KR101937314B1 - Rubber copolymer and thermoplastic resin composition comprising the same - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)And a functional group represented by the following formula (1) at both ends, a thermoplastic resin composition containing the same, and a molded article using the rubber copolymer.
[Chemical Formula 1]

(Wherein each substituent is as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a rubber copolymer and a thermoplastic resin composition containing the rubber copolymer.

Rubber copolymer and a thermoplastic resin composition containing the same.

The thermoplastic resin composition has a lower specific gravity than glass and metal and is excellent in properties such as moldability and impact resistance and is useful for a housing for an electric / electronic product, an automobile interior / exterior material, and a building exterior material. In particular, with the recent trend toward larger and lighter electric / electronic products, plastic products using thermoplastic resins are rapidly replacing existing glass and metal areas.

Among these thermoplastic resin compositions, a PC / ABS blend in which a rubber-modified aromatic vinyl copolymer resin such as acrylonitrile-butadiene-styrene (ABS) is blended with a polycarbonate (PC) resin is preferable because the impact resistance, The processability and the chemical resistance can be improved and the cost can be reduced without deterioration of the surface roughness of the substrate.

In addition, much research has been conducted to realize properties that a conventional thermoplastic resin composition can not realize by adding a readily obtainable material such as a polyester resin to a PC / ABS blend as a multi-component material.

However, when a multicomponent material is mixed with a PC or an ABS, the impact resistance, fluidity, and appearance characteristics of the thermoplastic resin composition may deteriorate due to lowering of compatibility between the respective components. For example, in the case of an impact reinforcement, there is a problem that the flame retardancy is reduced. In the case of a flame retardant, the impact resistance is reduced.

An object of the present invention is to provide a rubber copolymer excellent in impact resistance and flame retardancy and a thermoplastic resin composition containing the same.

The rubber copolymer according to one embodiment of the present invention comprises functional groups represented by the following general formula (1) at both terminals.

[Chemical Formula 1]

In Formula 1,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The rubber copolymer may include a functional group represented by the following formula (2) at both ends.

(2)

In Formula 2,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.

The rubber copolymer may be a polybutadiene rubber copolymer.

The rubber copolymer may be represented by the following general formula (3) or (4).

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

m1, m2, m3, n1 and n2 are each independently an integer of 1 to 1000.

Another embodiment of the present invention provides a thermoplastic resin composition comprising a polycarbonate resin and the rubber copolymer.

The rubber copolymer may be contained in an amount of 1 part by weight to 10 parts by weight based on 100 parts by weight of the polycarbonate resin.

The thermoplastic resin composition may further include an inorganic filler, a flame retardant, a flame retardant, a releasing agent, a lubricant, a plasticizer, a heat stabilizer, an antistatic agent, an antioxidant, a light stabilizer, a pigment, a dye or a combination thereof.

The thermoplastic resin composition may be prepared by mixing the polycarbonate resin and the rubber copolymer and then UV curing the mixture for 5 to 20 minutes.

The thermoplastic resin composition may have a notched Izod impact strength of 8 to 20 kgf · cm / cm measured with a 1/8 "thick specimen according to ASTM D256.

The present invention can provide a rubber copolymer excellent in impact resistance and flame retardancy, a thermoplastic resin composition containing the thermoplastic resin composition, and a molded article such as an electronic device housing manufactured using the thermoplastic resin composition.

1 is a schematic view showing a process of forming a crosslinked structure by self-assembly of a rubber copolymer end according to an embodiment of the present invention.
2 is a schematic cross-sectional view of an electronic device housing according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the appended claims.

As used herein, unless otherwise defined, at least one hydrogen in the compound is a C1 to C30 alkyl group; C1 to C10 alkylsilyl groups; A C3 to C30 cycloalkyl group; A C6 to C30 aryl group; A C2 to C30 heteroaryl group; A C1 to C10 alkoxy group; A C1 to C10 trifluoroalkyl group such as a fluoro group and a trifluoromethyl group; Or cyano group.

As used herein, unless otherwise defined, it is meant that one compound or substituent contains 1 to 3 heteroatoms selected from the group consisting of N, O, S, and P, with the remainder being carbon do.

As used herein, unless otherwise defined, the term " alkyl group "means a" saturated alkyl group "which does not include any alkenes or alkynes; Or "unsaturated alkyl group" comprising at least one alkenyl group or alkynyl group. Means a substituent wherein at least two carbon atoms constitute at least one carbon-carbon double bond, and "alkynyl group" means a substituent wherein at least two carbon atoms constitute at least one carbon-carbon triple bond it means. The alkyl group may be branched, straight-chain or cyclic.

