KR20130101695A - Transparent flame-retardant polycarbonate composition and article formed therefrom - Google Patents

Abstract

PURPOSE: A transparent flame retardant polycarbonate resin composition is provided to obtain excellent flame retardancy without loss of transparency, heat resistance, and impact resistance and to improve the ability to process molding. CONSTITUTION: A polycarbonate resin composition includes 100.0 parts by weight of a polycarbonate resin, 0.0001-0.15 parts by weight of a nitrate metal salt or a phosphate metal salt, 0.001-0.2 parts by weight of fluorinated sulfonic acid metal salt, and 0.2-6 parts by weight of a polysiloxane. The metal nitrate is represented by chemical formula 1: M^1(NO3)n, where M^1 is an alkali metal or an alkaline earth metal and n is 1 or 2. The phosphate metal sat is represented by chemical formula 2: M^2_x H_y (PO4)_z, where M^2 is an alkali metal or an alkaline earth metal, x is 1or 2, y is an integer from 0-2, z is 1 or 2, and x+y+z is 2<=x+y+z<=6.

Description

Transparent flame retardant polycarbonate resin composition and article formed therefrom {TRANSPARENT FLAME-RETARDANT POLYCARBONATE COMPOSITION AND ARTICLE FORMED THEREFROM}

The present invention relates to a transparent flame retardant polycarbonate resin composition and an article formed therefrom.

In general, polycarbonate resins are excellent in impact resistance, heat resistance and electrical insulation, and have high transparency, and are widely used not only for interior and exterior materials of electric and electronic products, automotive interior and exterior parts, but also for optical products requiring high transparency. However, since the flame retardant grade for injection and extrusion moldings is indispensable in recent years, it is necessary to prepare for this.

Polycarbonate resins by themselves have a V2 flame retardant rating of UL-94. However, halogen-based flame retardants have conventionally been added to polycarbonate resins to impart not only higher grades of flame retardancy, but also superior flame retardancy even at thin thicknesses. However, the restriction on the use of halogen flame retardants has been strengthened due to the human hazards of gases generated during combustion. In Europe, in particular, there are significant restrictions on imports, and overall restrictions on small interior and exterior products are expected in the future.

Therefore, instead of the halogen flame retardant, a polycarbonate resin is flame retarded using a phosphate ester flame retardant such as triphenol phosphate (TPP), lysosinol bis diphenyl phosphate (RDP), or bisphenol A bis diphenol phosphate (BDP). There is a case. However, in order to obtain a polycarbonate resin having a flame retardant grade of V0 class according to the UL-94 standard using a phosphate ester flame retardant, the amount of the phosphate ester flame retardant added should be 10% by weight relative to the total weight of the resin composition. However, when an excessive amount of the phosphate ester flame retardant is added, deterioration of physical properties such as heat resistance and transparency of the polycarbonate resin is caused, extrusion workability is lowered, and there is a problem of environmental pollution due to phosphorus (P).

Therefore, in recent years, in order to provide high heat resistance and flame retardance without using a halogen flame retardant and a phosphate ester flame retardant, sulfonic acid metal salts may be added to polycarbonate resin. When using a sulfonic acid-based metal salt in a small amount of about 0.5% by weight or less relative to the total weight of the resin composition to prepare a molding having a thickness of about 3 mm, it is known that the flame retardant grade according to the UL-94 standard of the manufactured molding is V0. have. However, when the thickness of the molding becomes thinner than 3 mm, it is known that the polycarbonate resin decomposes due to sulfonic acid-based metal salts, so that the mechanical properties of the resin composition are lowered and the flame retardancy is also lowered.

Based on these problems, a technique of using a silicone compound as a method for obtaining excellent flame retardancy and heat resistance while maintaining transparency is known. However, even in this case, it is difficult to exhibit excellent flame retardancy in a molded article having a thickness of about 2 mm, it is difficult to obtain a good transparent flame retardant product because it is difficult to obtain excellent permeability because haze (turbidity) occurs when an excessive amount is added.

The present invention is to provide a polycarbonate resin composition having excellent flame retardancy and molding processability without deterioration of physical properties such as transparency, heat resistance, impact resistance and the like.

