WO2021040269A1 - Thermoplastic resin composition comprising (meth)acrylate graft copolymer, and production method therefor - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising a (meth)acrylate graft copolymer, and a production method therefor, and more specifically, to a thermoplastic resin composition comprising a (meth)acrylate graft copolymer, and a production method therefor, the thermoplastic resin composition comprising A) a graft copolymer containing an alkyl acrylate rubber core and an alkyl methacrylate compound (co)polymer shell surrounding same, and B) a matrix resin, wherein: the rubber core has an average particle diameter of 40-100 nm; the A) graft copolymer has a degree of grafting of 20-100%; and the thermoplastic resin composition has a refractive index of above 1.46 to below 1.49, and a blackness L value of below 25.0. According to the present invention, the effect is achieved of providing: a thermoplastic resin composition comprising a (meth)acrylate graft copolymer, having good impact strength and excellent weather resistance, and especially expressing deep black well by having excellent coloring properties; and a production method therefor.

Description

Thermoplastic resin composition containing (meth)acrylate graft copolymer and method for producing same

[Mutual citation with application(s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0107752 filed on August 30, 2019, and all contents disclosed in the documents of the Korean patent application are included as part of this specification.

The present invention relates to a thermoplastic resin composition comprising a (meth)acrylate graft copolymer and a method for manufacturing the same, and more particularly, excellent impact strength and excellent weather resistance, and in particular, excellent colorability and deep black It relates to a thermoplastic resin composition containing this well-expressed (meth)acrylate graft copolymer and a method for producing the same.

Acrylonitrile-butadiene-styrene resin based on conjugated diene rubber (hereinafter referred to as'ABS resin') has excellent processability, mechanical properties, and appearance properties. It is widely used in construction materials, etc. However, since the ABS resin is based on a butadiene rubber containing a chemically unsaturated bond, the rubber polymer is easily aged by ultraviolet rays, so that the weather resistance is very weak. In order to solve this problem, ABS resin is sometimes used after painting, but environmental pollution is a problem during painting, and the painted product is difficult to recycle and has low durability.

In order to overcome the problems of the ABS resin as described above, an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (hereinafter referred to as'ASA resin') without an ethylenically unsaturated bond is used. Such ASA Although the resin has excellent weather resistance compared to ABS resin, it has excellent impact and colorability, but has a problem in that its appearance characteristics such as colorability are inferior to ABS resin-coated products, and also, the level of weatherability required by the market is getting higher and higher, which is insufficient to meet this. There is a limit.

Therefore, it is necessary to develop a resin that has superior coloring properties compared to existing ABS resins or ASA resins, but also excellent in weather resistance and impact strength.

〔Prior technical literature〕

[Patent Literature]

Korean Patent Registration No. 10-0815995

In order to solve the problems of the prior art as described above, the present invention includes a (meth)acrylate graft copolymer having excellent impact strength, excellent weather resistance, and particularly excellent colorability, so that deep black is well expressed. An object of the present invention is to provide a thermoplastic resin composition and a method for producing the same.

Another object of the present invention is to provide a molded article made of the thermoplastic resin composition of the present invention.

All of the above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a thermoplastic comprising a graft copolymer containing A) an alkyl (meth)acrylate rubber core and an alkyl methacrylate compound (co)polymer shell surrounding the same, and B) a matrix resin. As a resin composition, the rubber core has an average particle diameter of 40 to 100 nm, the A) graft copolymer has a graft ratio of 20 to 100%, and the thermoplastic resin composition has a refractive index greater than 1.46 to less than 1.49, and a blackness L value It provides a thermoplastic resin composition comprising a (meth)acrylate graft copolymer, characterized in that it is less than 25.0, and a method for producing the same.

According to the present invention, a thermoplastic resin composition comprising a (meth)acrylate graft copolymer, which has high impact strength, excellent weather resistance, and particularly excellent colorability, so that deep black is well expressed, and a method for producing the same It has the effect of providing molded products manufactured from.

Hereinafter, a thermoplastic resin composition comprising the (meth)acrylate graft copolymer of the present invention, a method of manufacturing the same, and a molded article manufactured therefrom will be described in detail.

As a thermoplastic resin composition comprising a (meth)acrylate graft copolymer and a matrix resin, the present inventors control the total refractive index of the thermoplastic resin composition to be low to a predetermined range while keeping the rubber size and graft ratio of the graft copolymer within a predetermined range. In this case, it was confirmed that the weather resistance and coloring properties were greatly improved while maintaining the same or higher impact strength, etc., and based on this, the present invention was completed by further focusing on research.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising A) a graft copolymer containing an alkyl (meth)acrylate rubber core and an alkyl methacrylate compound (co)polymer shell surrounding it, and B) a matrix resin. , The rubber core has an average particle diameter of 40 to 100 nm, the A) graft copolymer has a graft ratio of 20 to 100%, and the thermoplastic resin composition has a refractive index of greater than 1.46 to less than 1.49. In this case, the impact strength is high, the weather resistance is excellent, and in particular, the colorability is excellent, and there is an effect that deep black is well expressed.

In addition, the present invention is a thermoplastic resin composition comprising A) a graft copolymer containing an alkyl (meth)acrylate rubber core and an alkyl methacrylate compound (co)polymer shell surrounding the same, and B) a matrix resin, The rubber core has an average particle diameter of 40 to 100 nm, the A) graft copolymer has a graft ratio of 20 to 100%, and the thermoplastic resin composition has a refractive index of more than 1.46 to less than 1.49, and a blackness L value of less than 25.0. The thermoplastic resin composition described above may be included, and within this range, the impact strength is high, the weather resistance is excellent, and the colorability is particularly excellent, so that the deep black is well expressed.

In addition, the present invention is a thermoplastic resin composition comprising A) a graft copolymer containing an alkyl (meth)acrylate rubber core and an alkyl methacrylate compound (co)polymer shell surrounding the same, and B) a matrix resin, The rubber core has an average particle diameter of 40 to 100 nm, the A) graft copolymer has a graft ratio of 20 to 100%, the thermoplastic resin composition has a refractive index of more than 1.46 to less than 1.49, the refractive index of the rubber core, the ( Co) a thermoplastic resin composition characterized in that the refractive index of the polymer shell and the refractive index difference of the matrix resin is less than 0.04, and within this range, the impact strength is high and the weather resistance is excellent, and in particular, the colorability is excellent, so that the dip black is It has an effect that is well expressed.

Hereinafter, the thermoplastic resin composition of the present disclosure will be described in detail for each component.

A) Graft copolymer

The graft copolymer according to the present invention contains an alkyl (meth)acrylate rubber core and an alkyl methacrylate compound (co)polymer shell surrounding it, and in this case, there is an effect of excellent weather resistance and colorability.

