KR102274032B1 - Core-shell copolymer composition, method for preparing the copolymer composition and resin composition comprising the copolymer composition - Google Patents

Abstract

The present invention relates to a core-shell copolymer composition, and more particularly, to a core-shell copolymer, wherein silica particles containing a glycerol-based functional group are adsorbed onto a part or all of the surface of the core-shell copolymer. and the silica particles containing the glycerol-based functional group have a particle size of less than 80 nm, and the content of the silica particles containing the glycerol-based functional group is greater than 0 parts by weight to 28 parts by weight based on 100 parts by weight of the core-shell copolymer. Provided are a core-shell copolymer composition having a silica adsorption efficiency of 30% or more, a method for preparing the same, and a resin composition comprising the same.

Description

Core-shell copolymer composition, manufacturing method thereof, and resin composition comprising the same

The present invention relates to a core-shell copolymer composition, and more particularly, to a core-shell copolymer composition, a method for preparing the same, and a resin composition comprising the same.

Vinyl chloride resin is widely used in various fields due to its low price, easy hardness control, various application fields, and excellent physical and chemical properties. The vinyl chloride resin may be molded by mixing with various additives in order to supplement various physical properties including impact resistance of the vinyl chloride resin, rather than being used alone during product molding.

In this regard, acrylic resins without unsaturated double bonds have excellent weather resistance and are widely used as impact modifiers for outdoor plastic products with a lot of exposure to sunlight. For example, in products that require both impact resistance and weather resistance, such as window frames, a core-shell structure in which a methacrylic polymer having excellent compatibility with a vinyl chloride resin used as a base resin is grafted onto a rubbery core composed of an alkyl acrylate. Polymers are mainly used. However, there are frequent cases in which the physical properties of the surface of the product are deteriorated due to discoloration and deterioration of gloss due to dust, scratches, etc. on the surface when stored for a long time after molding the product or when exposed to the outdoors.

For example, Korean Patent Application Laid-Open No. 2008-0060731 discloses an acrylic impact modifier in which the rubber content and molecular weight of the shell are controlled, but in the case of this method, in general, during extrusion processing, the extrusion load is high and the extrusion amount is low. There is a problem in that the productivity is lowered, the production cost is increased accordingly, the manufactured molded article is discolored, and the surface properties are poor due to a decrease in gloss.

In addition, Korean Patent Application Laid-Open No. 2011-0084045 discloses an acrylic impact modifier including a separate lubricating shell on the shell to improve processability, but discoloration and gloss of the molded article still produced by this method The deterioration of the surface properties due to the deterioration has not been solved.

Accordingly, the development of an impact modifier capable of improving not only the impact resistance and workability of the vinyl chloride resin, but also the heat resistance and antifouling properties is continuously required.

US 2008-0060731 A US 2011-0084045 A

The problem to be solved in the present invention is the impact resistance and extrusion processability of a molded article prepared from a resin composition comprising a core-shell copolymer composition as an acrylic impact modifier in order to solve the problems mentioned in the technology that is the background of the invention. Of course, it is to improve surface properties by improving heat resistance and antifouling properties.

That is, the present invention was devised to solve the problems of the technology that is the background of the invention, and by adsorbing silica particles containing a glycerol-based functional group to the core-shell copolymer, the powder compactability of the core-shell copolymer (compact compaction) ) and excellent funnel flow, excellent extrusion processability of a resin composition comprising the core-shell copolymer composition, and a core-shell copolymer composition capable of improving impact resistance, heat resistance and antifouling properties of a molded article prepared from the resin composition An object of the present invention is to provide a method for preparing the same, and a resin composition comprising the same.

According to one embodiment of the present invention for solving the above problems, the present invention includes a core-shell copolymer, and silica particles containing a glycerol-based functional group on a part or all of the surface of the core-shell copolymer adsorbed, the silica particles containing the glycerol-based functional group have a particle size of less than 80 nm, and the content of the silica particles containing the glycerol-based functional group is greater than 0 parts by weight based on 100 parts by weight of the core-shell copolymer. It provides a core-shell copolymer composition that is less than 28 parts by weight and has a Silica Adsorption efficiency of 30% or more.

In addition, the present invention comprises the steps of i) polymerizing a monomer mixture for forming a core in the presence of a silica sol containing silica particles containing a cationic emulsifier and a glycerol-based functional group to prepare a core polymer (S10); ii) emulsion polymerization of the shell-forming monomer mixture in the presence of the core polymer prepared in step (S10) to prepare a core-shell copolymer (S20), and a glycerol-based functional group included in the silica sol Silica particles containing a particle size of less than 80 nm, the silica sol is added in an amount of more than 0 parts by weight to less than 40 parts by weight based on 100 parts by weight of the total content of the monomer mixture for forming the core and the monomer mixture for forming the shell, Provided is a method for preparing a core-shell copolymer composition in which the silica adsorption efficiency of the core-shell copolymer composition including the core-shell copolymer prepared in step (S20) is 30% or more.

In addition, the present invention provides a resin composition comprising the core-shell copolymer composition and a vinyl chloride polymer.

