WO2019132591A1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention comprises: about 100 parts by weight of polycarbonate resin; about 20 to about 60 parts by weight of mica which has been surface-treated with a silane compound; about 0.1 to about 20 parts by weight of a modified polyolefin comprising a repeating unit represented by chemical formula 1 and a repeating unit represented by chemical formula 2; and about 3 to about 20 parts by weight of a phosphorus flame retardant. The thermoplastic resin composition has excellent impact resistance, strength, flame retardancy, fluidity, and the like.

Description

Thermoplastic resin composition and molded article formed therefrom

The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in impact resistance, rigidity, flame retardancy, fluidity and the like, and a molded article formed from the thermoplastic resin composition.

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.

In recent years, portable electronic products and the like manufactured using a thermoplastic resin composition have become thinner and lighter, and are required to have high impact resistance and high rigidity in order to prevent product damage due to an external impact or the like. However, since stiffness and impact resistance are in conflict, existing thermoplastic resin compositions have limitations in achieving high strength and high impact resistance at the same time.

In addition, various inorganic and organic flame retardants are used in order to improve the flame retardancy of the thermoplastic resin composition. However, when the flame retardant is used in an excessive amount, the impact resistance may be lowered.

Therefore, it is necessary to develop a thermoplastic resin composition excellent in impact resistance, rigidity, flame retardancy, fluidity, balance of physical properties, and the like.

The background art of the present invention is disclosed in Japanese Laid-Open Patent Publication No. 2015-059138 and the like.

An object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance, rigidity, flame retardancy, fluidity and the like.

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

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

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises about 100 parts by weight of a polycarbonate resin; About 20 to about 60 parts by weight of a mica surface-treated with a silane compound; About 0.1 to about 20 parts by weight of a modified polyolefin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); And from about 3 to about 20 parts by weight of a phosphorus flame retardant;

[Chemical Formula 1]

(2)

Wherein R ₁ is a hydrogen atom or a methyl group, Y is -COOR ₂ (R ₂ is an alkyl group having 1 to 12 carbon atoms), a glycidyl-modified ester group, an arylate group, or a nitrile group (-CN) .

2. In one embodiment, the mica may have an average particle size of about 60 to about 300 microns and an aspect ratio of about 50 to about 150 in cross-section.

3. In one or two embodiments, the modified olefin may include about 50 to about 95% by weight of the repeating unit represented by the formula (1) and about 5 to about 50% by weight of the repeating unit represented by the formula (2) .

4. In the above-mentioned first to third embodiments, the phosphorus-based flame retardant may include at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound and a phosphazene compound.

5. In the above-mentioned Embodiments 1 to 4, the weight ratio of the mica and the modified polyolefin may be about 3: about 1 to about 40: about 1.

6. In Embodiments 1 to 5, the thermoplastic resin composition may have a notched Izod impact strength of about 3 to about 30 kgf · cm / cm in a 1/8 "thick specimen measured according to ASTM D256-10e1.

7. The thermoplastic resin composition according to any one of 1 to 6, wherein the thermoplastic resin composition has a flexural modulus of about 60,000 to about 90,000 kgf / cm ² measured at a speed of 2.8 mm / min using a 6.4 mm thick specimen according to ASTM D790 .

8. In the above-mentioned Embodiments 1 to 7, the flame retardancy of the thermoplastic resin composition of the 1.5 mm thick specimen measured by the UL-94 vertical test method may be V-0 or higher.

9. In the first to eight embodiments, the thermoplastic resin composition of the spiral (spiral) Forming temperature 260 ℃, mold temperature 60 ℃, injection pressure 1,500 kgf / cm ² and a thickness under the conditions of injection speed 120 mm / s 2 mm After injection molding in a mold of the type, the spiral flow length of the measured specimen may be from about 250 to about 300 mm.

10. Another aspect of the present invention relates to a molded article. Wherein the molded article is formed from the thermoplastic resin composition according to any one of 1 to 9 above.

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition excellent in impact resistance, rigidity, flame retardancy, fluidity and the like and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a polycarbonate resin; (B) mica; (C) a modified polyolefin; And (D) a phosphorus flame retardant.