The rubber core, for example, has an average particle diameter of 40 to 120 nm, 50 to 110 nm, preferably 60 to 110 nm, more preferably 60 to 100 nm, even more preferably 70 to 100 nm, Most preferably, it is 80 to 100 nm, and within this range, the weather resistance is remarkably improved and the coloring property is excellent.

The rubber core may include, for example, alkyl acrylate and alkyl methacrylate, and in this case, there is an effect of further improving weather resistance.

The alkyl methacrylate may be included as an example in the rubber core in 0 to 30% by weight, preferably 1 to 20% by weight, more preferably 3 to 10% by weight, this range There is an effect of improving weatherability without lowering the impact inside.

The rubber core may further include at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound as an example, and in this case, there is an effect of having excellent appearance characteristics.

The rubber core is, for example, 0 to 30% by weight, 0 to 20% by weight, 0.1 to 30% by weight of at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound based on a total of 100% by weight of monomers used in the core production. It may be included in wt% or 0.1 to 20 wt%, and there is an effect of having excellent appearance properties within this range.

As a specific example, the rubber core may include 0 to 20% by weight of the aromatic vinyl compound and 0 to 10% by weight of the vinyl cyan compound, based on 100% by weight of the total monomers used in manufacturing the core, preferably the aromatic vinyl 0.1 to 20% by weight of the compound and 0.1 to 10% by weight of the vinyl cyanide compound, more preferably 0.1 to 10% by weight of the aromatic vinyl compound and 0.1 to 5% by weight of the vinyl cyanide compound, and , There is an effect of excellent appearance characteristics within this range.

The refractive index of the rubber core may have a difference between the refractive index of the (co)polymer shell and the refractive index of the matrix resin preferably 0.03 or less, in a preferred embodiment 0.015 to 0.03, more preferably less than 0.03, more In a preferred embodiment , it may be more than 0.01 5 to less than 0.03, and in a more preferred embodiment, it may be more than 0.012 to less than 0.03, and in the most preferred embodiment, it may be more than 0.015 to less than 0.03, and within this range, the effect of excellent colorability There is.

In the present description, the difference in refractive index between certain components means the difference between the minimum refractive index value and the maximum refractive index value among them.

In the present description, the alkyl (meth)acrylate includes an alkyl acrylate and an alkyl methacrylate.

In the present description, the alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl It may be one or more selected from the group consisting of acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, and preferably a chain alkyl group having 1 to 4 carbon atoms. It may be a containing alkyl acrylate, more preferably butyl acrylate.

In the present description, the alkyl methacrylate may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples are methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylbutyl methacrylate. , 2-ethylhexyl methacrylate and lauryl methacrylate may be one or more selected from the group consisting of, preferably, may be an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably It is methyl methacrylate.

In the present description, a polymer comprising a compound refers to a polymer polymerized including the compound, and one unit in the polymerized polymer is derived from the compound.

The rubber core may comprise 0.01 to 3 parts by weight, preferably 0.1 to 1 part by weight of a crosslinking agent, based on a total of 100 parts by weight of the monomers used for preparing the graft copolymer, and within the above range, the impact resistance of the resin and There is an effect of improving weather resistance and the like.

As a specific example, in the rubber core, 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier are added and polymerized to form the core. It can be prepared, and there is an effect of improving the impact resistance and weather resistance of the resin within the above range.

The rubber core may include, for example, a polymer seed.

The polymer seed is, for example, 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and more, based on a total of 100 parts by weight of monomers used for preparing the graft copolymer, at least one monomer selected from alkyl acrylate and alkyl methacrylate. It may preferably include 4 to 15 parts by weight, and within this range, there is an excellent effect of impact resistance, weather resistance, balance of physical properties, and the like.

The polymer seed comprises, for example, 0 to 30% by weight, preferably 1 to 20% by weight, and more preferably 3 to 10% by weight of an alkyl methacrylate monomer based on the total 100% by weight of the monomers used in the seed preparation. And within this range, there is an excellent effect in impact resistance, weather resistance, and physical property balance.

The polymer seed may include, for example, 0 to 20% by weight of the aromatic vinyl compound and 0 to 10% by weight of the vinyl cyanide compound, based on a total of 100% by weight of monomers used in seed preparation, and optionally, the aromatic vinyl compound. 0.1 to 20% by weight and 0.1 to 10% by weight of the vinyl cyanide compound may be included, and as an example for this, 0.1 to 10% by weight of the aromatic vinyl compound and 0.1 to 5% by weight of the vinyl cyanide compound may be included. In addition, there is an effect of improving the appearance characteristics within this range.

In a preferred embodiment, the polymer seed may not contain an aromatic vinyl compound, a vinyl cyan compound, or both.

As a specific example, the polymer seed may be prepared by polymerization, including 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier, based on a total of 100 parts by weight of the monomers used to prepare the graft copolymer. , There is an advantage in that a polymer having an even size can be prepared within a short time within the above range, and polymer properties such as weather resistance and impact resistance are further improved.

In another specific example, the polymer seed may be prepared by polymerization, including 0.1 to 1 parts by weight of a crosslinking agent, 0.01 to 1 parts by weight of an initiator, and 0.5 to 1.5 parts by weight of an emulsifier, based on 100 parts by weight of the total monomers used for preparing the graft copolymer. In the above range, a polymer having an even size can be prepared within a short time, and polymer properties such as weather resistance and impact resistance can be further improved.

The polymer seed is preferably an alkyl acrylate alone, or a copolymerization of an alkyl acrylate and an alkyl methacrylate may be preferred, and an aromatic vinyl compound and/or a vinyl cyan compound may be additionally used as needed. In this case, there is an advantage in that weather resistance and mechanical strength are further improved.

The polymer seed may have, for example, an average particle diameter of 10 to 60 nm, preferably 30 to 60 nm, more preferably 30 to 50 nm, even more preferably 30 to 40 nm, and weather resistance and colorability within this range. It has an excellent advantage.

When preparing the polymer seed, at least one of an electrolyte and a grafting agent may be optionally further included.

The electrolyte may be used in an amount of 0.005 to 1 part by weight, 0.01 to 1 part by weight, or 0.05 to 1 part by weight based on 100 parts by weight of a total of monomers used for preparing the graft copolymer. Within this range, the polymerization reaction and the latex There is an effect of improving stability.

The electrolyte in this description is for example KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , Na ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , Na ₂ HPO ₄ , KOH, NaOH and Na ₂ S ₂ O _{7 It} may be one or more selected from the group consisting of, but is not limited thereto.

The grafting agent may be used in an amount of 0.01 to 3 parts by weight, 0.01 to 1 part by weight, or 0.01 to 0.5 parts by weight based on 100 parts by weight of a total of monomers used for preparing the graft copolymer. Within this range, the graft polymer There is an advantage that the graft rate can be improved, and other physical properties are also improved.

In the present description, the grafting agent is not particularly limited if it is a grafting agent generally used in the technical field to which the present invention belongs unless otherwise defined, and as an example, a compound containing an unsaturated vinyl group having two or more different reactivity may be used, For example, it may be one or more selected from allyl methacrylate, triallyl isocyanurate, triallyl amine, and diallyl amine, but is not limited thereto.