When the core-shell copolymer composition is prepared according to the present invention, it is possible to adsorb silica particles containing a glycerol-based functional group to the core-shell copolymer with high efficiency, and thus the prepared core-shell copolymer composition By improving powder compaction and funnel flow, the extrusion processability of the resin composition comprising the core-shell copolymer composition is improved, the impact resistance of a molded article prepared from the resin composition is improved, and heat resistance and antifouling properties are improved. Accordingly, there is an effect that the surface properties are improved.

1 is a silica particle containing a glycerol-based functional group according to the electrostatic properties between micelles formed from a cationic emulsifier and silica particles containing a glycerol-based functional group during the preparation of a core-shell copolymer composition according to the present invention; It is a schematic diagram showing the state adsorbed to the surface of the core-shell copolymer.
2 is a schematic diagram showing a state in which silica particles containing a glycerol-based functional group are adsorbed on the surface of the core-shell copolymer according to the electrostatic properties between micelles formed from an anionic emulsifier and silica particles containing a glycerol-based functional group to be.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

In the present invention, the term 'core' may mean a rubber component or a rubber polymer component constituting the core or core layer of the core-shell copolymer.

In the present invention, the term 'shell' may refer to a polymer component or a copolymer component that is graft-polymerized on the core of the core-shell copolymer to form a shell or a shell layer.

In the present invention, the term 'silica particles' refers to silica (SiO ₂ ) itself, or a silicon (Si) atom and an oxygen atom (O) bonded to each other in a shared state to "-O-Si-O-" and "-Si- It may refer to silica particles formed including a bonding structure such as "O-Si-".

In the present invention, the term 'adsorption' may refer to a form in which silica particles are attached to the surface of the core-shell copolymer in any form by a physical bond such as a chemical bond or an electrostatic bond.

In the present invention, the term 'silica sol' may mean a silica sol in which colloidal silica particles are dispersed in a dispersion medium.

In the present invention, the term '(meth)acrylate' may mean acrylate or methacrylate.

In the present invention, the term 'monomer-derived repeating unit' may refer to a component, structure, or material itself derived from a monomer, and refers to a repeating unit formed in the polymer by participating in the polymerization reaction during polymerization of the polymer. may be doing

In the present invention, the term 'latex' may mean that the polymer or copolymer polymerized by polymerization exists in a dispersed form in water, and as a specific example, the polymer or copolymer in rubber phase polymerized by emulsion polymerization is It may mean that the fine particles exist in a dispersed form in water in a colloidal state.

The core-shell copolymer composition according to the present invention includes a core-shell copolymer, and silica particles containing a glycerol-based functional group are adsorbed on a part or all of the surface of the core-shell copolymer, and the glycerol-based functional group Silica particles containing a particle size of less than 80 nm, the content of the silica particles containing the glycerol-based functional group is more than 0 parts by weight to less than 28 parts by weight based on 100 parts by weight of the core-shell copolymer, silica adsorption The efficiency (Silica Adsorption efficiency) may be 30% or more. As described above, when the silica particles containing the glycerol-based functional group having the particle size are adsorbed to the core-shell copolymer with the above content and the silica adsorption efficiency, the powder compaction of the core-shell copolymer composition And by improving the funnel flow, the extrusion processability of the resin composition comprising the core-shell copolymer composition is improved, the impact resistance of the molded article prepared from the resin composition is improved, and the surface properties are improved due to the improvement of heat resistance and antifouling properties has the effect of being

According to an embodiment of the present invention, the core may be a core polymer constituting the core of the core-shell copolymer, and a specific example may include a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms. and the shell may be a shell polymer that is grafted onto the core polymer and surrounds the core, and as a specific example, a repeating unit derived from a methyl (meth)acrylate monomer and a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms. It may include a unit.

According to an embodiment of the present invention, the alkyl (meth)acrylate monomer having 2 to 8 carbon atoms forming a repeating unit derived from the alkyl (meth)acrylate monomer having 2 to 8 carbon atoms included in the core and the shell, respectively, is ethyl ( Meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate and 2-ethyl It may be at least one member selected from the group consisting of hexyl (meth) acrylate, and in this case, a molded article prepared from the resin composition including the core-shell copolymer composition has excellent impact resistance.

In addition, according to an embodiment of the present invention, the core may further include a repeating unit derived from a crosslinkable monomer in addition to the repeating unit derived from the alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, in which case the core polymerization is performed. In addition, when the shell is formed by the graft, there is an effect of improving the polymerization reactivity. The crosslinkable monomer is ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, allyl (meth)acrylate, trimethylolpropane tri(meth)acrylate and pentaerythritol tetra(meth) ) (meth)acrylic crosslinkable monomers such as acrylates; It may be at least one selected from vinyl-based crosslinking monomers such as divinylbenzene, divinylnaphthalene and diallylphthalate.

According to an embodiment of the present invention, when the core further includes a repeating unit derived from a crosslinkable monomer, the content of the repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms is based on the total content of the core, 95 wt% to 99.9 wt%, 97 wt% to 99.9 wt%, or 98.5 wt% to 99.9 wt%, the content of the repeating unit derived from the crosslinkable monomer is 0.1 wt% to 5 wt% based on the total content of the core Weight %, 0.1 wt% to 3 wt%, may be 0.1 wt% to 1.5 wt%, within this range, the polymerization productivity is excellent, and the impact resistance of the molded article prepared from the composition including the core-shell copolymer composition It has an excellent effect.

