KR101151166B1 - Graft Copolymer, Method For Preparing The Same And Thermoplastic Resin Composition Containing The Same - Google Patents

Abstract

The present invention relates to a graft copolymer, a method for preparing the same, and a thermoplastic resin composition including the same, and more particularly, a hard particle having an average particle diameter of 150 to 300 nm by administering a cationic emulsifier when preparing a polymer latex having a refractive index of at least 1.5. Preparing a polymer seed, copolymerizing an alkyl acrylate monomer mixture to the polymer latex seed to produce a composite rubber polymer core having an average particle diameter of 300 to 600 nm, and forming a graft shell layer in the presence of the core It relates to a method for producing a graft copolymer comprising a and a thermoplastic resin composition comprising the same. According to the present invention, there is an advantage in that a large diameter rubber polymer latex can be produced in a short time, and when the graft copolymer of the present invention is mixed with a hard matrix, the effect of providing a thermoplastic resin composition excellent in weatherability, colorability and impact resistance is provided. have.

Alkyl acrylate rubber, aromatic vinyl compound, vinyl cyan compound, cationic emulsifier, weather resistance, colorability, impact resistance, thermoplastic resin composition

Description

Graft Copolymer, Method for Making the Same, and Thermoplastic Resin Composition Containing the Same {Graft Copolymer, Method For Preparing The Same And Thermoplastic Resin Composition Containing The Same}

The present invention relates to a graft copolymer, a method for preparing the same, and a thermoplastic resin composition including the same, and more particularly, a hard particle having an average particle diameter of 150 to 300 nm by administering a cationic emulsifier when preparing a polymer latex having a refractive index of at least 1.5. After preparing one polymer seed, a polymer rubber core is prepared by polymerizing an alkyl acrylate monomer mixture on the seed to produce a graft copolymer having excellent weather resistance, colorability, and impact resistance, a method for preparing the same, and a thermoplastic resin composition comprising the same. It is about.

ABS resin is an acrylonitrile-butadiene-styrene terpolymer and has excellent impact resistance, rigidity, chemical resistance and processability, and is widely used in various fields such as electric and electronics, construction, and automobiles. However, ABS resin has a problem that it is not suitable as an outdoor material because of poor weather resistance by using butadiene polymer as a rubber.

In order to obtain a thermoplastic resin having excellent physical properties and excellent weatherability and aging resistance, there should be no ethylenically unsaturated polymer in the graft copolymer. Representative examples of thermoplastic resins excellent in weatherability and aging resistance are ASA resins (acrylonitrile-styrene-acrylate terpolymers) using crosslinked alkyl acrylate rubber polymers that have proven to be suitable. Such ASA resin has excellent weather resistance and aging resistance, and is used in various fields such as automobiles, ships, leisure products, building materials, and gardening.

The preparation of ASA polymers excellent in weatherability and aging resistance is disclosed in German Patent No. 1,260,135, wherein the core used is a large diameter latex of crosslinked acrylate having an average particle diameter of 150 to 800 nm and a narrow particle size distribution. Compared to polymers prepared using small diameter polyacrylate latex, polymers comprising large diameter polyacrylate latex have improved notch impact strength, greater hardness and reduced shrinkage. However, the large-diameter graft copolymer has a disadvantage in that coloring is difficult and manufacturing time is large compared to the small-diameter graft copolymer.

U.S. Patent No. 4,224,419 discloses a crosslinked acrylate polymer having an average particle diameter of about 50 to 150 nm as a core, a styrene and acrylonitrile as a graft shell, for a weather resistant high impact thermoplastic resin that can be easily colored. A first graft copolymer, a crosslinked acrylate polymer having an average particle diameter of about 200 to 500 nm as a core, a second graft copolymer separately prepared from styrene and acrylonitrile as a graft shell, and acrylonitrile A hard component comprising a copolymer with styrene or a-methylstyrene, wherein the weight ratio between the core components is 90:10 to 35:65 and the ratio of the sum of the two core components is about 10 to 35 weight based on the mixture Molding materials which are% are described.

