KR102183327B1 - Thermoplastic resin composition, method for preparing the same composition and molding product comprising the same composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article prepared including the same, and more particularly, A) a) polymerized including an alkyl (meth)acrylate compound and a crosslinking agent, and an average particle diameter of 50 to 200 nm A phosphorus crosslinked rubber core and b) 30 to 80% by weight of an ASA-based graft copolymer comprising a polymerized non-crosslinked hard shell including an aromatic vinyl compound and a vinyl cyan compound and surrounding the crosslinked rubber core; B) 10 to 40% by weight of a hard thermoplastic resin; And C) 10 to 40% by weight of an alkyl (meth)acrylate-based polymer having a weight average molecular weight of 30,000 to 60,000 g/mol (not the same as the B) resin), and a method for preparing the same. .
The thermoplastic resin composition according to the present invention has excellent mechanical properties such as impact strength, colorability, and appearance properties such as injection gloss, and provides a coextrusion molded product having excellent gloss when used for coextrusion on a base layer such as PVC. There is an effect.

Description

Thermoplastic resin composition, a manufacturing method thereof, and a molded article manufactured including the same {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE SAME COMPOSITION AND MOLDING PRODUCT COMPRISING THE SAME COMPOSITION}

The present invention relates to a thermoplastic resin composition, a method of manufacturing the same, and a molded article manufactured including the same, and more particularly, excellent mechanical properties such as impact strength, colorability, and appearance properties such as injection gloss, while being gloss when coextruded with PVC, etc. It relates to a thermoplastic resin composition having very excellent properties, a method of manufacturing the same, and a molded article including the same.

ABS resins represented by acrylonitrile-butadiene-styrene terpolymers have excellent impact resistance, stiffness, chemical resistance, and processability, and are thus used in various fields such as electric and electronic, construction, and automobiles. However, since the ABS-based resin uses a butadiene rubber polymer containing a double bond, there is a problem that it is not suitable as an outdoor material due to poor weather resistance.

Therefore, when it is desired to obtain a thermoplastic resin having excellent physical properties and excellent weather resistance and aging resistance, an ethylenically unsaturated polymer that causes aging due to ultraviolet rays should not be present in the graft copolymer. Examples of such resins include acrylonitrile-styrene-acrylate (ASA)-based resins using a crosslinked alkyl acrylate rubber polymer. These ASA-based resins have excellent weather resistance and aging resistance, and are used in various fields such as automobiles, ships, leisure goods, construction materials, and horticulture. Looking at examples of ASA-based resin use, in most cases, ABS or PVC resin forms a base layer, and the ASA-based resin is coextruded to a thickness of 0.1 to 1 mm on the base layer to manufacture the final product. In this case, the surface characteristics of the ASA-based resin coextruded to the upper layer are the main factors that determine the quality of the final product. In particular, in the case of a product in which ASA resin is coextruded on the PVC base layer used for the window profile, colorability and gloss are important characteristics required.

The manufacturing method of ASA-based resin having weather resistance and aging resistance is described in German Patent No. 1,260,135, etc., and the rubber core used here is a crosslinked large diameter acrylate rubber latex with an average particle diameter of 150 to 800 nm and a narrow particle size distribution. . This improves the notch impact strength compared to the ASA-based resin manufactured using a small-diameter acrylate rubber latex, but as it is obtained in a pale pastel color rather than a bright color, its use is limited in the manufacture of colored molded articles with high saturation. There was a problem.

In order to improve the above problems, a first graft copolymer including a crosslinked alkyl acrylate rubber polymer having a small average particle diameter and a second graft copolymer including a crosslinked alkyl acrylate rubber polymer having a large average particle diameter A method of preparing an ASA-based resin composition by mixing has been proposed, but in this case, since the refractive index difference between the crosslinked alkyl acrylate polymer and the grafted styrene-acrylonitrile copolymer is large, light scattering occurs a lot and the clarity is There was a low problem.

In order to solve this problem, a method of lowering the refractive index of the matrix by using a terpolymer composed of an alkyl methacrylate-aromatic vinyl compound-vinyl cyan compound, an alkyl methacrylate polymer alone or a mixture thereof as a matrix resin has been disclosed.

However, the weather-resistant ASA-based resin prepared by the above-described method still does not have sufficient light transmittance, so the colorability is not satisfactory, and a method for improving glossiness, in particular, ASA-based, such as PVC (polyvinyl chloride) forming a base layer. There is no disclosure at all regarding the technique of improving the glossiness after coextrusion of the resin.

In order to solve the problems of the prior art as described above, the present invention has excellent mechanical properties such as impact strength, coloration properties, and appearance properties such as injection gloss, and particularly, when used for coextrusion on a base layer of PVC, etc. An object of the present invention is to provide a thermoplastic resin composition that can be improved and a method for producing the same.

Another object of the present invention is to provide a molded article having excellent appearance characteristics such as surface gloss and colorability while maintaining the mechanical properties inherent in ASA-based resins by injection or coextrusion of the thermoplastic resin composition with PVC or the like.

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 provides A) a) a crosslinked rubber core polymerized including an alkyl (meth)acrylate compound and a crosslinking agent, and has an average particle diameter of 50 to 200 nm, and b) surrounds the crosslinked rubber core and 30 to 80% by weight of an ASA-based graft copolymer comprising a polymerized non-crosslinked hard shell including a vinyl compound and a vinyl cyan compound; B) 10 to 40% by weight of a hard thermoplastic resin; And C) 10 to 40% by weight of an alkyl (meth)acrylate-based polymer having a weight average molecular weight of 30,000 to 60,000 g/mol (not the same as the B) resin); it provides a thermoplastic resin composition comprising: .

In addition, the present invention provides A) a) a crosslinked rubber core polymerized including an alkyl (meth)acrylate compound and a crosslinking agent, and has an average particle diameter of 50 to 200 nm, and b) encloses the crosslinked rubber core and contains an aromatic vinyl compound and a vinyl cyan compound. 30 to 80% by weight of an ASA-based graft copolymer including a polymerized non-crosslinked hard shell; B) 10 to 40% by weight of a hard thermoplastic resin; And C) 10 to 40% by weight of an alkyl (meth)acrylate polymer having a weight average molecular weight of 30,000 to 60,000 g/mol (not the same as the B) resin); and then extruding. It provides a method for producing a thermoplastic resin composition.