In the present specification, "a to b" representing numerical ranges are defined as "? A and? B".

(A) Polycarbonate resin

As the polycarbonate resin according to one embodiment of the present invention, a polycarbonate resin used for a conventional thermoplastic resin composition may be used. 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.

Specific 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) Propane, and the like, but the present invention 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.

In an embodiment, the polycarbonate resin may be branched and may contain, for example, from about 0.05 to about 2 mol% trifunctional or more polyfunctional compounds per total of diphenols used in the polymerization, , Or a compound having a trivalent or higher phenol group may be added to the polycarbonate resin.

In embodiments, 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 about 10,000 to about 50,000 g / mol, such as from about 15,000 to about 40,000 g / mol. The flowability (processability) and the like of the thermoplastic resin composition in the above range can be excellent.

In embodiments, the polycarbonate resin may have a melt flow index (MI) of from about 5 to about 80 g / 10 min, measured at 300 ° C under a load of 1.2 kg, in accordance with ISO 1133. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indexes.

(B) Mica

The mica of the present invention can improve the rigidity and the like without deteriorating the impact resistance of the thermoplastic resin composition, and a mica surface-treated with a silane compound can be used.

In a specific example, the mica may be in the form of a plate or an amorphous shape, and the average particle size (D50, particle size at the point where the distribution ratio is 50%) measured by a particle size analyzer (manufacturer: sympatec To about 300 [mu] m, for example from about 60 to about 200 [mu] m. Outside of the above range, the effect of improving the rigidity (flexural strength) and the like may be deteriorated, and the appearance characteristics may be deteriorated.

In addition, the mica may have an aspect ratio of about 50 to about 150 in cross-section. Here, the aspect ratio is a ratio of the long diameter to the short diameter of the mica cross section.

In a specific example, the mica surface-treated with the silane compound is a silane compound to which a silane compound is applied. Examples of the silane compound include vinyltrichlorosilane, vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane, vinyl Trimethoxysilane, 3-methacryloxypropyl-trimethoxysilane,? - (3,4-epoxycyclohexyl) -ethyltrimethoxysilane,? -Glycidoxypropyl-trimethoxysilane, Aminopropyl-trimethoxysilane, N-beta (aminoethyl) - gamma -aminopropyl-methyldiethoxysilane, 3-aminopropyl- Triethoxysilane, N-phenyl-γ-aminopropyl-trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyl-trimethoxysilane such as γ- Trimethoxysilane,? -Glycidoxypropyl-methyldiethoxysilane, and the like can be used. The surface of the mica-silane compound may be treated by a conventional method. For example, a screen printing method, a printing method, a spin coating method, a dipping method, or an ink jet method may be used.

In embodiments, the mica surface treated with the silane compound may comprise about 100 parts by weight of mica and about 0.1 to about 2 parts by weight of the silane compound. Within the above range, the thermoplastic resin composition may have excellent rigidity, impact resistance, heat resistance, and the like.

In an embodiment, the mica (B) may be included in about 20 to about 60 parts by weight, for example about 20 to about 55 parts by weight, based on about 100 parts by weight of the polycarbonate resin (A). When the content of the mica is less than about 20 parts by weight, the rigidity of the thermoplastic resin composition may be deteriorated. When the content of the mica exceeds about 60 parts by weight, impact resistance and fluidity may be deteriorated.

(C) Modified polyolefin

The modified polyolefin of the present invention can improve the impact resistance, fluidity and the like of the thermoplastic resin composition together with the above-mentioned mica. The modified polyolefin of the present invention comprises a polyolefin as a main chain and a functional group (an alkylcarboxylate group, a glycidyl- Aryl group, aryl group, aryl group, nitrile group, etc.). For example, a modified polyolefin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) can be used.

[Chemical Formula 1]

(2)

Wherein R ₁ is a hydrogen atom or a methyl group, Y is -COOR ₂ (R ₂ is an alkyl group having 1 to 12 carbon atoms), a glycidyl-modified ester group, an arylate group, or a nitrile group (-CN) .