On the other hand, European Patent No. 534,212 and U.S. Patent No. 5,932,655 prepare a large diameter and a small diameter graft copolymer, respectively, and prepare a hard component having a glass transition temperature higher than room temperature as a seed component to improve colorability and impact resistance. Presenting. European Patent No. 534,212 used hard seeds only for small diameter graft copolymers, and US Patent No. 5,932,655 used hard polystyrene seeds for both large and small diameter graft copolymers.

These known materials are excellent in weatherability and mechanical properties and have improved colorability. However, the improvement of the coloring properties of these materials is still insufficient, there is a problem that the manufacturing time takes a lot when producing a large diameter graft copolymer.

In order to solve the problems of the prior art as described above, the present invention is a graft copolymer having an effect of providing a manufacturing method capable of producing a large diameter graft copolymer in a short time and a thermoplastic resin composition excellent in weather resistance, colorability, impact resistance And it aims to provide the manufacturing method.

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

Based on 100 parts by weight of total monomers used to prepare the graft copolymer

a) 3 to 20 parts by weight of at least one compound selected from the group consisting of diene monomers, styrene monomers, vinyl cyan compounds, alkyl acrylate monomers and alkyl methacrylate monomers, 0.01 to 0.1 parts by weight of crosslinking agents, graf During the polymerization by administering a mixture containing 0.01 to 0.1 parts by weight of the tinting agent and 0.5 to 5.0 parts by weight of the anionic emulsifier, 0.1 to 2.0 parts by weight of the cationic emulsifier was administered and polymerized to have an average particle diameter of 150 to 300 nm and a refractive index of at least 1.5. Preparing a polymer latex seed;

b) a mixture comprising 20 to 70 parts by weight of an alkyl acrylate monomer, 0.05 to 0.5 parts by weight of a crosslinking agent, and 0.05 to 0.5 parts by weight of a grafting agent in 5 to 20 parts by weight of the seed prepared in step a) (based on solids). Polymerizing to prepare a large-diameter composite rubber polymer core having an average particle diameter of 300 to 600 nm; And

c) graft by 20 to 80 parts by weight of a monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an alkyl (meth) acrylate monomer in the presence of the core prepared in step (b) Preparing the copolymer;

It provides a method for producing a graft copolymer comprising a.

In addition, the present invention provides a thermoplastic resin composition comprising a graft copolymer and a hard matrix prepared above.

As described above, according to the present invention, there is an advantage that a large diameter graft copolymer latex can be manufactured in a short time, and when the thermoplastic resin composition comprising the graft copolymer of the present invention is prepared, There is an advantage to improve the pigment colorability, impact resistance in a balanced manner.

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

The inventors have found that the pigment colorability of thermoplastic resins containing alkyl acrylate rubbers is lowered because the refractive index of the alkyl acrylate rubbers is too low compared to copolymers comprising styrene, which is usually used as a matrix. In order to solve this problem, when copolymerizing a conventional monomer having a refractive index of at least 1.5 or more, such as styrene during the polymerization of the alkyl acrylate rubber, a large diameter hard seed manufacturing time takes much time.

In order to solve the above problems, the present inventors, while preparing a graft copolymer, by adjusting the appropriate stability by administering a cationic emulsifier during the preparation of a polymer latex seed having a refractive index of at least 1.5 so that intergranular microaggregation occurs To prepare a polymer latex seed having an average particle diameter of 150 to 300 nm and a refractive index of at least 1.5 in a short time, and to produce a composite rubber polymer core having an average particle diameter of 300 to 600 nm in the presence of the seed, wherein the aromatic vinyl compound, When a graft copolymer is prepared by emulsion polymerization of a monomer mixture selected from the group consisting of a vinyl cyan compound and an alkyl (meth) acrylate-based monomer, the graft copolymer is mixed with a hard matrix. Resin excellent in pigmentability and impact resistance while being excellent in weatherability It was confirmed that it is possible to manufacture.

Referring to the graft copolymer latex production method of the present invention in more detail.

a) polymer latex seed preparation

This step is to prepare a polymer latex seed having a refractive index of at least 1.5 and an average particle diameter of 150 to 300 nm.

