KR20190084549A - Core-shell copolymer, method for preparing the copolymer and resin composition comprising the copolymer - Google Patents

Abstract

The present invention relates to a core-shell structure, and, more specifically, to a core-shell structure, a preparation method thereof and a resin composition comprising the copolymer. The core-shell structure comprises: a core including a conjugated diene monomer derived repeating unit, an aromatic vinyl monomer derived repeating unit and a bisphenol F-based monomer derived repeating unit; and a shell covering the core and including an alkyl (meth)acrylate monomer derived repeating unit and an aromatic vinyl monomer derived repeating unit. The content of the bisphenol F-based monomer derived repeating unit is more than 0 wt% to less than 10 wt% with respect to the total content of the monomer derived repeating units in the core. If the core-shell structure of the present invention is used as an impact reinforcing agent of a vinyl chloride polymer, impact strength and an optical properties in trade-off relationship with each other can be improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a core-shell copolymer, a method for producing the core-shell copolymer, and a resin composition comprising the same. BACKGROUND ART [0002] CORE- SHELL COPOLYMER, METHOD FOR PREPARING THE COPOLYMER AND RESIN COMPOSITION COMPRISING THE COPOLYMER,

TECHNICAL FIELD The present invention relates to a core-shell copolymer, and more particularly, to a core-shell copolymer, a process for producing the same, and a resin composition containing the core-shell copolymer.

The vinyl chloride resin is inexpensive and easy to control hardness, has various application fields, is excellent in physical properties and chemical properties, and is widely used in various fields.

However, vinyl chloride resins have various disadvantages in terms of impact strength, workability, thermal stability, and heat distortion temperature. In order to compensate for these drawbacks, additives such as impact modifiers, processing aids, stabilizers and fillers are appropriately selected and used Has come. Among them, a methyl methacrylate-butadiene-styrene type terpolymer (hereinafter referred to as MBS copolymer) is mainly used as an impact modifier of a vinyl chloride resin, and in particular, a molded article of a transparent material using a vinyl chloride resin The use of which is increasing.

Optical properties such as transparency and gloss characteristics are important in molded products of transparent materials. Impact strength and optical properties, if desired to improve impact strength, deteriorate optical properties. If optical properties are to be improved, impact strength There is a limit in improving the impact strength and the optical characteristics at the same time in a trade-off relationship which is degraded. Accordingly, there is a continuing need to develop a technique capable of simultaneously improving the impact strength and whitening characteristics in the production of a transparent material using a vinyl chloride resin.

KR 2012-0024231 A

The object of the present invention is to solve the problems mentioned in the background of the invention by applying a core-shell copolymer as an impact modifier to a vinyl chloride resin, The impact strength and the optical characteristics are simultaneously improved.

That is, the present invention was conceived to solve the problems of the background art of the present invention, and it is an object of the present invention to simultaneously improve impact strength and optical characteristics of a molded article from a resin composition containing a vinyl chloride polymer and an impact modifier A core-shell copolymer which is an impact modifier, a method for producing the same, and a resin composition containing the same.

According to one embodiment of the present invention for solving the above problems, the present invention provides a core comprising a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an aromatic vinyl monomer, and a repeating unit derived from a bisphenol F-based monomer; And a shell surrounding the core and containing a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from an aromatic vinyl monomer, wherein the content of the repeating unit derived from the bisphenol F-based monomer is such that the content of the repeating unit derived from the monomer The core-shell copolymer is present in an amount of more than 0 wt% to less than 10 wt% with respect to the total amount of the repeating units.

The present invention also relates to a process for producing a core by polymerizing a core-forming monomer mixture comprising a conjugated diene-based monomer, an aromatic vinyl monomer and a bisphenol F-based monomer (S10); And (S20) polymerizing a shell-forming monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer in the presence of the core prepared in the step (S10) to prepare a core-shell copolymer , The content of the bisphenol F-based monomer is more than 0 wt% to less than 10 wt% with respect to the total content of the core-forming monomer mixture.