In the present description, the (co)polymer includes a polymer and a copolymer.

The alkyl methacrylate contained in the (co)polymer shell may be included in 65 to 100% by weight, preferably 80 to 99.5% by weight, more preferably in the (co)polymer shell, for example It may be included in an amount of 85 to 95% by weight, and within this range, there is an effect of excellent impact strength and weather resistance.

The (co)polymer shell may further include an alkyl acrylate as an example, and in this case, the impact strength is excellent.

The alkyl acrylate contained in the (co)polymer shell, for example, may be contained in an amount of 0.1 to 20% by weight, preferably 5 to 15% by weight, and impact within this range. There is an effect of excellent strength.

The (co)polymer shell may further include at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound as needed, and in this case, the impact strength is improved.

The difference in refractive index between the (co)polymer shell and the matrix resin is, for example, 0.005 or less, preferably less than 0.005, more preferably 0.003 or less, still more preferably 0.0025 or less, even more preferably 0.0021 or less, and within this range There is an effect excellent in colorability.

The (co)polymer shell may include, for example, 0 to 10% by weight of the aromatic vinyl compound and 0 to 5% by weight of the vinyl cyan compound, based on 100% by weight of the total monomers used in the shell preparation, preferably 0.1 to 10% by weight of the aromatic vinyl compound and 0.1 to 5% by weight of the vinyl cyanide compound, more preferably 0.1 to 5% by weight of the aromatic vinyl compound and 0.1 to 2.5% by weight of the vinyl cyanide compound It can be done, and there is an effect excellent in appearance characteristics within this range.

In the present description, the aromatic vinyl compound may be, for example, one or more selected from styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene, preferably styrene, but is not limited thereto.

In the present description, the vinyl cyan compound may be one or more selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile, and preferably acrylonitrile, but is not limited thereto.

The emulsifier is not particularly limited if it is an emulsifier generally used in the technical field to which the present invention belongs, and includes, for example, a salt of rosin acid, a salt of lauryl acid, a salt of oleic acid, a salt of stearic acid, etc. 20 low molecular weight carboxylates; An alkyl sulfosuccinic acid salt or a derivative thereof having 20 or less carbon atoms or 10 to 20 carbon atoms; Alkyl sulfates or sulfonates having 20 or less carbon atoms or 10 to 20 carbon atoms; A polyfunctional carboxylic acid or a salt thereof having 20 to 60, 20 to 55 or 30 to 55 carbon atoms and including at least 2 or more, preferably 2 to 3 carboxyl groups in the structure; And one or more phosphoric acid-based salts selected from the group consisting of monoalkyl ether phosphate or dialkyl ether phosphate.

In another example, the emulsifier is sulfoethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium styrene sulfonate, Sodium dodectyl allyl sulfosuccinate, styrene and sodium dodecyl allyl sulfosuccinate copolymer, polyoxyethylene alkylphenyl ether ammonium etc., alkenyl C16 Reactive emulsifiers selected from -18 succinic acid, di-potassium salt (alkenyl C16-18 succinic acid, di-potassium salt) and sodium methallyl sulfonate; And a non-reactive emulsifier selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acids.

In the present description, the monomer refers to an alkyl acrylate, an alkyl methacrylate, an aromatic vinyl compound, and a vinyl cyan compound.

The A) graft copolymer has, for example, a graft ratio of 20 to 100%, preferably 30 to 80%, and most preferably 40 to 70%, and has excellent appearance properties including colorability within this range and It has excellent impact properties.

As a specific example, the (co)polymer shell is prepared by adding 20 to 80 parts by weight of an alkyl methacrylate, 0.01 to 5 parts by weight of an emulsifier, and 0.01 to 3 parts by weight of an initiator based on 100 parts by weight of the total monomers used to prepare the graft copolymer. It can be prepared by graft polymerization, and has excellent effects in weather resistance and impact resistance within the above range.

The (co)polymer shell may optionally further include a molecular weight control agent to be polymerized, and the molecular weight control agent may be 0.01 to 2 parts by weight based on a total of 100 parts by weight of monomers used for preparing the graft copolymer, and 0.05 to It may be used in an amount of 2 parts by weight or 0.05 to 1 part by weight, and a polymer having a desired size within this range can be easily prepared.

In the present description, the term'based on a total of 100 parts by weight of monomers used in the preparation of the graft copolymer' means that the weight of the total monomers used in the production of seeds, cores and shells constituting the graft copolymer is based on 100 parts by weight, and , It may be referred to as'total 100 parts by weight of the graft copolymer' or'total 100 parts by weight of the rubber core and monomers combined.'

The molecular weight modifier may include mercaptans such as a-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan; Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide; And a sulfur-containing compound such as tetraethyl thiuram disulfide, dipentamethylene thiuram disulfide, diisopropylxanthogen disulfide; may be at least one selected from the group consisting of, preferably tertiary dodecylmercaptan, etc. It should be noted that the mercaptan compound of may be used, but is not limited thereto.

In the present description, the crosslinking agent is not particularly limited if it is a crosslinking agent commonly used in the technical field to which the present invention belongs unless otherwise defined, and as an example, an acrylic compound containing an unsaturated vinyl group and capable of serving as a crosslinking agent may be used. Specific examples: polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, divinylbenzene, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate , Neopentyl glycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropane ethoxylate triacrylate, trimethylpropane propoxylate triacrylate, pentaerythritol ethoxylate It should be noted that it may be one or more selected from the group consisting of triacrylate, pentaerythritol propoxylate triacrylate, and vinyl trimethoxysilane, but is not limited thereto.

In the present description, the initiator is not particularly limited if it is an initiator generally used in the technical field to which the present invention belongs, and for example, a water-soluble initiator, a fat-soluble initiator, or a mixture of these initiators may be used.

As the water-soluble initiator, for example, one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide may be used, but it should be noted that the present invention is not limited thereto.

Examples of the fat-soluble initiator include t-butyl peroxide, cumene hydroperoxide, p-methane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octa Noyl peroxide, dibenzoyl peroxide, diisopropylbenzene hydroperoxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate, azobis isobutyronitrile, azobis-2, It should be noted that at least one selected from the group consisting of 4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyric acid) methyl may be used, but is not limited thereto.

At least one of the steps of preparing the polymer seed, the step of producing the rubber core and the step of producing the (co)polymer shell according to the present invention preferably includes an activator to further accelerate the initiation reaction together with the above-described initiator. And, more preferably, it is included in the manufacturing step of the (co)polymer shell.

The activator may preferably include at least one selected from the group consisting of metal sulfinatoacetic acid salts and metal sulfonatoacetic acid metal salts, and in this case, there is an advantage of greatly improving weather resistance and colorability while maintaining equal or more impact strength and the like.