In addition, the present invention provides an injection molded article manufactured by injecting the thermoplastic resin composition and a coextrusion molded article manufactured by coextrusion of the thermoplastic resin composition and PVC.

According to the present invention, a thermoplastic resin composition having excellent surface gloss, coloring properties, etc., in the case of coextrusion on a PVC base layer, and a method of manufacturing the same, having excellent appearance characteristics while maintaining high weather resistance and mechanical properties inherent to the ASA-based graft copolymer. And there is an effect of providing a molded article manufactured including the same.

The present inventors improved the coextrusion properties of weather-resistant styrene-based thermoplastic resins such as those of conventional ASA-based resins to maintain high mechanical strength inherent to ASA-based resins, while providing excellent colorability and excellent surface gloss after coextrusion. During the research, a non-crosslinked hard shell containing a copolymer of an aromatic vinyl compound and a vinyl cyan compound was graft-copolymerized on a rubber core containing a crosslinked alkyl (meth)acrylate polymer having an average particle diameter of 50 to 200 nm. After preparing an ASA-based graft copolymer having a core-shell structure forming a rubber dispersion phase, it is a hard thermoplastic resin having a weight average molecular weight of 50,000 to 110,000 g/mol and an alkyl (meth) having a weight average molecular weight of 30,000 to 60,000 g/mol. The thermoplastic resin composition prepared by melt-mixing with a matrix resin containing an acrylate-based polymer significantly improves colorability, and when coextruded with PVC that forms a base layer, it was found to have excellent surface gloss. The present invention has been completed.

In particular, the present inventors confirmed that there is no correlation between the gloss of the injection-molded product of the thermoplastic resin composition containing the ASA-based graft copolymer and the gloss of the surface of the thermoplastic resin composition measured after coextrusion of the thermoplastic resin composition with PVC. I did. That is, it was impossible to improve the gloss after co-extrusion by applying the technology to improve the gloss of the conventional ASA injection molded product. The ASA-based thermoplastic resin composition according to the present invention has an extremely excellent gloss after coextrusion, and the thermoplastic resin composition of the present invention and a method of manufacturing the same will be described in detail below.

The thermoplastic resin composition of the present invention comprises A) a) a crosslinked rubber core polymerized including an alkyl (meth)acrylate compound and a crosslinking agent, and has an average particle diameter of 50 to 200 nm, and b) surrounds the crosslinked rubber core and contains an aromatic vinyl compound and a vinyl. 30 to 80% by weight of an ASA-based graft copolymer comprising a non-crosslinked hard shell polymerized including a cyan compound; B) 10 to 40% by weight of a hard thermoplastic resin; And C) 10 to 40% by weight of an alkyl (meth)acrylate-based polymer having a weight average molecular weight of 30,000 to 60,000 g/mol (not the same as the B) resin). Hereinafter, the thermoplastic resin composition of the present invention will be described in detail in a manner described above for each component.

A) ASA series Graft Copolymer

The ASA-based graft copolymer of the present disclosure is, for example, a) a crosslinked rubber core having an average particle diameter of 50 to 200 nm and is polymerized including an alkyl (meth)acrylate compound and a crosslinking agent, and b) surrounding the crosslinked rubber core and an aromatic vinyl It may be a graft copolymer having a core-shell structure including a polymerized non-crosslinked hard shell including a compound and a vinyl cyan compound.

The A) ASA-based graft copolymer may be included in 30 to 80% by weight, 40 to 70% by weight, or 45 to 55% by weight in the thermoplastic resin composition, and mechanical properties such as impact strength of the final resin composition within this range While this is excellent, there is an effect of excellent colorability, glossiness, particularly, surface gloss after coextrusion.

In addition, the ASA-based graft copolymer may have an average particle diameter (greater than the average particle diameter of the crosslinked rubber core), for example, 70 to 250 nm, 80 to 200 nm, or 80 to 150 nm, and the colorability of the final resin composition within this range , There is an advantage of excellent appearance characteristics such as gloss, and in particular, there is a feature of excellent surface gloss of a processed product manufactured by coextrusion of the resin composition such as PVC that forms a base layer.

The ASA-based graft copolymer may preferably have a graft rate of 35% or more and 35 to 50%, and most preferably 40 to 50%. Within this range, the final resin composition has excellent mechanical properties, such as impact strength, and excellent appearance quality such as surface gloss and colorability.

In the present description, the graft rate is, for example, a graft copolymer powder in an organic solvent such as acetone and sufficiently stirred, and after separating the solution using a centrifugal separator, methanol is added to the separated solution, so that the ungrafted portion is After obtaining, drying it and measuring the weight, it can be calculated according to Equation 1.

[Equation 1]

Graft rate (%) = (weight of monomer component grafted on rubber polymer/weight of graft copolymer) * 100

In a specific example, the ASA-based graft copolymer is a) 20 to 70% by weight or 30 to 60% by weight of the crosslinked rubber core; And b) 30 to 80% by weight or 40 to 70% by weight of the non-crosslinked hard shell; in this case, the final resin composition has excellent surface properties such as gloss and colorability, and has excellent mechanical strength. .

a) crosslinked rubber core

The a) crosslinked rubber core may be polymerized, including an alkyl (meth)acrylate compound, a crosslinking agent, and optionally a grafting agent.

In a specific example, the a) crosslinked rubber core is prepared by including A) 0.1 to 1.0 parts by weight of a crosslinking agent, and optionally 0.1 to 1.0 parts by weight of a grafting agent based on a total of 100 parts by weight of the monomers used in the production of the ASA-based graft copolymer. In this case, the final resin composition has an excellent balance of physical properties.