The present invention (a) 100 parts by weight of polycarbonate resin; (b) 0.0001 to 0.15 parts by weight of a metal nitrate salt or a metal phosphate salt; (c) 0.001 to 0.2 parts by weight of fluorinated sulfonic acid metal salt; And (d) provides a transparent flame retardant polycarbonate resin composition comprising 0.2 to 6 parts by weight of polysiloxane.

The present invention also provides an article formed of the transparent flame retardant polycarbonate resin composition described above.

The transparent flame retardant polycarbonate resin composition of the present invention includes a metal nitrate or a metal phosphate salt together with a polycarbonate resin, a fluorinated sulfonic acid metal salt and a polysiloxane, and by controlling the content thereof, excellent transparency, heat resistance, impact resistance and the like without deterioration in physical properties The flame retardancy can be exhibited and the molding processability can be improved to produce various types of articles.

Hereinafter, the present invention will be described in detail.

The present invention relates to a transparent flame retardant polycarbonate resin composition, including a polycarbonate resin, a fluorinated sulfonic acid metal salt and a polysiloxane, and characterized in that the metal nitrate salt or metal phosphate salt is controlled, and the content of each component is controlled to a specific range. Such a transparent flame retardant polycarbonate resin composition can improve flame retardancy without deteriorating transparency, and also has excellent heat resistance due to a high heat deformation temperature of about 127 to 135 ° C., and also has excellent impact resistance and molding processability. Therefore, in the case of the article formed of the transparent flame retardant polycarbonate resin composition of the present invention, even if the thickness is about 0.8 mm thin, the flame retardancy grade according to the UL-94 standard is excellent in flame retardancy of V0 grade regardless of the direction of the molded article, and the transparency Excellent and further thermally stable.

(a) polycarbonate resin

The transparent flame retardant polycarbonate resin composition of the present invention comprises a polycarbonate resin. The polycarbonate resin is a thermoplastic resin prepared by reacting diphenols with phosgene or carbonate diester. Since the polycarbonate resin is amorphous, the polycarbonate resin is transparent, has high mechanical strength, excellent heat resistance, electrical insulation, and high impact strength. In addition, the engineering plastics are very resistant to environmental changes due to the extremely small dimensional change due to moisture absorption and stable physical properties due to temperature changes.

Examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxy Phenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis -(3,5-dichloro-4-hydroxyphenyl) -propane and the like, which can be used alone or in combination of two or more. According to an example of the present invention, when 2,2-bis- (4-hydroxyphenyl) -propane is used, bisphenol A polycarbonate can be prepared.

The weight average molecular weight of the polycarbonate resin is not particularly limited, but when it is in the range of about 10,000 to 50,000, preferably in the range of about 15,000 to 25,000, heat resistance, drip prevention property and molding processability are more excellent.

(b) metal nitrates or metal phosphates

The transparent flame retardant polycarbonate resin of the present invention includes a metal nitrate salt or a metal phosphate salt. The metal nitrate salt or metal phosphate salt may be reacted with the following fluorinated sulfonic acid metal salt and polysiloxane during molding of the polycarbonate resin composition in a small amount to improve drip prevention properties in a flame retardancy test without deterioration of transparency.

The content of the metal nitrate salt or metal phosphate salt is preferably in the range of about 0.0001 to 0.15 parts by weight based on 100 parts by weight of the polycarbonate resin. If the content of the metal nitrate or the metal phosphate salt is less than about 0.0001 parts by weight, it may not increase the anti-drip property of the flame retardancy, and when the content of the metal nitrate salt or the metal phosphate is greater than about 0.15 parts by weight, it may cause a large amount of gas generation and decomposition of the polycarbonate resin. As a result, the molding process itself may become difficult.

Examples of the metal nitrate salts usable in the present invention include metal nitrate salts represented by the following Chemical Formula 1, but are not limited thereto.

In Formula 1,

M ¹ is a metal selected from the group consisting of alkali metals and alkaline earth metals, preferably sodium (Na), potassium (K), magnesium (Mg) or calcium (Ca) and the like,

n is the valence of M ¹ and is an integer of 1 or 2.

Examples of the metal nitrate salt represented by Formula 1 include potassium nitrate (KNO ₃ ), sodium nitrate (Na (NO ₃ )), calcium nitrate (Ca (NO ₃ ) ₂ ), magnesium nitrate (Mg (NO ₃ ) ₂ ), and the like. There is, but is not limited to this.

Examples of the metal phosphate salt that can be used in the present invention include a metal phosphate salt represented by the following Chemical Formula 2, but is not limited thereto.