In addition, according to an embodiment of the present invention, the content of the methyl (meth) acrylate monomer-derived repeating unit included in the shell is 68.5 wt% to 99.8 wt%, 70 wt% to 95 wt%, based on the total content of the shell Weight %, or may be 80% to 95% by weight, and the content of the repeating unit derived from the alkyl (meth)acrylate monomer having 2 to 8 carbon atoms included in the shell is 0.2% by weight to 31.5% by weight based on the total content of the shell. It may be weight %, 5 weight % to 30 weight %, or 5 weight % to 20 weight %, and within this range, impact resistance, surface properties and heat resistance of a molded article prepared from a resin composition including the core-shell copolymer composition This has an excellent effect.

In addition, according to an embodiment of the present invention, the content of the core is 60% to 95% by weight, 70% to 95% by weight, or 80% to 95% by weight based on the total content of the core-shell copolymer. may be, and the content of the shell may be 5 wt% to 40 wt%, 5 wt% to 30 wt%, or 5 wt% to 20 wt%, based on the total content of the core-shell copolymer, within this range In the core-shell copolymer composition, the molded article prepared from the resin composition has excellent impact resistance and excellent balance between physical properties.

On the other hand, according to an embodiment of the present invention, the silica particles containing the glycerol-based functional group may have a particle size of less than 80 nm, 1 nm to 60 nm, or 4 nm to 50 nm, and within this range, extremely According to the dispersion of the fine particles, the powder properties of the core-shell copolymer composition to which the silica particles are adsorbed are improved, the extrusion processability of the resin composition comprising the same, and the impact resistance, heat resistance and abrasion resistance of a molded article prepared from the resin composition are improved. has the effect of improving The range of the particle size may mean a range of particle sizes including the respective sizes of the silica particles themselves, and may mean an average particle diameter of a plurality of silica particles.

In addition, according to an embodiment of the present invention, the silica particles contain a glycerol-based functional group on the surface of the silica particles, thereby preventing dust, etc. from adhering due to the negative electrostatic properties of the glycerol-based functional group. can be performed.

In addition, according to an embodiment of the present invention, the content of the silica particles containing the glycerol-based functional group is more than 0 parts by weight to less than 28 parts by weight, 0.03 parts by weight to 25 parts by weight based on 100 parts by weight of the core-shell copolymer. parts, or 0.03 parts by weight to 21 parts by weight, within this range, the powder properties of the core-shell copolymer composition are excellent, and the impact resistance and antifouling properties of the molded article prepared from the resin composition including the same are excellent.

According to an embodiment of the present invention, the glycerol-based functional group of the silica particles containing the glycerol-based functional group may be represented by the following formula (1).

[Formula 1]

*-O-SiR ¹ R ² -(CH ₂ ) _n -O(CH ₂ )-CH(OH)-CH ₂ OH

In Formula 1, R ¹ and R ² may each independently be hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and n may be an integer selected from 1 to 10. As a specific example, in Formula 1, R ¹ and R ² may each independently be an alkoxy group having 1 to 5 carbon atoms, and n may be an integer selected from 1 to 5. As a more specific example, in Formula 1, R ¹ and R ² may each independently be an alkoxy group having 1 to 3 carbon atoms, and n may be an integer selected from 2 to 4. * denotes a bonding position with silica particles. That is, the silica particles containing a glycerol-based functional group according to an embodiment of the present invention may contain a glycerol-based functional group on the surface of the silica particles. In addition, the silica particles including the glycerol-based functional group may be derived from the silica sol containing the silica particles.

In addition, according to an embodiment of the present invention, the silica adsorption efficiency of the core-shell copolymer composition may be 30% or more, 50% or more, 80% or more, or 80% to 99%, and silica within this range The particles are present in an adsorbed state in a uniformly dispersed form on the surface of the core-shell copolymer included in the core-shell copolymer composition to improve the powder properties of the core-shell copolymer composition, and It improves extrusion processability, and has the effect of improving the impact resistance, heat resistance, and abrasion resistance of the molded article manufactured from the resin composition.

In addition, the present invention provides a method for preparing the core-shell copolymer for preparing the core-shell copolymer. According to an embodiment of the present invention, the method for preparing the core-shell copolymer comprises i) polymerizing a monomer mixture for forming a core in the presence of a silica sol containing silica particles containing a cationic emulsifier and a glycerol-based functional group. preparing a core polymer (S10); ii) emulsion polymerization of the shell-forming monomer mixture in the presence of the core polymer prepared in step (S10) to prepare a core-shell copolymer (S20), and a glycerol-based functional group included in the silica sol Silica particles containing a particle size of less than 80 nm, the silica sol is added in an amount of more than 0 parts by weight to less than 40 parts by weight based on 100 parts by weight of the total content of the monomer mixture for forming the core and the monomer mixture for forming the shell, The silica adsorption efficiency of the core-shell copolymer composition including the core-shell copolymer prepared in step (S20) may be 30% or more.

According to an embodiment of the present invention, the polymerization of step (S10) and step (S20) is performed with a peroxide-based, redox, or azo-based initiator in the presence of a monomer mixture for forming a core and a monomer mixture for forming a shell, respectively. It may be carried out by radical polymerization using a, and may be carried out by an emulsion polymerization method.

