KR20070070326A - Polycarbonate resin composition with good transparence and flame retardancy - Google Patents

Abstract

Provided is a polycarbonate resin composition, which has excellent transparency and flame resistance while maintaining physical properties including mechanical strength and impact resistance. The polycarbonate resin composition comprises: (A) 100 parts by weight of a thermoplastic polycarbonate resin; (B) 0.01-5 parts by weight of a metal salt of an aromatic sulfone compound; and (C) 0.01-1 parts by weight of a metal salt of a perfluoroalkane sulfonic acid. The metal salt of an aromatic sulfone compound includes a metal salt of an aromatic sulfonamide or a metal salt of an aromatic sulfonic acid.

Description

Polycarbonate Resin Composition with Good Transparence and Flame Retardancy

Field of invention

The present invention relates to a polycarbonate thermoplastic resin excellent in transparency and flame retardancy. More specifically, the present invention comprises a polycarbonate resin, a metal salt of an aromatic sulfone compound, and a metal salt of perfluoroalkanesulfonic acid, and has excellent transparency and flame retardancy without deteriorating physical properties such as mechanical strength and impact resistance. It relates to a composition.

Background of the Invention

Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and electrical properties, and is applied to large-sized injection-molded materials such as electric, electronic and other office equipment. Therefore, flame retardancy and high mechanical strength should be maintained. In addition, there is an increasing demand for resins that do not contain halogen-based flame retardants because of the technology that can satisfy the flame retardancy while maintaining the transparency of the polycarbonate, and the human hazard of the gas generated during combustion.

In order to impart flame retardancy to such a transparent aromatic polycarbonate, a mixture of a fluorinated ethylene resin with a metal salt flame retardant and a halogen flame retardant has been conventionally used. However, fluorinated ethylene-based resins and metal salt-based flame retardants used to secure flame retardancy of polycarbonate resins have caused a decrease in transparency, which is one of the advantages of polycarbonate.

In order to overcome such a drop in transparency, alloys with silicone-based additives and silicone-based copolymers are commonly used. As an example of using silicone-based additives, US Pat. No. 4,954,549 discloses UL94 V-0 flame retardancy of 1/16 "thick specimens by mixing tri-aryl-silicone materials with polycarbonate resins.

U.S. Patent No. 5,955,542 discloses that a flame retardant additive composed of a copolymer of an aryl group-containing silicone composition and a diorganic polysiloxane composition enhances the flame retardancy of a resin composed of an aromatic component.

US Pat. Nos. 6,284,824 and 6,326,425 disclose the effect of maintaining transparency and increasing flame retardancy of polycarbonate resins containing organopolysiloxane.

In addition, US Pat. No. 5,187,243 discloses a result of securing both flame retardancy and mechanical properties through an alloy of an aryl-siloxane polymer and a polycarbonate as an example of an alloy with a silicone copolymer.

However, the patents using the silicone-based additives or copolymers listed above are classified as non-halogen flame retardants and have an advantage of being environmentally friendly. However, they have disadvantages such as reduced transparency, relatively high cost, and limited implementation of various colors when used as exterior materials. .

In order to solve the above problems, the present inventors add a metal salt of an aromatic sulfone compound, which is a non-halogen flame retardant, and a metal salt of perfluoroalkanesulfonic acid, to the polycarbonate resin, thereby reducing transparency, impact resistance, and mechanical strength without deterioration. And to develop a polycarbonate resin composition excellent in flame retardancy.

An object of the present invention is to provide a polycarbonate resin composition excellent in transparency.

Another object of the present invention is to provide a polycarbonate resin composition excellent in flame retardancy.

Still another object of the present invention is to provide a polycarbonate resin composition having excellent transparency and flame retardancy while maintaining a balance of physical properties such as mechanical strength, heat resistance, impact resistance, thermal stability, workability and appearance characteristics.

Still another object of the present invention is to provide a polycarbonate resin composition which does not generate halogen gas at the time of combustion and is excellent in environment-friendly transparency and flame retardancy.

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

Summary of the Invention

Polycarbonate resin composition excellent in transparency and flame retardancy according to the present invention (A) 100 parts by weight of a thermoplastic polycarbonate resin; (B) 0.01 to 5 parts by weight of a metal salt of an aromatic sulfone compound; And (C) 0.01 to 1 part by weight of a metal salt of perfluoroalkanesulfonic acid.

Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

(A) polycarbonate resin

The aromatic polycarbonate resin used in the present invention is prepared by reacting diphenols represented by the following formula (1) with phosgene, halogen formate or carbonic acid diester.

[Formula 1]

Wherein A represents a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cyclo alkylidene, -S- or -SO _2- .

Specific examples of the diphenol represented by the formula (1) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl ) -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 etc. are mentioned.

In the specific examples of the diphenol, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1- Bis- (4-hydroxyphenyl) -cyclohexane and the like are preferred, and the most widely used aromatic polycarbonates are prepared from 2,2-bis- (4-hydroxyphenyl) -propane, also called bisphenol-A. Most preferably.