The metal salt is, for example, an alkali metal salt, and preferably a sodium salt, and in this case, there is an advantage of greatly improving weather resistance and colorability while maintaining equal or more impact strength and the like.

The sulfinatoacetic acid metal salt and the sulfonatoacetic acid metal salt may preferably independently contain one or more functional groups, and preferably contain a hydroxy group as the functional group, and in this case, while maintaining equal or more impact strength, etc., weather resistance and There is an advantage of greatly improving colorability.

The sulfinatoacetic acid metal salt containing a hydroxy group as the functional group is a specific example of disodium 2-hydroxy-2-sulfinatoacetate, etc., and sulfonatoacetic acid containing a hydroxy group as the functional group The metal salt is a specific example of disodium 2-hydroxy-2-sulfonatoacetate, etc. In this case, there is an advantage of greatly improving weather resistance and colorability while maintaining equal or more impact strength and the like.

The activator may preferably include a compound represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen, a C1 to C10 alkyl group, or *-(C=O)OM ₂ , _{but both R 1} and R ₂ are not hydrogen, and M ₁ and M ₂ are the same as or different from each other, and each independently is an alkali metal.

When the compound represented by Formula 1 is used, the grafting ratio of the graft copolymer can be significantly increased to improve appearance characteristics including colorability.

In addition, the compound represented by Formula 1 does not use textrose or sodium formaldehyde sulfoxylate, which is used as a reducing agent, but also a compound containing divalent iron ions such as iron sulfate, which is an existing activator, and fatigue, which is an existing chelating agent. Even if a small amount of sodium phosphate or sodium ethylenediamine tetraacetate is used compared to the existing one, a high graft rate of the graft copolymer can be secured. In particular, dextrose, which is a reducing agent, is a material that is easily heat discolored, and thus excellent weather resistance is secured by removing it.

In Formula 1, M ₁ and M ₂ are the same as or different from each other, and each independently is preferably Na or K, and more preferably Na.

In Formula 1, it is preferable that _{R 1} and R ₂ are the same as or different from each other, and each independently hydrogen or -(C=O)OM _2.

If the above-described conditions are satisfied, the graft ratio of the graft copolymer can be significantly increased to improve appearance characteristics including colorability, and at the same time, excellent weather resistance can be secured.

The activator may more preferably include a compound represented by the following formula (2).

[Formula 2]

The activator according to the present disclosure is preferably continuously added for a predetermined time in order to maintain excellent activity uniformly and to improve the graft rate of the graft copolymer. In addition, for continuous injection, the activator is preferably added in a mixed state with a solvent. In this case, the solvent may be water, for example.

In the present description, the term'continuous injection' means not'batch injection', and for example, within the polymerization reaction time range, 10 minutes or more, 30 minutes or more, 1 hour or more, preferably 2 hours or more drop-by-drop by drop), little by little, step by step, or continuous flow.

The activator may be added in an amount of 0.01 to 1 parts by weight or 0.1 to 0.8 parts by weight based on 100 parts by weight of the total monomers added during the preparation of the graft copolymer, and within this range, the graft rate is remarkably increased, resulting in colorability and appearance. There is an effect of improving characteristics.

The manufacturing step carried out including the activator preferably includes at least one selected from the group consisting of a compound containing divalent iron ions and a chelating agent.

Further, in order to stably impart the catalytic activity of the polymerization initiator, a compound containing divalent iron ions such as ferrous sulfate, for example, is included in an amount of 0.0001 to 0.01 parts by weight based on 100 parts by weight of the total monomers used in the preparation of the graft copolymer. And, for example, a chelating agent such as sodium pyrophosphate and/or sodium ethylenediamine tetraacetate may be included in an amount of 0.001 to 0.1 parts by weight based on a total of 100 parts by weight of the monomer used in the preparation of the graft copolymer, and polymerization is initiated within this range. There is an advantage in that it can further promote and improve the weather resistance of the polymer to be produced.

In the step of preparing the graft copolymer of the present disclosure, for example, a reducing agent such as a conventional dextrose may not be used, and in this case, there is an effect of improving weather resistance.

The graft copolymer latex obtained through the step of preparing the rubber core and the (co)polymer shell may, for example, be characterized in that the coagulation content is 1% or less, preferably 0.5% or less, more preferably 0.1 % Or less. Within the above-described range, the productivity of the resin is excellent, and mechanical strength and appearance characteristics are improved.

In the present description, the coagulated content (%) can be calculated by measuring the weight of the coagulated product generated in the reaction tank, the total weight of the rubber, and the weight of the monomer, and the following equation (1).

[Equation 1]

The graft copolymer latex may be in a powder form through conventional processes such as agglomeration, washing, and drying. For example, a metal salt or an acid is added to the graft copolymer latex to aggregate at a temperature of 60 to 100°C. And, it is stated that it may be prepared in a powder form through aging, dehydration, washing and drying processes, but is not limited thereto.

The present invention is a core production step of preparing a rubber core by introducing and polymerizing a monomer containing an alkyl (mat) acrylate as an example; And a method for preparing a graft copolymer comprising; and in the presence of the prepared rubber core, a monomer including an alkyl methacrylate compound and an emulsifier are added to prepare a shell by graft polymerization to prepare a shell. I can. This manufacturing method may also be defined or limited to all of the above.

In another example, the present invention provides a seed preparation step of polymerizing a monomer including an alkyl (meth)acrylate to prepare a polymer seed; b) adding a monomer containing an alkyl (meth)acrylate in the presence of the prepared polymer seed, and polymerizing it to prepare a rubber core; And c) adding a monomer containing an alkyl methacrylate in the presence of the prepared rubber core, an emulsifier, and performing graft polymerization to prepare a shell to prepare a shell; Can include. This manufacturing method may also be defined or limited to all of the above.

Other conditions not specified in the method for preparing the graft copolymer described above, that is, polymerization conversion rate, reaction pressure, reaction time, gel content, etc., are not particularly limited if they are within the ranges commonly used in the technical field to which the present invention belongs, It is stated that appropriate selection and implementation can be performed as needed.

B) matrix resin

The matrix resin according to the present invention is a thermoplastic resin that plays a role of imparting excellent colorability by lowering the refractive index.

The matrix resin may preferably include a poly(alkyl methacrylate) resin, more preferably a polymethyl methacrylate resin, and in this case, excellent weather resistance and appearance characteristics can be secured.

The poly(alkyl methacrylate) resin may further include an alkyl acrylate as an example, and in this case, there is an effect of excellent impact resistance.

The alkyl acrylate may be included in 0.1 to 20% by weight, preferably 1 to 15% by weight, and more preferably 1 to 10% by weight in the poly(alkyl methacrylate) resin as an example. Although included, there is an effect excellent in impact resistance within this range.

