KR101692106B1 - Acrylic impact modifier with core-shell structure and composition of acrylic resin comprising thereof - Google Patents

Abstract

The present invention relates to a resin composition which is excellent in compatibility with a matrix resin such as a polymethyl methacrylate resin and contains a phosphoric acid anionic emulsifier represented by the general formula (1) Shell structure, a process for producing the same, and an acrylic impact modifier having a core-shell structure prepared from the acrylic-type impact modifier composition. Accordingly, the acrylic impact modifier composition having a core-shell structure can stably encapsulate the acrylic seed and increase the grafting ratio of the graft copolymer shell. By the emulsifier present in the graft copolymer shell, The compatibility with the acrylate-based impact modifier increases, and the impact strength is improved while maintaining excellent transparency of the polymethyl methacrylate resin including the acrylic impact modifier of the core-shell structure.

Description

[0001] The present invention relates to an acrylic impact modifier having a core-shell structure and an acrylic resin composition containing the acrylic-based impact modifier,

The present invention relates to a thermoplastic resin composition which is excellent in compatibility with a polymethyl methacrylate resin, including a phosphoric acid anionic emulsifier represented by the general formula (1), and has a core-shell structure capable of improving impact strength while maintaining excellent transparency of the resin Acrylic impact modifier composition, a process for producing the same, and an acrylic impact modifier having a core-shell structure prepared therefrom.

Acrylic resins such as polymethylmethacrylate resins are excellent in transparency and weatherability as well as excellent in hardness, chemical resistance, surface gloss and adhesiveness, and can be used for optical applications such as optical lenses, optical disks and light guide plates, Such as decorative parts, automotive rear lights, instrument panel covers, outdoor exterior materials, and the like.

However, the polymethylmethacrylate resin has excellent optical properties, but has a relatively low impact resistance as compared with other resins. Accordingly, techniques for improving low impact resistance in order to easily apply to various fields have been studied.

In general, a method of blending an impact modifier to improve the impact resistance of the polymethyl methacrylate resin is known. However, since the impact modifier mainly uses an initiator containing a functional group or a rubber containing butadiene, the impact modifier has a problem of deterioration in reactivity and weatherability, and the effect of improving the impact resistance according to the impact modifier content is relatively small.

Further, when a large amount of an impact modifier is used, there is a problem that the heat resistance is lowered and the transparency is lowered. Therefore, there is a need to develop an impact modifier that can effectively improve the impact resistance of a polymethyl methacrylate resin and maintain excellent transparency without lowering the transparency of the resin.

Under the above background, the inventors of the present invention have found that an acrylic impact modifier having a core-shell structure from an acrylic impact modifier composition having a core-shell structure containing a phosphoric acid anionic emulsifier represented by the general formula (1) in a rubber core and a graft copolymer shell And blending it with a polymethylmethacrylate resin. As a result, it has been confirmed that the transparency of the resin can be maintained at an excellent level and the impact strength can be improved, thereby completing the present invention.

JP 2002-146198 A

The object of the present invention is to provide a core-shell material which is excellent in compatibility with a polymethyl methacrylate resin, including a phosphoric acid anionic emulsifier represented by the general formula (1), and can improve impact strength while maintaining excellent transparency of the resin. Acrylic impact modifier composition of the present invention.

Another object of the present invention is to provide a method for producing an acrylic impact modifier composition having the core-shell structure.

It is still another object of the present invention to provide an acrylic impact modifier having a core-shell structure prepared from the acrylic impact modifier composition of the core-shell structure.

It is still another object of the present invention to provide a polymethyl methacrylate resin composition comprising the acrylic impact modifier of the core-shell structure.

In order to solve the above-mentioned problems, the present invention provides an ink composition comprising 5 to 25% by weight of an acrylic seed containing an alkyl methacrylate monomer; 40% to 65% by weight of a rubber core formed on the acrylic seed and comprising an alkyl acrylate monomer; And 15 to 45% by weight of a graft copolymer shell formed on the rubber core, the graft copolymer shell comprising an alkyl methacrylate monomer, an alkyl acrylate monomer and at least one monomer selected from aromatic vinyl monomers, Wherein the core-graft copolymer shell comprises a phosphate-based anionic emulsifier represented by the following formula (1).

[Chemical Formula 1]

Wherein R is alkyl having from 10 to 14 carbon atoms, n is an integer from 4 to 8, and m is 1 or 2.

The present invention also relates to a method for producing an impact modifier composition comprising the steps of: preparing a seed by emulsion-polymerizing a monomer mixture containing 5 to 99 parts by weight of an alkyl methacrylate monomer per 100 parts by weight of the total of monomers constituting the core- (Step 1); Adding a monomer mixture containing 30 to 70 parts by weight of an alkyl acrylate monomer to the prepared seed and emulsifying to prepare a rubber core (step 2); And a monomer mixture comprising 10 to 50 parts by weight of an alkyl methacrylate monomer and 0.005 to 50 parts by weight of an alkyl acrylate monomer and at least one monomer of an aromatic vinyl monomer were added to the rubber core prepared above, Wherein the monomer mixture comprises 0.1 to 0.5 parts by weight of a phosphate-based anionic emulsifier represented by the general formula (1), respectively, in the step 2 and the step (3) The present invention provides a method for producing an acrylic impact modifier composition having a shell structure.

The present invention also relates to a core-shell structure comprising an acrylic seed, a rubber core surrounding the seed, and a graft copolymer shell surrounding the rubber core, made from the acrylic impact modifier composition of the core-shell structure described above An acrylic impact modifier is provided.

Further, the present invention relates to a composition comprising 15 to 25% by weight of an acrylic impact modifier of the above core-shell structure; And 75 to 85% by weight of a polymethylmethacrylate resin.