In a more specific example, the a) crosslinked rubber core is A) 20 to 70 parts by weight of an alkyl (meth)acrylate compound based on a total of 100 parts by weight of the monomers used in preparing the ASA-based graft copolymer resin, 0.1 to 1.0 parts by weight of the crosslinking agent , 0.1 to 1.0 parts by weight of a grafting agent, 0.1 to 2.5 parts by weight of an emulsifier, 0.01 to 2 parts by weight of a polymerization initiator may be prepared by emulsion polymerization under a reaction temperature of 30 to 85°C by continuously adding a batch or continuously over 1 to 7 hours. It should be noted that it is not limited thereto.

In the present description, continuous injection is a substitute for batch injection, and the material to be introduced into the reaction is added for a predetermined period of time, for example, 30 minutes or more, 1 hour or more, or 1 hour 30 minutes or more, before the end of the reaction, 3 hours or less, or 2 It is assumed that all cases of continuous injection without a break for less than an hour or in a drop by drop method are included.

The continuous injection may be, for example, the addition of the reactant at an input amount of 5 to 50 parts/hr or 10 to 30 parts/hr per hour.

In the present description, the alkyl (meth)acrylate may be an alkyl acrylate, an alkyl methacrylate, and a mixture thereof.

The alkyl (meth)acrylate compound may be, for example, an alkyl (meth)acrylate compound having 2 to 8 carbon atoms or 4 to 8 carbon atoms of the alkyl group, and specific examples include methyl acrylate, ethyl acrylate, butyl acrylate, It may be one or more selected from the group consisting of ethylhexyl acrylate, butyl methacrylate and ethylhexyl methacrylate, and preferably includes butyl acrylate or ethylhexyl acrylate.

The alkyl (meth)acrylate compound may preferably be used in an amount of 20 to 70 parts by weight or 35 to 60 parts by weight based on a total of 100 parts by weight of monomers used in the production of A) ASA-based graft copolymers, and this range There are excellent effects in both appearance properties such as colorability of the final resin composition and mechanical properties such as impact strength within.

The crosslinking agent is not particularly limited as long as it is a crosslinking agent commonly used in the technical field to which the present invention belongs, and preferably ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, and trimethylol methane triacrylate may be one or more selected from the group consisting of, and , Preferably, ethylene glycol dimethacrylate may be used, but is not limited thereto.

The crosslinking agent A) may be used in an amount of 0.1 to 1 parts by weight or 0.1 to 0.5 parts by weight based on a total of 100 parts by weight of the monomers used to prepare the ASA-based graft copolymer resin, and within this range, the surface gloss after coextrusion is excellent. Yet, it has excellent mechanical properties such as impact strength.

The grafting agent is not particularly limited as long as it is a compound commonly used in the technical field to which the present invention belongs, and preferably allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallylamine (TAA), and It may be one or more selected from the group consisting of diallylamine (DAA), preferably allyl methacrylate, but is not limited thereto.

The grafting agent A) may be used in an amount of 0.1 to 1 parts by weight or 0.1 to 0.5 parts by weight based on a total of 100 parts by weight of the monomers used to prepare the ASA-based graft copolymer resin, and within this range, the impact strength of the final resin composition It has excellent mechanical properties such as, but has excellent surface properties such as surface gloss and colorability after coextrusion.

The polymerization initiator is not particularly limited as long as it is a compound commonly used in the technical field to which the present invention pertains, and for example, a peroxide or azo initiator may be selectively used in combination with an oxidation-reduction initiator.

The emulsifier is selected from the group consisting of an alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms at a pH of 3 to 9, an alkyl sulfuric acid ester metal salt having 12 to 20 carbon atoms, an alkyl sulfonic acid metal salt having 12 to 20 carbon atoms, and derivatives thereof. One or more types may be used, and in this case, the stability of the latex is excellent during emulsion polymerization, and the polymerization conversion rate of the finally obtained polymer is high.

In the present description, a derivative refers to a compound in which one or two or more hydrogen or functional groups of the original compound are substituted with a halogen or alkyl group as an example of another atom or group of atoms.

As a specific example, the emulsifier is dicyclohexyl sulfosuccinate sodium salt, di 2-ethylhexyl sulfosuccinate sodium salt, di 2-ethylhexyl sulfosuccinate potassium salt, dioctyl sulfosuccinate sodium salt, dioctyl 1 selected from the group containing sulfosuccinate potassium salt, sodium lauric sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, potassium dodecyl sulfate and potassium octadecyl sulfate, etc. It should be noted that it may be more than a species, but is not limited thereto.

The emulsifier A) may be used in an amount of 0.1 to 2.5 parts by weight or 1 to 1.5 parts by weight based on a total of 100 parts by weight of the monomers used in preparing the ASA-based graft copolymer resin, and crosslinking having a desired average particle diameter within the above range Rubber cores can be made.

The a) crosslinked rubber core may have an average particle diameter of 50 to 200 nm as an example, preferably 80 to 150 nm, and most preferably 80 to 120 nm. Within this range, there is an advantage in that the final resin composition has excellent impact strength and colorability, but has excellent surface gloss when coextruded on a base layer such as PVC.

In the present description, the average particle diameter can be measured by using the intensity gaussian distribution of the Nicomp 370HPL equipment, for example, by the dynamic light scattering method.

The a) crosslinked rubber core may preferably have a glass transition temperature (Tg) of -70 to -20°C, more preferably -60 to -25°C, and most preferably -50 to- It is 25℃. There is an excellent effect of the impact strength within the above range.

In the present description, the glass transition temperature can be measured using a Perkin Elmer's Pyris 6 DSC equipment by differential scanning calorimetry as an example.

b) Non-crosslinking Hard shell

The non-crosslinked hard shell surrounds the crosslinked rubber core and includes a copolymer of an aromatic vinyl compound and a vinyl cyan compound.

In the present description, the non-crosslinked hard shell refers to a polymer that does not contain a crosslinking agent, that is, a polymer polymerized without including a crosslinking agent.

For example, the non-crosslinked hard shell is A) 22 to 55 parts by weight of an aromatic vinyl compound, 8 to 25 parts by weight of a vinyl cyan compound in the presence of the crosslinked rubber core latex based on a total of 100 parts by weight of the monomers used in the production of the ASA-based graft copolymer. Parts, 0.5 to 3 parts by weight of emulsifier, 0.05 to 2 parts by weight of polymerization initiator, 0.1 to 2 parts by weight of molecular weight control agent may be prepared by emulsification graft polymerization at 50 to 85°C by continuously adding sunlight or over 2 to 7 hours .

