KR101267271B1 - Thermoplastic Resin Having Excellent Low Gloss Characteristic and Good Weatherability - Google Patents

Abstract

The thermoplastic resin composition according to the present invention comprises (A) 20 to 90% by weight of a vinyl-based thermoplastic resin including a network-like dispersed phase and (B) 10 to 80% by weight of a polycarbonate resin, and excellent impact strength and mechanical properties. It provides a thermoplastic resin composition and its molded article excellent in low light properties and weatherability while maintaining the.

Low light properties, weather resistance, ASA resin, rubber particles

Description

Thermoplastic Resin Having Excellent Low Gloss Characteristic and Good Weatherability}

The present invention relates to a thermoplastic resin composition excellent in low light properties and weather resistance and a molded article thereof. More specifically, the present invention is a thermoplastic resin composition prepared by kneading a vinyl-based thermoplastic resin, including a network-like dispersed phase, polycarbonate resin and additives, while maintaining excellent impact strength and mechanical properties, and excellent low light properties and weather resistance, and molded articles thereof It is about.

Generally, ABS (Acrylonitrile-Butadiene-Styrene) resin has excellent impact resistance and processability, and has excellent mechanical strength and heat deformation temperature, and because of its beautiful appearance characteristics, automobiles, electrical and electronic equipment, office equipment, home appliances, toys, stationery, etc. It is widely used for various uses. However, the butadiene-based rubber component used in the ABS resin contains a chemically labile double bond, and is easily aged by sunlight and ultraviolet rays. Therefore, ABS resin is limited to the use of electric and electronic parts, agricultural equipment, road signs, building finishing materials, door panels, window frames, leisure / household goods, sporting goods, and automobile goods for outdoor use. In order to improve the weather resistance of ABS resin, a method of adding a weather stabilizer is used, but the effect is not great. Instead of butadiene rubber, it is replaced with ASA (acrylate-styrene-acrylonitrile) resin using chemically stable acrylic rubber. The research is active. However, even when chemically stable acrylic rubber is used, it is difficult to apply to weather resistant products that require high impact due to the low impact strength efficiency of acrylic rubber. In order to overcome this, products mixed with engineering plastics such as polycarbonate are used. The case is increasing.

On the other hand, with increasing interest in sensitized resins out of cold feeling plastics, there is an increasing demand for resins that can produce low-gloss soft surfaces without coating. In particular, as environmental regulations are being tightened, the application range of low-gloss resins that can be directly molded while being able to omit the coating process is gradually expanding.

Such a low gloss resin manufacturing method is largely divided into three degrees. The most widely used method is to apply a matte additive-quenching agent using inorganic fillers or acrylic resins or crosslinked styrene resins. The second method is to remove the gloss in the post-processing process. Such a method includes a method of producing a low light effect through an injection or painting process using a corrosion mold. The third method is to adjust the size of the dispersed phase particles in the matrix to form a microscale rough surface. The surface thus formed scatters incident light to lower gloss.

Although it is convenient to implement a low light effect using an additive in various aspects, the uniformity of the gloss is not constant according to the dispersion state of the additive, and thus the quality is limited. In addition, the high specific gravity of the additives commonly used may result in a higher specific gravity of the final product. Using injection or painting process through the corrosive mold is disadvantageous in terms of environment since the introduction of additional processes may increase manufacturing costs and cause pollution. The method of controlling the gloss by adjusting the particle size of the dispersed phase in the matrix has the advantage that no additional process is required, but the method of raising the dispersed phase of the ASA (acrylate-styrene-acrylonitrile) resin to a level that can realize low light characteristics Almost not commercialized, a method of realizing low light characteristics by increasing the volume of the dispersed phase by merely flocculating the small dispersed phases with each other is used as an alternative. However, the method of realizing low light characteristics by agglomerating these dispersed phases requires not only an additional process of reaggregating particles after the polymerization process to make the dispersion, but also agglomeration of the agglomerated phase in the re-kneading process with the engineering plastic for physical property improvement. Has a fundamental technical problem.

In order to lower the gloss of the resin, US Patent No. 5,475,053 and Korean Patent No. KR 0245948 used a spherical graft copolymer as a matting agent, and US Patent No. 4,652,614 used a spherical graft having a rubber content of 5 to 80%. Copolymers were used. In US Patent No. 4,668,737, spherical rubber particles having a core / shell (DorB / shBll) structure of 0.05-20 μm were used. In addition, US Patent No. 5,237,004 used polymer particles of 2 ~ 15 ㎛ size. However, when using an additive in the form of rubber particles as described above, not only the manufacturing cost is high, but also a problem of peeling, deterioration of physical properties, or partly glossiness may occur.

An object of the present invention is to provide a thermoplastic resin composition excellent in low light properties and a molded article thereof.

Another object of the present invention is to provide a thermoplastic resin composition having excellent weather resistance and a molded article thereof.

Still another object of the present invention is to provide a thermoplastic resin composition and a molded article having excellent light resistance and weather resistance while maintaining excellent impact resistance and mechanical properties.

The above and other objects of the present invention can be achieved by the present invention described in detail below.

The present invention provides a thermoplastic resin composition excellent in low light properties and weather resistance, and a method of manufacturing the same.

The thermoplastic resin composition excellent in low light properties and weather resistance according to the present invention comprises (A) 20 to 90% by weight of a vinyl-based thermoplastic resin including a dispersed phase of a network shape and (B) 10 to 80% by weight of a polycarbonate resin, It provides a thermoplastic resin composition and its molded article excellent in low light characteristics and weather resistance while maintaining excellent impact strength and mechanical properties.