Specifically, the polymer latex seed is based on 100 parts by weight of the total monomers used in the graft copolymer iii) 3 to 20 parts by weight of monomers to form a polymer having a refractive index of at least 1.5, ii) 0.01 to 1.5 parts by weight of a polymerization initiator, Iii) 0.01 to 1.0 parts by weight of electrolyte, iii) 0.01 to 0.1 parts by weight of crosslinking agent, iii) 0.01 to 0.1 parts by weight of grafting agent, iii) 0.5 to 5.0 parts by weight of anionic emulsifier and distilled water during polymerization. 0.1 to 2.0 parts by weight of the systemic emulsifier may be prepared by a continuous administration method.

 As the monomer forming the polymer having the refractive index of at least 1.5, a diene monomer, a styrene monomer, a vinyl cyan compound, or the like may be used, and a monomer copolymerizable with the monomers may be further used if necessary.

The diene monomer, the styrene monomer, and the vinyl cyan compound may be used as a general monomer used in the art, and specifically, the diene monomer may be 1,3-butadiene, isoprene, chloroprene or the like. The styrene monomer may be styrene, α-methyl styrene, p-methyl styrene, vinyl toluene, or the like, and the vinyl cyan compound may be acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like. .

As the monomer copolymerizable with the monomers, an alkyl acrylate monomer, an alkyl (meth) acrylate monomer, or the like may be used.

Specifically, the alkyl acrylate monomers are preferably those having 2 to 8 carbon atoms of alkyl, more preferably those having 4 to 8 carbon atoms of alkyl, butyl acrylate, ethyl hexyl acrylate, and the like may be used. As the (meth) acrylate monomer, one having 1 to 4 carbon atoms of alkyl is preferable, and more preferably methyl methacrylate, ethyl methacrylate and the like can be used as those having 1 to 2 carbon atoms of alkyl.

The monomer forming the polymer having a refractive index of at least 1.5 is preferably included in an amount of 3 to 20 parts by weight based on 100 parts by weight of the total monomers used for preparing the graft copolymer. There is a problem that the strength is lowered, and when it exceeds 20 parts by weight, there is a problem that the impact strength is lowered.

As the polymerization initiator, water-soluble persulfates such as sodium persulfate or potassium persulfate, cumene hydroperoxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, Or a fat-soluble persulfate such as benzoyl peroxide, a peroxy compound, an oxidation-reduction system, or the like.

As the electrolyte, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ or Na ₂ HPO ₄ or the like may be used alone or in combination of two or more thereof.

The crosslinking agent is also referred to as a cross-linking agent, and refers to a material that acts as a bridge between the chains of the chain-shaped polymer, specifically, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylol methane triacrylamide It is preferable to use a rate or the like.

The grafting agent is used in the graft polymerization reaction, which is a polymerization reaction in which a straight chain polymer is used as a stem and other kinds of polymers are bound together like branches, and specifically, allyl methacrylate (AMA) and triallyl isocyanate. It is preferable to use an anurate (TAIC), triallylamine (TAA), diallylamine (DAA) and the like.

Although there is no restriction | limiting in particular as said anionic emulsifier, It is excellent in latex stability at the time of emulsion polymerization, and a polymerization rate becomes high, Alkyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, fatty acid soap, or rosin acid alkali Salts and the like can be used. The said emulsifier can be used individually or in mixture of 2 or more types.

The anionic emulsifier is preferably used 0.5 to 5.0 parts by weight based on 100 parts by weight of the total monomer used in the graft copolymer production. If the content is less than 0.5 parts by weight, latex stability is deteriorated, and if it exceeds 5.0 parts by weight, the particle size does not become large enough to cause a problem that the impact strength is lowered.

As the cationic emulsifier, a quaternary ammonium salt or an alkyl amine salt having one or more alkyl groups may be used, and the quaternary ammonium salt is preferably ammonium composed of one alkyl group and three methyl groups or an ammonium salt composed of two alkyl groups and two methyl groups. It is preferable that carbon number of said alkyl group is 5-20.

Specifically, the cationic emulsifier may be dioctadecyl dimethyl ammonium salt, dodecyl trimethyl ammonium salt, dodecyl benzyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt, octyl benzyl trimethyl ammonium salt and the like.

The cationic emulsifier is preferably used 0.1 to 2.0 parts by weight based on 100 parts by weight of the total monomers used to prepare the graft copolymer. When the content is less than 0.1 part by weight, the seed polymer latex having a refractive index of at least 1.5 is less than 150 nm, so that the average particle diameter of the final large-diameter alkyl acrylate composite rubber polymer latex is less than 250 nm, and the impact strength is lowered. There is a problem in that excess coagulation occurs when the part is exceeded.