In the present description, the aromatic vinyl compound may be one or more selected from styrene compounds such as styrene, alpha-methylstyrene, para-methylstyrene, and vinyl toluene, and preferably styrene, unless otherwise specified. .

In the present description, the vinyl cyan compound may be one or more selected from acrylonitrile, ethacrylonitrile, methacrylonitrile and the like, unless otherwise specified, and preferably includes acrylonitrile.

In the present description, the molecular weight control agent is not particularly limited as long as it is a compound commonly used for the purpose of controlling the molecular weight of the polymer in the technical field to which the present invention belongs, and preferably t-dodecyl mercaptan, n-dodecyl mercaptan, n- It may be one or more selected from mercaptan compounds such as octyl mercaptan.

The emulsifier and polymerization initiator may be, for example, a) the same compound as the emulsifier and polymerization initiator used in manufacturing the crosslinked rubber core.

The ASA-based graft copolymer latex obtained after completion of the emulsified graft polymerization may have a total solid content of 40 to 60% by weight or 40 to 55% by weight, for example, and the stability of the latex within this range is excellent and productivity is excellent. It has a high advantage.

In addition, the ASA-based graft copolymer latex can be obtained as a powdery ASA-based graft copolymer through conventional coagulation, washing, dehydration, and drying processes.

As an example, a coagulant such as sulfuric acid, magnesium sulfate, calcium chloride, and aluminum sulfate may be added to the ASA-based graft copolymer latex to coagulate at atmospheric pressure, followed by washing, dehydration, and drying to obtain a powdery graft copolymer, but is limited thereto. no.

B) rigid thermoplastic resin

In the present invention, the hard thermoplastic resin is used as a matrix resin in which the A) ASA-based graft copolymer is dispersed.

The hard thermoplastic resin may preferably have a weight average molecular weight (Mw) of 50,000 to 110,000 g/mol, more preferably 60,000 to 100,000 g/mol, most preferably 70,000 to 90.000 g/ mol.

When the weight average molecular weight of the hard thermoplastic resin is within the above-described range, it is excellent in fluidity and thus processing and molding are easy, and mechanical properties such as impact strength are maintained high.

In the present description, the weight average molecular weight can be measured by gel permeation chromatography, for example.

The hard thermoplastic resin is a hard polymer having a glass transition temperature (Tg) of 60 to 140°C or 80 to 130°C, for example, and has excellent mechanical properties such as impact strength while being easy to process and mold within the above range.

The hard thermoplastic resin may be polymerized, including at least one selected from an alkyl (meth)acrylate compound, an aromatic vinyl compound, and a vinyl cyan compound, and preferably necessarily includes an aromatic vinyl compound.

In the present description, the rigid thermoplastic resin is a non-grafted polymer containing at least one selected from an alkyl (meth) acrylate compound, an aromatic vinyl compound, and a vinyl cyan compound, and the A) ASA-based graft copolymer (core-shell structure) It is different.

In one example, the hard thermoplastic resin is copolymerized including 30 to 80% by weight of an aromatic vinyl compound, 5 to 40% by weight of a vinyl cyanide compound, and 0 to 50% by weight or more than 0 to 50% by weight of an alkyl (meth)acrylate compound. Within this range, the final resin composition has excellent surface properties such as colorability and glossiness, and has excellent mechanical properties such as impact strength.

In another example, the hard thermoplastic resin may be copolymerized including 40 to 70% by weight of an aromatic vinyl compound, 5 to 15% by weight of a vinyl cyan compound, and 15 to 50% by weight of an alkyl (meth)acrylate compound, and this range There is an excellent effect in the balance of physical properties such as colorability and impact strength within.

In a specific example, the hard thermoplastic resin is polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-(ethylene-propylene-butadiene rubber)-styrene copolymer, styrene-methylmeta It should be noted that it may be one or more selected from acrylate copolymers and acrylonitrile-styrene-methylmethacrylate copolymers, but is not limited thereto.

In addition, the hard thermoplastic resin is included in 10 to 40% by weight, 20 to 40% by weight, or 20 to 30% by weight as an example of the thermoplastic resin composition, within this range, appearance properties such as colorability of the final resin composition, mechanical strength The back is excellent, but the surface gloss after coextrusion is excellent.

C) Alkyl ( Met ) Acrylate system polymer

In the present invention, the alkyl (meth)acrylate-based polymer is used as a matrix resin in which the A) ASA-based graft copolymer is dispersed, as in the above B) hard thermoplastic resin.

The alkyl (meth)acrylate-based polymer may preferably have a weight average molecular weight of, for example, 30,000 to 60,000 g/mol, 40,000 to 60,000 g/mol, or 40,000 to 55,000 g/mol, and within this range As the flow index is appropriate, the processability and formability are excellent, and mechanical properties such as impact strength are excellent.

The alkyl (meth)acrylate-based polymer may be a hard polymer having a glass transition temperature (Tg) of 60 to 140°C or 80 to 130°C, for example, and in this case, processing and molding of the resin composition is easy and mechanical strength is high. Can be maintained.

The alkyl (meth)acrylate polymer is, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylhexyl methacrylate, decyl methacrylate, methyl acrylate, ethyl acrylate , Propyl acrylate, butyl acrylate, and ethylhexyl acrylate may be a polymer containing one or more alkyl (meth) acrylate-based compounds selected from the group consisting of acrylate, preferably polymethyl methacrylate, but this It should be noted that it is not limited.

In addition, the alkyl (meth) acrylate polymer may be, for example, a polymer in which at least one of an aromatic vinyl compound or a vinyl cyan compound is copolymerized with an alkyl (meth) acrylate compound. (In this case, the alkyl (meth)acrylate polymer is not the same as the above B) hard thermoplastic resin)

As an example, the alkyl (meth)acrylate-based polymer is a copolymer comprising 70 to 100% by weight of an alkyl (meth)acrylate compound and 0 to 30% by weight of at least one compound selected from an aromatic vinyl compound or a vinyl cyan compound In this case, the final resin composition can be easily processed and molded, has excellent mechanical strength, and has excellent surface gloss after coextrusion.