The alkyl group may be a C1 to C20 alkyl group, and specifically may be a C1 to C6 lower alkyl group, a C7 to C10 intermediate alkyl group, or a C11 to C20 higher alkyl group.

"Aromatic" means a compound in which all elements of the cyclic substituent have p-orbital, and these p-orbital forms a conjugation. Specific examples thereof include an aryl group and a heteroaryl group.

An "aryl group" includes a single ring or a fused ring (i.e., a plurality of rings that divide adjacent pairs of carbon atoms) substituents.

"Heteroaryl group" means that the aryl group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

Unless otherwise specified herein, (meth) acrylate means acrylate or methacrylate. The (meth) acrylic acid alkyl ester means an acrylic acid alkyl ester or a methacrylic acid alkyl ester, and the (meth) acrylic acid ester means an acrylic acid ester or a methacrylic acid ester.

Unless otherwise defined herein, "copolymerization" may mean block copolymerization, random copolymerization, graft copolymerization or alternating copolymerization, and the term "copolymer" means a block copolymer, random copolymer, graft copolymer or alternating copolymer It can mean merging.

In one embodiment of the present invention, there is provided a rubber copolymer comprising functional groups represented by the following general formula (1) at both terminals.

[Chemical Formula 1]

In Formula 1,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

For example, the rubber copolymer may contain a functional group represented by the following formula (2) at both terminals.

(2)

In Formula 2,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.

The functional groups represented by the formula (1), for example, the functional groups represented by the formula (2), are hydrogen bonded to each other through UV curing to form a weak crosslinked structure, and ultimately, a supramolecular rubber copolymer can be formed. (See Fig. 1)

Specifically, at the extrusion high temperature (for example, at a temperature of 90 ° C or higher), the dissolution of the terminal functional group in the supramolecular rubber copolymer (the functional group represented by the formula (1), for example, the functional group represented by the formula (2)) dissociates the rubber copolymer , And at a low temperature (for example, at a temperature lower than 90 ° C), a weak crosslinking structure is formed by self-assembly, and a supramolecular rubber copolymer can be formed. That is, at the high temperature, the supramolecular rubber copolymer absorbs the energy required for dissociation of the terminal functional group, and can emit the energy at a low temperature while having excellent flame retardancy.

That is, in general, the rubber copolymer in the thermoplastic resin composition is excellent in impact resistance, but has a problem in that the flame retardancy is lowered. However, in the rubber copolymer according to one embodiment, physical bonding and chemical bonding by UV Rubber, such as butadiene rubber, can increase the intermolecular cohesive force through physical bonding and chemical bonding, thereby improving the flame retardant property in a trade off relationship.

The rubber copolymer may be a polybutadiene rubber copolymer.

For example, the rubber copolymer may be represented by the following formula (3) or (4).

(3)

[Chemical Formula 4]

In the above formulas (3) and (4)

m1, m2, m3, n1 and n2 are each independently an integer of 1 to 1000.

Another embodiment of the present invention includes a thermoplastic resin composition comprising a polycarbonate resin and the rubber copolymer.

Hereinafter, each component contained in the thermoplastic resin composition will be described in detail.

Polycarbonate resin

The polycarbonate resin used in the present invention is a polycarbonate resin used in a conventional thermoplastic resin composition.

For example, an aromatic polycarbonate resin prepared by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic acid diester can be used.

Examples of the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) But is not limited thereto. (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1- ) Cyclohexane can be used. Specifically, 2,2-bis (4-hydroxyphenyl) propane called bisphenol-A can be used.

The polycarbonate resin may be used in the presence of a branched chain. For example, the polycarbonate resin may be used in an amount of 0.05 mol% to 2 mol% of a trifunctional or more polyfunctional compound, And further adding a compound having a phenol group.

The polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin or a blend thereof.

The polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as a bifunctional carboxylic acid.

In embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC) of from 10,000 g / mol to 200,000 g / mol, such as from 15,000 g / mol to 40,000 g / mol However, the present invention is not limited thereto.

In an embodiment, the polycarbonate resin has a melt flow index (MI) of 10.3 g / 10 min to 12.7 g / 10 min, measured at 250 ° C under a load of 10 kg, according to ISO 1133, The melt flow index (MI) measured at 250 ° C under a load of 1.2 kg may be 9.8 g / 10 min to 10.8 g / 10 min, but is not limited thereto. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indexes.

Rubber copolymer

The rubber copolymer used in the present invention is as described above.