The cationic emulsifier is preferably continuously administered during the polymerization by collectively administering components other than the cationic emulsifier. When the cationic emulsifier is administered after the polymerization is completed, the polymer latex seed having a refractive index of at least 1.5 does not become large enough, so that the impact strength is lowered.

The polymer latex having a refractive index of at least 1.5 polymerized under the above conditions preferably has an average particle diameter of 150 to 300 nm.

b) Preparation of large diameter composite rubber polymer latex cores

This step is a step of preparing a large diameter composite rubber polymer latex core by adding and copolymerizing an alkyl acrylate monomer, a crosslinking agent, a grafting agent, an anionic emulsifier, and a polymerization initiator in the presence of the polymer latex seed prepared in step a).

Specifically, the large-diameter composite rubber polymer latex core is present in the presence of a polymer latex seed having a refractive index of at least 1.5 based on 100 parts by weight of the total monomers used to prepare the graft copolymer, i) 20 to 70 parts by weight of an alkyl acrylate monomer, ii 0.05 to 0.5 parts by weight of crosslinking agent, i) 0.05 to 0.5 parts by weight of grafting agent, i) 0.03 to 5.0 parts by weight of anionic emulsifier, i) 0.02 to 1.5 parts by weight of polymerization initiator, and distilled water, Manufacture.

The alkyl acrylate monomers are particularly suitable as butyl acrylate and ethyl hexyl acrylate as alkyl acrylates having 2 to 8 carbon atoms, preferably 4 to 8 carbon atoms in the alkyl moiety.

The alkyl acrylate monomer is preferably included in 20 to 70 parts by weight based on 100 parts by weight of the total monomers used in the graft copolymer production, when the content is less than 20 parts by weight, the impact strength is lowered, If it exceeds 70 parts by weight, there is a problem that the tensile strength is lowered.

As the crosslinking agent, the grafting agent, the anionic emulsifier and the polymerization initiator, the same material as used in step a) may be used.

 The prepared large diameter composite rubber polymer latex core has an average particle diameter of 300 to 600 nm and a gel content of 50 to 95 wt%.

c) graft copolymer preparation

This step is a monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, and an alkyl (meth) acrylate monomer in the presence of the core prepared in step b), an anionic emulsifier, a polymerization initiator, and It is a step of preparing a graft copolymer by adding and polymerizing a molecular weight regulator.

Specifically, the graft copolymer is in the presence of the prepared large diameter composite rubber polymer latex core based on 100 parts by weight of the total monomers used in the graft copolymer iii) aromatic vinyl compound, vinyl cyan compound, alkyl (meth) 20 to 80 parts by weight of monomers selected from the group consisting of acrylate monomers, ii) 0.5 to 3 parts by weight of anionic emulsifier, iii) 0.02 to 2 parts by weight of polymerization initiator, iii) 0.01 to 0.5 parts by weight of molecular weight regulator And distilled water in batch or continuously over 2 to 6 hours and prepared by emulsion polymerization.

As the aromatic vinyl compound, it is preferable to use a styrene monomer derivative. For example, styrene, α-methyl styrene, p-methyl styrene or vinyl toluene may be used. The vinyl cyan compound may be acrylonitrile. Or methacrylonitrile may be used. As the alkyl (meth) acrylate monomer, methyl methacrylate and ethyl methacrylate are particularly preferred as alkyl methacrylate having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms in the alkyl moiety. .

As the anionic emulsifier and polymerization initiator, the same material as used in step a) may be used.

The molecular weight modifier is used to control the molecular weight of the graft polymer, it is preferable to use a tertiary dodecyl mercaptan.

After administering an antioxidant and a stabilizer to the graft copolymer latex prepared as described above, the solution is grafted to an aqueous solution of an inorganic salt such as aluminum chloride, sodium sulfate, sodium nitrate, calcium chloride, or flocculant solution such as sulfuric acid or hydrochloric acid at 50 to 120 ° C. The graft copolymer latex was recovered to recover the wet powder of the graft copolymer from the graft copolymer latex, and the wet powder of the recovered graft copolymer was dehydrated and dried to obtain a graft copolymer in a dry powder state. can do.