The acrylic-based impact modifier composition of the core-shell structure according to the present invention comprises a phosphoric acid anionic emulsifier represented by the general formula (1) in a rubber core and a graft copolymer shell to stably encapsulate the acrylic-based seed and to control the graft ratio of the graft copolymer shell . In addition, compatibility with the polymethylmethacrylate resin, which is a matrix resin, is increased by the emulsifier present in the graft copolymer shell, and the excellent transparency of the polymethylmethacrylate resin containing the acrylic-based impact modifier of the core- So that the impact strength can be improved.

Accordingly, the acrylic-based impact modifier of the core-shell structure prepared from the acrylic-based impact modifier composition of the core-shell structure according to the present invention is useful as an impact modifier for acrylic resins such as polymethylmethacrylate resin, Lt; / RTI >

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

The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention relates to a core-shell structure which is used as an impact modifier of an acrylic resin such as polymethylmethacrylate resin and is excellent in compatibility with the resin and can improve the impact strength without lowering the transparency of the resin An acrylic impact modifier composition is provided.

Acrylic resins such as polymethylmethacrylate resins are excellent in transparency and weatherability as well as being excellent in hardness, chemical resistance, surface gloss, and adhesiveness, and are widely used as various substitutes for various industries, particularly glass. However, The impact resistance is so low that the thickness of the product can be increased or used only for limited use.

Therefore, a method of modifying the impact modifier by using an impact modifier has been proposed to compensate for the low impact modulus. However, the conventional modifier using the impact modifier has a small effect of improving the impact strength and a problem of lowering the hardness and transparency when used in a large amount .

Accordingly, the present invention includes a phosphate-based anionic emulsifier represented by the following formula (1) in a rubber core and a graft copolymer shell to improve compatibility with an acrylic resin such as a polymethyl methacrylate resin, And an acrylic impact modifier composition having a core-shell structure capable of improving the impact strength while maintaining a high impact strength.

The acrylic-based impact modifier composition of the core-shell structure according to an embodiment of the present invention comprises 5 to 25% by weight of an acrylic seed containing an alkyl methacrylate monomer; 40% to 65% by weight of a rubber core formed on the acrylic seed and comprising an alkyl acrylate monomer; And 15 to 45% by weight of a graft copolymer shell formed on the rubber core, the graft copolymer shell comprising an alkyl methacrylate monomer, an alkyl acrylate monomer and at least one monomer selected from aromatic vinyl monomers, Wherein the core and graft copolymer shell comprises a phosphate-based anionic emulsifier represented by the following formula (1).

[Chemical Formula 1]

Wherein R is alkyl having from 10 to 14 carbon atoms, n is an integer from 4 to 8, and m is 1 or 2.

Preferably, R may be alkyl of 12 to 14 carbon atoms.

The acrylic seed may contain 5 to 99 parts by weight of the alkyl methacrylate monomer, preferably 10 to 50 parts by weight based on 100 parts by weight of the total amount of the monomers constituting the impact modifier composition. If the alkyl methacrylate monomer is contained in an amount of less than 5 parts by weight, the particle size of the acrylic seed composition containing the acrylic methacrylate monomer is too small, and the particle size of the finally formed core-shell acrylic impact modifier composition becomes too small, In contrast, when the amount exceeds 99 parts by weight, the particle size of the acrylic-based impact modifier composition having a core-shell structure to be finally formed is too large to maintain excellent impact strength, and transparency deteriorates .

In addition, the acrylic seed may further include 0.5 to 90 parts by weight of an alkyl acrylate monomer based on 100 parts by weight of the total of the monomers constituting the impact modifier composition. And preferably 10 parts by weight to 50 parts by weight.

The acrylic seed may have an average particle size of 180 nm to 220 nm. If the average particle diameter is less than 180 nm, the particle diameter may be too small to exhibit sufficient impact strength. If the average particle diameter exceeds 220 nm, the transparency may be deteriorated.

The alkyl methacrylate monomer contained in the acrylic seed may be one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate and n-butyl methacrylate, Lt; / RTI >

The alkyl acrylate monomers which may additionally be included in the acrylic seeds include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acryl , And preferably at least one selected from the group consisting of n-butyl acrylate and n-butyl acrylate.

In addition, the acrylic seed according to the present invention may further comprise a crosslinkable monomer, wherein the crosslinkable monomer is used in an amount of 0.05 part by weight to 100 parts by weight based on 100 parts by weight of the total amount of the monomers constituting the acrylic impact modifier composition of the core- 5 parts by weight. If the amount of the cross-linkable monomer is less than 0.05 part by weight, the particle stability of the acrylic seed may be deteriorated. If the cross-linking monomer is contained in an amount exceeding 5 parts by weight, the impact- The impact strength of the polymethylmethacrylate resin contained as the resin may be lowered.

The crosslinkable monomer may be at least one selected from the group consisting of 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, Acrylate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, divinylbenzene, polyethylene glycol acrylate, polyethylene glycol methacrylate, and butylene glycol dimethacrylate Acrylate, and allyl methacrylate may be preferably used.

The acrylic seed may be contained in the acrylic-based impact modifier composition of the core-shell structure at a ratio of 5 wt% to 25 wt% based on the total weight of the impact modifier composition, as mentioned above. If the amount is less than 5% by weight, the number of particles decreases and the interval between the particles increases, so that the impact strength of the polymethyl methacrylate resin using the acrylic impact modifier composition containing the same may be lowered. , There is a problem that the graft copolymer shell having an excessive amount of small-diameter particles and relatively formed on the outermost surface decreases in thickness, and thus the rubber core can not be sufficiently enclosed and the cohesion characteristics become poor.

The rubber core according to the present invention may contain 30 to 70 parts by weight of an alkyl acrylate monomer based on 100 parts by weight of the total of the monomers constituting the impact modifier composition. If the content of the alkyl acrylate monomer exceeds the above range, the desired impact strength may not be obtained.

The rubber core may further comprise 1 to 40 parts by weight of an aromatic vinyl monomer based on 100 parts by weight of the total of the monomers constituting the impact modifier composition.