In an embodiment, the content of the rubber copolymer is 1 to 10 parts by weight, for example 1 to 6 parts by weight, specifically 2 to 5 parts by weight, based on 100 parts by weight of the polycarbonate resin have. In the above range, the thermoplastic resin composition may have excellent impact resistance, flame retardancy, and mechanical properties.

additive

The thermoplastic resin composition according to an embodiment of the present invention may further contain additives such as an inorganic filler, a flame retardant, a flame retardant aid, a releasing agent, a lubricant, a plasticizer, a heat stabilizer, a dripping inhibitor, an antioxidant, a light stabilizer, a pigment, .

In the specific examples, the additive used in the conventional thermoplastic resin composition may be used without limitation. Examples of the inorganic filler include glass fiber, wollastonite, whisker, basalt fiber, talc, mica, and the like, but are not limited thereto. The content of the inorganic filler may be 0.1 to 40 parts by weight, for example, 0.5 to 30 parts by weight based on 100 parts by weight of the polycarbonate resin. Within the above range, the polycarbonate resin composition may be excellent in appearance, mechanical properties, dimensional stability, flame retardancy, and the like.

The additives other than the above-mentioned inorganic fillers may include phosphate compounds, phosphonate compounds, phosphinate compounds, phosphine oxide compounds, phosphazene compounds, Flame retardants such as metal salts; Release agents such as polyethylene wax, fluorine-containing polymer, silicone oil, metal salts of stearic acid, metal salts of montanic acid, and montanic ester wax; Nucleating agents such as clay; Antioxidants such as hindered phenol-based compounds; Mixtures thereof, and the like may be used, but the present invention is not limited thereto. The additive excluding the inorganic filler may be included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the polycarbonate resin, but is not limited thereto.

The thermoplastic resin composition according to an embodiment of the present invention may be obtained by mixing the polycarbonate resin and the rubber copolymer and then UV curing the mixture for 5 minutes to 20 minutes. When the UV curing time is less than 5 minutes or more than 20 minutes, the impact resistance is lowered.

The thermoplastic resin composition may be in the form of a pellet obtained by melt-extruding the above components and mixing them at a temperature of 200 ° C to 280 ° C, for example, 250 ° C to 260 ° C, using a conventional twin-screw extruder.

In a specific example, the thermoplastic resin composition has a notch Izod impact strength of 8 kgf · cm / cm to 20 kgf · cm / cm, for example, 10 kgf · cm / cm, measured with a 1/8 "thick sample according to ASTM D256, cm to 16 kgf cm / cm.

2 is a schematic cross-sectional view of an electronic device housing according to an embodiment of the present invention. In the drawings, the size of elements constituting the invention is exaggerated for clarity of description, and is not limited thereto.

As shown in FIG. 2, an electronic device housing according to an embodiment of the present invention includes a metal frame 10; And at least one plastic member (20) in contact with at least one surface of the metal frame (10), wherein the plastic member is formed from the thermoplastic resin composition.

In the embodiment, the shapes of the metal frame 10 and the plastic member 20 are not limited to the drawings, and may have various shapes. However, the metal frame 10 and the plastic member 20 have a structure in which at least one side is in contact with each other. The contacting structure may be implemented by gluing or inserting, and the contacting method is not limited.

In a specific example, the metal frame 10 may be a stainless steel frame, a plastic member, or the like, which is applicable to a conventional electronic device housing, and is commercially available.

In an embodiment, the plastic member 20 may be formed from the polycarbonate resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding and the like. Specifically, the plastic member 20 may be a front cover, a rear cover, or the like of a 22-inch to 70-inch television, a monitor, or the like.

In an embodiment, the difference in coefficient of thermal expansion (CTE) between the metal frame and the plastic member may be between 0.1 and 0.5, for example between 0.3 and 0.45.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples and comparative examples are for illustrative purposes only and are not intended to limit the present invention.

(Synthesis of Rubber Copolymer)

Synthetic example  One

Ureido-4 [1H] -pyrimidinone was synthesized through 2-amino-4-hydroxy-6-methylpyrimidine and 1,6-hexyldiisocyanate. Hydroxyl telechelic polybutadiene and the synthesized ureido-4 [1H] -pyrimidinone were reacted in a dimethylformamide solvent through dibutyltin dilaurate catalyst to obtain a supramolecular rubber copolymer. (See Scheme 1 below)

[Reaction Scheme 1]

(In Case 1, m, n and p are each independently an integer of 5 to 1000,

In Case 2, q and r are each independently an integer of 5 to 500.)