The graft copolymer dry powder prepared as described above is kneaded and used by a conventional kneading apparatus together with a hard matrix made of different thermoplastic resins depending on the purpose of the final product.

The dry powder and the melt-kneaded hard matrix prepared in the present invention are not particularly limited, but have a glass transition temperature of at least 60 ° C. or higher, and a reactant including at least one monomer of an aromatic vinyl compound, a vinyl cyan compound, and methyl methacrylate. It is preferable to use a single or two or more types of polymers formed by polymerizing or polymers formed by polymerization of monomers or monomer mixtures having polar functional groups such as polyols, polycarboxylic acids, vinyl chlorides, polyamines and the like. For example, poly methyl methacrylate, acrylonitrile styrene copolymer, acrylonitrile butadiene styrene copolymer, acrylonitrile ethylene propylene diene styrene copolymer, polycarbonate resin, polybutylene terephthalate, polyethylene terephthalate, poly Vinyl chloride, polystyrene, methyl methacrylate styrene copolymer, acrylonitrile styrene methyl methacrylate copolymer, polyacetal resin, polyphenylene ether, polyamide resin and the like.

Although there is no restriction | limiting in particular in content of the graft copolymer and hard matrix in the thermoplastic resin composition of this invention, 10-90 weight part of graft copolymers and 90-10 weight part of hard matrices are preferable based on 100 weight part of thermoplastic resin compositions.

As melt kneading method of the graft copolymer and the hard matrix, kneaders such as an extruder, a half-variable mixer, and a pressurized kneader can be used, and if necessary, dyes, pigments, oxidation stabilizers, UV stabilizers, reinforcing agents, fillers, flame retardants , Blowing agents, lubricants, plasticizers and the like can be added.

The invention is explained in more detail through the following examples. However, these embodiments are merely exemplary and do not limit the technical scope of the present invention.

[Example]

The average particle diameter of the latex in this example was measured using an intensity Gaussian distribution (Nicomp 370HPL) by dynamic laser light scattering.

Example 1

a) preparing a polymer latex seed having a refractive index of at least 1.5

5 parts by weight of styrene, 0.025 parts by weight of ethylene glycol dimethacrylate, 0.025 parts by weight of allyl methacrylate, lauryl in a nitrogen-substituted polymerization reactor (autoclave) based on 100 parts by weight of the total monomers used to prepare the graft copolymer. 1.5 parts by weight of sodium sulfate, 0.2 parts by weight of sodium carbonate and 50 parts by weight of distilled water were collectively administered, and the reaction temperature was raised to 70 ° C. Then, 0.025 parts by weight of potassium persulfate was administered in a batch to initiate the reaction, and 20 minutes after the reaction proceeded, diocta After 0.3 parts by weight of decyl dimethyl ammonium salt was continuously administered for 40 minutes, the reaction was terminated to obtain a polymer latex having a refractive index of at least 1.5. The average particle diameter of the polymer latex having a polymerized refractive index of at least 1.5 was 170 nm.

b) Manufacture of large diameter composite rubber polymer latex cores

50 parts by weight of butyl acrylate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of allyl methacrylate, in the presence of a polymer latex having a refractive index of at least 1.5 based on 100 parts by weight of the total monomers used to prepare the graft copolymer. A mixture of 0.5 parts by weight of sodium lauryl sulfate, 0.1 parts by weight of cumene hydroperoxide and 40 parts by weight of distilled water was continuously administered at 70 ° C. for 3 hours to prepare a composite rubber polymer latex. The average particle diameter of the prepared composite rubber polymer latex was 350 nm.

c) graft copolymer preparation

33.75 parts of styrene, 11.25 parts of acrylonitrile, 0.7 parts of sodium lauryl sulfate, 0.01 parts of tertiary dodecyl mercaptan, 0.15 parts of cumene hydroperoxide, and distilled water in the presence of the polymerized composite rubber polymer latex. The polymerization reaction was carried out while the mixture of the parts by weight was continuously administered at 75 ° C. for 2 hours. In addition, in order to increase the polymerization conversion rate, after the completion of the administration, the temperature was raised to 75 ° C, and then further reacted for 1 hour, and the reactor internal temperature was cooled to 60 ° C to terminate the polymerization reaction to prepare a graft copolymer latex.