The vinyl-based thermoplastic resin including the (A) network-shaped dispersed phase of the present invention is 5 to 35% by weight of the (meth) acrylic acid alkyl ester polymer (a1) and 65 to 95% of the aromatic vinyl-vinyl cyanide copolymer (a2). It is preferably composed of weight percent.

In the embodiment of the present invention, the (meth) acrylic acid alkyl ester polymer (a1) is obtained by polymerizing a compound having a (meth) acrylic acid alkyl ester, an unsaturated carboxylic acid or an anhydride thereof, and a hydroxy group.

In an embodiment of the present invention, the (meth) acrylic acid alkyl ester polymer (a1) includes chains including (meth) acrylic acid alkyl ester units and unsaturated carboxylic acid or anhydride units thereof in the main chain, and the unsaturated carboxyl The carboxylic acid group of an acid or its anhydride unit is linked by a compound having a hydroxy group and a ester ester bond.

In another embodiment of the present invention, the (meth) acrylic acid alkyl ester polymer (a1) is obtained by polymerizing a (meth) acrylic acid alkyl ester, an unsaturated compound having a hydroxy group, and a compound having a carboxyl group.

In another embodiment of the present invention, the (meth) acrylic acid alkyl ester polymer (a1) comprises chains comprising a (meth) acrylic acid alkyl ester unit and an unsaturated compound unit having a hydroxy group in the main chain, and the hydroxy The hydroxy group of the unsaturated compound unit having a group is connected by ester bond with the carboxyl group of the compound having a carboxyl group.

In the embodiment of the present invention, the aromatic vinyl-vinyl cyanide copolymer (a2) is 60 to 95% by weight of an aromatic vinyl compound, 5 to 40% by weight of a vinyl cyanide compound, and 0 to 10% by weight of (meth) acrylic acid alkyl ester Is polymerized, and the weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer (a2) is preferably 150,000 to 300,000.

In an embodiment of the present invention, the (B) polycarbonate resin is preferably prepared by reacting diphenols with a compound selected from the group consisting of phosgene, halogen acid esters, carbonate esters and combinations thereof.

The present invention has the effect of providing a thermoplastic resin composition and its molded article excellent in low light characteristics and weather resistance while maintaining excellent impact strength and mechanical properties.

The thermoplastic resin having excellent low light characteristics and weather resistance according to an embodiment of the present invention has excellent impact strength by blending a vinyl-based thermoplastic resin (B) polycarbonate resin including a dispersed phase of (A) network shape and differentiated from the conventional products. And low light characteristics and weather resistance while maintaining mechanical properties. It can be widely applied to the molding of various products that are used as unpainted coatings. In particular, automobiles, mechanical parts, electrical and electronic parts, communication devices, office equipment, miscellaneous goods, etc. It can be usefully used for the same molded article.

Hereinafter, specific contents of the present invention will be described in detail below.

(A) Vinyl-based thermoplastic resin including network- shaped dispersed phase

The vinyl-based thermoplastic resin containing the (A) network-shaped dispersion phase of this invention contains the (meth) acrylic-acid alkylester type polymer (a1) which is a network-shaped dispersion phase, and the aromatic vinyl-vinyl cyanide copolymer (a2) which is a continuous phase. .

The vinyl-based thermoplastic resin (A) including the network-shaped dispersed phase includes 5 to 35% by weight of the (meth) acrylic acid alkyl ester polymer (a1) and 65 to 95% by weight of the aromatic vinyl-vinyl cyanide copolymer (a2). do. Preferably, the vinyl-based thermoplastic resin (A) including the network-shaped dispersed phase is 5 to 25% by weight of the (meth) acrylic acid alkyl ester polymer (a1) and 75 to 95% by weight of the aromatic vinyl-vinyl cyanide copolymer (a2). Contains% When the content of the (meth) acrylic acid alkyl ester polymer (a1) is less than 5% by weight or more than 35% by weight, it is difficult to obtain a thermoplastic resin having excellent low light properties and weather resistance aimed at by the present invention.

The (meth) acrylic acid alkyl ester polymer (a1) forms a polydisperse phase of a vinyl-based thermoplastic resin including the (A) network-shaped dispersion phase, and the aromatic vinyl-vinyl cyanide copolymer (a2) is the (A) network. A bicontinuous phase of the vinyl-based thermoplastic resin including the dispersed phase of the shape is achieved. Specifically, as shown in FIGS. 1 and 3, the (meth) acrylic acid alkyl ester polymer (a1) forms a network-shaped dispersed phase, and the aromatic vinyl-vinyl cyanide copolymer (a2) forms a continuous phase. It is characterized by. When the vinyl-based thermoplastic resin (A) including the dispersed phase of the network shape does not have a dispersed network shape, it is difficult to have excellent low light characteristics, impact resistance and the like.

In one embodiment of the present invention, the (meth) acrylic acid alkyl ester polymer (a1) is composed of (meth) acrylic acid alkyl ester, unsaturated carboxylic acid or anhydrides thereof, and a compound having a hydroxy group or optionally an aromatic vinyl compound And / or optionally a vinyl cyanide compound may be further polymerized.