According to an embodiment of the present invention, the step (S10) is a step for polymerizing the core polymer forming the core of the core-shell copolymer included in the core-shell copolymer composition, and emulsifying the monomer mixture for forming the core. It may be carried out by polymerization.

According to an embodiment of the present invention, the monomer mixture for forming the core may include the aforementioned alkyl (meth)acrylate monomer having 2 to 8 carbon atoms, and may further include a crosslinking monomer if necessary. and the type and content of each monomer may be the same as the above-described type of the monomer and the content of the monomer-derived repeating unit.

On the other hand, according to an embodiment of the present invention, the emulsion polymerization of step (S10) may be carried out in the presence of an emulsifier, in this case, the emulsifier may be a cationic emulsifier. The cationic emulsifier imparts a positive charge on the surface of micelles formed from the emulsifier to polymerize the core polymer and the core-shell copolymer during emulsion polymerization of the core polymer and the core-shell copolymer. , has an effect of improving the adsorption property of silica particles containing a negative glycerol-based functional group according to the electrostatic properties (see FIG. 1 ). That is, unlike the present invention, in the case of using an anionic emulsifier during the emulsion polymerization of the step (S10), a negative charge is imparted to the surface of the micelles, and the silica particles containing the glycerol-based functional group and the electrostatic Since the adsorption efficiency of silica particles is lowered due to the miraculous repulsive action (see FIG. 2 ), it is preferable to use a cationic emulsifier.

According to an embodiment of the present invention, the cationic emulsifier is 0.5 parts by weight to 3 parts by weight, 0.5 parts by weight to 2 parts by weight, or based on 100 parts by weight of the total content of the monomer mixture for forming the core and the monomer mixture for forming the shell. It may be added in an amount of 1 to 2 parts by weight, and within this range, the polymerization reactivity of the steps (S10) and (S20) is excellent, and the silica particles containing a glycerol-based functional group and the adsorption efficiency are excellent.

In addition, according to an embodiment of the present invention, the cationic emulsifier may be at least one selected from the group consisting of hexadecyl trimethylammonium chloride, dodecyl trimethylammonium chloride and didecyl dimethylammonium chloride, in this case (S10) While excellent in polymerization reactivity in the steps and (S20), there is an effect of excellent adsorption efficiency with silica particles containing a glycerol-based functional group.

In addition, according to an embodiment of the present invention, the silica sol containing the silica particles containing the glycerol-based functional group contains the glycerol-based functional group on micelles formed from the cationic emulsifier with the silica particles containing the glycerol-based functional group. to adsorb silica particles, which is added in the form of a silica sol containing silica particles to improve the dispersibility of the silica particles containing the glycerol-based functional group during emulsion polymerization and to improve accessibility to the micelles it could be

According to an embodiment of the present invention, the silica sol may have a pH of 3 to 11, 5 to 10, or 7 to 8, and within this range, the silica particles containing a glycerol-based functional group included in the silica sol are negatively charged. By maintaining the properties, there is an effect of easy adsorption to the surface of the core-shell copolymer. On the other hand, the pH of the silica sol may be changed and maintained depending on the type of emulsifier input during emulsion polymerization. In the polymerization environment in which the cationic emulsifier is added, the pH is maintained, but in the polymerization environment in which the anionic emulsifier is added, The pH may be lowered to lower the silica adsorption efficiency.

According to an embodiment of the present invention, the content of the silica particles containing a glycerol-based functional group included in the silica sol, that is, the total solid content (TSC) of the silica particles in the silica sol, is 10 weight based on the total content of the silica sol. % to 70% by weight, 20% to 60% by weight, or 30% to 40% by weight, and within this range, the dispersibility of the silica particles in the silica sol is excellent, so that the core-shell copolymer of silica particles Accessibility is improved, and thus, there is an effect of excellent silica adsorption efficiency.

According to one embodiment of the present invention, the silica sol containing the silica particles containing the glycerol-based functional group is preferably added in the step (S10), which is that the silica particles approach the micelles formed by the cationic emulsifier. This is because it is possible to maximize the time for adsorption by maximizing the silica adsorption efficiency. It is also possible to introduce the silica particles in the step (S20) to be described later, but in this case, the silica adsorption efficiency may be reduced.

In addition, according to an embodiment of the present invention, the silica sol is more than 0 parts by weight to less than 40 parts by weight, 1 part by weight to 40 parts by weight based on 100 parts by weight of the total content of the monomer mixture for forming the core and the monomer mixture for forming the shell. It may be added in parts, or 1 part by weight to 30 parts by weight, and has the effect of maximizing the silica adsorption efficiency within this range.

In addition, according to an embodiment of the present invention, the step (S20) is a step for polymerizing the core-shell copolymer by forming a shell of the core-shell copolymer included in the core-shell copolymer composition, and forming the shell. It may be carried out by graft polymerization of the monomer mixture for the core polymer.

According to an embodiment of the present invention, the monomer mixture for forming the shell may include the above-described methyl (meth) acrylate monomer and an alkyl (meth) acrylate monomer having 2 to 8 carbon atoms, and the type of each monomer and the content may be the same as the type of the above-described monomer and the content of the repeating unit derived from the monomer.

In addition, according to an embodiment of the present invention, the polymerization of the (S10) step and the (S20) step may be carried out at a temperature of 70 ℃ to 150 ℃, or 70 ℃ to 130 ℃, the polymerization of each step It may be carried out in the presence of various solvents and additives commonly used for carrying out the process.