The matrix resin may have, for example, a weight average molecular weight of 50,000 to 200,000 g/mol, preferably 80,000 to 150,000 g/mol, more preferably 90,000 to 130,000 g/mol, and within this range, glossiness, processability and weatherability It has an excellent effect.

In this description, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent. ) Can be measured relative to the standard PS (standard polystyrene) sample.

The poly(alkyl methacrylate) resin may be prepared by mixing a crosslinking agent and an initiator with a monomer including alkyl methacrylate, for example, and then bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and preferably suspension polymerization Or it is prepared by emulsion polymerization.

The initiator is not particularly limited if it is a conventional initiator used in the production of a poly(alkyl methacrylate) resin, and an azo initiator such as 2,2'-azobis 2'4-dimethyl-valeronitrile is preferable. can do.

Substances required for reaction such as solvents and emulsifiers, which must be added or changed according to the polymerization method, or conditions such as polymerization temperature and polymerization time are generally applied according to each polymerization method when preparing poly(alkyl methacrylate) resins. In the case of or conditions, it is not particularly limited, and may be appropriately selected as necessary.

C) Thermoplastic resin composition

The thermoplastic resin composition of the present invention may include, for example, 20 to 80% by weight of the graft copolymer and 20 to 80% by weight of the matrix resin, preferably 30 to 70% by weight of the graft copolymer and the matrix It may contain 30 to 70% by weight of the resin, most preferably 40 to 60% by weight of the graft copolymer and 40 to 60% by weight of the matrix resin, and within this range, colorability and impact resistance and It has excellent weather resistance.

The refractive index of the thermoplastic resin composition is, for example, more than 1.46 to less than 1.49, 1.47 to less than 1.488, or more than 1.47 to less than 1.488, preferably more than 1.46 to 1.485 or less, more preferably more than 1.46 to less than 1.485, and , More preferably, it is more than 1.46 to 1.48 or less, and within this range, there is an advantage that the colorability is excellent and deep black is well expressed.

The thermoplastic resin composition is, for example, an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer, based on a total weight of 100 parts by weight of the graft copolymer and the matrix resin, 0 to 10 parts by weight, preferably 1 to It may contain 10 parts by weight, more preferably 1 to 5 parts by weight, and there is an advantage in that impact strength and workability are greatly improved within this range.

The alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer may be, for example, a copolymer in which an aromatic vinyl compound and a vinyl cyan compound are graft-polymerized on an alkyl acrylate rubber having an average particle size of 100 to 500 nm. There is an effect of excellent gloss and processability within the range.

In a more specific example, the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer is an aromatic vinyl compound 30 to 60% by weight and vinyl in 20 to 60% by weight of an alkyl acrylate rubber having an average particle size of more than 100 nm to 500 nm or less. 10 to 20% by weight of the cyanogen compound may be a graft-polymerized copolymer, and within this range, there is an effect of excellent gloss and processability.

In another example, the alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer is an aromatic vinyl compound 30 to 50% by weight and a vinyl cyanide compound in 40 to 60% by weight of an alkyl acrylate rubber having an average particle size of 200 to 400 nm. 10 to 15% by weight may be a graft-polymerized copolymer, and within this range, there is an effect of excellent gloss and processability.

The method for producing the thermoplastic resin composition of the present invention is characterized in that it includes the step of mixing and extruding the thermoplastic resin composition of the present invention. In this case, it has good impact strength, excellent weather resistance, and particularly excellent colorability, so that deep black is well expressed.

The extrusion can be carried out under conditions of 190 to 260 °C and 100 to 300 rpm, preferably 200 to 240 °C and 150 to 200 rpm, for example, and within this range, a thermoplastic resin having excellent processability and desired physical properties The composition can be prepared.

The method for preparing the thermoplastic resin composition further comprises at least one additive selected from the group consisting of a flame retardant, a lubricant, an antibacterial agent, a release agent, a nucleating agent, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, a dye, and a compatibilizer. In addition, the additive may preferably be included in an amount of 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight, even more preferably, based on 100 parts by weight of the total composition including the graft copolymer and the matrix resin. Is included in an amount of 1 to 5 parts by weight, and within this range, the desired effect of the additive can be fully expressed without deteriorating the inherent physical properties of the resin.

The lubricant may be selected from, for example, ethylene bis stearamide, oxidized polyethylene wax, metal stearate, and various silicone oils, and the amount used is 0.1 to 5 parts by weight based on a total of 100 parts by weight of the composition including the graft copolymer and the matrix resin. It is in the range of 0.1 to 2 parts by weight, more preferably 0.1 to 2 parts by weight.

D) Molded product

The molded article of the present invention is characterized in that it is manufactured from the thermoplastic resin composition of the present invention. In this case, the impact strength is good, the weather resistance is excellent, and the colorability is particularly excellent, so that a deep black is well expressed.

The molded article may preferably be an automobile exterior material, more preferably a non-painting product such as a filler or a lamp housing, and in this case, the impact strength, weather resistance, and colorability have the advantage of greatly satisfying the needs of the molded article. .

The present invention may include, as an example, a method of manufacturing a molded article comprising the step of injecting the thermoplastic resin composition of the present disclosure or pellets thereof.

The injection may be carried out under conditions of 190 to 260° C. and 30 to 80 bar, preferably 200 to 240° C. and 40 to 60 bar, for example, and within this range, processing is easy and desired impact strength, weather resistance, and There is an advantage in that the coloring property is well expressed.

For example, the molded article has a blackness (L value) of 25 . It is less than 0, preferably 24.5 or less, more preferably 24.0 or less, preferred examples are 24.5 to 20, more preferred examples are 24 to 22, and within this range, there is an effect of excellent overall physical property balance and excellent colorability.

Other conditions not explicitly described in the thermoplastic resin composition and the molded article are not particularly limited if they are within the range commonly practiced in the technical field to which the present invention pertains, and may be appropriately selected as necessary.

Hereinafter, a preferred embodiment is presented to aid in the understanding of the present invention, but it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the present invention and the scope of the technical idea, but the following examples are only illustrative of the present invention, It is natural that such modifications and modifications fall within the appended claims.

[Example]

Example 1

<Seed manufacturing step>

Batch administration of 5 parts by weight of butyl acrylate, 1.4 parts by weight of sodium dodecyl sulfate, 0.05 parts by weight of ethylene glycol dimethacrylate, 0.05 parts by weight of allyl methacrylate, 0.1 parts by weight of potassium hydroxide and 60 parts by weight of distilled water to a nitrogen-substituted reactor Then, after raising the temperature to 70°C, 0.05 parts by weight of potassium persulfate was added to initiate the reaction. After that, polymerization was carried out for 1 hour. The average size of the rubber polymer seed particles obtained after completion of the reaction was 45 nm and the refractive index was 1.46.