The rubber core may have an average particle size of 250 nm to 300 nm. At this time, the average particle diameter of the rubber core may mean the average particle diameter of the entire rubber core including the acrylic seed. If the average particle diameter is less than 250 nm, the particle diameter may be too small to exhibit sufficient impact strength. If the average particle diameter exceeds 300 nm, the transparency may be deteriorated.

The alkyl acrylate monomer contained in the rubber core may be the same as or included in the above-mentioned materials.

The aromatic vinyl-based monomer which may additionally be included in the rubber core is selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, alkylstyrene substituted with an alkyl group having _{1 to 3} carbon atoms and styrene substituted with a halogen May be one or more selected, and may preferably be styrene.

In addition, the rubber core may include a phosphoric acid anionic emulsifier represented by the formula (1). The phosphate-based anionic emulsifier represented by Formula 1 may be included in the rubber core in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the total monomers constituting the acrylic impact modifier composition.

The phosphate anionic emulsifier represented by the above formula (1) is usually prepared by dissolving sodium di (polyoxyethylene alkyl ether) phosphate or disodium polyoxyethylene alkyl ether phosphate And may be called differently depending on the number (n value) of repeating units and R.

The phosphoric acid anionic emulsifier represented by Formula 1 according to an embodiment of the present invention may have a number of repeating units (n value) of 4 to 8 and R may be alkyl having 10 to 14 carbon atoms, The number of R is 4 to 8, and R is alkyl of 12 to 14 carbon atoms.

Specifically, the phosphate anionic emulsifier may be selected from the group consisting of sodium di (hexaoxyethylene lauryl ether) phosphate, sodium di (hexaoxyethylene tridecyl ether) phosphate (sodium di (hexaoxyethylene tridecyl ether) ) phospate, sodium di (hexaoxyethylene myristyl ether) phosphate, disodium hexaoxyethylene lauryl ether phosphate, disodium hexaoxyethylene tridecyl Disodium hexaoxyethylene tridecyl ether phosphate and disodium hexaoxyethylene myristyl ether phosphate may be used.

In addition, the rubber core may further include a crosslinkable monomer, and the crosslinkable monomer may be the same as or included in the above-mentioned materials, and may be used within the aforementioned range.

The rubber core may be included in the acrylic impact modifier composition of the core-shell structure as mentioned above in a proportion of 40 wt% to 65 wt% based on the total weight of the impact modifier composition. If it is contained in an amount of less than 40% by weight, the impact strength may be lowered because of the rubbery property capable of absorbing the impact. When the content exceeds 65% by weight, the proportion of the graft copolymer shell is relatively decreased, The graft copolymer shell formed on the rubber core may not sufficiently wrap the rubber core, and the acrylic impact modifier composition having a core-shell structure containing the rubber core and the polymethyl methacrylate resin as a matrix resin Resulting in poor compatibility and dispersibility, resulting in a problem of deteriorating the processability of the resin, as well as deteriorating the impact strength improving effect.

The graft copolymer shell according to the present invention comprises 10 to 50 parts by weight of an alkyl methacrylate monomer based on 100 parts by weight of the total of the monomers constituting the impact modifier composition and the alkyl acrylate monomer and the aromatic vinyl based And 0.005 to 50 parts by weight of at least one monomer selected from the group consisting of monomers.

The graft copolymer shell may have an average particle size of 320 nm to 340 nm. The average particle diameter of the graft copolymer shell may be an average particle diameter of the entire graft copolymer shell including the rubber core. If the average particle diameter is less than 320 nm, the impact strength may be lowered. If the average particle diameter exceeds 340 nm, the transparency may be lowered.

The alkyl methacrylate monomers, alkyl acrylate monomers and aromatic vinyl monomers contained in the graft copolymer shell are as mentioned above.

The graft copolymer shell may contain 0.1 part by weight to 0.5 part by weight of the phosphoric acid anionic emulsifier represented by the formula 1, based on 100 parts by weight of the total monomers constituting the impact modifier composition.

The above-mentioned phosphate anionic emulsifier is the same as mentioned above.

The graft copolymer shell may be contained in an amount of 15 to 45% by weight based on the total weight of the impact modifier composition in the acrylic impact modifier composition of the core-shell structure as mentioned above. If it is contained in an amount of less than 15% by weight, the rubber core can not be sufficiently wrapped and can not perform a proper role as a processing aid. Therefore, the impact resistance of a polymethyl methacrylate resin using a core- If the content exceeds 45% by weight, the proportion of the rubber core is relatively decreased, and the graft copolymer shell is formed too thick, so that the effect of improving the impact strength can be reduced.

The acrylic impact modifier composition of the core-shell structure according to the present invention may be preferably such that the rubber core surrounds the acrylic seed and the graft copolymer shell surrounds the rubber core.

In addition, the acrylic impact modifier composition of the core-shell structure according to an embodiment of the present invention may further include an emulsifier commonly used in the art in addition to the above-described phosphate anionic emulsifier, if necessary, , Molecular weight modifiers, and oxidation-reduction catalysts.

The emulsifier may be, for example, a phosphate salt, a sulfonate salt or a sulfate salt, and the phosphate salt may be sodium polyoxyethylene alkyl phosphate, sodium polyoxyethylene alkyl aryl phosphate, or the like. The sulfonate salt may be sodium alkylbenzene sulfonate, sodium alkylaryl naphthalene sulfonate, sodium dialkyl sulfosuccinate, and the like, and the sulfate salt may be sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfide, or the like.

Examples of the polymerization initiator include, but are not limited to, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; butyl hydroperoxide, cumene hydroperoxide, p-menthol hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxyisobutyrate, and diisopropylbenzene hydroperoxide; Nitrogen compounds such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl.

Examples of the molecular weight regulator include, but are not limited to, mercaptans such as? -Methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; Sulfur-containing compounds such as tetraethyldiuram disulfide, dipentamethylenediuram disulfide, and diisopropylkantogen disulfide, and the like.

The oxidation-reduction catalyst may be, for example, sodium formaldehyde sulfoxylate, ethylenediamine tetrasodium nitrate, ferrous sulfate, sodium pyrophosphate, dextrose, and the like.