( Example )

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) Polycarbonate resin

A bisphenol-A polycarbonate resin (flow index (measured according to MI, ISO 1133 at 250 캜, 10 kg): 11.5 ± 1.2 g / 10 min) was used.

(B) a rubber copolymer

(Case 1 in Synthesis Example 1) in which 25 wt% of ureido-4 [1H] -pyrimidinone was substituted at the rubber end was added to a polybutadiene rubber (PBR) having a Z-average of 310 nm of 75 wt% Respectively.

Example  1 to Example  6 and Comparative Example  One

Each of the above components was added in the amounts shown in Table 1 below, UV-cured, and then extruded at 250 ° C to prepare pellets. The pellets were dried at 80 DEG C for 4 hours and then passed through a 6 Oz extruder (molding temperature 250 DEG C to 280 DEG C, mold temperature 50 DEG C to 150 DEG C) C) to prepare specimens. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 2 below.

How to measure property

(1) Notch Izod impact strength (unit: kgf cm / cm): A notch was formed on a 1/8 "Izod (IZOD) specimen by the evaluation method described in ASTM D256.

(2) Melt-flow index (MI, unit: g / 10 min): measured according to ASTM D1238 at 260 ° C under a load of 2.16 kg.

(3) HDT (1.82 MPa) (占 폚): According to ASTM D648 standard, the thickness was 6.4 mm and the load was 1.82 MPa.

(4) Tensile strength (5 mm / min) and flexural strength (2.8 mm / min): Measured using UTM (Instron).

(5) Flame retardancy: Measured using UL94 equipment.

(Unit: parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 (A) Polycarbonate resin 100 100 100 100 100 100 100 (B) a rubber copolymer 2 2 2 2 4 6 - UV curing time (minutes) - 5 10 20 5 5 -

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Notch Izod impact strength 1/8 "(kgf · cm / cm) 10.5 14.2 12.7 8.8 15.7 13.9 9.1 Pyrolysis temperature 1.82 MPa (占 폚) 126.3 125.9 125.7 126.4 125.5 126.1 127.3 Tensile (5mm) TE (%) 93 74 67 63 80 95 65 TS (kgf / cm ² ) 600 640 680 690 650 650 640 curve
(2.8 mm) FM (kgf / cm ² ) 21.9k 24.3k 26.3k 28.8k 25.4k 26.8k 22.8k FS (kgf / cm ² ) 900 950 970 990 990 900 940 Flame Retardant 2.0 T V-1 V-0 V-0 V-0 V-0 V-0 V-2

From Table 1 and Table 2, it can be confirmed that the thermoplastic resin composition comprising the polycarbonate resin and the rubber copolymer according to one embodiment is excellent in impact resistance and flame retardancy. Further, it can be confirmed that the impact resistance is the best when the UV curing time is about 5 minutes.

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. It will be understood that the invention can be practiced in a specific form. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (9)

Polycarbonate resin, and
A rubber copolymer containing a functional group represented by the following formula (1)
Wherein the thermoplastic resin composition comprises:
[Chemical Formula 1]

In Formula 1,
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.
The method of claim 1,
Wherein the rubber copolymer comprises a functional group represented by the following formula (2) at both terminals:
(2)

In Formula 2,
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ is a substituted or unsubstituted C1 to C10 alkylene group.
The method of claim 1,
Wherein the rubber copolymer is a polybutadiene rubber copolymer.
The method of claim 1,
Wherein the rubber copolymer is a thermoplastic resin composition represented by the following formula (3) or (4)
(3)

[Chemical Formula 4]

In the above formulas (3) and (4)
m1, m2, m3, n1 and n2 are each independently an integer of 1 to 1000.
delete The method of claim 1,
The rubber copolymer
And 1 part by weight to 10 parts by weight of the polycarbonate resin relative to 100 parts by weight of the polycarbonate resin.
The method of claim 1,
Wherein the thermoplastic resin composition further comprises an inorganic filler, a flame retardant, a flame retardant aid, a release agent, a lubricant, a plasticizer, a heat stabilizer, a dropping inhibitor, an antioxidant, a light stabilizer, a pigment, a dye or a combination thereof.
The method of claim 1,
Wherein the thermoplastic resin composition is obtained by mixing the polycarbonate resin and the rubber copolymer and then UV-curing the mixture for 5 to 20 minutes.
The method of claim 1,
Wherein the thermoplastic resin composition has a notched Izod impact strength of 8 to 20 kgf · cm / cm measured with a 1/8 "thick sample according to ASTM D256.

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