<Polymer core manufacturing step>

Mixing the polymer seed with 45 parts by weight of butyl acrylate, 0.7 parts by weight of sodium dodecyl sulfate, 0.2 parts by weight of ethylene glycol dimethacrylate, 0.2 parts by weight of allyl methacrylate, 35 parts by weight of distilled water and 0.1 parts by weight of potassium persulfate The mixture was continuously added at 70° C. for 2.0 hours, and polymerization was further performed for 1 hour after completion of the addition. The average size of the particles of the rubber polymer obtained after completion of the reaction was 100 nm, and the refractive index of the rubber polymer was 1.46.

<Polymer Graft Shell Manufacturing Step>

In the reactor from which the core was obtained, 23 parts by weight of distilled water, 45 parts by weight of methyl methacrylate, 5 parts by weight of butyl acrylate, 1.5 parts by weight of potassium rosinate salt as an emulsifier and 0.1 parts by weight of n-octyl mercaptan and cumene hide as an initiator. A mixture of 0.1 parts by weight of loperoxide uniformly mixed with an aqueous solution (concentration: 5% by weight) containing 0.3 parts by weight of 2-hydroxy-2-sulfinatoacetic acid disodium salt as an activator and 0.03 parts by weight of sodium pyrophosphate, 1st sulfide A polymerization reaction was carried out by continuously adding 0.0006 parts by weight of iron mixed solution at 75° C. for 3.0 hours. After the continuous addition was completed, the polymerization was further polymerized at 75° C. for 1 hour, and then cooled to 60° C. to terminate the polymerization reaction to prepare a graft copolymer latex. The average size of the graft copolymer particles obtained after completion of the reaction was 125 nm, and the shell refractive index of the graft copolymer was 1.487. In addition, the total refractive index of the graft copolymer was 1.4735 and the graft rate was 70%.

<Preparation of Graft Copolymer Powder>

The prepared (meth)acrylate graft copolymer latex was subjected to atmospheric pressure coagulation at 60 to 85°C by applying 1.0 part by weight of an aqueous calcium chloride solution, then aged at 70 to 95°C, dehydrated and washed, and heated with 80°C hot air. After drying for a period of time, a graft copolymer powder was prepared.

<Production of matrix resin>

To a nitrogen-substituted reactor, 95 parts by weight of methyl methacrylate, 5 parts by weight of methyl acrylate, 200 parts by weight of distilled water, 0.3 parts by weight of polyvinyl alcohol and 0.3 parts by weight of n-octyl mercaptan as a suspending agent were collectively administered, and the reactor internal temperature was 80 After raising it to °C and adding 0.1 parts by weight of AIBN as an initiator to initiate the reaction, the polymerization reaction was carried out for 70 minutes while maintaining the temperature inside the reaction tank at 80°C, and then the temperature of the reaction tank was raised to 110°C, followed by additional polymerization for 30 minutes. The polymerized beads were washed using a dehydrator and dried at 80° C. for 2 hours in a fluidized bed dryer. The molecular weight of the prepared polymethyl methacrylate resin was 120,000 g/mol and the refractive index was 1.487.

<Production of thermoplastic resin composition>

50 parts by weight of the graft copolymer powder, 50 parts by weight of the polymethyl methacrylate resin, 1.5 parts by weight of a lubricant, 1.0 part by weight of an antioxidant, 1.0 part by weight of a UV stabilizer, and 1 part by weight of a black colorant were added and mixed. This was prepared in the form of pellets using a 36 pie extrusion kneader at a cylinder temperature of 220° C., and then injected into the pellets to prepare a physical property specimen. At this time, the refractive index of the entire thermoplastic resin composition was 1.4813. In addition, the difference in refractive index between the shell and the matrix resin and the rubber refractive index was 0.027, and the difference between the shell and the matrix resin was 0.0021.

Example 2

In the seed production step in Example 1, 4.5 parts by weight of butyl acrylate and 0.5 parts by weight of methyl methacrylate were used instead of 5 parts by weight of butyl acrylate, 1.6 parts by weight of sodium dodecyl sulfate was used, and butyl acrylate was used in the core production step. Except that 40.5 parts by weight of butyl acrylate and 4.5 parts by weight of methyl methacrylate were used instead of 45 parts by weight, the same was performed.At this time, the graft ratio of the graft copolymer was 58% and the refractive index of the rubber was 1.463, The refractive index was 1.475. And the refractive index of all the thermoplastic resin compositions was 1.482. In addition, the difference in refractive index between the shell and the matrix resin was 0.024, and the difference in refractive index between the shell and the matrix resin was 0.0021.

Example 3

In the seed production step in Example 1, 4.0 parts by weight of butyl acrylate and 1 part by weight of methyl methacrylate were used instead of 5 parts by weight of butyl acrylate, 1.8 parts by weight of sodium dodecyl sulfate was used, and butyl acrylate was used in the core production step. The same was carried out except that 36 parts by weight of butyl acrylate and 9 parts by weight of methyl methacrylate were used instead of 45 parts by weight.At this time, the graft ratio of the graft copolymer was 49% and the refractive index of the rubber was 1.466, The refractive index was 1.4765. In addition, the refractive index of the entire thermoplastic resin composition was 1.4828, the difference between the refractive index of the shell and the matrix resin and the refractive index of the rubber was 0.021, and the difference between the refractive index of the shell and the matrix resin was 0.0021.

Example 4

Except that 90 parts by weight of methyl methacrylate and 10.0 parts by weight of butyl acrylate were used instead of methyl acrylate in the step of preparing the matrix resin in Example 1, the refractive index of the matrix resin was 1.487, and the graft copolymer The refractive index was 1.4735. In addition, the refractive index of the entire thermoplastic resin composition was 1.48, the difference between the refractive index of the shell and the matrix resin and the rubber refractive index was 0.027, and the difference between the refractive index of the shell and the matrix resin was 0.0000.

Example 5

In Example 1, 40 parts by weight of methyl methacrylate and 10 parts by weight of butyl acrylate were used in the step of preparing the graft shell in Example 1, and 80 parts by weight of methyl methacrylate and 20 parts by weight of butyl acrylate were used instead of the methyl acrylate in the step of preparing the matrix resin. Except that, it was carried out in the same manner. The refractive index of the matrix resin was 1.484, and the refractive index of the graft copolymer was 1.472. In addition, the refractive index of the entire thermoplastic resin composition was 1.478, the difference between the refractive index of the shell and the matrix resin and the refractive index of the rubber was 0.024, and the difference between the refractive index of the shell and the matrix resin was 0.0000.

Example 6

In Example 1, 1.8 parts by weight of sodium dodecyl sulfate, 0.15 parts by weight of ethylene glycol dimethacrylate, 0.15 parts by weight of allyl methacrylate were used in the production of the seed in Example 1, and 0.3 parts by weight of ethylene glycol dimethacrylate in the production of the rubber core. It was carried out in the same manner except that 0.3 parts by weight of allyl methacrylate was used. The average size of the obtained seed particles was 30 nm, and the average size of the rubber polymer particles was 60 nm. And the graft ratio of the graft copolymer was 55%, and the refractive index of the entire thermoplastic resin composition was 1.4813, the difference between the refractive index of the shell and the matrix resin and the rubber refractive index was 0.024, and the difference between the refractive index of the shell and the matrix resin was 0.0021.