The present invention also provides a process for preparing an acrylic impact modifier composition having the core-shell structure.

The method of preparing the acrylic-based impact modifier composition of the core-shell structure according to an embodiment of the present invention comprises adding 5 to 99 parts by weight of alkyl methacrylate to 100 parts by weight of total monomers constituting the core- Preparing a seed by emulsion-polymerizing a monomer mixture comprising a cyrrlate monomer (step 1); Adding a monomer mixture containing 30 to 70 parts by weight of an alkyl acrylate monomer to the prepared seed and emulsifying to prepare a rubber core (step 2); And a monomer mixture comprising 10 to 50 parts by weight of an alkyl methacrylate monomer and 0.005 to 50 parts by weight of an alkyl acrylate monomer and at least one monomer of an aromatic vinyl monomer were added to the rubber core prepared above, (Step 3), wherein the monomer mixture comprises 0.1 to 0.5 parts by weight of a phosphate-based anionic emulsifier represented by the following general formula (1).

[Chemical Formula 1]

Wherein R is alkyl having from 10 to 14 carbon atoms, n is an integer from 4 to 8, and m is 1 or 2.

Step 1 is a step of preparing an acrylic seed by emulsion polymerization of an alkyl methacrylate monomer to produce an acrylic seed. In this case, the emulsion polymerization may be carried out by introducing a crosslinking monomer together with the alkyl methacrylate, and an acrylic type seed may be prepared through a crosslinking reaction.

In the preparation of the acrylic seed, the alkyl acrylate monomer may be further added within the above-mentioned range.

The alkyl methacrylate monomers, alkyl acrylate monomers and crosslinkable monomers used for preparing the acrylic seeds may be the same as the above-mentioned materials, and may contain additives such as a polymerization initiator, an emulsifier, a molecular weight modifier, and an oxidation- May be further added. The additive may be the same as the above-mentioned material.

In step 2, an alkyl acrylate monomer and a phosphoric acid anionic emulsifier represented by the formula (1) are added to the acrylic seed to form a rubber core on the acrylic seed prepared in step 1, . The rubber core may be formed so as to surround the acrylic seed. At this time, the emulsion polymerization may be carried out by adding a crosslinkable monomer together with the alkyl acrylate monomer.

Further, the aromatic vinyl monomer may be further added within the above-mentioned range when the rubber core is prepared.

The alkyl acrylate monomer, the phosphoric acid anionic emulsifier, the aromatic vinyl monomer and the crosslinkable monomer used in the production of the rubber core may be the same as the above-mentioned materials, and if necessary, An additive such as an emulsifier other than anionic anionic emulsifier, a molecular weight regulator, and an oxidation-reduction catalyst may be further added. The additive may be the same as the above-mentioned material.

The step 3 is a step for obtaining an acrylic impact modifier composition having a core-shell structure, in which the rubber core prepared in step 2 is mixed with an alkyl methacrylate monomer, an alkyl acrylate monomer and an aromatic vinyl monomer And a phosphate anionic emulsifier represented by the above formula (1) are added and graft copolymerized to form a graft copolymer shell on the rubber core. The graft copolymer shell may be formed so as to surround the rubber core. At this time, the graft copolymerization may be carried out by further adding a crosslinkable monomer by emulsion graft copolymerization.

The alkyl methacrylate monomers, the alkyl acrylate monomers, the aromatic vinyl monomers, and the phosphate anionic emulsifiers represented by the above formula (1) used in the preparation of the graft copolymer shell may be the same as the above- May be the same as the above-mentioned materials. If necessary, an additive such as an emulsifier, a molecular weight modifier, and an oxidation-reduction catalyst may be added in addition to the polymerization initiator, the phosphoric acid anionic emulsifier, and the additive may be the same as the above-mentioned materials.

Meanwhile, the method for preparing the acrylic impact modifier composition of the core-shell structure according to an embodiment of the present invention may include the step of aggregating, dehydrating and drying the acrylic impact modifier composition of the core- May be further included. Thus, an acrylic impact modifier powder having a core-shell structure can be obtained.

The coagulation, dewatering and drying are not particularly limited and can be carried out by a method commonly known in the art.

In addition, the present invention provides an acrylic impact modifier having a core-shell structure prepared from the above acrylic core impact modifier composition having a core-shell structure.

The acrylic impact modifier of the core-shell structure according to an embodiment of the present invention is characterized in that the rubber core surrounds the acrylic seed, and the graft copolymer shell surrounds the rubber core.

The acrylic impact modifier of the core-shell structure is characterized in that the thickness ratio of the acrylic seed, the rubber core and the graft copolymer shell is r ₁ : r ₂ -r ₁ : r ₃ -r ₂ = 0.9 to 1.1: 0.25 to 0.45: To 0.3.

Here, r ₁ is a distance from the center of the graft copolymer to the outer surface of the acrylic seed, r ₂ is a distance from the center to the outer surface of the rubber core, and r ₃ is a distance from the center to the outer surface of the graft copolymer shell will be.

The acrylic impact modifier of the core-shell structure may be used as an impact modifier of a thermoplastic resin, and may preferably be used as an impact modifier of an acrylic resin. More preferably, it can be used as an impact modifier of a polymethyl methacrylate resin.

Further, the present invention relates to a composition comprising 15 to 25% by weight of an acrylic impact modifier of the above core-shell structure; And 75 to 85% by weight of a polymethylmethacrylate resin.

The polymethylmethacrylate resin prepared from the polymethylmethacrylate resin composition containing the acrylic impact modifier of the core-shell structure according to an embodiment of the present invention has characteristics of excellent impact strength and transparency.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example  One

Hereinafter, all the materials used in the preparation of the acrylic impact modifier powder having the core-shell structure shown below are based on 100 parts by weight of the total of the monomers (methyl methacrylate, butyl acrylate and styrene) constituting the impact modifier powder.