In an embodiment, the modified polyolefin may be prepared by polymerizing an olefin with at least one compound selected from the group consisting of an alkyl (meth) acrylate, an ethylenically unsaturated group-containing modified ester, an ethylenically unsaturated group-containing arylate, and acrylonitrile.

In an embodiment, the modified olefin comprises about 50 to about 95 weight percent, for example, about 70 to about 93 weight percent of the repeating unit represented by Formula 1 and about 5 to about 50 weight percent of the repeating unit represented by Formula 2, , Such as from about 7 to about 30 weight percent. Within the above range, the thermoplastic resin composition may have excellent impact resistance, compatibility, and the like.

In embodiments, the modified polyolefin may be in the form of random, block, multi-block copolymers, or combinations thereof.

In embodiments, the modified polyolefin has a melt flow index, measured at 190 占 폚 and 2.16 kgf, of from about 0.01 to about 40 g / 10 minutes, such as from about 0.1 to about 10 g / 10 minutes, according to ASTM D1238 .

In an embodiment, the modified polyol pine (C) may be included in an amount of about 0.1 to about 20 parts by weight, for example about 1 to about 10 parts by weight, relative to about 100 parts by weight of the polycarbonate resin (A). When the content of the modified polyolefin is less than about 0.1 part by weight, the impact resistance and the like of the thermoplastic resin composition may be deteriorated. When the content is more than about 20 parts by weight, rigidity and the like may be lowered.

In embodiments, the weight ratio (B: C) of the mica (B) and the modified polyolefin (C) is from about 3: about 1 to about 40: about 1, such as about 4: about 1 to about 30: Lt; / RTI > Within the above range, the impact resistance, rigidity, balance of physical properties and the like of the thermoplastic resin composition may be more excellent.

(D) Phosphorous flame retardant

The phosphorus-based flame retardant according to one embodiment of the present invention may be a phosphorus-based flame retardant used in a conventional thermoplastic resin composition. For example, a phosphorus flame retardant such as a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a phosphazene compound, Can be used. These may be used alone or in combination of two or more.

In an embodiment, the phosphorus flame retardant may include an aromatic phosphate ester compound (phosphate compound) represented by the following formula (3).

(3)

Wherein R ₁ , R ₂ , R ₄ and R ₅ are each independently a hydrogen atom, a C 6 -C 20 (C 6 -C 20) aryl group, or a C 6 -C 20 aryl R ₃ is a C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group such as resorcinol, hydroquinone, bisphenol-A, and bisphenol- And n is an integer of 0 to 10, for example, 0 to 4.

When n is 0, the aromatic phosphoric acid ester compound represented by the formula (1) may be a diaryl phosphate such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, triazylenyl phosphate, tri (2,6-dimethyl (2,4,6-trimethylphenyl) phosphate, tri (2,4,6-trimethylphenyl) phosphate, tri (2,4,6-trimethylphenyl) phosphate, Bis (2,6-dimethylphenyl) phosphate], resorcinol bis [bis (2,4,6-trimethylphenyl) phosphate] (2,4-ditertiary butylphenyl) phosphate], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], and hydroquinone bis [bis Oligomer type phosphoric acid ester-based compound having 2 or more It is not limited. They may be applied alone or in the form of a mixture of two or more.

In an embodiment, the phosphorus flame retardant (D) may be included in about 3 to about 20 parts by weight, for example about 5 to about 15 parts by weight, relative to about 100 parts by weight of the polycarbonate resin (A). When the content of the modified polyolefin is less than about 3 parts by weight, the flame retardancy and the like of the thermoplastic resin composition may be deteriorated. When the content is more than about 20 parts by weight, heat resistance and the like may be lowered.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition. Examples of the additives include, but are not limited to, antioxidants, lubricants, fillers, mold release agents, nucleating agents, stabilizers, pigments, dyes, and mixtures thereof. When the additives are used, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, relative to about 100 parts by weight of the polycarbonate resin.

The thermoplastic resin composition according to one embodiment of the present invention is prepared by mixing the above components and melt-extruding at a temperature of about 200 to about 280 캜, for example, about 220 to about 250 캜, using a conventional twin-screw extruder. .