When the aromatic vinyl compound and the vinyl cyanide compound are polymerized together, the chains of the (meth) acrylic acid alkyl ester polymer (a1) may be (meth) acrylic acid alkyl ester units, unsaturated carboxylic acid or anhydride units thereof, and aromatic vinyl. The compound compound unit and the vinyl cyanide compound unit will be included. As described above, the chains of the polymer (a1) are connected to each other by ester bonds of the carboxyl group and the hydroxy group included in the compound having a hydroxy group, thereby forming a dispersed phase in a network shape.

In another embodiment of the present invention, the compound having a hydroxy group is a saturated compound and may be included as a linking group by ester bonding with the unsaturated carboxylic acid or an anhydride thereof contained as a main chain unit in a (meth) acrylic acid alkyl ester polymer. And a network can be formed in this way.

In another embodiment of the present invention, the compound having a hydroxy group is an unsaturated compound, which is included as a unit of the main chain in the (meth) acrylic acid alkyl ester polymer and ester-bonds with the unsaturated carboxylic acid or anhydride thereof to form a network. can do.

Preferably, the (meth) acrylic acid alkyl ester polymer (a1) has a content of 60 to 95% by weight of the monomer other than the compound having the hydroxy group in the (meth) acrylic acid alkyl ester, unsaturated carboxylic acid or 1-20 wt% of anhydride, 0-20 wt% of an aromatic vinyl compound, and 0-10 wt% of a vinyl cyanide compound. Preferably, the compound having a hydroxy group may be included in an amount of 0.1 to 3 equivalents relative to the unsaturated carboxylic acid or anhydride thereof.

When the content of each component is out of the above composition, the thermoplastic resin may not sufficiently express weatherability and low light properties, and thus it is difficult to achieve the object of the present invention.

In particular, when the equivalent ratio of the compound having the hydroxy group to the unsaturated carboxylic acid or anhydride thereof is less than 0.1, the connection between the polymer (a1) chains is not sufficient to form a network-shaped dispersed phase. In addition, when the equivalent ratio exceeds 3, the compound having a hydroxy group that does not participate in the reaction acts like a plasticizer in the continuous phase, so that the heat resistance may deteriorate rapidly.

It is preferable that the (meth) acrylic-acid alkylester which comprises the said (meth) acrylic-acid alkylester type polymer (a1) is a (meth) acrylic-acid alkylester which has a C1-C10 alkyl group. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acryl Rate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate and the like can be used, but are not necessarily limited thereto. These may be applied alone or in mixture of two or more. Of these, butyl acrylate is preferred.

As the aromatic vinyl compound, styrene, alphamethyl styrene, paramethyl styrene, or the like may be used, but is not limited thereto. These may be applied alone or in mixture of two or more. Among these, styrene is preferable.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used, but is not necessarily limited thereto. These may be applied alone or in mixture of two or more. Among these, acrylonitrile is preferable.

The said unsaturated carboxylic acid or its anhydride is carboxylic acid or carboxylic anhydride which has a double bond of a carbon atom and a carbon atom in a molecule | numerator. 　 Examples of the unsaturated carboxylic acid or anhydride thereof include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, and the like. It doesn't happen. These may be applied alone or in mixture of two or more.

The compound having a hydroxy group preferably has 2 to 10 hydroxy groups, more preferably 2 to 5 hydroxy groups. In addition, the compound having a hydroxy group is preferably a saturated compound in which all carbon atoms in the molecule are bonded with only a single bond. Examples of the compound having a hydroxy group include alkanediol having 2 to 10 carbon atoms, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polyol and the like. These may be applied alone or in mixture of two or more.

Examples of the alkanediol having 2 to 10 carbon atoms include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and the like. However, it is not necessarily limited thereto. Examples of the polyethylene glycol include PEG300, PEG600, PEG1500, etc., depending on the molecular weight, but are not necessarily limited thereto. Examples of the polyol include xylitol, glycerin, erythritol, sorbitol, and hydritol (Hydroxy Value) of 50-500 and an acrylic or ether-based polyol having a molecular weight of 500-5000 and the like, but are not necessarily limited thereto.

In another embodiment of the present invention, the (meth) acrylic acid alkyl ester polymer (a1) of the present invention is polymerized with a (meth) acrylic acid alkyl ester, an unsaturated compound having a hydroxy group, and a compound having a carboxyl group. In this case, the hydroxy group of the unsaturated compound unit having a hydroxy group may be connected to the carboxyl group of the compound having a carboxyl group by an ester bond to form a dispersed phase having a network shape.

In another embodiment of the present invention, the (meth) acrylic acid alkyl ester polymer (a1) forming the dispersed phase of the thermoplastic resin is a (meth) acrylic acid alkyl ester, an unsaturated compound having a hydroxy group, and a compound having a carboxyl group The polymerization may be performed or the aromatic vinyl compound and the vinyl cyanide compound may be further polymerized.

Specifically, the (meth) acrylic acid alkyl ester polymer comprising the (meth) acrylic acid alkyl ester and an unsaturated compound having a hydroxy group is polymerized to include a (meth) acrylic acid alkyl ester unit and an unsaturated compound unit having a hydroxy group. The chains of (a1) are made up. And the hydroxy group of the unsaturated compound unit which has the said hydroxy group is connected by ester bond with the carboxyl group of the compound which has the said carboxyl group. Accordingly, the chains of the (meth) acrylic acid alkyl ester polymer (a1) are connected to each other to form a dispersed phase in a network shape.