In addition, according to an embodiment of the present invention, the core polymer and the core-shell copolymer prepared in the (S10) and (S20) steps are obtained in the form of latex in which the polymer and the copolymer are dispersed in a solvent, respectively. After preparing the core-shell copolymer latex in the step (S20), in order to obtain a core-shell copolymer composition including the core-shell copolymer in the form of powder, agglomeration, aging, dehydration and drying, etc. of the process can be carried out.

In addition, there is provided a resin composition comprising the core-shell copolymer composition according to the present invention as an impact modifier. The resin composition may include the core-shell copolymer and the vinyl chloride polymer. That is, the resin composition may be a vinyl chloride resin composition.

According to an embodiment of the present invention, the vinyl chloride polymer may be used without limitation as long as it is a vinyl chloride polymer including a repeating unit derived from a vinyl chloride monomer, and the resin composition is the core based on 100 parts by weight of the vinyl chloride polymer. -The shell copolymer composition may be included in an amount of 1 to 10 parts by weight, or 3 to 8 parts by weight, within this range, the extrusion processability of the resin composition is improved, and the impact resistance of a molded article prepared from the resin composition is improved. It has the effect of improving the surface properties according to the improvement of heat resistance and antifouling properties.

In addition to the core-shell copolymer composition and the vinyl chloride polymer, the resin composition according to the present invention may contain, if necessary, a stabilizer, a processing aid, a heat stabilizer, a lubricant, a pigment, a dye, and an oxidation agent within a range that does not reduce the physical properties thereof. An additive such as an inhibitor may be further included.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are intended to illustrate the present invention, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, and the scope of the present invention is not limited thereto.

Example

Example 1

<Core manufacturing>

Prepare a reactor of a four-neck flask equipped with a stirrer, thermometer, nitrogen inlet and circulation condenser, and contain glycerol-based functional groups having a particle size of 12 nm with 80 parts by weight of deionized water (DDI water) and 40% by weight of total solid content. 15 parts by weight of a silica sol (manufactured by Akzonobel, product name: Bindzil CC401), 0.01 parts by weight of ferrous sulfate, and 0.19 parts by weight of disodium ethylenediaminetetraacetate, and 0.19 parts by weight of disodium ethylenediaminetetraacetate were added, and the temperature inside the reactor was maintained at 55 ° C. did it

On the other hand, 50 parts by weight of ionized water, 1 part by weight of hexadecyl trimethylammonium chloride, 89.55 parts by weight of butyl acrylate, and 0.45 parts by weight of allyl methacrylate were added to prepare a monomer pre-emulsion, and when the reactor internal temperature reached 55 ° C. , the monomer-free emulsion was continuously added for 5 hours, and at the same time, 0.15 parts by weight of cumene hydroperoxide and 0.20 parts by weight of sodium formaldehyde sulfoxylate were continuously added as polymerization initiators for 5 hours to proceed with the reaction. After the addition of the monomer-free emulsion was completed, after 30 minutes, 0.01 parts by weight of cumene hydroperoxide and 0.20 parts by weight of sodium formaldehyde sulfoxylate were additionally added and aged for 1 hour to prepare a core polymer latex.

<Preparation of core-shell copolymer>

In the presence of the prepared core polymer latex, the temperature inside the reactor was maintained at 55° C. to polymerize the shell. Then, 15 parts by weight of ionized water, 9.8 parts by weight of methyl methacrylate, 0.2 parts by weight of butyl acrylate, 0.05 parts by weight of cumene hydroperoxide and 0.05 parts by weight of sodium formaldehyde sulfoxylate were added to the reactor at once to proceed with the reaction. . After 30 minutes of completion of the addition, 0.01 parts by weight of cumene hydroperoxide and 0.01 parts by weight of sodium formaldehyde sulfoxylate were additionally added and aged for 1 hour to prepare a core-shell copolymer latex.

The polymerization conversion rate of the prepared core-shell copolymer latex was 99%, the average particle diameter of the core-shell copolymer in the latex was 2,000 nm, and the total solid content was 40% by weight.

Example 2

In Example 1, when manufacturing the core, silica sol (manufactured by Akzonobel, product name: Bindzil CC401) was added in 25 parts by weight instead of 15 parts by weight, and 1.5 parts by weight instead of 1 part by weight of hexadecyl trimethylammonium chloride was added, except that It was carried out in the same manner as in Example 1.

Example 3

In Example 1, when manufacturing the core, instead of 15 parts by weight of silica sol (manufactured by Akzonobel, product name: Bindzil CC401), silica containing silica particles containing a glycerol-based functional group having a particle size of 7 nm with a total solid content of 30% by weight It was carried out in the same manner as in Example 1, except that 15 parts by weight of the sol (manufactured by Akzonobel, product name: Bindzil CC301) was added.

Example 4

In Example 1, when preparing the core, 79.6 parts by weight of butyl acrylate instead of 89.55 parts by weight and 0.4 parts by weight of allyl methacrylate instead of 0.45 parts by weight were added, and when preparing the core-shell copolymer, methyl methacrylate was added It was carried out in the same manner as in Example 1, except that 19.6 parts by weight instead of 9.8 parts by weight and 0.4 parts by weight instead of 0.2 parts by weight of butyl acrylate were added.