The present invention also provides a resin composition comprising the core-shell copolymer and the vinyl chloride polymer.

When the core-shell copolymer according to the present invention is used as an impact modifier of a vinyl chloride polymer, there is an effect of simultaneously improving the impact strength and the optical property which are in a trade-off relationship with each other.

The terms and words used in the description of the present invention and in the claims should not be construed to be limited to ordinary or dictionary terms and the inventor should appropriately interpret the concepts of the terms appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The term " core " in the present invention is intended to supplement mechanical properties of the core-shell copolymer. It is meant that the monomer forming the core is a polymer component or a copolymer component And may be a rubber component, or a rubber polymer component, which constitutes the core or core layer of the core-shell copolymer.

The term " shell " in the present invention refers to a shell or shell layer of a core-shell copolymer, in which the monomers forming the shell are graft polymerized to the core of the core-shell copolymer, May refer to a polymer component, or a copolymer component.

The term " monomer-derived repeating unit " in the present invention refers to a component derived from a monomer, a structure thereof, or a substance itself, and when the polymer is polymerized, the introduced monomer means a repeating unit .

The core-shell copolymer according to the present invention comprises a core comprising a repeating unit derived from a conjugated diene monomer, a repeating unit derived from an aromatic vinyl monomer, and a repeating unit derived from a bisphenol F monomer; And a shell surrounding the core and containing a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from an aromatic vinyl monomer, wherein the content of the repeating unit derived from the bisphenol F-based monomer is such that the content of the repeating unit derived from the monomer Relative to the total amount of the repeating units, may be more than 0 wt% to less than 10 wt%.

According to one embodiment of the present invention, the core-shell copolymer contains repeating units derived from a bisphenol F-based monomer having flexibility in the chain and having higher flexibility than the usual repeating unit derived from maleic anhydride, -Shell copolymer as an impact modifier, the impact strength and the optical property of the molded article are simultaneously improved, and the compatibility with the shell is improved, and the processability is also excellent.

According to an embodiment of the present invention, the core may contain 50 wt% to 90 wt%, 60 wt% to 90 wt% of repeating units derived from a conjugated diene monomer, Or from 70 wt% to 85 wt% of repeating units derived from aromatic vinyl monomer, from 5 wt% to 45 wt%, from 5 wt% to 35 wt%, or from 10 wt% to 25 wt% of repeating units derived from aromatic vinyl monomers and from 0 wt% To less than 10% by weight, greater than 0% by weight to 8% by weight, greater than 0% by weight to 5% by weight, or 1% by weight to 5% by weight, It is possible to simultaneously improve the impact strength and optical characteristics of molded articles formed by using the resin composition containing the co-polymer as an impact modifier, and to improve the compatibility with the shell and to improve the workability.

According to an embodiment of the present invention, the conjugated diene-based monomer for forming the repeating unit derived from the conjugated dienic monomer may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-butadiene, 1,3-pentadiene, and isoprene.

According to an embodiment of the present invention, the aromatic vinyl monomer for forming the repeating unit derived from an aromatic vinyl monomer may be selected from the group consisting of styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, Vinylnaphthalene, vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.

According to one embodiment of the present invention, the bisphenol F-based monomer for forming the repeating unit derived from the bisphenol F-based monomer contains a polymerizable group capable of copolymerizing with bisphenol F or a conjugated diene-based monomer and an aromatic vinyl monomer Lt; RTI ID = 0.0 > F < / RTI > According to an embodiment of the present invention, the bisphenol F-based monomer may be a crosslinkable monomer to form a crosslinked portion between the conjugated diene-based monomer and the aromatic vinyl monomer copolymerized in the core and the shell.

Bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol G, bisphenol M, bisphenol S and bisphenol P having a bisphenol- , Bisphenol PH, bisphenol TMC, bisphenol Z, and the like can be obtained by reacting a hydrogen atom of a methylene group (-CH ₂ -) present between both phenolic groups of bisphenol F with a methyl group, a trifluoromethyl group, an ethyl group, Hexane group or the like, or the methylene group itself may be substituted with a dichloromethane group, a sulfoperoxide group, a 1,3-bis (2-propyl) benzene group, a 1,4- Or a phenol group is substituted with an isopropyl group, a phenyl group, or the like, and when a monomer-derived repeating unit having each bisphenol-based structure is formed, the steric hindrance is larger than that of the bisphenol F- Is limited, such as rotation of rosewood, can not have added flexibility to the chain, and the impact strength is lowered, it may reduce the optical properties, may be preferred to use a bisphenol F-based monomer in accordance with the present invention.

According to an embodiment of the present invention, the repeating unit derived from bisphenol F monomer may be a repeating unit derived from bisphenol F acrylate monomer. In this case, when the core is polymerized, polymerization reaction is excellent and compatibility with shell It has excellent effect. As a specific example, the repeating unit derived from the bisphenol F-based monomer may be a repeating unit derived from a bisphenol F diacrylate-based monomer. As a more specific example, the bisphenol F diacrylate monomer-derived repeating unit may be a copolymer of a bisphenol F group and a diacrylate group with an alkylene oxide as a linking group in order to impart flexibility to the chain and exhibit a molecular structure with high transparency May be a repeating unit derived from bisphenol F (alkylene oxide) _n diacrylate containing bisphenol F (ethylene oxide) _n diacrylate, preferably bisphenol F (ethylene oxide) _n diacrylate, n is an integer selected from 1 to 10, 1 to 5, or 4, and n is the total number of repeating units of ethylene oxide existing between both sides of bisphenol F and each acrylate) In this case, it is preferable to use a resin composition having flexibility in the chain and high transparency and containing the core-shell copolymer as an impact modifier, Improved impact strength and optical properties of the molded article at the same time, and further enhance the compatibility with the shell to have excellent processability even effect.

According to an embodiment of the present invention, the shell may be formed by graft-polymerizing an alkyl (meth) acrylate monomer and an aromatic vinyl monomer contained in the shell-forming monomer mixture on the core, (Meth) acrylate monomer-containing repeating unit and an aromatic vinyl monomer-containing repeating unit, and may contain the repeating unit derived from the alkyl (meth) acrylate monomer and the repeating unit derived from an aromatic vinyl monomer Has excellent compatibility with a matrix resin in a resin composition, and has an excellent processability, an impact strength and an optical property.

According to an embodiment of the present invention, the content of the repeating unit derived from an alkyl (meth) acrylate monomer is 40% by weight to 70% by weight, 40% by weight to 60% by weight %, Or 40% by weight to 50% by weight of repeating units derived from an aromatic vinyl monomer and 30% by weight to 60% by weight, 40% by weight to 60% The impact strength and the optical characteristics of the molded article are simultaneously improved by using the resin composition containing the core-shell copolymer as the impact modifier, and the compatibility with the core is improved, and the processability is also excellent. Here, the alkyl (meth) acrylate monomer may mean alkyl acrylate or alkyl methacrylate.

According to an embodiment of the present invention, the repeating unit derived from the alkyl (meth) acrylate monomer may be a repeating unit derived from methyl (meth) acrylate; And recurring units derived from an alkyl (meth) acrylate having 2 to 8 carbon atoms, and specific examples thereof include recurring units derived from methyl methacrylate and recurring units derived from alkyl acrylate having 2 to 8 carbon atoms, In this case, compatibility with the bisphenol F-based monomer-derived repeating unit in the core is excellent, and the processability and impact strength are excellent.