That is, one embodiment and the other embodiment of the present invention are the same in that the chains of the (meth) acrylic acid alkyl ester polymer (a1) are connected to each other by an ester bond to form a network. However, in one embodiment of the present invention, an unsaturated carboxyl compound or anhydride thereof is included in the chains of the polymer (a1) as part of the repeating unit, and a compound having a hydroxy group serves to link the chains. In contrast, in another embodiment of the present invention, an unsaturated compound having a hydroxy group forms part of the repeating unit, and a compound having a carboxyl group connects the chains of the polymer (a1). In other words, in one embodiment of the present invention is a case where the compound having a carboxyl group is formed as a unit of the main chain in the (meth) acrylic acid alkyl ester polymer (a1) and forms a network by an ester bond. Another embodiment of the invention is a case where a compound having a hydroxy group is included as a unit of the main chain in the (meth) acrylic acid alkyl ester polymer (a1).

The aromatic vinyl-vinyl cyanide copolymer (a2) constituting the continuous phase of the vinyl-based thermoplastic resin (A) including the network-shaped dispersed phase according to the present invention is obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound.

The aromatic vinyl cyanide copolymer (a2) may be formed by polymerizing (meth) acrylic acid alkyl ester together with an aromatic vinyl compound and a vinyl cyanide compound.

Preferably, the aromatic vinyl-vinyl cyanide copolymer (a2) is polymerized with 60 to 95% by weight of an aromatic vinyl compound, 5 to 40% by weight of a vinyl cyanide compound, and 0 to 10% by weight of (meth) acrylic acid alkyl ester. It is done. When the content of each component deviates from the above composition, impact resistance, yellowness, flow characteristics, and the like, which are basic physical properties of the weather resistant thermoplastic resin, may change rapidly, thereby deviating from the object of the present invention.

More preferably, the aromatic vinyl-vinyl cyanide copolymer (a2) polymerizes 60 to 84% by weight of the aromatic vinyl compound, 15 to 35% by weight of the vinyl cyanide compound, and 1 to 5% by weight of the (meth) acrylic acid alkyl ester. It is done.

Styrene, alphamethyl styrene, paramethyl styrene, etc. may be used as the aromatic vinyl compound constituting the aromatic vinyl-vinyl cyanide copolymer (a2), but is not necessarily limited thereto. These may be applied alone or in mixture of two or more. Among these, styrene is preferable.

Acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used as the vinyl cyanide compound used in the aromatic vinyl cyanide copolymer (a2), but is not limited thereto. These may be applied alone or in mixture of two or more. Among these, acrylonitrile is preferable.

The (meth) acrylic acid alkyl ester constituting the aromatic vinyl-vinyl cyanide copolymer (a2) is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acryl Rate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate and the like can be used, but are not necessarily limited thereto. These may be applied alone or in mixture of two or more. Among them, butyl acrylate is preferable.

The weight average molecular weight of the aromatic vinyl cyanide copolymer (a2) is 150,000 to 300,000, preferably 180,000 to 250,000. If the weight average molecular weight of the continuous phase is less than 150,000, the size of the dispersed phase becomes excessively large, and thus the impact strength during the manufacture of the product may decrease rapidly or peeling may occur. On the contrary, when the weight average molecular weight of the continuous phase exceeds 300,000, the size of the dispersed phase may be too small, thereby lowering the low light characteristics of the final product.

It is preferable to manufacture the vinyl type thermoplastic resin (A) containing the said network-shaped dispersed phase by continuous block polymerization. In general, it is not easy to produce the network-shaped dispersion phase described above by the method of emulsion polymerization or suspension polymerization, which is a method of producing a rubber phase, and an aromatic vinyl-vinyl cyanide copolymer It is because it is difficult to efficiently manufacture a weather-resistant thermoplastic resin excellent in low light properties because the final product must be manufactured separately by a method such as melt extrusion.

The thermoplastic resin composition having excellent low light properties and weather resistance of the present invention includes 20 to 90 wt% of the vinyl-based thermoplastic resin including the dispersed phase in the form of (A) network based on the total amount of the resin composition. When the content of the vinyl-based thermoplastic resin including the dispersed phase of the (A) network form is less than 20% by weight, it is difficult to realize a target low light property, and when it is 90% by weight or more, the impact resistance is sharply lowered, thereby making it difficult to achieve the basic target properties.

The vinyl-based thermoplastic resin including the (A) network-shaped dispersed phase used in the present invention can be produced by the following method.

Specifically, first, 60 to 95% by weight of (meth) acrylic acid alkyl ester, 1 to 20% by weight of unsaturated carboxylic acid or anhydride thereof, 0 to 20% by weight of aromatic vinyl compound and 0 to 10% by weight of vinyl cyanide compound are mixed. To prepare a first monomer mixture. The first monomer mixture is continuously added to a first reactor of a plurality of reactors connected in series, and the first monomer mixture is polymerized to have a polymerization conversion ratio of 85 to 95% to prepare a polymer.

When the polymer is prepared from the first monomer mixture in the first reactor, the polymer is continuously introduced into the second reactor, while 60 to 95 weight% of the aromatic vinyl compound, 5 to 40 weight% of the vinyl cyanide compound, and ( A second monomer mixture comprising 0 to 10% by weight of a meta) acrylic acid alkyl ester and a compound having a hydroxy group are continuously added to the second reactor. The compound having a hydroxy group is preferably added at a ratio of 0.1 to 3 equivalents relative to the unsaturated carboxylic acid or anhydride thereof introduced into the first reactor. And the polymer, the second monomer mixture and the compound having hydroxy groups are polymerized in a second reactor.