Comparative Example 1

In Example 1, it was carried out in the same manner as in Example 1, except that silica sol (manufactured by Akzonobel, product name: Bindzil CC401) was not added during the manufacture of the core.

Comparative Example 2

In Example 1, during the preparation of the core, 0.1 parts by weight of acetic acid and 1 part by weight of sodium lauryl sulfate were added instead of 1 part by weight of hexadecyl trimethylammonium chloride to the monomer pre-emulsion. did.

Comparative Example 3

In Example 1, when manufacturing the core, instead of silica sol (manufactured by Akzonobel, product name: Bindzil CC401), 15 parts by weight of a silica sol containing non-functional silica particles having a particle size of 40 nm with a total solid content of 30% by weight was added. Except it was carried out in the same manner as in Example 1.

Comparative Example 4

In Example 1, when manufacturing the core, instead of silica sol (manufactured by Akzonobel, product name: Bindzil CC401), silica sol containing silica particles containing a glycerol-based functional group having a particle size of 80 nm with a total solid content of 30 wt% and a particle size of 15 wt. It was carried out in the same manner as in Example 1, except that parts were added.

Comparative Example 5

In Example 1, the core was manufactured in the same manner as in Example 1, except that 40 parts by weight of silica sol (manufactured by Akzonobel, product name: Bindzil CC401) was added instead of 15 parts by weight.

Experimental example

Experimental Example 1

The silica adsorption efficiency of the core-shell copolymer compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 5 was measured by the following method, and the type and content of the monomers added at each step, the type and content of the silica sol, and the type of the emulsifier and Tables 1 and 2 together with the contents.

* Silica adsorption efficiency (%): the core-shell copolymer latex prepared in each Example and Comparative Example was centrifuged at 3,000 rpm for 1 hour, and the upper layer containing silica particles not adsorbed to the particles After removing the supernatant and drying at room temperature, the dried sample was heated to 800 °C in a thermogravimetric analyzer (TGA) at a rate of 10 °C/min to measure the amount of weight loss, and silica The adsorption efficiency was calculated using Equation 1 below.

[Equation 1]

Silica Adsorption Efficiency (%, Silica Adsorption Efficiency) = (weight of residual inorganic silica / weight of added silica) X 100

division Example One 2 3 4 core monomer BA ¹⁾ (parts by weight) 89.55 89.55 89.55 79.6 AMA ²⁾ (parts by weight) 0.45 0.45 0.45 0.4 shell monomer MMA ³⁾ (parts by weight) 9.8 9.8 9.8 19.6 BA ¹⁾ (parts by weight) 0.2 0.2 0.2 0.4 Monomer total content (parts by weight) 100 100 100 100 silica sol content (parts by weight) 15 25 15 15 Silica particle size (nm) 12 12 7 12 surface coating functional group glycerol glycerol glycerol glycerol Monomer Free Emulsion pH 7 8 7 7 emulsifier HTA ⁴⁾ (parts by weight) One 1.5 One One SLS ⁵⁾ (parts by weight) - - - - Silica adsorption efficiency (%) 88 92 90 87 1) BA: butyl acrylate
2) AMA: allyl methacrylate
3) MMA: methyl methacrylate
4) HTA: hexadecyl trimethylammonium chloride
5) SLS: Sodium Lauryl Sulfate

division comparative example One 2 3 4 5 core monomer BA ¹⁾ (parts by weight) 89.55 89.55 89.55 89.55 89.55 AMA ²⁾ (parts by weight) 0.45 0.45 0.45 0.45 0.45 shell monomer MMA ³⁾ (parts by weight) 9.8 9.8 9.8 9.8 9.8 BA ¹⁾ (parts by weight) 0.2 0.2 0.2 0.2 0.2 Monomer total content (parts by weight) 100 100 100 100 100 silica sol content (parts by weight) 0 15 15 15 40 Silica particle size (nm) 12 12 40 80 12 surface coating functional group glycerol glycerol - glycerol glycerol Monomer Free Emulsion pH 7 2 7 7 7 emulsifier HTA ⁴⁾ (parts by weight) One - One One One SLS ⁵⁾ (parts by weight) - One - - - Silica adsorption efficiency (%) 0 15 10 22 70 1) BA: butyl acrylate
2) AMA: allyl methacrylate
3) MMA: methyl methacrylate
4) HTA: hexadecyl trimethylammonium chloride
5) SLS: Sodium Lauryl Sulfate

As shown in Tables 1 and 2, the core-shell copolymer compositions of Examples 1 to 5 prepared according to the present invention showed very high silica adsorption efficiency of 80% or more.