According to one embodiment of the present invention, the alkyl group having 2 to 8 carbon atoms in the alkyl (meth) acrylate having 2 to 8 carbon atoms forming the repeating unit derived from the alkyl (meth) acrylate monomer having 2 to 8 carbon atoms is preferably a Lt; / RTI > linear alkyl group of 3 to 8 carbon atoms and a branched alkyl group of 3 to 8 carbon atoms. As specific examples, the alkyl (meth) acrylate monomer may be selected from the group consisting of ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, ) Acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

According to an embodiment of the present invention, the aromatic vinyl monomer for forming the repeating unit derived from an aromatic vinyl monomer in the shell may be the same as or different from the aromatic vinyl monomer for forming a repeating unit derived from an aromatic vinyl monomer in the core Specific examples thereof include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- -Hexyl naphthalene. ≪ / RTI >

According to an embodiment of the present invention, the shell includes a first shell including the repeating unit derived from the alkyl (meth) acrylate monomer and a second shell including the repeating unit derived from the aromatic vinyl monomer In this case, the compatibility with the core from the first shell is maximized, the compatibility with the matrix resin from the second shell is maximized, and the processability of the resin composition containing the core-shell copolymer as the impact modifier is improved , And the impact strength and the optical characteristics of the molded article obtained therefrom are excellent.

Further, according to an embodiment of the present invention, the shell may have a graft rate of 90% or more, 90% to 99%, or 95% to 99%, sufficiently forming a shell from a high graft rate within this range, Strength and optical characteristics.

According to an embodiment of the present invention, the core-shell copolymer may contain 60 wt% to 90 wt%, 60 wt% to 80 wt%, or 65 wt% of the core, To 75% by weight of the shell and 10% to 40%, 20% to 40%, or 25% to 35% by weight of the shell, and within this range, the core- The molded article molded from the resin composition containing the resin composition has excellent processability and impact strength, and has an excellent thermal stability.

The present invention also provides a method for producing a core-shell copolymer for producing the core-shell copolymer. The method for producing a core-shell copolymer comprises: (S10) polymerizing a core-forming monomer mixture comprising a conjugated diene monomer, an aromatic vinyl monomer, and a bisphenol F monomer to produce a core; And (S20) polymerizing a shell-forming monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer in the presence of the core prepared in the step (S10) to prepare a core-shell copolymer , The content of the bisphenol F-based monomer may be more than 0 wt% to less than 10 wt% with respect to the total amount of the core-forming monomer mixture.

According to an embodiment of the present invention, the core-shell copolymer manufacturing method may include step of polymerizing the core and the shell stepwise by steps (S10) and (S20), and (S10) , Polymerizing the core of the core-shell copolymer, and then polymerizing the shell on the core through step (S20).

According to an embodiment of the present invention, the step (S10) may be a step for producing a core of the core-shell copolymer, and the type of each monomer in the core-forming monomer mixture charged in the step (S10) The content may be the same as the kind and content of each monomer for forming each monomer-derived repeating unit contained on the core described above.

According to an embodiment of the present invention, the step (S20) may be a step for preparing a shell of the core-shell copolymer, and the step (S20) The kind and content may be the same as the kind and content of each monomer for forming each monomer-derived repeating unit contained on the shell described above.

According to an embodiment of the present invention, the polymerization in the step (S10) and the step (S20) may be carried out by emulsion polymerization, bulk polymerization, solution polymerization or suspension polymerization, In the presence of a peroxide, a redox, or an azo-based initiator, and may be carried out by emulsion polymerization in view of easily producing a core-shell copolymer, Accordingly, emulsifying agents can be included. The core and the core-shell copolymer produced in the step (S10) and the step (S20) may be in the form of a core latex and a core-shell copolymer latex, respectively, in which the core and the core- And a process such as agglomeration, aging, dehydration and drying may be carried out in order to obtain the core-shell copolymer in the form of a powder from the core-shell copolymer.