Example 7

When preparing the core rubber in Example 1, 65 parts by weight of butyl acrylate, 0.3 parts by weight of ethylene glycol dimethacrylate, and 0.3 parts by weight of allyl methacrylate were used. A mixture of 3 parts by weight of acrylate, 1.5 parts by weight of potassium rosinate salt as an emulsifier and 0.6 parts by weight of n-octyl mercaptan and 0.6 parts by weight of cumene hydroperoxide as an initiator, and 2-hydroxy-2-sulpy as an activator The same was carried out except for using an aqueous solution (concentration: 5% by weight) containing 0.18 parts by weight of disodium natoacetate salt, 0.02 parts by weight of sodium pyrophosphate, and 0.0004 parts by weight of ferrous sulfide, and at this time, the graft ratio of the graft copolymer The refractive index of this 35% and graft copolymer was 1.4681. And the same was carried out except that 35 parts by weight of graft copolymer powder and 65 parts by weight of polymethyl methacrylate resin were used as the matrix resin when preparing the thermoplastic resin composition. At this time, the refractive index of the entire thermoplastic resin composition was 1.482 and the shell and The difference between the refractive index of the matrix resin and the rubber refractive index was 0.0291, and the difference between the refractive index of the shell and the matrix resin was 0.0021.

Example 8

In the preparation of the seed in Example 1, 4.5 parts by weight of butyl acrylate, 0.4 parts by weight of styrene, and 0.1 parts by weight of acrylonitrile were used instead of 5 parts by weight of butyl acrylate. It was carried out in the same manner except for using a rate of 40.5 parts by weight, styrene 3.6 parts by weight, and acrylonitrile 0.9 parts by weight, and the average size of the seed particles was 40 nm, the average size of the core rubber particles was 95 nm, and the rubber refractive index was 1.4716, and the graft. The copolymer had a refractive index of 1.4793 and a grafting ratio of 60%. In addition, the refractive index of the entire thermoplastic resin composition was 1.4842, the difference in refractive index between the shell and the matrix resin and the rubber refractive index was 0.0175, and the difference in the refractive index between the shell and the matrix resin was 0.0021.

Example 9

When preparing the shell in Example 3, 47.5 parts by weight of methyl methacrylate, 2 parts by weight of styrene, and 0.5 parts by weight of acrylonitrile were used instead of 45 parts by weight of methyl methacrylate and 5 parts by weight of butyl acrylate. Except for using 95 parts by weight of methyl methacrylate and 5 parts by weight of methyl acrylate instead of 95 parts by weight of methyl methacrylate, 4 parts by weight of styrene, and 1 part by weight of acrylonitrile, the graft copolymer The refractive index was 1.48, the graft rate was 45%, and the refractive indexes of the shell and matrix resin were 1.4943. In addition, the refractive index of the entire thermoplastic resin composition was 1.487, the difference between the refractive index of the shell and the matrix resin and the refractive index of the rubber was 0.0283, and the difference between the refractive index of the shell and the matrix resin was 0.0000.

Example 10

When preparing the thermoplastic resin composition in Example 1, the same was carried out except that 3 parts by weight of a large-diameter graft copolymer powder having an average size of 300 nm of acrylate rubber particles (manufactured by ASA SA927, LG Chem) was additionally used. I did.

Comparative Example 1

When preparing the shell in Example 1, 36.5 parts by weight of styrene and 13.5 parts by weight of butyl acrylate were used instead of 45 parts by weight of methyl methacrylate and 5 parts by weight of butyl acrylate, and t-dodecyl mercaptan 0.1 instead of n-octyl mecaptan. Except for the use of parts by weight, the same was carried out, and at this time, the graft copolymer had a graft ratio of 30%, a shell having a refractive index of 1.56, and a graft copolymer having a refractive index of 1.51. In addition, the refractive index of the entire thermoplastic resin composition was 1.499, the difference between the refractive index of the shell and the matrix resin and the refractive index of the rubber was 0.1, and the difference of the refractive index between the shell and the matrix resin was 0.37.

Comparative Example 2

In Example 1, except that 0.8 parts by weight of sodium dodecyl sulfate was used to prepare the core, the same was carried out, and at this time, the average particle size of the polymer seed was 63 nm and the average size of the core rubber particle was 130 nm.

Comparative Example 3

When preparing the shell in Example 1, an aqueous solution containing 1.2 parts by weight of n-octyl mercaptan, 0.18 parts by weight of dextrose instead of the mixture as an activator, 0.02 parts by weight of sodium pyrophosphate, and 0.0004 parts by weight of ferrous sulfide (concentration: 5 parts by weight) %) was used in the same manner. At this time, the graft ratio of the graft copolymer was 19%.

Comparative Example 4

In Example 1, except that 30 parts by weight of butyl acrylate, 0.4 parts by weight of ethylene glycol dimethacrylate, and 0.4 parts by weight of allyl methacrylate were used in the manufacture of the rubber core in Example 1, and at this time, the graft copolymer The graft rate was 120%.

Comparative Example 5

In the same manner as in Example 1, except that 40 parts by weight of methyl methacrylate, 8 parts by weight of styrene, and 2 parts by weight of acrylonitrile were used instead of 45 parts by weight of methyl methacrylate and 5 parts by weight of butyl acrylate. In this case, the refractive index of the shell was 1.5072, and the refractive index of the graft copolymer was 1.4836. In addition, the refractive index of the entire thermoplastic resin composition was 1.4868, the difference between the refractive index of the shell and the matrix resin and the refractive index of the rubber was 0.0472, and the difference between the refractive index of the shell and the matrix resin was 0.0181.

Comparative Example 6

In Example 1 above, 3.7 parts by weight of butyl acrylate and 1.3 parts by weight of styrene were used instead of 5 parts by weight of butyl acrylate in the production of the seed in Example 1, and 1.7 parts by weight of sodium dodecyl sulfate were used, and 45 parts by weight of butyl acrylate was used in the production of the rubber core. Instead, it was carried out in the same manner, except that 33.3 parts by weight of butyl acrylate and 11.7 parts by weight of styrene were used.At this time, the average size of the seed particles was 45 nm, the average size of the core rubber particles was 100 nm, the rubber refractive index was 1.494, and the graft copolymer The refractive index of was 1.4915 and the graft rate was 50%. In addition, the refractive index of the entire thermoplastic resin composition was 1.49, the difference between the refractive index of the shell and the matrix resin and the refractive index of the rubber was 0.005, and the difference between the refractive index of the shell and the matrix resin was 0.0000.