(1) Production of acrylic seed

80 parts by weight of ion-exchanged water was charged into a 3 L reactor, and the temperature was raised to 70 DEG C with nitrogen washing. 0.05 parts by weight of sodium dodecyl sulfate (SLS, 3 wt% solution), 4.48 parts by weight of methyl methacrylate (MMA), 0.5 parts by weight of butyl acrylate (BA) 0.02 part by weight of methacrylate (AMA) was added at one time. When the internal temperature of the reactor was stabilized at 70 캜, 0.1 part by weight of potassium persulfate (KPS, 3 wt% solution) was added to initiate polymerization. After aging for 1 hour, 0.1 part by weight of sodium dodecyl sulfate (SLS, 2 wt% solution), 13.44 parts by weight of methyl methacrylate (MMA), 1.5 parts by weight of butyl acrylate (BA) AMA) were further added and stirred to effect emulsion polymerization. Thereafter, 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, and 0.05 part by weight of diisopropylbenzene hydroperoxide were added dropwise under a nitrogen atmosphere and an internal temperature of 70 캜 for 1 hour. (DIPHP, 50 wt% solution) were added to the reaction mixture to terminate the reaction and aged for 1 hour to prepare an acrylic seed.

The particle size of the prepared acrylic seed was 190 nm and the refractive index was 1.4901.

(2) Manufacture of rubber core

 In order to form the rubber core on the acrylic seed prepared in (1) above, 25 parts by weight of ion-exchanged water, 0.4 part by weight of sodium dodecyl sulfate, 45 parts by weight of butyl acrylate 45 , 0.025 part by weight of ethylenediaminetetra sodium acetate, 0.1 part by weight of styrene, 0.5 part by weight of allyl methacrylate, and 0.4 part by weight of sodium di (hexaoxyethylene lauryl ether) , 0.1 part by weight of sodium formaldehyde sulfoxylate and 0.1 part by weight of diisopropylbenzene hydroperoxide were continuously introduced for 4 hours. At this time, the internal temperature of the reactor was maintained at 70 占 폚. After the addition, the rubber core was formed by aging for 1 hour.

At this time, the conversion ratio of the polymerized rubber core was 99%, the average particle diameter was 280 nm, and the refractive index was 1.4901.

(3) Preparation of an acrylic impact modifier powder having a core-shell structure

In order to form a graft copolymer shell on the rubber core prepared in (2) above, 12 parts by weight of ion-exchanged water, 0.2 part by weight of sodium dodecyl sulfate, and 24 parts by weight of methyl methacrylate , 1 part by weight of methyl acrylate and 0.4 part by weight of sodium di (hexaoxyethylene lauryl ether) phosphate, 0.00235 parts by weight of ethylenediaminetetra sodium acetate, 0.0015 part by weight of ferrous sulfate, sodium formaldehyde 0.01 part by weight of sulfoxylate and 0.02 part by weight of diisopropylbenzene hydroperoxide were continuously added for 2 hours to proceed the reaction. At this time, the reactor temperature was maintained at 70 占 폚. After the addition, the mixture was aged at 70 DEG C for 1 hour to obtain an acrylic impact modifier having a final core-shell structure. The conversion of the acrylic impact modifier of the core-shell structure thus prepared was 99%, the average particle size was 320 nm, and the refractive index was 1.4901.

Ion exchange water was added to the prepared acrylic-type impact modifier having a core-shell structure to reduce the final solids content to 15% by weight or less, and then the temperature was raised to 80 ° C with stirring with a stirrer. A calcium chloride aqueous solution having a concentration of 22 wt% was added thereto to prepare a mixture in the form of a slurry. The mixture was heated to 90 DEG C or higher and aged, followed by cooling. The cooled mixture was washed with ion-exchanged water, filtered, and dried to obtain an acrylic impact modifier having a powdered core-shell structure.

(4) Preparation of polymethyl methacrylate resin

20% by weight of the acrylic impact modifier powder of the core-shell structure prepared in (3) above and 80% by weight of polymethyl methacrylate resin (LG-MMA, IF830A) were mixed to prepare a mixture, 0.2 part by weight of the lubricant, 0.1 part by weight of the antioxidant and 0.01 part by weight of the light stabilizer were added and kneaded to prepare a polymethyl methacrylate resin pellet using a twin screw extruder.

Example  2

Except that sodium di (hexaoxyethylene lauryl ether) phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell, To prepare a polymethyl methacrylate resin pellet.

Example  3

Except that sodium di (hexaoxyethylene lauryl ether) phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell, To prepare a polymethyl methacrylate resin pellet.

Example  4

Except that disodium hexaoxyethylene lauryl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming a rubber core and a graft copolymer shell. Methacrylate resin pellets were prepared.

Example  5

Except that disodium hexaoxyethylene tridecyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming a rubber core and a graft copolymer shell. Methacrylate resin pellets were prepared.

Example  6

Except that disodium hexaoxyethylene myristyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. Methacrylate resin pellets were prepared.

Example  7

Except that sodium di (tetraoxyethylene lauryl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and the graft copolymer shell. To prepare a polymethyl methacrylate resin pellet.

Example  8

Except that sodium di (octoxyethylene lauryl ether) phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. To prepare a polymethyl methacrylate resin pellet.

Example  9

Except that sodium di (tetraoxyethylene tridecyl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. To prepare a polymethyl methacrylate resin pellet.

Example  10

Except that sodium di (octoxyethylene tridecyl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. To prepare a polymethyl methacrylate resin pellet.

Example  11

Except that sodium di (tetraoxyethylene lauryl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming a rubber core and a graft copolymer shell. To prepare a polymethyl methacrylate resin pellet.

Example  12

Except that sodium di (octoxyethylene lauryl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and the graft copolymer shell. To prepare a polymethyl methacrylate resin pellet.

Example  13

Except that disodium tetraoxyethylene lauryl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell, Methacrylate resin pellets were prepared.

Example  14

Except that disodium octaoxyethylene lauryl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. Methacrylate resin pellets were prepared.