In Formula 2,

M ² is a metal selected from the group consisting of alkali metals and alkaline earth metals, preferably sodium (Na), potassium (K), magnesium (Mg), calcium (Ca) and the like,

x is an integer of 1 or 2,

y is an integer from 0 to 2,

z is an integer of 1 or 2,

x + y + z is 2 ≦ x + y + z ≦ 6.

Non-limiting examples of the metal phosphate salt represented by Formula 2 include sodium dihydrogen phosphate (NaH ₂ PO ₄ ), disodium hydrogen phosphate (Na ₂ HPO ₄ ), trisodium phosphate (Na ₃ PO ₄ ), and the like. phosphate; Potassium phosphates such as potassium dihydrogen phosphate (NaH ₂ PO ₄ ), dipotassium hydrogen phosphate (Na ₂ HPO ₄ ), tripotassium phosphate (Na ₃ PO ₄ ); Calcium phosphates such as calcium dihydrogen phosphate (CaH ₂ PO ₄ ), dicalcium hydrogen phosphate (Ca ₂ HPO ₄ ), tricalcium phosphate (Ca ₃ PO ₄ ); Magnesium phosphate such as magnesium dihydrogen phosphate (MgH ₂ PO ₄ ), dipotassium hydrogen phosphate (Mg ₂ HPO ₄ ), tripotassium phosphate (Mg ₃ PO ₄ ), and the like.

(c) fluorinated sulfonic acid metal salts

The transparent flame retardant polycarbonate resin composition of the present invention contains a fluorinated sulfonic acid metal salt. The fluorinated sulfonic acid metal salt may react with the metal nitrate salt or metal phosphate salt during molding of the resin composition, thereby improving flame retardancy of the polycarbonate resin composition without decomposition of the polycarbonate resin, and further improving heat resistance and impact resistance.

Examples of the fluorinated sulfonic acid metal salt include a compound represented by the following Chemical Formula 3, but are not limited thereto.

In Formula 3,

M ³ is a metal selected from the group consisting of alkali metals and alkaline earth metals, preferably potassium (K), sodium (Na), calcium (Ca), magnesium (Mg) and the like,

p is an integer of 1 to 4,

q is the valence of M ³ and is 1 or 2.

Non-limiting examples of the fluorinated sulfonic acid metal salt represented by Formula 3 include potassium perfluorobutane sulfonate.

The content of such fluorinated sulfonic acid metal salt is preferably in the range of about 0.001 to 0.2 parts by weight based on 100 parts by weight of the polycarbonate resin. If the content of the fluorinated sulfonic acid metal salt is less than about 0.001, the flame retardancy may not be expressed, and when the content of the fluorinated sulfonic acid metal salt is greater than about 0.2 part by weight, the desired properties may not be satisfied due to decomposition of the polycarbonate resin and an increase in turbidity.

(d) polysiloxanes

The transparent flame retardant polycarbonate resin composition of the present invention contains polysiloxane. The polysiloxane may react with the metal nitrate salt or metal phosphate salt during molding of the resin composition to improve flame retardancy and heat resistance.

Examples of the polysiloxane include poly (methylphenyl) siloxane, poly (diphenyl) siloxane, dimethylsiloxane-diphenylsiloxane, copolymers of dimethylsiloxane-methylphenylsiloxane, and the like, but are not limited thereto.

The content of such polysiloxane is preferably about 0.2 to 6 parts by weight based on 100 parts by weight of polycarbonate resin. If the content of the polysiloxane is less than about 0.2 part by weight, the flame retardancy of the polycarbonate resin composition may be lowered, while when the content of the polysiloxane is greater than 6 parts by weight, turbidity may increase and physical properties may be impaired.

The transparent flame retardant polycarbonate resin composition of the present invention, in addition to the above-described components, antioxidants, heat stabilizers, ultraviolet stabilizers, anti-drip agents, if necessary, so long as the properties of the resin composition, such as flame retardancy, transparency, heat resistance, impact resistance, etc. It may further include additives such as antistatic agents, pigments and dyes. These additives may be added to the composition in amounts known in the art.