On the other hand, in Comparative Example 2, in which an anionic emulsifier was added instead of a cationic emulsifier, the pH of the monomer pre-emulsion was very low to 2 due to the anionic emulsifier, and the silica adsorption efficiency of the core-shell copolymer composition prepared therefrom It was also confirmed that it was greatly reduced by the electrostatic repulsive force. In addition, in Comparative Example 3, in which the silica sol containing non-functional silica particles not containing a glycerol-based functional group was added, the electrostatic properties were not exhibited, and it was confirmed that the silica adsorption efficiency was greatly reduced. In addition, even when a silica sol containing silica particles containing a glycerol-based functional group is used, in Comparative Example 4 with a large silica particle size, it is difficult to access the silica particles to the surface of the core-shell copolymer, so that the silica adsorption efficiency It can be seen that this is very low

Experimental Example 2

Evaluating the powder properties of the core-shell copolymer compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 5, and each physical property of a molded article prepared from a resin composition containing the core-shell copolymer composition as an impact modifier In order to do this, the core-shell copolymer latex prepared in Examples 1 to 4 and Comparative Examples 1 to 5 was sprayed under the conditions of chamber inlet 160 ° C, outlet 65 Å, rotary 10,000 rpm. A core-shell copolymer powder was obtained by spray-drying. Next, 100 parts by weight of a vinyl chloride resin (manufactured by LG Chem, product name LS100), 4.2 parts by weight of a calcium-zinc stabilizer, 4 parts by _{weight of titanium dioxide (TiO 2} , CR834), 10 parts by weight of _{calcium carbonate (CaCO 3 , Omiya 1T)} and 5 parts by weight of each of the core-shell copolymer powders obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were added, kneaded in a Henschel mixer while raising the temperature to 120 °C at 1,500 rpm, and cooled to 50 °C to resin A composition compound was prepared. The powder properties, extrusion amount, impact strength, thermal stability and antifouling properties were measured by the following method using the powder and compound prepared above, and are shown in Tables 3 and 4 below.

* Powder properties

1) Powder compressibility (%, compaction): For the core-shell copolymer powders of Examples 1 to 4 and Comparative Examples 1 to 5 obtained by spray drying, the powder compressibility was 30 g of the core-shell copolymer in the cup. The powder was put and tapped with a weight of 3.5 kg for 3 minutes, then placed on an 18 mesh screen and vibrated for 100 seconds, and the ratio of the weight of the powder remaining on the screen to the initial weight of the powder was calculated.

2) Funnel flow (sec, funnel flow): Funnel flow was measured by a funnel flow test according to ASTM D-1895. Powder compressibility means that the lower the ratio of the weight of the powder remaining on the screen is, the better, and the funnel flow means that the less time the powder flows along the funnel flow, the better.

* Extrusion amount (g/min): Using a Haake extruder, the prepared resin composition compound was subjected to a temperature of 180° C. in cylinder 1, 182° C. in cylinder 2, 185° C. in cylinder 3, and a temperature of the die. Under the conditions of 190 ° C. and a screw speed of 40 rpm, a 3.2 mm thick specimen was extruded and the amount of extrusion for 1 minute was measured.

* Impact strength (Notched Izod Impact Strengte, kgf cm/cm): Impact strength at 24 °C according to standard measurement method ASTM D256, Method A using a 1/8" thick specimen with a notch was measured.

* Thermal stability (ΔYI): Yellowness of the specimen processed for 3 minutes at 200 ° C. using the resin composition compound prepared above using a two roll-mill, and the specimen processed for 18 minutes (YI, Yellow Index) was measured using Hunterlab UltraScan Pro, a colorimeter, and the amount of change in yellowness (= yellowness of specimens processed for 18 minutes - yellowness of specimens processed for 3 minutes) was calculated.

* Antifouling properties

1) Anti-dirt pickup (ΔL): A sheet was prepared with a size of 5 cm x 8 cm for the specimen processed for 3 minutes during the thermal stability evaluation, and pulverized carbon carbon), and then removed after 24 hours, and the ΔL value (= L value after test - L value before test) was calculated. The lower the ΔL value, that is, the smaller the change amount, the better the vibration resistance.

^{2) dry wear (ΔL, ΔGloss%): 1dm 3} of sand is placed in a glass tube with a diameter of 50 mm and an outlet diameter and length of 1.5 mm and 20 mm, 5 cm in width X 8 cm in length. Dropped at an angle of 30° for 100 seconds from a height of 65 mm on a sheet of the size of , washed with cold water, dried and ΔL (= L value after test - L value before test) and ΔGloss% (= Gloss% value after test - Gloss% value before test) was calculated. The lower ΔL and ΔGloss%, that is, the smaller the change amount, the better the dry abrasion resistance.

division Example One 2 3 4 Powder properties powder compressibility (%) 20 10 15 13 funnel flow (sec) 15 10 12 14 Extrusion amount (g/min) 85 88 86 92 impact strength (kgf cm/cm) 17 15 16 15 thermal stability (ΔYI) 2 1.5 1.8 3 Antifouling properties dustproof (ΔL) 5 4 3 6 dry abrasiveness (ΔL) 4 3 2 5 (△Gloss%) 10 8 7 12

division comparative example One 2 3 4 5 Powder properties powder compressibility (%) 85 65 68 65 40 funnel flow (sec) 75 70 72 68 20 Extrusion amount (g/min) 68 70 69 65 90 impact strength (kgf cm/cm) 9 9 10 10 8 thermal stability (ΔYI) 14 15 12 13 2 Antifouling properties dustproof (ΔL) 30 14 25 12 11 dry abrasiveness (ΔL) 32 28 26 22 22 (△Gloss%) 35 30 28 24 25

As shown in Tables 3 and 4, the resin composition comprising the core-shell copolymer composition of Examples 1 to 5 prepared according to the present invention as an impact modifier is a silica comprising silica particles containing a glycerol-based functional group. Compared to Comparative Example 1 in which no sol was added, powder compressibility and funnel flow were significantly improved, and when molding a molded article prepared from a resin composition including the core-shell copolymer composition, the extrusion amount was improved, so that the extrusion processability was excellent. , it was confirmed that the impact strength and thermal stability of the molded product were significantly improved as well as antifouling properties.