In another example, the alkyl (meth)acrylate-based polymer is a copolymer comprising 80 to 100% by weight of an alkyl (meth)acrylate compound, 0 to 10% by weight of an aromatic vinyl compound, and 0 to 10% by weight of a vinyl cyanide compound. In this case, while having excellent mechanical properties such as impact strength of the final resin composition, the surface gloss after coextrusion is excellent.

The alkyl (meth)acrylate-based polymer may be characterized in that the acid value measured according to ASTM D974 is, for example, 1 to 10 KOH mg/g or 2 to 8 KOH mg/g, and this range After co-extrusion within, the surface gloss is excellent.

In addition, the alkyl (meth) acrylate-based polymer is included in an example of 10 to 40% by weight, 20 to 40% by weight, or 20 to 30% by weight of the thermoplastic resin composition, within this range, such as coloring properties of the final resin composition It has the advantage of excellent appearance characteristics and mechanical strength, but excellent surface gloss after coextrusion.

The B) hard thermoplastic resin or C) alkyl (meth)acrylate-based polymer of the present disclosure may be a polymer optionally polymerized including an antioxidant, for example, 0.05 to 1 part by weight or 0.05 to 1 part by weight based on 100 parts by weight of the total polymer. It can be polymerized by including 0.5 parts by weight of an antioxidant, and in this case, the surface properties such as colorability and glossiness of the final resin composition are excellent.

The thermoplastic resin composition of the present disclosure is, for example, A) a) a crosslinked rubber core polymerized including an alkyl (meth)acrylate compound and a crosslinking agent and having an average particle diameter of 50 to 200 nm, and b) an aromatic vinyl compound surrounding the crosslinked rubber core. And 30 to 80% by weight of an ASA-based graft copolymer comprising a polymerized non-crosslinked shell including a vinyl cyan compound; B) 10 to 40% by weight of a hard thermoplastic resin; And C) 10 to 40% by weight of an alkyl (meth)acrylate polymer having a weight average molecular weight of 30,000 to 60,000 g/mol (not the same as the above B) resin); and then extruding. have.

During the kneading, at least one additive selected from the group consisting of a lubricant, an antioxidant, an ultraviolet stabilizer, and a pigment may be further included.

The additive may be further included in an amount of 0.1 to 5 parts by weight or 0.2 to 2 parts by weight based on 100 parts by weight of the resin composition, and within this range, the effect of the additive may be realized while maintaining high physical properties of the resin composition. have.

It should be noted that the kneading and extrusion may be performed under a temperature of 180 to 280°C or 200 to 250°C, but is not limited thereto.

Furthermore, the thermoplastic resin composition of the present disclosure may be manufactured into an injection molded article through an injection process.

The injection-molded article of the present disclosure is characterized by having an excellent mechanical strength with an Izod impact strength (1/4", notched at 23°C) measured according to ASTM D256 as an example of 15 kgcm/cm or more or 15 to 20 kgcm/cm. You can do it.

In addition, the thermoplastic resin composition of the present disclosure may be co-extruded on a base layer of PVC, PMMA, etc. to be produced as a co-extrusion molded product, and as an example, the thermoplastic resin composition of the present disclosure may be co-extruded with PVC to form a co-extruded sheet. .

The co-extrusion molded article of the present disclosure may be characterized in that the gloss of the thermoplastic resin composition surface measured according to ASTM D528 as an example is 80 or more, 83 or more, 80 to 90, or 85 to 90, which has excellent co-extrusion gloss.

In the description of the thermoplastic resin composition of the present disclosure, the method of manufacturing the same, and the molded article manufactured including the same, other conditions not explicitly described are not particularly limited if they are within the range commonly practiced in the technical field to which the present invention belongs. It is stated that it can be performed by selecting appropriately.

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

[Example]

Example One

A) ASA series Graft Copolymer production

a) Preparation of crosslinked rubber core

In a nitrogen-substituted reactor, 50 parts by weight of distilled water, 7 parts by weight of butyl acrylate, 1.1 parts by weight of sodium di2-ethylhexyl sulfosuccinate sodium salt, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of allyl methacrylate , 0.07 parts by weight of potassium hydroxide was added at once, and after raising the internal temperature of the reaction tank to 70° C., 0.03 parts by weight of potassium persulfate was added to perform polymerization reaction for 1 hour. 1 hour after the addition of potassium persulfate, distilled water 20 parts by weight, butyl acrylate 43 parts by weight, sodium di2-ethylhexyl sulfosuccinate sodium salt 0.3 parts by weight, ethylene glycol dimethacrylate 0.1 parts by weight, allyl meta A mixture of 0.3 parts by weight of acrylate and 0.03 parts by weight of potassium persulfate was continuously added at 70° C. for 3 hours, and polymerization was further performed for 1 hour after completion of the addition. The average particle diameter of the latex-phase crosslinked rubber core obtained after completion of the polymerization reaction was 100 nm.

b) Non-crosslinking reshuffle Shell Produce

The crosslinked rubber core latex was mixed with 37.5 parts by weight of styrene, 12.5 parts by weight of acrylonitrile, 1.2 parts by weight of potassium rosinate, 0.05 parts by weight of potassium persulfate, 0.06 parts by weight of tertiary dodecyl mercaptan, and 50 parts by weight of distilled water. Polymerization was carried out while continuously added at 70° C. for 3 hours. In addition, in order to increase the polymerization conversion rate, the temperature was raised to 75° C. after the addition was completed, and the mixture was further reacted for 1 hour and then cooled to 60° C.

The average particle diameter on the latex phase of the final ASA graft copolymer obtained after completion of the reaction was 130 nm, and the total solid weight fraction in the latex was 46%.