According to an embodiment of the present invention, the step (S10) may be performed at 30 to 65 ° C, or 40 to 60 ° C, and the step (S20) may be performed at 40 to 70 ° C, To 65 占 폚, the polymerization stability is excellent within this range, and the effect of improving the grafting rate upon formation of the shell is obtained.

The resin composition according to the present invention may comprise the core-shell copolymer and the vinyl chloride polymer. That is, the resin composition may be a vinyl chloride resin composition.

According to one embodiment of the present invention, the resin composition comprises 1 to 20 parts by weight, 1 to 15 parts by weight, or 1 to 5 parts by weight of the core-shell copolymer per 100 parts by weight of the vinyl chloride polymer. 10 parts by weight, and the impact strength and optical characteristics of the molded article molded from the resin composition within this range are excellent.

The resin composition according to the present invention may contain, in addition to the vinyl chloride polymer and the core-shell copolymer, a stabilizer, a processing aid, a heat stabilizer, a lubricant, a pigment, a dye, And the like.

Also, according to one embodiment of the present invention, the resin composition may include the vinyl chloride polymer in the form of a master batch prepared by pre-mixing with the various additives.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood, however, that the following examples are illustrative of the present invention and that various changes and modifications can be made within the scope and spirit of the present invention, which are obvious to those of ordinary skill in the art and do not limit the scope of the present invention.

Example

Example 1

≪ Preparation of core &

In a 120 L high-pressure polymerization reactor equipped with a stirrer, 150 parts by weight of ion-exchanged water, 0.5 part by weight of potassium hydroxide, 2.0 parts by weight of potassium oleate as an emulsifier, 0.0047 weight parts of ethylenediaminetetra sodium acetate , 0.003 part by weight of ferrous sulfate, 0.02 part by weight of sodium formaldehyde sulfoxylic acid and 0.1 part by weight of diisopropylbenzene hydroperoxide. Here the 1, 3-butadiene (BD) 79% by weight of styrene (SM) 18 wt% of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA) consisting of 3% by weight of the core forming monomer mixture 100 , And the mixture was polymerized at 50 DEG C for 12 hours to obtain a latex containing the core. At this time, the final polymerization conversion ratio was 98%, and the average particle diameter of the core in the latex was 100 nm.

≪ Preparation of Core-Shell Copolymer >

70 parts by weight (based on solid content) of the obtained core was charged into a closed reactor to 100 parts by weight of the total of the obtained core and shell-forming monomer mixture, 0.0094 part by weight of ethylenediaminetetra sodium acetate, 0.006 part by weight of ferrous sulfate and 0.04 part by weight of sodium formaldehyde sulfoxylic acid were added, and then 1.0 part by weight of potassium oleate as an emulsifier and 12 parts by weight of methyl methacrylate (MMA) and 1.0 part by weight of ethyl acrylate (EA) 15 parts by weight of ion-exchanged water and 0.05 part by weight of t-butyl hydroperoxide were continuously added for 10 minutes, and polymerization was carried out at 60 DEG C for 2 hours. Then, 18 parts by weight of styrene (SM) as a monomer, 0.0094 part by weight of ethylenediaminetetra sodium acetate, 0.006 part by weight of ferrous sulfate, 0.04 part by weight of sodium formaldehyde sulfoxylate, 0.15 part by weight of potassium oleate, And 0.05 part by weight of t-butyl hydroperoxide were charged, and polymerization was carried out at 60 DEG C for 2 hours to obtain a latex containing the core-shell copolymer. At this time, the measured graft rate was 98%.

≪ Preparation of Core-shell Copolymer Powder >

0.5 parts by weight of an antioxidant (Irganox-245) was added to 100 parts by weight (based on solid content) of the latex containing the core-shell copolymer obtained above, agitated with an aqueous sulfuric acid solution while stirring, And water were separated, followed by dehydration and drying to obtain a core-shell copolymer powder.