On the other hand, Comparative Example 2 in which an anionic emulsifier was added instead of a cationic emulsifier, Comparative Example 3 in which a silica sol containing non-functional silica particles not containing a glycerol-based functional group was added, and silica particles containing a glycerol-based functional group In the case of Comparative Example 4 with a large silica particle size, the degree of improvement in powder compressibility and funnel flow of the core-shell copolymer composition was insignificant, even if a silica sol was used. When molding the molded article prepared from the resin composition, the extrusion amount was maintained or decreased at the same level, and it was confirmed that the impact strength, thermal stability and antifouling properties of the molded article were all at the same level.

In addition, in the case of Comparative Example 5, in which an excessive amount of silica sol containing silica particles containing a glycerol-based functional group was added, the impact strength of the molded article prepared from the resin composition containing the core-shell copolymer composition was rather reduced. there was. This is because silica particles in the silica sol aggregate with each other and the dispersibility is lowered due to the excessive addition of the silica sol, and accordingly, the silica adsorption efficiency stops at a certain level, and the effect of improving the powder properties and the antifouling properties of the molded article is relatively insignificant, It is thought that the excessively added silica particles remained as impurities in the core-shell copolymer composition, thereby lowering the impact strength.

From the above results, the present inventors prepared a core-shell copolymer composition according to the present invention and improved the powder compaction and funnel flow of the core-shell copolymer composition when using it as an impact modifier of the resin composition. Thus, it was confirmed that the extrusion processability of the resin composition comprising the core-shell copolymer composition was improved, the impact resistance of a molded article prepared from the resin composition was improved, and the surface properties were improved due to the improvement of heat resistance and antifouling properties.

Claims (12)

a core-shell copolymer;
Silica particles containing a glycerol-based functional group are adsorbed on a part or all of the surface of the core-shell copolymer,
The silica particles containing the glycerol-based functional group have a particle size of less than 80 nm,
The content of the silica particles containing the glycerol-based functional group is more than 0 parts by weight to less than 28 parts by weight based on 100 parts by weight of the core-shell copolymer,
A core-shell copolymer composition having a silica adsorption efficiency of 30% or more. According to claim 1,
The core of the core-shell copolymer includes a repeating unit derived from an alkyl (meth)acrylate monomer having 2 to 8 carbon atoms,
The shell of the core-shell copolymer is a core-shell copolymer composition comprising a repeating unit derived from a methyl (meth) acrylate monomer and a repeating unit derived from an alkyl (meth) acrylate monomer having 2 to 8 carbon atoms. According to claim 1,
The silica particles containing the glycerol-based functional group has a particle size of 4 nm to 50 nm core-shell copolymer composition. According to claim 1,
The content of the silica particles containing the glycerol-based functional group is 0.1 parts by weight to 21 parts by weight based on 100 parts by weight of the core-shell copolymer composition. According to claim 1,
The glycerol-based functional group of the silica particles containing the glycerol-based functional group is a core-shell copolymer composition represented by the following Chemical Formula 1:
[Formula 1]
*-O-SiR ¹ R ² -(CH ₂ ) _n -O(CH ₂ )-CH(OH)-CH ₂ OH
In Formula 1,
R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms,
n is an integer selected from 1 to 10,
* is a bonding position with silica particles. According to claim 1,
The silica adsorption efficiency of the core-shell copolymer composition is 80% or more of the core-shell copolymer composition. i) preparing a core polymer by polymerizing the monomer mixture for forming a core in the presence of a silica sol containing silica particles containing a cationic emulsifier and a glycerol-based functional group (S10);
ii) emulsion polymerization of the monomer mixture for shell formation in the presence of the core polymer prepared in step (S10) to prepare a core-shell copolymer (S20),
The silica particles containing a glycerol-based functional group included in the silica sol have a particle size of less than 80 nm,
The silica sol is added in an amount of more than 0 parts by weight to less than 40 parts by weight based on 100 parts by weight of the total content of the monomer mixture for forming the core and the monomer mixture for forming the shell,
A method for preparing a core-shell copolymer composition wherein the silica adsorption efficiency of the core-shell copolymer composition comprising the core-shell copolymer prepared in step (S20) is 30% or more. 8. The method of claim 7,
The cationic emulsifier is added in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the total content of the monomer mixture for forming the core and the monomer mixture for forming the shell. 8. The method of claim 7,
The cationic emulsifier is at least one selected from the group consisting of hexadecyl trimethylammonium chloride, dodecyl trimethylammonium chloride and didecyl dimethylammonium chloride. 8. The method of claim 7,
The content of silica particles containing a glycerol-based functional group included in the silica sol is 10 wt% to 70 wt% based on the total content of the silica sol. A resin composition comprising the core-shell copolymer composition according to any one of claims 1 to 6 and a vinyl chloride polymer. 12. The method of claim 11,
The content of the core-shell copolymer composition is 1 part by weight to 10 parts by weight based on 100 parts by weight of the vinyl chloride polymer resin composition.

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