with a small amount of molecular weight regulator.

As the mercaptan-based molecular weight modifier of b) used in the present invention, tertiary dodecyl mercaptan is mainly used. In addition, n-mercaptan, n-dodecyl mercaptan, mercaptanethanol, and the like may be used. The molecular weight modifier is preferably included in 0.05 to 0.5 parts by weight.

The mixture of 1 to 2 types of rubber latexes of the diene type or alkyl acrylate component of the above mentioned c) i) rubber particle diameter of 2500 to 3500 kPa, and gel content of 65 to 95% The monomer selected from the group consisting of the aromatic vinyl monomer of c) ii), the vinyl cyan monomer, and the maleic anhydride monomer is preferably graft copolymerized in a ratio of 20:80 to 40:60.

The reactive emulsifier of d) used in the present invention may be an anionic emulsifier having an allyl group, a (meth) acryloyl group, and a propenyl group, or a neutral emulsifier.

The anionic emulsifier having an allyl group may be representative of sulfate salts of polyoxyethylene allylglycidyl nonylphenyl ether. Examples of useful anionic emulsifiers include ADEKARIA SOAP SE series (manufactured by Asahi Denka), and neutral allyl groups. Systemic emulsifiers are polyoxyethylene allylglycidyl nonylphenyl ether series, and useful in the market include ADEKARIA SOAP NE series (manufactured by Asahi Denka). Useful in the market as an anionic emulsifier having a (meth) acryloyl group are ELEMINOL RS series (manufactured by Sanyo kasei), and a neutral emulsifier includes a RMA-560 series (manufactured by Nippon Surfactant). In addition, anionic emulsifiers having a propene group include the almonium sulfate salts of polyoxyethylene allylglycidyl nonyl propenyl phenyl ether, and those useful in the market include the AQUARON HS series, and the neutral emulsifier is AQUARON BC. (Daiichi kogyo Seiyaku Co., Ltd.) series.

The reactive emulsifiers described above are selected from one or more of them, or are alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like. Reactive emulsifiers may be used in addition to 0.5 to 2.0 parts by weight.

The amount of the reactive emulsifier used during the acrylonitrile-butadiene-styrene polymerization of the present invention is preferably 0.1 to 2.0 parts by weight.

In addition, the present invention is a method for producing an acrylonitrile-butadiene-styrene resin, the polymerization is carried out by adding 0.1 to 5.0 parts by weight of a cyclo oligosaccharide compound and 0.05 to 0.5 parts by weight of a mercaptan-based molecular weight regulator with respect to 100 parts by weight of the resin component. It can provide a method for producing acrylonitrile-butadiene-styrene resin comprising the step of.

The cyclo oligosaccharide-based compound and the molecular weight modifier used in the reaction of the present invention may be added in a batch or may be emulsified together with the monomer and the emulsifier to be continuously added.

In the production method of the present invention, it is preferable to add 0.05 to 0.5 parts by weight of a polymerization initiator upon polymerization, and as a redox catalyst initiator, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropyl benzenehydro peroxide, and At least one member selected from the group consisting of peroxides and at least one member selected from the group consisting of sodium formaldehyde sloxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium sulfite Preferred are mixtures of reducing agents.

In the emulsion polymerization of the present invention, the polymerization temperature is 40 to 80 ° C, and the polymerization time is preferably carried out at 2 to 7 hours.

Acrylonitrile-butadiene-styrene latex emulsion-polymerized by the production method of the present invention is obtained by agglomeration using a coagulant sulfuric acid, MgSO ₄ , CaCl ₂ , or Al ₂ (SO ₄ ) to obtain a final powder. The solid coagulation produced during the reaction is calculated by the following Equation 1, and the degree of formation of the film is measured by grasping the amount of the resulting film after leaving the latex for 24 hours.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

[Examples 1 and 2]

Example 1

30 parts by weight of polybutadiene rubber latex having a particle diameter of 2500 to 3000 mm 3 and a gel content of 65 to 85% in a nitrogen-substituted polymerization reactor and 25 parts of polybutadiene rubber latex having a particle size of 2500 to 3000 m 3 and a gel content of 70 to 95% 90 parts by weight of ion-exchanged water, 0.2 parts by weight of potassium rosinate emulsifier and 0.1 parts by weight of Latemul ASK, 15.8 parts by weight of styrene, 6.7 parts by weight of acrylonitrile, 0.15 parts by weight of tertiary dodecylmercaptan, 0.1 beta-cyclodextrin 0.1 Parts by weight, 0.048 part by weight of sodium pyrophosphate, 0.062 part by weight of dextrose, 0.001 part by weight of ferrous sulfide, and 0.08 part by weight of tertiary butyl hydroperoxide at 45 deg. C and the reaction temperature was raised to 70 deg. The reaction was carried out while rising.