Example  15

Except that disodium tetraoxyethylene tridecyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. Methacrylate resin pellets were prepared.

Example  16

Except that disodium octaoxyethylene tridecyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and the graft copolymer shell. Methacrylate resin pellets were prepared.

Example  17

Except that disodium tetraoxyethylene myristyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and the graft copolymer shell. Methacrylate resin pellets were prepared.

Example  18

Except that disodium octaoxyethylene myristyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming a rubber core and a graft copolymer shell. Methacrylate resin pellets were prepared.

Comparative Example  One

0.2 part by weight of a lubricant, 0.1 part by weight of an antioxidant and 0.01 part by weight of a light stabilizer were added to 100 parts by weight of the polymethylmethacrylate resin (manufactured by LG-MMA, IF830A) A polymethyl methacrylate resin pellet was prepared using an extruder.

Comparative Example  2

Except that sodium di (hexaoxyethylene lauryl ether) phosphate, which is a phosphate anionic emulsifier, was not used in the formation of the rubber core and graft copolymer shell, and that polymethyl methacrylate To prepare a resin pellet.

Comparative Example  3

Except that sodium di (hexaoxyethylene lauryl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. Methyl methacrylate resin pellets were prepared.

Comparative Example  4

Except that sodium di (hexaoxyethylene lauryl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell, To prepare a polymethyl methacrylate resin pellet.

Comparative Example  5

Except that disodium hexaoxyethylene octyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming a rubber core and a graft copolymer shell. 0.0 > pellets < / RTI >

Comparative Example  6

Except that disodium hexaoxyethylene hexadecyl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. Methacrylate resin pellets were prepared.

Comparative Example  7

Except that sodium di (dioxyethylene lauryl ether) phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell, To prepare a polymethyl methacrylate resin pellet.

Comparative Example  8

Except that sodium di (decaoxyethylene lauryl ether) phosphate was used instead of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and the graft copolymer shell. To prepare a polymethyl methacrylate resin pellet.

Comparative Example  9

Except that disodium dioxyethylene lauryl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming the rubber core and graft copolymer shell. Methacrylate resin pellets were prepared.

Comparative Example  10

Except that disodium decaoxyethylene lauryl ether phosphate was used in place of sodium di (hexaoxyethylene lauryl ether) phosphate in forming a rubber core and a graft copolymer shell. Methacrylate resin pellets were prepared.

Table 1 shows the types of the phosphate anionic emulsifiers used in the production of the acrylic impact modifier of each of the core-shell structures prepared in Examples 1 to 18 and Comparative Examples 1 to 10.

division Phosphate anionic emulsifier m value n value The carbon number of R Example 1 Sodium di (hexaoxyethylene lauryl ether) phosphate 2 6 12 Example 2 Sodium di (hexaoxyethylene tridecyl ether) phosphate 2 6 13 Example 3 Sodium di (hexaoxyethylene myristyl ether) phosphate 2 6 14 Example 4 Disodium hexaoxyethylene lauryl ether phosphate One 6 12 Example 5 Disodium hexaoxyethylene tridecyl ether phosphate One 6 13 Example 6 Disodium hexaoxyethylene myristyl ether phosphate One 6 14 Example 7 Sodium di (tetraoxyethylene lauryl ether) phosphate 2 4 12 Example 8 Sodium di (octaoxyethylene lauryl ether) phosphate 2 8 12 Example 9 Sodium di (tetraoxyethylene tridecyl ether) phosphate 2 4 13 Example 10 Sodium di (octaoxyethylene tridecyl ether) phosphate 2 8 13 Example 11 Sodium di (tetraoxyethylene myristyl ether) phosphate 2 4 14 Example 12 Sodium di (octaoxyethylene myristyl ether) phosphate 2 8 14 Example 13 Disodium tetraoxyethylene lauryl ether phosphate One 4 12 Example 14 Disodium octaoxyethylene lauryl ether phosphate One 8 12 Example 15 Disodium tetraoxyethylene tridecyl ether phosphate One 4 13 Example 16 Disodium octaoxyethylene tridecyl ether phosphate One 8 13 Example 17 Disodium tetraoxyethylene myristyl ether phosphate One 4 14 Example 18 Disodium octaoxyethylene myristyl ether phosphate One 8 14 Comparative Example 1 No core-shell acrylic impact modifier used Comparative Example 2 No phosphate anionic emulsifier used Comparative Example 3 Sodium di (hexaoxyethylene octyl ether) phosphate 2 6 8 Comparative Example 4 Sodium di (hexaoxyethylene hexadecyl ether) phosphate 2 6 16 Comparative Example 5 Disodium hexaoxyethylene octyl ether phosphate One 6 8 Comparative Example 6 Disodium hexaoxyethylene hexadecyl ether phosphate One 6 16 Comparative Example 7 Sodium di (dioxyethylene lauryl ether) phosphate 2 2 12 Comparative Example 8 Sodium di (decaoxyethylene lauryl ether) phosphate 2 10 12 Comparative Example 9 Disodium dioxyethylene lauryl ether phosphate One 2 12 Comparative Example 10 Disodium decaoxyethylene lauryl ether phosphate One 10 12 * The number of carbon atoms of m, n and R is as shown in formula (1).
The preferable range of * n is an integer of 4 to 8, and the preferable range of the number of carbon atoms of R is 10 to 14. [

Experimental Example

In order to comparatively analyze the properties of each of the polymethyl methacrylate resin pellets prepared in Examples 1 to 18 and Comparative Examples 1 to 10, impact strength and optical properties (refractive index, haze) were measured and the results are shown in Table 2 Respectively.

(1) Impact strength (impact resistance, kgf · m / m)

The impact strength was analyzed according to ASTM D256. Each of the polymethyl methacrylate resin pellets prepared in Examples 1 to 18 and Comparative Examples 1 to 10 was molded to a thickness of 1/8 "to prepare specimens. The specimens were supported on an Izod impact tester, The energy and specimen breaking width were measured and the impact strength value was obtained by the following equation. The impact speed of the hammer was about 240 cm / sec.