The solvent is preferably added in an amount of 0 to 20 parts by weight, an initiator is added in an amount of 0.01 to 0.05 parts by weight, and a molecular weight regulator is added in an amount of 0 to 0.5 parts by weight based on 100 parts by weight of the second monomer mixture. .

In the present invention, the plurality of reactors are composed of 2 to 5 reactors, the polymerization is preferably carried out continuously through each reactor.

And the final polymerization conversion to the thermoplastic resin in the final reactor after the polymerization is preferably 50 to 70%, more preferably 50 to 65%.

In another embodiment of the present invention, after producing a final polymer consisting of a network-like dispersed phase and a continuous phase through a continuous polymerization process in a plurality of reactors as described above, the final polymer using a devolatilization tank of high temperature and vacuum state The step of separating the unreacted material from can be further coarse. The prepared thermoplastic resin may be formed into pellets using a pelletizer or the like.

(B) polycarbonate resin

The polycarbonate resin (B) of the present invention may be prepared by reacting a compound selected from the group consisting of diphenols represented by the following formula (1) with phosgene, halogen acid esters, carbonate esters and combinations thereof.

[Formula 1]

(In the formula 1,

A is a single bond, substituted or unsubstituted C1 to C30 linear or branched al-chelene group, substituted or unsubstituted C2 to C5 alkenylene group, substituted or unsubstituted C2 to C5 alkylidene group, Substituted or unsubstituted C1 to C30 linear or branched haloalkylene group, substituted or unsubstituted C5 to C6 cycloalkylene group, substituted or unsubstituted C5 to C6 cycloalkenylene group, substituted or unsubstituted C5 to C10 cycloalkylidene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C1 to C20 linear or branched alkoxylene group, halogen acid ester group, carbonate ester group, A linking group selected from the group consisting of CO, S and SO ₂ ,

Each R ₁ and R ₂ are each independently a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group,

n ₁ and n ₂ are each independently an integer of 0 to 4,

The "substituted" is a hydrogen atom substituted with a substituent selected from the group consisting of a halogen group, C1 to C30 alkyl group, C1 to C30 haloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group and combinations thereof I mean)

The diphenols represented by the above formula (1) may be composed of two or more of them to form a repeating unit of a polycarbonate resin. Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol- (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) Ether, and the like. Among the diphenols, specifically 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4- Hydroxyphenyl) cyclohexane can be used. Moreover, 2, 2-bis (4-hydroxyphenyl) propane can be used more specifically among these.

The polycarbonate resin may have a weight average molecular weight of 10,000 to 200,000 g / mol, may be used specifically 20,000 to 50,000 g / mol. When the weight average molecular weight of the polycarbonate resin is within the above range, it is possible to obtain physical properties such as excellent impact strength, and to have appropriate fluidity, thereby obtaining excellent processability.

The polycarbonate resin may be a mixture of copolymers prepared from two or more kinds of diphenols. Also, the polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like.

Bisphenol-A type | system | group polycarbonate resin etc. are mentioned as said linear polycarbonate resin. Examples of the branched polycarbonate resins include those produced by reacting polyfunctional aromatic compounds such as trimellitic anhydride, trimellitic acid, and the like with diphenols and carbonates. The polyfunctional aromatic compound may be included in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate resin. As said polyester carbonate copolymer resin, what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate is mentioned. In this case, as the carbonate, diaryl carbonates such as diphenyl carbonate, ethylene carbonate (Ethylene Carbonate), and the like may be used. 　

The thermoplastic resin composition having excellent low light properties and weather resistance of the present invention contains 10 to 80 wt% of the (B) polycarbonate resin based on the total amount of the resin composition. When the (B) polycarbonate resin content is less than 10% by weight, it is difficult to achieve the target impact strength, when more than 80% by weight it is difficult to implement excellent low light properties and weather resistance.

The thermoplastic resin composition excellent in the low light characteristics and weather resistance used in the present invention can be prepared by the following method.

The thermoplastic resin composition excellent in the low light characteristics and weather resistance of the present invention is one or more additives such as flame retardants, heat stabilizers, impact modifiers, antioxidants, light stabilizers, pigments, dyes, inorganic fillers, etc., according to the respective applications in addition to the components described above. It may further include. Examples of the inorganic additives include asbestos, glass fibers, talc, sulfates and the like. The additive may be used in an amount of 30 parts by weight or less, for example, 0.001 to 30 parts by weight based on 100 parts by weight of the aforementioned components (A) + (B).

Specimens prepared from the thermoplastic resin composition of the present invention may be 1 to 80 glossiness measured using a 60-degree glossiness.

The thermoplastic resin composition of the present invention can be produced by a general method for producing a resin composition. For example, the components and additives of the present invention may be mixed at the same time, and then melt-extruded in an extruder to prepare pellets.

There is no particular limitation on the method for producing a molded article with the thermoplastic resin composition of the present invention, for example, extrusion molding, injection molding or casting molding may be applied. The molding method can be easily carried out by those skilled in the art to which the present invention pertains.

In one specific embodiment of the present invention, the thermoplastic resin composition is injection molded under conditions of a molding temperature of 180 to 280 ° C and a mold temperature of 40 to 80 ° C to manufacture a molded article.