The polymerization conversion of the polymerized latex was 99.5%.

The obtained latex was subjected to atmospheric coagulation at 85 ° C. using an aqueous calcium chloride solution, and then aged at 95 ° C. for dehydration and washing, followed by drying for 30 minutes with hot air at 90 ° C. to obtain graft copolymer particles having a multilayer structure. .

40 parts by weight of the obtained graft copolymer particles and 60 parts by weight of a styrene-acrylonitrile copolymer (LG Chemical, product name: 92HR) based on 100 parts by weight of the total monomers used to prepare the graft copolymer, and a hard matrix. 1 part by weight of lubricant, 0.5 part by weight of antioxidant, 0.5 part by weight of UV stabilizer, and 1 part by weight of carbon black were added and mixed. This was produced in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and the pellets were injected to prepare physical specimens. Using this, Izod impact strength, pigment colorability, etc. were measured as follows.

A) Izod impact strength (1/4 ”notched at 23 ° C., -20 ° C. kg? Cm / cm) —measured according to ASTM D256.

B) Pigment coloring-L value of the coloring test piece was measured using a color difference meter. The lower the L value, the lower the brightness, resulting in a dark black color, which means that the pigment colorability is good.

C) Weather resistance-After dissipation of the resin for 2000 hours at 83 ℃ and water spray cycle of 18 minutes / 120 minutes in a weatherometer (ATLAS Ci35A), the degree of discoloration with colorimeter (ΔE) Was measured.

Here, ΔE is an arithmetic mean value of Hunter Lab values before and after the 2000 hour weather resistance experiment, and the closer to 0, the better the weather resistance.

[Example 2]

Example 1 was carried out in the same manner as in Example 1, except that 0.6 part by weight instead of 0.3 part by weight of polymer latex dioctadecyl dimethyl ammonium salt having a refractive index of at least 1.5 was used. The average particle diameter of the polymer latex having a refractive index of at least 1.5 was 230 nm and the average particle diameter of the composite rubber polymer latex was 450 nm.

[Example 3]

In Example 1, a polymer latex having a refractive index of at least 1.5 was used in the same manner as in Example 1, except that 4 parts by weight of styrene and 1 part by weight of methyl methacrylate were used instead of 5 parts by weight of styrene. The average particle diameter of the polymer latex having a refractive index of at least 1.5 was 160 nm and the average particle diameter of the composite rubber polymer latex was 345 nm.

Comparative Example 1

In Example 1, a polymer latex having a refractive index of at least 1.5 was used in the same manner as in Example 1, except that 0 parts by weight instead of 0.3 parts by weight of octadecyl dimethyl ammonium salt was used. The average particle diameter of the polymer latex having a refractive index of at least 1.5 was 80 nm and the average particle diameter of the composite rubber polymer latex was 160 nm.

Comparative Example 2

In Example 1, except that 2.5 parts by weight instead of 0.3 parts by weight of dioctadecyl dimethyl ammonium salt was prepared in the polymer latex manufacturing step having a refractive index of at least 1.5.

In the polymer latex manufacturing step having a refractive index of at least 1.5, the latex lost stability and polymerization was not possible.

Comparative Example 3

Example 1, except that 0.3 parts by weight of octadecyl dimethyl ammonium salt in the step of preparing a polymer latex having a refractive index of at least 1.5 was administered at the end of the reaction 1 hour after the start of the reaction was carried out in the same manner as in Example 1. The average particle diameter of the polymer latex having a refractive index of at least 1.5 was 120 nm and the average particle diameter of the composite rubber polymer latex was 235 nm.