In the above equation, Nw represents the width (m) of the test piece entrance portion, and E represents the energy (kgf · m) required for destroying the test piece.

(2) Optical characteristics

The haze (%) was obtained by injection molding each of the polymethyl methacrylate resin pellets prepared in Examples 1 to 18 and Comparative Examples 1 to 10 to prepare a specimen having a thickness of 3.175 mm, and the test was conducted according to ASTM D1003.

Each of the polymethylmethacrylate resin pellets prepared in Examples 1 to 18 and Comparative Examples 1 to 10 was injection-molded to prepare specimens having a thickness of 2 mm. The specimens were subjected to ASTM D1298 at 25 DEG C using an Abbe refractometer Respectively.

division Optical characteristic Impact strength (kgf · m / m) Haze (%) Refractive index Example 1 0.90 1.4901 5.6 Example 2 0.91 1.4901 5.7 Example 3 0.95 1.4901 5.9 Example 4 0.86 1.4901 5.6 Example 5 0.87 1.4901 5.7 Example 6 0.89 1.4901 5.9 Example 7 0.88 1.4901 5.6 Example 8 0.91 1.4901 5.8 Example 9 0.90 1.4901 5.7 Example 10 0.92 1.4901 5.9 Example 11 0.93 1.4901 5.9 Example 12 0.96 1.4901 5.9 Example 13 0.85 1.4901 5.7 Example 14 0.88 1.4901 5.6 Example 15 0.89 1.4901 5.7 Example 16 0.91 1.4901 5.8 Example 17 0.92 1.4901 5.9 Example 18 0.92 1.4901 5.9 Comparative Example 1 0.80 1.4901 1.9 Comparative Example 2 1.20 1.4901 4.5 Comparative Example 3 0.85 1.4901 4.8 Comparative Example 4 1.10 1.4901 5.7 Comparative Example 5 0.84 1.4901 4.6 Comparative Example 6 1.10 1.4901 5.5 Comparative Example 7 0.90 1.4901 4.9 Comparative Example 8 1.30 1.4901 5.3 Comparative Example 9 0.89 1.4901 4.9 Comparative Example 10 1.20 1.4901 5.3

As shown in Table 2, the polymethyl methacrylate resins of Examples 1 to 18 including the core-shell acrylic impact modifier according to the present invention were compared with the polymethyl methacrylate resins of Comparative Examples 1 to 10 , And thus it was confirmed that it exhibits excellent impact strength while having high transparency.

Specifically, the polymethyl methacrylate resins of Examples 1 to 18, which were prepared using an acrylic impact modifier having a core-shell structure containing a phosphate-based anionic emulsifier according to the present invention in a core and a shell, The acrylic-based impact-induced impact of the core-shell structure which did not contain a phosphate anionic emulsifier in the core and the shell, exhibited remarkably excellent impact strength while showing similar degree of transparency as compared with the polymethyl methacrylate resin of Comparative Example 1 which was not used It was confirmed that the polymethyl methacrylate resin of Comparative Example 2 using the reinforcing agent was significantly superior in transparency and impact strength.

In addition, the polymethyl methacrylate resin of Comparative Examples 3 to 6, which used an acrylic impact modifier containing a core-shell structure containing a phosphoric acid anionic emulsifier or a phosphoric acid anionic emulsifier out of the carbon number range of R proposed in the present invention And the poly (methyl methacrylate) resins of Comparative Examples 7 to 10 using an acrylic impact modifier having a core-shell structure including a phosphate anionic emulsifier out of the range of the n value (number of repeating units) As a result of comparison, the polymethylmethacrylate resins of Examples 1 to 18 according to the present invention exhibited excellent properties at the same time with a balance of transparency and impact strength. Thus, in Comparative Examples 3 to 6 and Comparative Examples 7 to 10 The polymethyl methacrylate resin exhibits a significantly low impact strength when the transparency is somewhat excellent, and the transparency It exhibited a phenomenon of degradation.

Accordingly, the acrylic impact modifier having a core-shell structure containing the phosphate-based anionic emulsifier according to the present invention in the core and the shell can improve the impact strength and the transparency of the resin to be blended therewith.

Claims (24)

15% to 25% by weight of an acrylic impact modifier for a polymethyl methacrylate resin having a core-shell structure; And 75% to 85% by weight of a polymethyl methacrylate resin,
Wherein the acrylic impact modifier for polymethyl methacrylate resin is an acrylic impact modifier prepared from an acrylic impact modifier composition for a polymethyl methacrylate resin having a core-shell structure, comprising an acrylic seed, a rubber core surrounding the seed, Shell structure having a core-shell structure,
The acrylic-based impact modifier composition for a polymethyl methacrylate resin of the above-mentioned core-shell structure,
From 5% to 25% by weight of an acrylic seed comprising an alkyl methacrylate monomer;
40% to 65% by weight of a rubber core formed on the acrylic seed and comprising an alkyl acrylate monomer; And
And 15 to 45% by weight of a graft copolymer shell formed on the rubber core, the graft copolymer shell comprising an alkyl methacrylate monomer, an alkyl acrylate monomer, and at least one monomer selected from aromatic vinyl monomers,
Wherein the rubber core and the graft copolymer shell comprise a phosphate-based anionic emulsifier represented by the following formula (1), wherein the core-shell structure is an acrylic impact modifier composition for polymethyl methacrylate resin, Resin composition:
[Chemical Formula 1]