The invention may be better understood by reference to the following examples, which are intended to be illustrative of the invention and are not intended to limit the scope of protection which is defined by the appended claims.

Example

Specifications of each component used in the following Examples and Comparative Examples are as follows.

(A-1) Vinyl-based thermoplastic resin including network-shaped dispersed phase

Toluene 100 to 100 parts by weight of the first monomer mixture consisting of 90 parts by weight of butyl acrylate, 5 parts by weight of styrene, 2 parts by weight of acrylonitrile and 3 parts by weight of acrylic acid The first reactant was prepared by mixing parts by weight, 0.2 parts by weight of benzoyl peroxide (BPO) and 0.05 parts by weight of t-dodecyl mercaptan (TDM). The prepared first reactant was introduced at a rate of 1 kg / hr into the first reactor (R-1) of a continuous polymerization reactor in which three reactors in which a jacket was installed and easy to control the reaction temperature were connected in series were kept at 80 ° C. for 8 hours. The polymerization was prepared by allowing the polymerization to proceed. At this time, the polymerization conversion rate was 90%.

The polymer produced in the first reactor (R-1) was continuously introduced into the second reactor (R-2) of the continuous polymerization reactor at a rate of 1 kg / hr. And 10 parts by weight of toluene, 100 parts by weight of the second monomer mixture consisting of 72 parts by weight of styrene (SM), 25 parts by weight of acrylonitrile (AN), 3 parts by weight of butyl acrylate (BA), 1,1-bis (t- A second reactant by mixing 0.02 part by weight of butylperoxy) cyclohexane (PHX-D), 0.1 part by weight of t-dodecyl mercaptan (TDM), and 1.47 part by weight (1.0 equivalent ratio) of polyethylene glycol (PEG600) having a molecular weight of 600 Was prepared. The prepared second reactant was introduced into the second reactor (R-2) of the continuous polymerization reactor at a rate of 8.5 kg / hr, and polymerization was performed at a temperature of 110 ° C. for 2 hours to prepare a polymer. At this time, the polymerization conversion rate was 25%.

The polymer produced in the second reactor (R-2) was continuously added to the third reactor (R-3) of the continuous polymerization reactor to proceed for 2 hours residence time at 130 ℃ temperature. The polymerization conversion rate at this time was 55%.

The polymerization product discharged from the third reactor (R-3) was continuously added to a devolatilization tank maintained at 240 ° C. and 20 Torr to remove unreacted monomers and solvents, and pellet-shaped network using a pelletizer. Weatherable resins were prepared comprising the dispersed phase in form. An electron micrograph of rubbery particles of weathering resin including the prepared dispersed phase of the network form is shown in FIG. 1.

(A-2) Vinyl-Based Thermoplastic Resin Containing Network-Shaped Disperse Phase

To 100 parts by weight of the first monomer mixture consisting of 88 parts by weight of butyl acrylate (BA), 5 parts by weight of styrene (SM), 2 parts by weight of acrylonitrile (AN) and 5 parts by weight of 2-hydroxyethyl acrylate (HEA) 100 parts by weight of toluene, 0.2 parts by weight of benzoyl peroxide (BPO) and 0.05 parts by weight of t-dodecyl mercaptan (TDM) were mixed and used as the first reactant to be introduced into the first reactor (R-1), and styrene (SM) 10 parts by weight of toluene, 1,1-bis (t-butylperoxy) in 100 parts by weight of a second monomer mixture consisting of 75 parts by weight, 23 parts by weight of acrylonitrile (AN) and 2 parts by weight of butyl acrylate (BA). 0.02 parts by weight of cyclohexane (PHX-C), 0.1 parts by weight of t-dodecyl mercaptan (TDM) and 0.95 parts by weight (dec. 1.0 equivalent) of decandioic acid were added to the second reactor (R-2). 2 A network-containing dispersed phase was prepared in the same manner as in (A-1) except that it was used as a reactant. Weather resistant resins were prepared. An electron micrograph of the rubbery particles of the weatherable resin including the dispersed phase in the form of a network is shown in FIG. 2.

(B) polycarbonate resin

Cheil Industries, Inc. used an INFINO SD-1080 product.

(E-1) vinyl-based thermoplastic resin having a general spherical dispersed phase

STAREX WR-9130 from Cheil Industries was used. An electron micrograph of the weather resistant resin having a general spherical dispersed phase used in the comparative example is shown in FIG. 3.

(E-2) vinyl-based thermoplastic resin having a general spherical dispersed phase

Cheil Industries, Inc. used STAREX WR-9330. The electron micrograph of the weather resistant resin which has a general spherical dispersed phase used in the comparative example is shown in FIG.

(F) antioxidant

Octadiyl-3 '(4-hydroxy-3,5-di-tert-butylphenyl) propionate was used as a hindered phenolic antioxidant.

Example  1 to 12

Each of the components was added to the content as described in Tables 1 to 3, and then melted and kneaded and extruded to prepare pellets. At this time, the extrusion was used a twin screw extruder, the L / B is 29, the diameter is 45 mm, the cylinder temperature is set to 220 ℃. The prepared pellet was dried at 80 ° C. for 3 hours, and then injected into a 6 Oz injection machine under conditions of a molding temperature of 180 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a specimen.