The obtained latex was subjected to atmospheric pressure coagulation at 85° C. using an aqueous calcium chloride solution, then aged at 95° C., dehydrated and washed, and then dried for 30 minutes with hot air at 90° C. to obtain an ASA graft copolymer powder. At this time, the graft rate of the ASA graft copolymer was measured to be 41%.

B) Preparation of rigid thermoplastic resin

1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane 0.02 parts by weight, n-dodecyl in a mixed solution in which 20 parts by weight of toluene, 60 parts by weight of styrene, and 20 parts by weight of acrylonitrile are dissolved 0.12 parts by weight of mercaptan, and Ivgacure (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2 as a hindered phenolic antioxidant ,4,6-(1H,3H,5H)-trione) 0.1 parts by weight of the polymerization solution was added to the 26L reactor at a rate of 14L/hr, and polymerization was performed at a temperature of 140℃ in the first reactor, and 150 in the second reactor. When the polymerization was carried out at °C and the polymerization conversion rate was about 60% or more, the unreacted monomer and the reaction medium were removed in a volatilization tank at a temperature of 215 °C to prepare a pellet-type styrene-acrylonitrile resin. The weight average molecular weight of the prepared resin was 70,000 g/mol.

C) Alkyl ( Met ) Acrylate system Preparation of polymer

100 parts by weight of methyl methacrylate, 200 parts by weight of distilled water, 0.3 parts by weight of polyvinyl alcohol, and 2.0 parts by weight of n-octyl mercaptan were collectively administered to a nitrogen-substituted reactor, and the internal temperature of the reaction tank was raised to 80°C and AIBN as an initiator. 0.1 parts by weight of (azobisisobutyronitrile) was added to initiate the reaction, and 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 and further polymerization was performed 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 weight average molecular weight of the prepared alkyl (meth)acrylate-based polymer was 50,000 g/mol.

Preparation of thermoplastic resin composition

A) 50 parts by weight of ASA graft copolymer powder prepared above, B) 25 parts by weight of hard thermoplastic resin, C) 1 part by weight of lubricant, 0.5 parts by weight of antioxidant, and 25 parts by weight of alkyl (meth)acrylate-based polymer 0.5 parts by weight of an ultraviolet stabilizer was added and mixed. This was prepared in the form of pellets using a 40 pie extrusion kneader at a cylinder temperature of 220°C, and the pellet was injection-processed to prepare a specimen for measuring physical properties.

Specimens for the colorability test were prepared by extruding and injection in the same manner by adding 1 part by weight of carbon black when mixing the composition.

In addition, a specimen for coextrusion test for evaluating the surface characteristics after coextrusion was prepared as follows.

The PVC layer was melt-kneaded at 170°C through a 130 pi L/D 20 twin screw extrusion kneader, and the thermoplastic resin composition was melt-kneaded at 180°C through a 60 pi L/D 20 single screw extrusion kneader. During coextrusion, PVC and the thermoplastic resin composition were supplied to a coextrusion die at a weight ratio of 9:1, and then passed through a water-cooled calibrator to prepare a test specimen for coextrusion.

Example 2

It was carried out in the same manner as in Example 1, except that B) a hard thermoplastic resin prepared by the following method was used.

B) Preparation of rigid thermoplastic resin

In Example 1, B) 20 parts by weight of toluene, 60 parts by weight of styrene, 20 parts by weight of acrylonitrile, 20 parts by weight of toluene instead of 0.12 parts by weight of n-dodecyl mercaptan, 40 parts by weight of styrene, methyl Methyl methacrylate-styrene-acrylonitrile in pellet form in the same manner as in Example 1, except that 30 parts by weight of methacrylate, 10 parts by weight of acrylonitrile, and 0.11 parts by weight of n-dodecyl mercaptan were used. The resin was prepared. The weight average molecular weight of the prepared resin was 80,000 g/mol.

Example 3

It was carried out in the same manner as in Example 1, except that the C) alkyl (meth)acrylate-based polymer prepared by the following method was used.

C) Alkyl ( Met ) Acrylate system Preparation of polymer

In Example 1, the above Example except that 80 parts by weight of methyl methacrylate and 20 parts by weight of ethyl acrylate were mixed and used instead of 100 parts by weight of methyl methacrylate when preparing the alkyl (meth) acrylate-based polymer. An alkyl (meth)acrylate-based polymer was prepared in the same manner as in 1. The weight average molecular weight of the prepared polymer was 45,000 g/mol.

Comparative example One

In Example 1, a) the same method as in Example 1, except that 0.6 parts by weight of sodium di 2-ethyl hexyl sulfosuccinate sodium salt, which is initially introduced in the initial reaction, is added in an amount of 0.6 parts by weight instead of 1.1 parts by weight when preparing the crosslinked rubber core. It was carried out. The average particle diameter of the latex phase a) crosslinked rubber core obtained by the above method was 280 nm.

In addition, the graft rate of the A) ASA-based graft copolymer prepared using the thus prepared a) crosslinked rubber core was measured to be 43%.

Comparative example 2

In Example 1, a) was carried out in the same manner as in Example 1, except that the step of preparing the crosslinked rubber core was carried out as follows.

a) Preparation of crosslinked rubber core

In a nitrogen-substituted reactor 50 parts by weight of distilled water, 5 parts by weight of butyl acrylate, 1.8 parts by weight of sodium di2-ethylhexyl sulfosuccinate sodium salt, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.1 parts by weight of allyl methacrylate , 0.07 parts by weight of potassium hydroxide was added at once, and after raising the internal temperature of the reaction tank to 75° C., 0.04 parts by weight of potassium persulfate was added to perform polymerization for 1 hour. 1 hour after the addition of potassium persulfate, distilled water 20 parts by weight, butyl acrylate 45 parts by weight, sodium di2-ethylhexyl sulfosuccinate sodium salt 0.6 parts by weight, ethylene glycol dimethacrylate 0.1 parts by weight, allyl meta A mixture of 0.2 parts by weight of acrylate and 0.03 parts by weight of potassium persulfate was continuously added at 70° C. for 3 hours, and polymerization was further performed for 1 hour after completion of the addition. The average particle diameter of the latex-phase crosslinked rubber core obtained after completion of the polymerization reaction was 45 nm.