[Comparative Example 4]

20 minutes after the start of the reaction in the polymer latex manufacturing step having a refractive index of at least 1.5 in Example 1, except that 0.3 parts by weight of dioctadecyl dimethyl ammonium salt was collectively administered in the same manner as in Example 1. A large amount of coagulum occurred in the polymer latex manufacturing step with a refractive index of at least 1.5.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Izod
Impact Strength (23 ℃)
(Kgcm / cm) 30.5 33.1 28.7 2.9 - 10.5 20.1 Weatherability 2.2 2.5 2.0 2.7 - 2.5 2.6 Pigment coloring 18.3 19.0 17.1 13.2 - 15.1 19.8

When carried out in the same manner as in Example 1 in Table 1, a large diameter graft copolymer latex can be prepared in a short time, and the thermoplastic resin including the same has excellent weather resistance and excellent pigment colorability and impact resistance. However, when the cationic emulsifier was not used as in Comparative Example 1, the impact strength was greatly decreased, and when the cationic emulsifier was used in excess as in Comparative Example 2, the latex lost stability and polymerization was not possible. When the systemic emulsifier was administered after completion of the polymer latex seed production reaction having a refractive index of at least 1.5, the impact strength was lowered due to insufficient size. In addition, when the cationic emulsifier is collectively administered as in Comparative Example 4, there is a problem that a large amount of coagulum is generated.

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.

Claims (14)

Based on 100 parts by weight of total monomers used to prepare the graft copolymer a) 3 to 20 parts by weight of at least one compound selected from the group consisting of diene monomers, styrene monomers, vinyl cyan compounds, alkyl acrylate monomers and alkyl methacrylate monomers, 0.01 to 0.1 parts by weight of crosslinking agents, graf During the polymerization by administering a mixture containing 0.01 to 0.1 parts by weight of the tinting agent and 0.5 to 5.0 parts by weight of the anionic emulsifier, 0.1 to 2.0 parts by weight of the cationic emulsifier was administered and polymerized to have an average particle diameter of 150 to 300 nm and a refractive index of at least 1.5. Preparing a polymer latex seed; b) polymerizing a mixture comprising 20 to 70 parts by weight of an alkyl acrylate monomer, 0.05 to 0.5 parts by weight of a crosslinking agent and 0.05 to 0.5 parts by weight of a grafting agent, in 5 to 20 parts by weight of the seed prepared in step a) (based on solids). To prepare a large diameter composite rubber polymer core having an average particle diameter of 300 to 600 nm; And c) graft by 20 to 80 parts by weight of a monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an alkyl (meth) acrylate monomer in the presence of the core prepared in step (b) Preparing the copolymer; Method for producing a graft copolymer, characterized in that it comprises a. The method of claim 1, The diene monomer is at least one member selected from the group consisting of 1,3-butadiene, isoprene and chloroprene Method for preparing the graft copolymer. The method of claim 1, The styrene monomer is characterized in that at least one member selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene and vinyl toluene. Method for preparing the graft copolymer. The method of claim 1, The alkyl acrylate monomer is characterized in that at least one member selected from the group consisting of butyl acrylate and ethyl hexyl acrylate. Method for preparing the graft copolymer. The method of claim 1, The alkyl methacrylate monomer is characterized in that at least one member selected from the group consisting of methyl methacrylate and ethyl methacrylate. Method for preparing the graft copolymer. The method of claim 1, The at least one aromatic vinyl compound is selected from the group consisting of styrene, alpha-methylstyrene, para-methylstyrene and vinyltoluene. Method for preparing the graft copolymer. The method of claim 1, The cationic emulsifier is an alkyl amine salt, wherein the alkyl group has 5 to 20 carbon atoms Process for preparing graft copolymers. The method of claim 1, The cationic emulsifier is a quaternary ammonium salt consisting of one alkyl group and three methyl groups or a quaternary ammonium salt consisting of two alkyl groups and two methyl groups, wherein the alkyl group has 5 to 20 carbon atoms. Process for preparing graft copolymers. The method of claim 1, The cationic emulsifier is at least one member selected from the group consisting of dioctadecyl dimethyl ammonium salt, dodecyl trimethyl ammonium salt, dodecyl benzyl dimethyl ammonium salt, hexadecyl trimethyl ammonium salt and octyl benzyl trimethyl ammonium salt Process for preparing graft copolymers. The method of claim 1, Characterized in that the cationic emulsifier is continuously administered during polymerization by collectively administering the components other than the cationic emulsifier in step a). Process for preparing graft copolymers. The method of claim 1, The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol At least one selected from the group consisting of dimethacrylate, trimethylolpropane trimethacrylate, and trimethylol methane triacrylate Method for preparing the graft copolymer. The method of claim 1, The large-diameter composite rubber polymer core is characterized in that the gel content of 50 to 95% by weight Method for preparing the graft copolymer. delete delete