Example 2

In Example 1, the preparation of the core, the I Styrene core forming monomer mixture was 16% by weight instead of 18% by weight of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA), 3 wt.% Instead of 5% by weight, based on the total weight of the composition.

Example 3

In Example 1, the preparation of the core, the I Styrene core forming monomer mixture was 20% by weight instead of 18% by weight of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA), 3 wt.% Instead of 1% by weight based on the total weight of the composition.

Comparative Example 1

Except that the same amount of divinylbenzene (DVB) was added in place of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA) in the core-forming monomer mixture in the production of core in Example 1 above. The procedure of Example 1 was repeated.

Comparative Example 2

(Ethylene oxide) dimethacrylate (BPA (EO) ₄ ) instead of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA) in the core- DMA) were added in the same amount.

Comparative Example 3

In Example 1, 11% by weight of styrene in the core-forming monomer mixture was used instead of 18% by weight, and 3% by weight of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA) 10% by weight based on the total weight of the composition.

Comparative Example 4

1% by weight of divinylbenzene (DVB) was used instead of 3% by weight of bisphenol F (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA) in the core- (Ethylene oxide) dimethacrylate (BPA (EO) DMA) in an amount of 2% by weight.

Comparative Example 5

2% by weight of divinylbenzene (DVB) and 3% by weight of bisphenol A (ethylene oxide) ₄ diacrylate (BPF (EO) ₄ DA) in the core- (Ethylene oxide) dimethacrylate (BPA (EO) DMA) in an amount of 1% by weight.

Experimental Example

In order to evaluate the impact strength, transparency and surface gloss of a molded article molded from a resin composition containing the core-shell copolymer prepared in Examples 1 to 3 and Comparative Examples 1 to 5 as an impact modifier, Composite specimens were prepared and evaluated and are shown in Table 1 together with the composition of each core-shell copolymer.

1) Preparation of resin composition specimen

100 parts by weight of a vinyl chloride polymer (manufactured by LG Chemical Co., Ltd., product name: 080S), 1.5 parts by weight of a heat stabilizer (tin stearate), 1.0 part by weight of an internal lubricant (potassium stearate), 0.3 parts by weight of an external lubricant (paraffin wax) 0.5 part by weight of PA-910 manufactured by LG Chemical Co., Ltd.) and 0.5 part by weight of pigment were thoroughly mixed at a temperature of 130 캜 using a high-speed stirrer and then cooled to prepare a vinyl chloride polymer master batch. Seven parts by weight of the core-shell copolymer powder prepared in each of Examples 1 to 3 and Comparative Examples 1 to 5 was added to the vinyl chloride polymer masterbatch prepared above, and a roll of 195 ° C was used for 5 minutes To prepare a sheet having a thickness of 0.5 mm.

2) Impact strength

A rotary test specimen was prepared by cutting the prepared resin composition specimen to a size of 3 cm (width) × 14 cm (length), and rotated at a high temperature (20 ° C. to 26 ° C.) at 950 rpm to 1,050 rpm The impact efficiency was calculated by measuring the number of broken specimens. The higher the impact efficiency, the better the impact strength.

3) Transparency

Based on the evaluation method of ASTM D-1003, the prepared resin composition specimen was measured for total transmittance (TT) and haze using a Haze Meter HZ-V3 instrument. The lower the total transmitted light (TT) and the haze, the better the transparency.

4) Surface gloss

The surface of the resin composition specimen was measured with a gloss meter UD instrument manufactured by TOYO SEIKI Co., Ltd. at 60 DEG angle, and the surface gloss of the resin composition specimen was measured using a Suga Test Instruments The Yellowness Index (YI) was measured using a surface color measuring device of the present invention. The higher the degree of gloss of 60 DEG, the lower the yellowing index (YI), the better the surface gloss.