In addition, the graft rate of the A) ASA-based graft copolymer prepared using the thus prepared a) crosslinked rubber core was measured to be 36%.

Comparative example 3

In Example 1, a) was carried out in the same manner as in Example 1, except that the step of preparing the crosslinked rubber core was carried out as follows.

a) Preparation of crosslinked rubber core

In a nitrogen-substituted reactor, 50 parts by weight of distilled water, 7 parts by weight of butyl acrylate, 1.1 parts by weight of sodium di2-ethylhexyl sulfosuccinate sodium salt, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.05 parts by weight of allyl methacrylate , 0.07 parts by weight of potassium hydroxide was added at once, and after raising the internal temperature of the reaction tank to 70° C., 0.03 parts by weight of potassium persulfate was added to perform polymerization reaction for 1 hour. 1 hour after the addition of potassium persulfate, distilled water 20 parts by weight, butyl acrylate 43 parts by weight, sodium di2-ethylhexyl sulfosuccinate sodium salt 0.3 parts by weight, ethylene glycol dimethacrylate 0.1 parts by weight, allyl meta A mixture of 0.05 parts by weight of acrylate and 0.03 parts by weight of potassium persulfate was continuously added at 70° C. for 3 hours, and polymerization was further performed for 1 hour after completion of the addition. The average particle diameter of the latex-phase crosslinked rubber core obtained after completion of the polymerization reaction was 100 nm.

In addition, the graft rate of the A) ASA-based graft copolymer prepared using the thus prepared a) crosslinked rubber core was measured to be 31%.

Comparative example 4

In the preparation of the thermoplastic resin composition in Example 1, A) 50 parts by weight of ASA graft copolymer powder, B) 25 parts by weight of hard thermoplastic resin, C) A) instead of 25 parts by weight of alkyl (meth)acrylate-based polymer It was carried out in the same manner as in Example 1, except that 50 parts by weight of ASA graft copolymer powder and 50 parts by weight of C) alkyl (meth)acrylate-based polymer were added.

Comparative example 5

In the preparation of the thermoplastic resin composition in Example 1, A) 50 parts by weight of ASA graft copolymer powder, B) 25 parts by weight of hard thermoplastic resin, C) A) instead of 25 parts by weight of alkyl (meth)acrylate-based polymer It was carried out in the same manner as in Example 1, except that 50 parts by weight of ASA graft copolymer powder and 50 parts by weight of B) hard thermoplastic resin were added.

Comparative example 6

In Example 1, a pellet-type styrene-acrylonitrile resin was prepared in the same manner as in Example 1, except that n-dodecyl mercaptan was used in an amount of 0.03 parts by weight instead of 0.12 parts by weight when preparing a hard thermoplastic resin. Was prepared. The weight average molecular weight of the prepared resin was 150,000 g/mol.

Comparative example 7

In Example 1, a pellet-type styrene-acrylonitrile resin was prepared in the same manner as in Example 1, except that n-dodecyl mercaptan was used in an amount of 1.2 parts by weight instead of 0.12 parts by weight when preparing the hard thermoplastic resin. Was prepared. The weight average molecular weight of the prepared resin was 40,000 g/mol.

Comparative example 8

In Example 1, C) the alkyl (meth)acrylate-based polymer was prepared in the same manner as in Example 1, except that 0.6 parts by weight of n-octyl mercaptan was used instead of 2.0 parts by weight. At this time, the weight average molecular weight of the prepared alkyl (meth)acrylate-based polymer was 100,000 g/mol.

Comparative example 9

In Example 1, C) when preparing an alkyl (meth)acrylate-based polymer, was carried out in the same manner as in Example 1, except that 6.0 parts by weight of n-octyl mercaptan was used instead of 2.0 parts by weight. At this time, the weight average molecular weight of the prepared alkyl (meth)acrylate-based polymer was 20,000 g/mol.

[Test Example]

The properties of the specimens prepared in the Examples and Comparative Examples were measured by the following method, and the results are shown in Tables 1 and 2 below.

1. Injection gloss: According to ASTM D528, the injection gloss of the specimen was measured at a 45° angle.

2. Izod impact strength (kgcm/cm, 23°C): According to ASTM D256, a notch was made in a 1/4" thick specimen.

3. Pigment colorability: The L value of a colored specimen with a thickness of 1/8" was measured using a color difference meter. The lower the L value, the lower the brightness and the darker black color, which means that the colorability of the pigment is good.

4. Coextrusion Gloss: The gloss of the thermoplastic resin surface of the test specimen for coextrusion was measured at a 45° angle according to ASTM D528.

division Example One 2 3 a) Average particle diameter of crosslinked rubber core (nm) 100 100 100 A) Graft rate of ASA-based copolymer (%) 41 41 41 B) Mw of hard thermoplastic resin (g/mol) 70,000 80,000 70,000 C) Mw (g/mol) of alkyl (meth)acrylate-based polymer 50,000 50,000 45,000 A) ASA-based copolymer usage 50 50 50 B) Hard thermoplastic resin used 25 25 25 c) Alkyl (meth)acrylate polymer used 25 25 25 Colorability (L value) 25.09 24.85 24.96 Impact strength 15.2 16.6 17.2 Injection varnish 90 92 87 Coextrusion polish 86 88 83

division Comparative example One 2 3 4 5 6 7 8 9 a) Average particle diameter of crosslinked rubber core (nm) 280 45 100 100 100 100 100 100 100 A) Graft rate of ASA-based copolymer (%) 43 36 31 41 41 41 41 41 41 B) Mw of hard thermoplastic resin (g/mol) 70,000 70,000 70,000 - 70,000 150,000 40,000 70,000 70,000 C) Mw (g/mol) of alkyl (meth)acrylate-based polymer 50,000 50,000 50,000 50,000 - 50,000 70,000 100,000 20,000 A) ASA-based copolymer usage 50 50 50 50 50 50 50 50 50 B) Hard thermoplastic resin used 25 25 25 0 50 25 25 25 25 c) Alkyl (meth)acrylate polymer used 25 25 25 50 0 25 25 25 25 Colorability (L value) 26.88 24.53 25.49 24.65 25.31 25.11 25.23 25.74 25.30 Impact strength 30.2 5.3 13.3 6.2 16.6 19.1 6.6 17.2 4.2 Injection varnish 90 90 88 92 95 92 99 89 91 Coextrusion polish 53 55 51 85 46 42 61 44 89

As shown in Tables 1 and 2, the thermoplastic resin compositions (Examples 1 to 4) according to the present substrate have high impact strength, colorability, and injection gloss, and excellent surface gloss after coextrusion, but thermoplastic resin compositions that do not conform to the present description. It was confirmed that the resin composition (Comparative Examples 1 to 9) generally had low surface gloss after coextrusion.