Here, 10 parts by weight of ion-exchanged water, 0.8 parts by weight of potassium rosinate emulsifier, 0.2 parts by weight of Latemul ASK, 15.8 parts by weight of styrene, 6.7 parts by weight of acrylonitrile, and 0.10 parts by weight of cumene hydroperoxide were mixed at 70 ° C. After continuous injection for minutes, the reaction was terminated by raising the temperature to 80 ℃ and aged for 1 hour. At this time, 0.048 part by weight of sodium pyrophosphate, 0.062 part by weight of dextrose, and 0.001 part by weight of ferrous sulfide were used as redox initiators.

The polymerization conversion rate of the final polymer was 98.9% and molecular weight was 120,000. 0.5 weight part of antioxidant emulsion liquid was added here, it aggregated and dried using sulfuric acid, and the acrylonitrile- butadiene-styrene resin powder was obtained.

Example 2

In the same manner as in Example 1, except that 0.1 parts by weight of beta-cyclodextrin and 0.15 parts by weight of tertiary dodecyl mercaptan as added in the preparation of the monomer mixture emulsifier was continuously added to 70 ℃ of The same procedure as in Example 1 was carried out except that the solution was continuously fed at a temperature of 60 minutes. Conversion rate was 98.7% and a molecular weight was 118,000. The monomer and various additive composition ratios are shown in Table A2.

[Comparative Examples 1 and 2]

It carried out in the same manner as in Example 1, but was carried out in the same manner as in Example 1 except that the composition was added as shown in Table 1.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Bulk administration (parts by weight) Ion exchange water 90 90 90 110 Rubber with 65 to 85% gel 30 30 30 30 Rubber with 70-95% gel 25 25 25 25 Responsive Emulsifier (Latemul ASK) 0.1 0.1 - - Rosin acid potassium salt 0.2 0.2 0.4 0.4 Grade 3 Dodecyl Mercaptan 0.15 - 0.3 - Beta cyclodextrin 0.1 - - - Styrene 158 15.8 15.8 15.8 Acrylonitrile 6.7 6.7 6.7 6.7 Continuous administration (part by weight) Ion exchange water 10 10 10 10 Responsive Emulsifier (Latemul ASK) 0.2 0.2 - - Rosin acid potassium salt 0.8 0.8 10 1.0 Grade 3 Dodecyl Mercaptan - 0.15 - 0.3 Beta cyclodextrin - 0.1 - - Styrene 15.8 15.8 15.8 15.8 Acrylonitrile 6.7 6.7 6.7 6.7 Final polymer Polymerization conversion rate 98.9% 98.7% 97.6% 97.1% Molecular Weight 125,000 118,000 120,000 100,000 Coagulation content 0.020% 0.018% 0.030% 0.040%

30 g of acrylonitrile-butadiene-styrene resin prepared in Examples 1 or 2, and Comparative Examples 1 or 2, 70 g of styrene-acrylonitrile copolymer prepared by matrix solution polymerization, 0.5 g of antioxidant, and After adding 1.0 g of lubricant to prepare a final acrylonitrile-butadiene-styrene resin composition, physical properties were measured by the following method, and the results are shown in Table 2 below.

A) Izod impact strength-1/4 Izod impact strength in ASTM D256 (㎏ ㎝ / ㎝)

Measured accordingly.

B) Chemical resistance-measured using ESCR method. Strain (%) value for HCFC

Was determined to be 0.4% or more.

C) Odor-A sense of smell through the sense of smell was evaluated as a low score.

D) fluidity-measured according to ASTM D1238 (g / 10 min, 10 kg / 220 ° C.).