In embodiments, the thermoplastic resin composition may have a notched Izod impact strength of from about 3 to about 30 kgf · cm / cm, for example, from about 3.2 to about 20 kgf / cm 2, as measured in accordance with ASTM D256-10e1, Cm / cm.

In an embodiment, the thermoplastic resin composition has a flexural modulus of about 60,000 to about 90,000 kgf / cm ² , such as about 60,000 to about 90,000 kgf / cm ² , measured at a speed of 2.8 mm / min using a 6.4 mm thick specimen according to ASTM D790 About 85,000 kgf / cm < ² >.

In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 or more of a 1.5 mm thick specimen measured by the UL-94 vertical test method.

In the specific example, the thermoplastic resin composition is injection-molded from a spiral mold having a thickness of 2 mm at a molding temperature of 260 캜, a mold temperature of 60 캜, an injection pressure of 1,500 kgf / cm ² and an injection speed of 120 mm / Then the spiral flow length of the measured specimen may be from about 250 to about 300 mm, for example from about 265 to about 290 mm.

The molded article according to the present invention is formed from the thermoplastic resin composition. For example, the thermoplastic resin composition can be produced from the thermoplastic resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded articles are excellent in impact resistance, rigidity, flame retardancy, fluidity, and balance of physical properties thereof, and thus are useful as interior / exterior materials for electric and electronic products. In particular, it can be used for interior / exterior materials such as mobile phones and notebooks.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

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

(A) Polycarbonate resin

A bisphenol-A type polycarbonate resin having a weight average molecular weight (Mw) of 25,000 g / mol (manufacturer: Lotte Hidan material, product name: SC-1190) was used.

(B) inorganic filler

(Trade name: imerys, product name: SUZORITE 150PO) surface-treated with (B1) silane compound (? -Glycidoxypropyltrimethoxysilane) was used.

(B2) talc (manufacturer: Imerys minerals, product name: Luzenac ST30) was used.

(B3) A surface-treated mica (manufacturer: imerys, product name: SUZORITE 150S) was used.

(C) Impact modifier

(C1) modified polyolefin (ethylene / alkyl (meth) acrylate copolymer, manufacturer: DuPont, product name: Elvaloy AC1330) was used.

(C2) 45% by weight of styrene and 55% by weight of acrylonitrile (weight ratio: 75/25) were graft-copolymerized with polybutadiene rubber (PBR) having an average particle size (Z- Were used.

(D) Flame retardant

Bisphenol-A diphosphate (manufactured by Yoke Chemical, product name: BDP) was used.

Example  1 to 5 and Comparative Example  1 to 7

The above components were added in the amounts shown in Tables 1 and 2, and then extruded at 240 ° C to prepare pellets. The pellets were extruded at a temperature of 230 ° C. and a mold temperature of 60 ° C. in a 6 Oz extruder at a temperature of 80 ° C. for 3 hours or more, . The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.

How to measure property

(1) Impact resistance evaluation: Notch Izod impact strength (unit: kgf · cm / cm) of a 1/8 "thick specimen was measured according to ASTM D256-10e1.

(2) Stiffness evaluation: The flexural modulus (unit: kgf / cm ² ) of the 6.4 mm thick specimen was measured at a rate of 2.8 mm / min according to ASTM D790.

(3) Evaluation of flame retardancy: The flame retardancy of a 1.5 mm thick specimen was measured according to UL-94 vertical test method.

(4) Evaluation of fluidity: After injection molding in a spiral mold having a thickness of 2 mm at a molding temperature of 260 캜, a mold temperature of 60 캜, an injection pressure of 1,500 kgf / cm ² and an injection speed of 120 mm / The spiral flow length (unit: mm) of the spiral flow was measured.