In particular, thermoplastic resin compositions (Comparative Examples 1 to 9) that do not conform to the present description exhibit a strong inverse proportional relationship between impact strength and surface gloss after coextrusion, and if the surface gloss after coextrusion is excellent, the impact strength is low (Comparative Example 2 , 4, 7, 9), it was confirmed that when the impact strength was high, the tendency of poor surface gloss after coextrusion (Comparative Examples 1, 3, 5, 6, 8) was clearly indicated.

In addition, as shown in Tables 1 and 2, the thermoplastic resin composition according to the present disclosure (Examples 1 to 3) and the thermoplastic resin composition (Comparative Examples 1 to 9) that do not have similar injection gloss characteristics, but the surface after coextrusion The gloss is much superior to the thermoplastic resin composition according to the present disclosure, and through this result, it was confirmed that the injection gloss characteristics of the thermoplastic resin composition have no correlation with the surface gloss after coextrusion.

Claims (18)

A) a) a crosslinked rubber core polymerized including an alkyl (meth)acrylate compound and a crosslinking agent and having an average particle diameter of 50 to 200 nm, and b) polymerized including an aromatic vinyl compound and a vinyl cyanide compound wrapped around the crosslinked rubber core 45 to 55% by weight of an ASA-based graft copolymer comprising a non-crosslinked hard shell;
B) 20 to 30% by weight of a hard thermoplastic resin; And
C) 20 to 30% by weight of an alkyl (meth)acrylate polymer having a weight average molecular weight of 40,000 to 55,000 g/mol (not the same as the above B) resin); including,
The A) ASA-based graft copolymer is characterized in that the graft rate is 40 to 50%.
Thermoplastic resin composition. The method of claim 1,
The A) ASA-based graft copolymer comprises a) 20 to 70% by weight of the crosslinked rubber core; And b) 30 to 80% by weight of the non-crosslinked hard shell; characterized in that it comprises
Thermoplastic resin composition. The method of claim 1,
The a) crosslinked rubber core is polymerized including 0.1 to 1.0 parts by weight of a crosslinking agent and 0.1 to 1.0 parts by weight of a grafting agent based on a total of 100 parts by weight of monomers used in the production of A) ASA-based graft copolymer.
Thermoplastic resin composition. The method of claim 1,
The a) crosslinked rubber core, characterized in that the glass transition temperature (Tg) is -70 to -20 ℃
Thermoplastic resin composition. delete The method of claim 1,
The A) ASA-based graft copolymer has an average particle diameter of 70 to 250 nm (greater than the average particle diameter of the core).
Thermoplastic resin composition. The method of claim 1,
The B) rigid thermoplastic resin, characterized in that the weight average molecular weight is 50,000 to 110,000 g/mol
Thermoplastic resin composition. The method of claim 1,
The B) hard thermoplastic resin, characterized in that the glass transition temperature (Tg) is 60 to 140 ℃
Thermoplastic resin composition. The method of claim 1,
The B) hard thermoplastic resin is characterized in that it is polymerized by including at least one selected from an alkyl (meth)acrylate compound, an aromatic vinyl compound, and a vinyl cyan compound.
Thermoplastic resin composition. The method of claim 9,
The B) hard thermoplastic resin is characterized in that it is polymerized including 30 to 80% by weight of an aromatic vinyl compound, 5 to 40% by weight of a vinyl cyan compound, and 0 to 50% by weight of an alkyl (meth)acrylate compound.
Thermoplastic resin composition. The method of claim 1,
The C) alkyl (meth)acrylate-based polymer is characterized in that it is polymerized including 70 to 100% by weight of an alkyl (meth)acrylate compound and 0 to 30% by weight of at least one compound selected from an aromatic vinyl compound or a vinyl cyan compound. With
Thermoplastic resin composition. The method of claim 1,
The C) alkyl (meth)acrylate-based polymer is characterized in that the glass transition temperature (Tg) is 60 to 140 ℃
Thermoplastic resin composition. The method of claim 1,
The C) alkyl (meth)acrylate-based polymer has an acid value measured according to ASTM D974 of 1 to 10 KOH mg/g.
Thermoplastic resin composition. A) a) a crosslinked rubber core polymerized including an alkyl (meth)acrylate compound and a crosslinking agent and having an average particle diameter of 50 to 200 nm, and b) polymerized including an aromatic vinyl compound and a vinyl cyanide compound wrapped around the crosslinked rubber core 45 to 55% by weight of an ASA-based graft copolymer comprising a non-crosslinked hard shell; B) 20 to 30% by weight of a hard thermoplastic resin; And C) 20 to 30% by weight of an alkyl (meth)acrylate-based polymer (not the same as the B) resin) having a weight average molecular weight of 40,000 to 55,000 g/mol; and then extruding, wherein the A ) ASA-based graft copolymer, characterized in that the graft rate is 40 to 50%
Method for producing a thermoplastic resin composition. It is prepared by injecting the thermoplastic resin composition of any one of claims 1 to 4 and 6 to 13,
Characterized in that the Izod impact strength (1/4", notched at 23℃) measured according to ASTM D256 is 15 kgcm/cm or more
Injection molded products. delete Is prepared by coextrusion of the thermoplastic resin composition according to any one of claims 1 to 4 and 6 to 13 and PVC,
Characterized in that the glossiness of the surface of the thermoplastic resin composition measured according to ASTM D528 is 80 or more
Coextrusion molding. delete