Comparative Example  1 to 12

Each of the components was added to an amount as described in Tables 1 to 3, followed by melting and kneading extrusion to prepare pellets. At this time, the extrusion was used a twin screw extruder having a L / B of 29, a diameter of 45 mm, the cylinder temperature is set to 220 ℃. The prepared pellet was dried at 80 ° C. for 3 hours, and then injected into a 6 Oz injection machine under conditions of a molding temperature of 180 to 280 ° C. and a mold temperature of 40 to 80 ° C. to prepare a specimen.

(A-1) (A-2) (E-1) (E-2) (B) (F) Example 1 90 10 0.3 Example 2 85 15 0.3 Example 3 90 10 0.3 Example 4 85 15 0.3 Comparative Example 1 90 10 0.3 Comparative Example 2 85 15 0.3 Comparative Example 3 90 10 0.3 Comparative Example 4 85 15 0.3

(A-1) (A-2) (E-1) (E-2) (B) (F) Example 5 65 45 0.3 Example 6 50 50 0.3 Example 7 65 45 0.3 Example 8 50 50 0.3 Comparative Example 5 65 45 0.3 Comparative Example 6 50 50 0.3 Comparative Example 7 65 45 0.3 Comparative Example 8 50 50 0.3

(A-1) (A-2) (E-1) (E-2) (B) (F) Example 9 30 70 0.3 Example 10 20 80 0.3 Example 11 30 70 0.3 Example 12 20 80 0.3 Comparative Example 9 30 70 0.3 Comparative Example 10 20 80 0.3 Comparative Example 11 30 70 0.3 Comparative Example 12 20 80 0.3

How to measure property

After the specimens prepared according to Examples 1 to 6 and Comparative Examples 1 to 12 were allowed to stand at 23 ° C. and a relative humidity of 50% for 48 hours, their physical properties were measured in the following manner, and the results are shown in Tables 4 to 6 below. Indicated.

(1) Izod impact strength: Izod impact strength (1/8 "and 1.4", kgf · Dm / Dm) was measured according to ASTM B256.

(2) Flow index (MBlt InBBx): Flow index was measured under conditions of 250 ℃, 10kg according to ASTM B1238.

(3) Viket softening temperature (ViDat softBning tBmpBraturB): Viket softening temperature was measured under the condition of B / 50 according to ASTM B1525.

(4) Tensile strength: Tensile strength (5nmm / min, kgf / Dm ² ) was measured according to ASTM B638.

(5) Elongation: Elongation (5nmm / min,%) was measured according to ASTM B638.

(6) Glossiness: 60 degree glossiness was measured using BYK-GarBnBr Gloss MBtBr.

(7) Color difference (ΔB) and yellowness degree change (ΔYI): Measured according to JIS K7105.

Izod8 MI VST FS TS Glossiness ΔE ΔYI Example 1 12.9 48.46 89.4 659 433 21.9 18.3 20.2 Example 2 14.3 51.01 91.2 678 451 23.2 18.1 21.1 Example 3 13.4 46.9 89.1 629 430 20.1 17.5 20 Example 4 14.6 45.2 89.6 660 459 21.8 16.9 21.5 Comparative Example 1 12.6 46.1 89.8 605 386 95.5 27.3 30.5 Comparative Example 2 13.5 44.8 89.9 618 394 96.7 26.4 28.6 Comparative Example 3 14.7 44.1 87.6 637 411 94.2 28.1 31.3 Comparative Example 4 15.1 43.5 90.2 667 466 94.8 26.4 27.9

Izod8 MI VST FS TS Glossiness ΔE ΔYI Example 5 40.6 45.93 100.2 791 535 46.2 16.1 19.3 Example 6 48.4 40.57 104.8 838 564 46 15.2 18.5 Example 7 41.5 44.3 101 802 541 45 15.7 17.1 Example 8 50 40.2 103.9 825 552 47.7 16.5 17.5 Comparative Example 5 43.2 33.2 100.1 746 481 96.4 26.2 28.7 Comparative Example 6 44.9 30.8 101.1 761 499 97.2 24.6 26.1 Comparative Example 7 43.5 31.3 101.3 788 526 93.9 28.6 30.7 Comparative Example 8 53.4 28.5 105.2 810 550 95.6 25.3 27.3

Izod8 MI VST FS TS Glossiness ΔE ΔYI Example 9 57.5 32.13 122 921 606 71 14 18.1 Example 10 65.3 26.31 126.6 937 627 76.2 13.2 17.4 Example 11 58.4 31.3 121.5 932 607 70.9 12.8 16.2 Example 12 67.2 24.4 124.3 941 634 74.3 13.2 16.9 Comparative Example 9 51.8 21.3 115.5 857 568 97.8 20.1 24.6 Comparative Example 10 55.3 18.4 116.5 870 583 96.9 21.9 24.4 Comparative Example 11 60.4 20.9 117.2 899 607 94.5 23.2 27.1 Comparative Example 12 69.3 15.9 119.8 916 637 96.1 22.7 25.6

As can be seen from the results in Tables 4 to 6, in Examples 1 to 12 using vinyl-based thermoplastic resins (A-1) and (A-2) containing a network-shaped dispersed phase, the impact strength and other physical properties were maintained. It was confirmed that excellent low light characteristics and weathering stability are implemented.

In Comparative Examples 1 to 12 using vinyl-based thermoplastic resins (B-1) and (B-2) having the same amount of spherical dispersed phases, there was almost no change in glossiness with respect to the content change due to small rubber dispersed phase particles. Due to the nature of the polymerization process produced in a batch form, it can be seen that the weathering stability is significantly lowered due to additives such as emulsifiers and dispersion stabilizers.