		Example
		One	2	3	4	5
(A) (parts by weight)		100	100	100	100	100
(B) (parts by weight)	(B1)	40	43	43	35	55
	(B2)	-	-	-	-	-
	(B3)	-	-	-	-	-
	(B4)	-	-	-	-	-
(C) (parts by weight)	(C1)	One	5	10	5	5
	(C2)	-	-	-	-	-
(D) (parts by weight)		12	12	12	12	12
Notch Izod strength		3.7	5.2	6.8	5.6	3.2
Flexural modulus		70,000	69,000	68,000	60,000	85,000
Flame retardancy		V-0	V-0	V-0	V-0	V-0
Spiral flow length		265	275	280	282	265

		Comparative Example
		One	2	3	4	5	6	7
(A) (parts by weight)		100	100	100	100	100	100	100
(B) (parts by weight)	(B1)	-	-	43	15	65	43	43
	(B2)	43	-	-	-	-	-	-
	(B3)	-	43	-	-	-	-	-
(C) (parts by weight)	(C1)	5	5	-	5	5	0.05	22
	(C2)	-	-	5	-	-	-	-
(D) (parts by weight)		12	12	12	12	12	12	12
Notch Izod strength		2.8	2.5	2.3	5.2	2.1	2.9	13
Flexural modulus		59000	69000	68,000	30,000	97,000	68,000	49,000
Flammability (1.5 mm)		V-0	V-0	V-0	V-0	V-0	V-0	fail
Spiral flow length		255	275	265	294	232	255	285

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in impact resistance, rigidity, flame retardancy, fluidity and the like.

On the other hand, in the case of Comparative Example 1 using talc B2 instead of the surface-treated mica B1 of the present invention, it was found that the impact resistance, rigidity and the like were lowered. Instead of the surface treated mica B1 of the present invention In the case of Comparative Example 2 using the non-surface treated mica (B3), it can be seen that the rigidity and the like are lowered. In the case of Comparative Example 3 using g-ABS (C2) instead of the modified polyolefin (C1) of the present invention, it is found that the impact resistance and the like are lowered. In the case of Comparative Example 4 using the lower limit of the mica (B1) of the present invention, it was found that the rigidity and the like were lowered. In Comparative Example 5, which was used in excess of the upper limit, the impact resistance, flowability and the like were lowered. In Comparative Example 6 using the modified polyolefin (C1) of the present invention for less than the lower limit, the impact resistance and the like were lowered. In Comparative Example 7, which was used in excess of the upper limit, rigidity and flame retardancy were found to be lowered.

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.

Claims (10)

1. About 100 parts by weight of a polycarbonate resin;

   About 20 to about 60 parts by weight of a mica surface-treated with a silane compound;

   About 0.1 to about 20 parts by weight of a modified polyolefin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); And

   About 3 to about 20 parts by weight of a phosphorus flame retardant;

   [Chemical Formula 1]

   

   (2)

   

   In Formula 2, R ₁ is a hydrogen atom or a methyl group, Y is -COOR ₂ (R ₂ is an alkyl group having 1 to 12 carbon atoms), a glycidyl-modified ester group, an arylate group, or a nitrile group.
2. The thermoplastic resin composition of claim 1, wherein the mica has an average particle size of about 60 to about 300 microns and an aspect ratio of about 50 to about 150 in cross-section.
3. The thermoplastic resin composition according to claim 1, wherein the modified olefin comprises about 50 to about 95% by weight of the repeating unit represented by the formula (1) and about 5 to about 50% by weight of the repeating unit represented by the formula (2) Composition.
4. The thermoplastic resin composition according to claim 1, wherein the phosphorus flame retardant comprises at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, and a phosphazene compound.
5. The thermoplastic resin composition of claim 1, wherein the weight ratio of the mica and the modified polyolefin is from about 3: 1 to about 40: 1.
6. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of 1/8 "thick specimen measured according to ASTM D256-10e1 of about 3 to about 30 kgf · cm / cm .
7. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flexural modulus of about 60,000 to about 90,000 kgf / cm ² measured at a speed of 2.8 mm / min using a 6.4 mm thick specimen according to ASTM D790 Thermoplastic resin composition.
8. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flame retardancy of V-0 or more of a 1.5 mm thick specimen measured by a UL-94 vertical test method.
9. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a spiral mold having a thickness of 2 mm at a molding temperature of 260 캜, a mold temperature of 60 캜, an injection pressure of 1,500 kgf / cm ² and an injection speed of 120 mm / Wherein the spiral flow length of the specimen after injection molding is from about 250 to about 300 mm.
10. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 9.