Wherein R is lauryl, tridecyl or myristyl, n is an integer from 4 to 8, and m is 1 or 2.
delete The method according to claim 1,
The phosphate-based anionic emulsifier represented by the formula (1) may be at least one selected from the group consisting of sodium di (hexaoxyethylene lauryl ether) phosphate, sodium di (hexaoxyethylene tridecyl ether) phosphate, sodium di (hexaoxyethylene myristyl ether) Wherein the polymethylmethacrylate resin composition is at least one selected from the group consisting of hexaoxyethylene lauryl ether phosphate, disodium hexaoxyethylene tridecyl ether phosphate and disodium hexaoxyethylene myristyl ether phosphate.
The method according to claim 1,
Wherein the rubber core comprises 0.1 to 0.5 parts by weight of a phosphoric acid anionic emulsifier represented by the general formula (1) based on 100 parts by weight of the total of monomers constituting the impact modifier composition. Composition.
The method according to claim 1,
Wherein the graft copolymer shell comprises 0.1 part by weight to 0.5 part by weight of a phosphate anionic emulsifier represented by the general formula (1) based on 100 parts by weight of the total of monomers constituting the impact modifier composition. Acrylate resin composition.
The method according to claim 1,
Wherein the acrylic seed comprises 5 to 99 parts by weight of an alkyl methacrylate monomer based on 100 parts by weight of the total of monomers constituting the impact modifier composition.
The method according to claim 1,
Wherein the acrylic seed further comprises 0.5 to 90 parts by weight of an alkyl acrylate monomer based on 100 parts by weight of the total of the monomers constituting the impact modifier composition.
The method according to claim 1,
Wherein the rubber core comprises 30 to 70 parts by weight of an alkyl acrylate monomer based on 100 parts by weight of the total of monomers constituting the impact modifier composition.
The method according to claim 1,
Wherein the rubber core further comprises 1 to 40 parts by weight of an aromatic vinyl monomer based on 100 parts by weight of the total of the monomers constituting the impact modifier composition.
The method according to claim 1,
The graft copolymer shell may contain 10 to 50 parts by weight of an alkyl methacrylate monomer, 0.005 to 50 parts by weight of an alkyl acrylate monomer, and an aromatic vinyl monomer, based on 100 parts by weight of the total of monomers constituting the impact modifier composition And at least one monomer selected from the group consisting of monomers.
The method according to claim 1,
Wherein the alkyl methacrylate monomer is at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate.
The method according to claim 1,
Wherein the alkyl acrylate monomer is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate Based on the total weight of the poly (methyl methacrylate) resin composition.
The method according to claim 1,
Wherein the aromatic vinyl-based monomer is at least one member selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, vinyltoluene, alkylstyrene substituted with a C _1-3 alkyl group, and halogen- Polymethyl methacrylate resin composition.
The method according to claim 1,
Wherein the acrylic seed and the rubber core further comprise 0.05 to 5 parts by weight of a crosslinkable monomer based on 100 parts by weight of the total of monomers constituting the impact modifier composition.
15. The method of claim 14,
The crosslinkable monomer may be at least one selected from the group consisting of 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, Acrylate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, divinylbenzene, polyethylene glycol acrylate, polyethylene glycol methacrylate, and butylene glycol dimethacrylate Acrylate and at least one member selected from the group consisting of acrylate, methacrylate, and acrylate.
Based on 100 parts by weight of the total of the monomers constituting the core-shell structure impact modifier composition,
1) 5 parts by weight to 99 parts by weight of an alkyl methacrylate monomer;
2) adding a monomer mixture containing 30 to 70 parts by weight of an alkyl acrylate monomer to the seed thus prepared, followed by emulsification to prepare a rubber core; And
3) A monomer mixture comprising 10 to 50 parts by weight of an alkyl methacrylate monomer, 0.005 to 50 parts by weight of an alkyl acrylate monomer and at least one monomer of an aromatic vinyl monomer was added to the rubber core prepared above Graft-copolymerizing,
The acrylic-based impact modifier composition for a polymethyl methacrylate resin having a core-shell structure, which comprises the phosphate-based anionic emulsifier represented by the following Formula 1 in each of the above-mentioned 2) and 3), 0.1 to 0.5 parts by weight of the monomer mixture, And,
15 to 25% by weight of an acrylic impact modifier for a polymethyl methacrylate resin having a core-shell structure prepared from the acryl-based impact modifier composition for a polymethyl methacrylate resin having the core-shell structure prepared above; And 75% by weight to 85% by weight of a polymethyl methacrylate resin to prepare a mixture. The method for producing a polymethyl methacrylate resin composition according to claim 1,
[Chemical Formula 1]

Wherein R is lauryl, tridecyl or myristyl, n is an integer from 4 to 8, and m is 1 or 2.
18. The method of claim 16,
The phosphate-based anionic emulsifier represented by the formula (1) may be at least one selected from the group consisting of sodium di (hexaoxyethylene lauryl ether) phosphate, sodium di (hexaoxyethylene tridecyl ether) phosphate, sodium di (hexaoxyethylene myristyl ether) Wherein the poly (methyl methacrylate) resin is at least one selected from the group consisting of hexaoxyethylene lauryl ether phosphate, disodium hexaoxyethylene tridecyl ether phosphate and disodium hexaoxyethylene myristyl ether phosphate.
18. The method of claim 16,
The monomer mixture of 2) and 3) further comprises 0.05 to 5 parts by weight of a crosslinkable monomer based on 100 parts by weight of the total of monomers constituting the impact modifier composition. ≪ / RTI >
19. The method of claim 18,
Wherein the crosslinking monomer is allyl methacrylate. ≪ RTI ID = 0.0 > 21. < / RTI >
18. The method of claim 16,
Further comprising the step of agglomerating, dehydrating and drying the acrylic-based impact modifier composition having the core-shell structure prepared after the step (3).
delete The method according to claim 1,
The thickness ratio of the acrylic seed, the rubber core and the graft copolymer shell is r ₁ : r ₂ -r ₁ : r ₃ -r ₂ = 0.9 to 1.1: 0.25 to 0.45: 0.2 to 0.3,
Wherein r ₁ is a distance from the center of the graft copolymer to the outer surface of the acrylic seed, r ₂ is a distance from the center to the outer surface of the rubber core, and r ₃ is a distance from the center to the outer surface of the graft copolymer shell Wherein the poly (methyl methacrylate) resin composition comprises: delete delete