As shown in Table 1, according to the present invention, the impact strength of a molded article molded from a resin composition containing a core-shell copolymer containing a repeating unit derived from a bisphenol F-based monomer as an impact modifier on a core, It was confirmed that all the optical characteristics of the surface gloss were remarkably improved as compared with Comparative Example 1 using divinylbenzene which is a crosslinkable monomer commonly used in cores.

On the other hand, even in the case of using the bisphenol-based monomer, in Comparative Example 2 using the bisphenol A-based monomer instead of the bisphenol F-based monomer according to the present invention, the optical characteristics were lowered as the impact strength was improved, And Comparative Example 3 in which an excess amount of bisphenol F-based monomer was added and the amount of bisphenol F-based monomer was increased, It was confirmed that the content of the forming monomer was reduced and the effect of improving the impact strength and optical characteristics was only marginal.

Even in the case of using the conventional crosslinkable monomer divinylbenzene and bisphenol A monomer simultaneously, even in the case of Comparative Examples 4 and 5 not containing the bisphenol F-based monomer according to the present invention, the impact strength and optical characteristics It was confirmed that the effect was all at a minimal level.

From the above results, the present inventors have found that when the core-shell copolymer produced according to the present invention is used as an impact modifier of a vinyl chloride polymer, it is possible to simultaneously improve the impact strength and the optical characteristics in a trade- Respectively.

Claims (10)

A core comprising a repeating unit derived from a conjugated diene monomer, a repeating unit derived from an aromatic vinyl monomer, and a repeating unit derived from a bisphenol F-based monomer; And
A shell surrounding the core, the shell comprising a repeating unit derived from an alkyl (meth) acrylate monomer and a repeating unit derived from an aromatic vinyl monomer,
The content of the bisphenol F-based monomer-derived repeating unit is more than 0 wt% to less than 10 wt% with respect to the total amount of the repeating units derived from the monomer contained in the core. The method according to claim 1,
Wherein the core contains 50% by weight to 90% by weight of repeating units derived from conjugated diene monomer, 5% by weight to 45% by weight of repeating units derived from aromatic vinyl monomer, and a repeating unit derived from bisphenol F From 0% to less than 10% by weight of monomeric repeat units. The method according to claim 1,
The content of the repeating unit derived from the bisphenol F-based monomer is 1% by weight to 5% by weight based on the total amount of the repeating units derived from the monomer contained in the core. The method according to claim 1,
Wherein the repeating unit derived from the bisphenol F monomer is a bisphenol F acrylate monomer-derived repeating unit. 5. The method of claim 4,
A bisphenol F acrylate-based monomer-derived repeating units of bisphenol F (ethylene oxide) _n diacrylate (Bisphenol F (ethylene oxide) _n diacrylate, n is from 1 to 10 selected integer) a core derived from the repeating unit-shell copolymer. The method according to claim 1,
The repeating unit derived from the alkyl (meth) acrylate monomer is preferably a repeating unit derived from methyl (meth) acrylate; And a repeating unit derived from an alkyl (meth) acrylate having 2 to 8 carbon atoms. The method according to claim 1,
Wherein the core-shell copolymer comprises 60 to 90% by weight of the core and 10 to 40% by weight of the shell, based on the total content of the core-shell copolymer. (S10) polymerizing a core-forming monomer mixture comprising a conjugated diene-based monomer, an aromatic vinyl monomer, and a bisphenol F-based monomer to prepare a core; And
Forming a core-shell copolymer by polymerizing a shell-forming monomer mixture comprising an alkyl (meth) acrylate monomer and an aromatic vinyl monomer in the presence of the core produced in the step (S10)
Wherein the content of the bisphenol F-based monomer is more than 0 wt% to less than 10 wt% with respect to the total content of the core-forming monomer mixture. A resin composition comprising a core-shell copolymer according to any one of claims 1 to 7 and a vinyl chloride polymer. 10. The method of claim 9,
Wherein the resin composition comprises 1 to 20 parts by weight of the core-shell copolymer with respect to 100 parts by weight of the vinyl chloride polymer.