Comparative Example 7

In Example 1, 30 parts by weight of butyl acrylate, 2.5 parts by weight of sodium dodecyl sulfate, 0.4 parts by weight of ethylene glycol dimethacrylate, 0.4 parts by weight of allyl methacrylate were used when preparing the rubber core without the seed production process in Example 1, and the shell The preparation was carried out in the same manner except that 63 parts by weight of methyl methacrylate, 7 parts by weight of butyl acrylate, 1.5 parts by weight of potassium rosinate and 0.13 parts by weight of n-octyl mercaptan were used as emulsifiers. The average size of the obtained rubber core particles was 36 nm, the average size of the graft copolymer particles obtained after the reaction was completed was 55 nm, and the refractive index of the graft copolymer shell was 1.487. In addition, the total refractive index of the graft copolymer was 1.4789 and the graft rate was 110%. The refractive index of the entire thermoplastic resin composition was 1.49, the difference between the refractive index of the shell and the matrix resin and the rubber refractive index was 0.027, and the difference between the refractive index of the shell and the matrix resin was 0.003.

[Test Example]

The properties of the thermoplastic resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Table 1 below.

* Colorability (blackness): Based on the CIE1976 L*a*b* colorimeter, the color L value was measured using a color meter (model name Color Eye 7000A). At this time, if L=100, it means pure white, and if L=0, it means pure black. The lower the L value, the better the black feeling.

* Impact strength (kgf/cm ² ): As the Izod impact strength, the thickness of the specimen was 1/4" and measured by the method of standard measurement ASTM D256.

* Weather resistance: Accelerated weathering test equipment (weather-o-meter, ATLAS company Ci4000, xenon arc lamp, Quartz(inner)/S.Boro(outer) filter, irradiznce 0.55W/m ² at 340nm) applied to SAE J1960 conditions It can be measured by conducting the test for 3,000 hours.

The following ΔE is an arithmetic average value before and after the accelerated weather resistance experiment, and the closer the value is to 0, the better the weather resistance is.

* Gray Scale: Weatherability was evaluated based on the standard gray color table of discoloration. The larger the value, the better the weather resistance.

* Glossiness (45 °): It was measured at a 45 degree angle with a gloss meter, and the larger the gloss value, the better the surface gloss, and it was measured according to ASTM D528.

* Average particle diameter: The average particle size can be measured using the dynamic light scattering method, and in detail, it can be measured using the Nicomp 380 equipment (product name, manufacturer: PSS).

* Refractive index: The powder was pressed at 190 degrees and measured with a refractometer (REICHERT MARK).

* Graft rate: The graft copolymer powder is dissolved in acetone, stirred for 24 hours, and then centrifuged at 20000 rpm for 3 hours to separate insoluble and soluble components. The insoluble matter obtained by separating was dried for 24 hours, measured, and then calculated by the following calculation formula.

Graft rate (%) = (measured insoluble content-rubber content of the graft copolymer) / rubber content of the graft copolymer *100

division	Colorability	Impact strength	Weather resistance	Grayscale	Gloss
Example 1	23.6	8.8	1.6	Level 4	120
Example 2	23.8	8.3	1.5	Level 4	125
Example 3	23.9	7.1	1.3	Level 4	130
Example 4	23.5	9.5	1.7	Level 4	115
Example 5	23.3	10.2	1.9	Level 4	108
Example 6	23.4	7.5	1.4	Level 4	128
Example 7	23.9	8.3	1.5	Level 4	101
Example 8	24.0	7.2	2.1	Level 4	119
Example 9	24.4	8.1	2.3	Level 4	106
Example 10	24.3	12.3	2.5	Level 4	100
Comparative Example 1	25.6	8.9	3.9	Level 2~3	89
Comparative Example 2	24.8	9.2	3.1	Level 3	101
Comparative Example 3	25.2	3.5	2.1	Level 3	100
Comparative Example 4	24.0	3.1	2.0	Level 4	127
Comparative Example 5	25.1	4.5	2.8	Level 3	103
Comparative Example 6	23.8	3.4	3.0	Level 3	123
Comparative Example 7	24.1	2.1	2.1	Level 4	125

As shown in Table 1, when the thermoplastic resin composition according to the present invention (Examples 1 to 10) is outside the refractive index range of the thermoplastic resin composition according to the present invention (Comparative Examples 1 and 6), when outside the rubber particle size range (Comparative Examples 2 and 7), when out of the graft rate (Comparative Examples 3 and 4) and out of the range of blackness (Comparative Example 5), the impact strength is equal to or more, it can be confirmed that the weather resistance and colorability are remarkably excellent. there was.

Claims (13)

1. A) a graft copolymer containing an alkyl acrylate rubber core and an alkyl methacrylate compound (co)polymer shell surrounding it, and B) a thermoplastic resin composition comprising a matrix resin,

   The rubber core has an average particle diameter of 40 to 120 nm,

   The A) graft copolymer has a graft rate of 20 to 100%,

   The difference in the refractive index of the rubber core, the refractive index of the (co)polymer shell, and the refractive index of the matrix resin is less than 0.04,

   The thermoplastic resin composition is characterized in that the refractive index is greater than 1.46 to less than 1.49 and the blackness L value is less than 25.0

   Thermoplastic resin composition.
2. The method of claim 1,

   The matrix resin is characterized in that it comprises a poly (alkyl methacrylate) resin

   Thermoplastic resin composition.
3. The method of claim 2,

   The poly(alkyl methacrylate) resin is characterized in that it further comprises an alkyl acrylate

   Thermoplastic resin composition.
4. The method of claim 3,

   The alkyl acrylate is characterized in that it is contained in an amount of 0.1 to 20% by weight in the poly(alkyl methacrylate) resin.

   Thermoplastic resin composition.
5. The method of claim 1,

   The rubber core is characterized in that it further comprises an alkyl methacrylate

   Thermoplastic resin composition.
6. The method of claim 5,

   The alkyl methacrylate is characterized in that it is contained in an amount of 0.1 to 30% by weight in the rubber core.

   Thermoplastic resin composition.
7. The method of claim 1,

   The rubber core further comprises at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound.

   Thermoplastic resin composition.
8. The method of claim 1,

   The (co)polymer shell is characterized in that it further comprises an alkyl acrylate

   Thermoplastic resin composition.
9. The method of claim 8,

   The alkyl acrylate is characterized in that it is contained in an amount of 0.1 to 20% by weight in the (co)polymer shell.

   Thermoplastic resin composition.
10. The method of claim 1,

    The thermoplastic resin composition comprises 20 to 80% by weight of the graft copolymer and 20 to 80% by weight of the matrix resin.

    Thermoplastic resin composition.
11. The method of claim 1,

    The thermoplastic resin composition further comprises an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound copolymer

    Thermoplastic resin composition.
12. It comprises the thermoplastic resin composition of any one of claims 1 to 11, characterized in that

    Molded products.
13. It characterized in that it comprises the step of mixing and extruding the thermoplastic resin composition of any one of claims 1 to 11

    Method for producing a thermoplastic resin composition.