The flame retardant resin composition of the present invention can be obtained according to a general method for producing a resin composition known in the art. For example, the resin composition of the present invention is a polycarbonate resin described above; Metal nitrate salts or metal phosphate salts; Fluorinated sulfonic acid metal salts; And polysiloxanes are sufficiently mixed using premixing means such as a V-type blender, a mechanochemical device, an extrusion mixer, etc., and then granulated by an extrusion granulator or a briquetting machine, if necessary, and then melted with a melt kneader. It may be kneaded and then produced in pellet form by an apparatus such as a pelletizer.

On the other hand, the present invention can be produced articles of various forms using the above-described transparent flame-retardant polycarbonate resin composition. The thickness of the article is appropriately adjusted according to the use of the article. However, even if the thickness of the article is as thin as about 0.8 mm, the flame retardant grade according to the UL-94 standard is V0 class, regardless of the direction, excellent flame retardancy.

The method for producing an article formed of the transparent flame retardant polycarbonate resin composition is not particularly limited, and various molding methods known in the art, such as injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, and the like may be used. Can be.

Hereinafter, the present invention will be described in more detail. These examples are only for illustrating the present invention in more detail, it is apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

&Lt; Example 1 >

100 parts by weight of a polycarbonate resin of bisphenol A type (weight average molecular weight: 25,000), 0.002 parts by weight of potassium nitrate (KNO ₃ ), 0.1 part by weight of potassium perfluorobutane sulfonate, and 3 parts by weight of poly (methylphenyl) siloxane A transparent flame retardant polycarbonate resin composition was prepared.

<Example 2> to <Example 14> and <Comparative Example 1> to <Comparative Example 2>

As described in Table 1, except that the content of polycarbonate resin ('PC'), potassium nitrate, potassium perfluorobutane sulfonate ('KFBS') and poly (methylphenyl) siloxane of bisphenol A type was changed. In the same manner as in Example 1, a transparent flame retardant polycarbonate resin composition was prepared in pellet form.

PC
(Parts by weight) Potassium Nitrate
(Parts by weight) KFBS
(Parts by weight) Poly (methylphenyl) siloxane
(Parts by weight) Example 1 100 0.002 0.1 3 Example 2 100 0.001 0.1 3 Example 3 100 0.0005 0.1 3 Example 4 100 0.0001 0.1 3 Example 5 100 0.0002 0.1 3 Example 6 100 0.0002 0.1 2 Example 7 100 0.0002 0.1 One Example 8 101 0.0002 0.1 0.5 Example 9 103 0.0002 0.08 3 Example 10 104 0.0002 0.08 2 Example 11 105 0.0002 0.08 One Example 12 106 0.0002 0.08 0.5 Comparative Example 1 100 0.00005 0.1 3 Comparative Example 2 102 0.0002 0.1 0.3 Comparative Example 3 107 0.0002 0.08 0.3

< Comparative example  4> to < Comparative example  5>

Polytetrafluoroethylene ('PTFE') was used in place of the potassium nitrate used in Example 1, and as described in Table 2 below, a bicarbonate polycarbonate resin ('PC') and polytetrafluoroethylene (' PTFE '), potassium perfluorobutane sulfonate (' KFBS ') and poly (methylphenyl) siloxane, except that the content of the flame retardant polycarbonate resin composition in the same manner as in Example 1 Prepared.

PC
(Parts by weight) PTFE
(Parts by weight) KFBS
(Parts by weight) Poly (methylphenyl) siloxane
(Parts by weight) Comparative Example 4 100 0.2 0.5 5 Comparative Example 5 100 0.1 0.5 5 Comparative Example 6 100 0.05 0.5 5 Comparative Example 7 100 0.2 0.25 5 Comparative Example 8 100 0.1 0.25 5 Comparative Example 9 100 0.05 0.25 5 Comparative Example 10 100 0 0.08 5 Comparative Example 11 100 0 0.08 8 Comparative Example 12 100 0 0.08 10 Comparative Example 13 100 0 0.1 5 Comparative Example 14 100 0 0.1 8 Comparative Example 15 100 0 0.1 10

< Experimental Example  1>-property evaluation

The pellet-shaped polycarbonate resin composition obtained in Examples 1 to 15 and Comparative Examples 1 to 12, respectively, was extruded using a twin screw extruder (L / D = 35, Φ = 45 mm) to prepare pellet-shaped specimens. The physical properties of each of the prepared specimens were measured as follows, and the results are shown in Table 3 below.