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Izod impact strength (kgf ㎝ / ㎝) 28 29 27 26 Fluidity (g / 10min, 10 ㎏ / 220 ℃) 8.9 8.4 8.7 8.1 Chemical resistance 2 2 2 2 smell One One 3 4

Through the above Table 2, the acrylonitrile-butadiene-styrene resin of Example 1, or 2 in which the amount of tertiary dodecyl mercaptan is reduced by using a cyclo oligosaccharide compound beta cyclodextrin according to the present invention is Compared with Comparative Examples 1 or 2, physical properties such as Izod impact strength, fluidity, and chemical resistance were equivalent, but it was confirmed that the smell of the resin was significantly reduced.

As described above, the acrylonitrile-butadiene-styrene resin minimized the amount of the mercaptan-based molecular weight modifier using a cyclo oligosaccharide compound according to the present invention, while maintaining the intrinsic properties of the resin itself, while at the same time There is an effect that can significantly reduce the smell of.

Claims (9)

Acrylonitrile-butadiene-styrene resin composition, based on 100 parts by weight of the resin component a) 0.1 to 5.0 parts by weight of a cyclo oligosaccharide compound; And b) 0.05 to 0.5 parts by weight of a mercaptan-based molecular weight regulator Acrylonitrile-butadiene-styrene resin composition comprising a. The method of claim 1, The cyclo oligosaccharide-based compound of a) is a group consisting of α-, β-, γ-cyclodextrin, or cyclodextrin derivatives, cycloinurohexarose, cycloinuroheptatose, cycloinurooctose, and calsarene At least one selected from acrylonitrile-butadiene-styrene resin composition. The method of claim 1, Acrylonitrile-butadiene-styrene resin composition wherein the mercaptan-based molecular weight modifier of b) is selected from the group consisting of tertiary dodecyl mercaptan, n-mercaptan, n-dodecyl mercaptan, and mercaptanethanol . The method of claim 1, a) 0.1 to 5 parts by weight of a cyclo oligosaccharide compound; b) 0.05 to 0.2 parts by weight of a mercaptan-based molecular weight modifier; c) iii) diene type with different rubber content of rubber from 2500 to 3500 겔 and gel content of 65 to 95%; Or a mixture of 1 to 2 rubber latexes of an alkyl acrylate component 40 to 80 parts by weight of the mixture; And Ii) aromatic vinyl monomers, vinyl cyan monomers, and maleic anhydride monomers; 60 to 20 parts by weight of at least two monomers selected from the group consisting of 100 parts by weight of a resin component comprising a; And d) 0.1 to 2.0 parts by weight of a reactive emulsifier Acrylonitrile-butadiene-styrene resin composition comprising a. The method of claim 3, (C) i) a rubber particle diameter of 2500 to 3500 kPa, a gel content of 65 to 95% of a gel content, and a mixture of 1 to 2 kinds of rubber latexes of different diene or alkyl acrylate components and a) ii) The acrylonitrile-butadiene-styrene resin composition whose ratio of the monomer chosen from the group which consists of an aromatic vinyl monomer, a vinyl cyan monomer, and a maleic anhydride monomer is 20: 80-40: 60. The method of claim 4, wherein An anionic emulsifier in which the reactive emulsifier of d) has an allyl group of a sulfate salt of polyoxyethylene allyl glycidic nonylphenyl ether; Neutral emulsifiers having an allyl group of the polyoxyethylene allylglycidyl nonylphenyl ether series; Anionic emulsifier which has a (meth) acryloyl group; Anionic emulsifiers having a propene group of an aluminum sulfate salt of polyoxyethylene allylglycidyl nonyl propenyl phenyl ether; Acrylonitrile-butadiene-styrene resin composition selected from the group consisting of neutral emulsifiers. The method of claim 4, wherein Acrylonitrile-butadiene-styrene resin composition further comprising 0.5 to 2.0 parts by weight of the non-reactive emulsifier. The method of claim 7, wherein The acrylonitrile-butadiene-styrene resin wherein the non-reactive emulsifier is selected from the group consisting of alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid Composition. A method for producing acrylonitrile-butadiene-styrene resin, the method comprising polymerizing by adding 0.1 to 5.0 parts by weight of a cyclo oligosaccharide compound and 0.05 to 0.5 parts by weight of a mercaptan molecular weight regulator based on 100 parts by weight of a resin component. A method for producing acrylonitrile-butadiene-styrene resin.