On the other hand, in the case of using the vinyl-based thermoplastic resins (A-1) and (A-2) including the dispersed phase of the network shape prepared by the continuous bulk polymerization process, the amount of gloss reduction due to the dispersed phase of the network type is added. It can be confirmed that the confirmation decreases with increasing, and since the other additives are hardly used during the polymerization production process, it can be confirmed that the weather resistance is very excellent.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1 is an electron micrograph of rubbery particles of a vinyl-based thermoplastic resin including a dispersed phase of a network shape included in a thermoplastic resin composition having excellent low light characteristics and weather resistance according to one embodiment of the present invention, and FIG. 2 is another aspect of the present invention. It is an electron micrograph of the rubber-like particle | grains of a vinyl type thermoplastic resin containing the network-like dispersion | distribution phase contained in the thermoplastic resin composition excellent in the low light characteristic and weatherability which concerns on a specific example.

3 and 4 are electron micrographs of vinyl-based thermoplastic resins having a general spherical dispersed phase.

Claims (17)

(A) 20 to 90% by weight of a vinyl-based thermoplastic resin including a network-shaped dispersed phase; And (B) 10 to 80 wt% of a polycarbonate resin; The vinyl-based thermoplastic resin including the (A) network-shaped dispersed phase includes (a1) (meth) acrylic acid alkyl ester polymer and (a2) aromatic vinyl-vinyl cyanide copolymer, and has low light characteristics and weather resistance. Excellent thermoplastic resin composition. The vinyl-based thermoplastic resin of claim 1, wherein the vinyl-based thermoplastic resin including the (A) network-shaped dispersed phase comprises: (a1) 5 to 35 weight percent of (meth) acrylic acid alkyl ester polymer; And (a2) 65% to 95% by weight of an aromatic vinyl-vinyl cyanide copolymer, wherein the thermoplastic resin composition is excellent in low light characteristics and weather resistance. According to claim 1, wherein the polycarbonate resin (B) is excellent in low light properties and weather resistance, characterized in that the phenols are prepared by reacting with a compound selected from the group consisting of phosgene, halogen acid ester, carbonate ester and combinations thereof Thermoplastic resin composition. The method of claim 2, wherein the (a1) (meth) acrylic acid alkyl ester polymer is polymerized by including a (meth) acrylic acid alkyl ester, an unsaturated carboxylic acid or an anhydride thereof, and a compound having a hydroxy group. A thermoplastic resin composition excellent in low light characteristics and weather resistance. The compound according to claim 4, wherein the compound having a hydroxy group is a saturated compound and ester-bonded with the unsaturated carboxylic acid or anhydride thereof contained as a unit of a main chain in the (meth) acrylic acid alkyl ester polymer, or is unsaturated. A thermoplastic resin composition having excellent low light properties and weather resistance, which is a compound, and is included as a unit of a main chain in the (meth) acrylic acid alkyl ester polymer while being ester-bonded with the unsaturated carboxylic acid or its anhydride. The method according to claim 4, wherein 60 to 95% by weight of the (meth) acrylic acid alkyl ester, 1 to 20% by weight of an unsaturated carboxylic acid or anhydride thereof, and 0 to 20% by weight of an aromatic vinyl compound, except for the compound having a hydroxy group. %, 0 to 10% by weight of a vinyl cyanide compound is polymerized, and the compound having a hydroxy group is contained in an amount of 0.1 to 3 equivalents based on the unsaturated carboxylic acid or its anhydride. Thermoplastic resin composition. The thermoplastic resin composition according to claim 4, wherein the (meth) acrylic acid alkyl ester is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms. The group of claim 4, wherein the unsaturated carboxylic acid or anhydride thereof is composed of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and fumaric acid anhydride. Thermoplastic resin composition comprising at least one selected from. The compound having a hydroxy group according to claim 4, characterized in that it comprises at least one selected from the group consisting of alkanediol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol and polyol having 2 to 10 carbon atoms. Thermoplastic resin composition. The thermoplastic resin composition of claim 6, wherein the aromatic vinyl compound includes at least one selected from the group consisting of styrene, alphamethyl styrene, and paramethyl styrene. The thermoplastic resin composition of claim 6, wherein the vinyl cyanide compound comprises at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The aromatic vinyl-vinyl cyanide copolymer of claim 2, wherein the aromatic vinyl-vinyl cyanide copolymer comprises 60 to 95% by weight of an aromatic vinyl compound; 5 to 40 weight percent of a vinyl cyanide compound; And 0 to 10% by weight of (meth) acrylic acid alkyl ester; thermoplastic resin composition excellent in low light characteristics and weather resistance. 13. The thermoplastic resin composition of claim 12, wherein the aromatic vinyl compound comprises at least one selected from the group consisting of styrene, alphamethyl styrene, and paramethyl styrene. The thermoplastic resin composition of claim 12, wherein the vinyl cyanide compound comprises at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The thermoplastic resin composition according to claim 12, wherein the (meth) acrylic acid alkyl ester is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 10 carbon atoms. The thermoplastic resin composition of claim 2, wherein the weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer (a2) is 150,000 to 300,000. 17. The thermoplastic resin composition according to any one of claims 1 to 16, wherein the thermoplastic resin has a glossiness of 1 to 80 measured using a 60 degree glossiness device.

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