(1) Haze

When light was incident on the surface of a specimen having a thickness of 1.5 mm using a C-light source, a haze value expressed as a ratio (%) of scattered light to incident light was measured. At this time, the lower the number of haze indicates that the transparency is excellent.

(2) Izod impact strength

The Izod impact strength (kgf · cm / cm) of the specimen having a thickness of 1/8 ”was measured according to ASTM D256.

(3) heat deflection temperature

According to ASTM D648 conditions, the heat deflection temperature was measured for each specimen of 1/4 inch thickness at a load of 18.6 Kg.

(4) Flammability

Flame retardancy of the 1.5 mm thick specimen was measured according to the UL94 standard.

Haze (%) Izod impact strength (kgfcm / cm) Heat deformation temperature (캜) Flame retardant (grade) Example 1 1.43 88 128.4 V-0 Example 2 1.16 89 128.6 V-0 Example 3 1.08 89 128.3 V-0 Example 4 0.94 88 128.7 V-0 Example 5 1.12 88 127.9 V-0 Example 6 1.06 89 129.2 V-0 Example 7 1.08 90 130.4 V-0 Example 8 0.98 90 131.8 V-0 Example 9 1.08 89 128.4 V-0 Example 10 1.02 90 130.4 V-0 Example 11 0.99 90 131.2 V-0 Example 12 0.84 89 131.8 V-0 Comparative Example 1 0.92 90 128.3 V-1 Comparative Example 2 0.85 90 131.9 V-1 Comparative Example 3 0.78 90 132.2 V-1 Comparative Example 4 12.42 55 122.6 V-0 Comparative Example 5 8.73 58 123.5 V-0 Comparative Example 6 4.82 52 124.2 V-0 Comparative Example 7 11.67 62 123.8 V-0 Comparative Example 8 7.34 64 124.3 V-0 Comparative Example 9 3.38 60 125.4 V-0 Comparative Example 10 1.85 72 124.5 V-0 Comparative Example 11 2.34 68 124.6 V-0 Comparative Example 12 3.16 70 123.5 V-0 Comparative Example 13 2.05 68 124.7 V-0 Comparative Example 14 2.56 72 124.1 V-0 Comparative Example 15 3.28 71 123.4 V-0

As can be seen in Table 3, the polycarbonate resin composition of Examples 1 to 12 including a polycarbonate resin, a fluorinated sulfonic acid metal salt, a polysiloxane, and a metal nitrate salt or a metal phosphate salt according to the present invention is a conventional polycarbonate resin composition ( Unlike Comparative Examples 4 to 15), while the flame resistance was improved, the transparency and the impact resistance were improved, and the heat deformation temperature was also improved. In particular, the polycarbonate resin compositions of Examples 1 to 12 were significantly higher in transparency than the resin compositions of Comparative Examples 4 to 9 containing polytetrafluoroethylene instead of metal nitrate salts.

In addition, the resin composition (Examples 1 to 12) in which the content of each component is adjusted to a specific range according to the present invention contains a polycarbonate resin composition or polysiloxane of Comparative Example 1 containing a metal nitrate salt outside the content range. In contrast to the polycarbonate resin compositions of Comparative Examples 2 and 3 included outside the range, the flame retardancy was improved.

Claims (4)

(a) 100 parts by weight of polycarbonate resin;
(b) 0.0001 to 0.15 parts by weight of metal nitrate salt or metal phosphate salt;
(c) 0.001 to 0.2 parts by weight of fluorinated sulfonic acid metal salt; And
(d) 0.2 to 6 parts by weight of polysiloxane
Transparent flame retardant polycarbonate resin composition comprising a. The transparent flame retardant polycarbonate resin composition according to claim 1, wherein the metal nitrate salt is represented by the following Chemical Formula 1:
[Formula 1]

(In Formula 1,
M ¹ is an alkali metal or alkaline earth metal,
n is an integer of 1 or 2). The transparent flame retardant polycarbonate resin composition according to claim 1, wherein the metal phosphate salt is represented by the following Chemical Formula 2:
(2)

(In the formula (2)
M ² is an alkali metal or alkaline earth metal,
x is an integer of 1 or 2,
y is an integer from 0 to 2,
z is an integer of 1 or 2,
x + y + z is 2 ≦ x + y + z ≦ 6. The article formed from the transparent flame-retardant polycarbonate resin composition in any one of Claims 1-3.