The weight average molecular weight of the polycarbonate suitable for producing the resin composition of the present invention is 10,000 to 500,000, particularly preferably 15,000 to 100,000.

As the polycarbonate resin of the present invention, a branched chain may be used, and preferably 0.05 to 2 mol% of a trivalent or more polyfunctional compound, for example, trivalent or higher, based on the total amount of diphenols used for polymerization. It can be prepared by adding a compound having more phenol groups.

Examples of the polycarbonate used in the production of the resin composition of the present invention include homo-polycarbonates and co-polycarbonates, and may also be used in the form of a blend of co-polycarbonates and homo-polycarbonates.

In addition, the polycarbonate of the present invention may be partially or wholly replaced by an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a bifunctional carboxylic acid.

In the polycarbonate resin composition having excellent transparency and flame retardancy according to the present invention, the other components are mixed based on 100 parts by weight of the (A) polycarbonate resin.

(B) metal salts of aromatic sulfone compounds

Examples of the metal salt of the aromatic sulfone compound used in the resin composition according to the present invention include a metal salt of aromatic sulfonamide represented by the following Chemical Formula 2 or 3, or a metal salt of aromatic sulfonic acid represented by the following Chemical Formula 4:

[Formula 2]

(Wherein Ar represents a phenyl group or an alkyl-substituted phenyl group and M represents a metal cation);

[Formula 3]

(Wherein Ar represents a phenyl group or an alkyl-substituted phenyl group, R ₃ represents an organic group which may contain a sulfonyl group or a carbonyl group, or Ar may bond with R _3, and M represents a metal cation);

[Formula 4]

(Wherein R ₄ and R ₅ are the same or independently of each other, a C ₁ -C ₆ aliphatic group, a phenyl group, a biphenyl group or an alkyl substituted phenyl group, x is 0 or an integer of 1 to 6, y is 1 to 6 Is an integer having a value of M represents a metal cation).

Preferred examples of metal salts of aromatic sulfonamides used in the present invention include metal salts of saccharin, metal salts of N- (p-tolylsulfonyl) -p-toluenesulfoimide, and N- (N'-benzylaminocarbonyl) sulphates. Metal salts of panylimide and metal salts of N- (phenylcarboxyl) -sulfanimide.

Examples of the metal salt of aromatic sulfonic acid include metal salts of diphenyl sulfone-3-sulfonic acid, metal salts of diphenyl sulfone-3,3'-disulfonic acid, and metal salts of diphenyl sulfone-3,4'-disulfonic acid.

The metal salt of the aromatic sulfonamide and the metal salt of aromatic sulfonic acid may be used in combination of one kind or more. Suitable metals used at this time include metals of group I (alkali metals) such as sodium and potassium, metals of group II (alkaline earth metals), copper, aluminum, and the like, and alkali metals are particularly preferred.

Among the metal salts of the aromatic sulfonamides, potassium salts of N- (p-tolylsulfonyl) -p-toluenesulfoimide or potassium salts of N- (N'-benzylaminocarbonyl) sulfanimide are particularly preferable. Among the aromatic sulfonic acid metal salts, potassium salts of diphenylsulfone-3-sulfonic acid and potassium salts of diphenylsulfone-3,3'-disulfonic acid are particularly preferable.

As for the quantity of the metal salt (B) of the aromatic sulfone compound used for the polycarbonate resin composition excellent in transparency and flame retardance of this invention, 0.01-5 weight part is preferable. If an amount outside this range is used, the flame retardancy may significantly lower the transparency.

(C) metal salts of perfluoroalkanesulfonic acid

The metal salt of the perfluoroalkanesulfonic acid of the present invention has the structure of Formula 5:

[Formula 5]

(Wherein M is a metal cation and l represents an integer of 1 to 8).

Preferred examples of the metal salt of perfluoroalkanesulfonic acid include metal salts of perfluoromethanesulfonic acid, metal salts of perfluoroethanesulfonic acid, metal salts of perfluoropropanesulfonic acid, metal salts of perfluorobutanesulfonic acid, and metal salts of perfluoropentanesulfonic acid. And metal salts of perfluorohexane sulfonic acid, metal salts of perfluoroheptanesulfonic acid, metal salts of perfluorooctane sulfonic acid, and the like. You may use these in combination of 1 type or more.

Suitable metals used for the metal salt of perfluoroalkanesulfonic acid include metals of group I (alkali metals) such as sodium and potassium, metals of group II (alkaline earth metals), copper, aluminum, and the like. desirable. Among these, potassium salts of perfluorobutanesulfonic acid and potassium salts of perfluoropentanesulfonic acid are particularly preferable.

The amount of the metal salt (C) of perfluoroalkanesulfonic acid used in the polycarbonate resin composition excellent in transparency and flame retardancy of the present invention is preferably 0.01 to 1 part by weight. Using an amount outside this range may lower the flame retardancy.

In addition to the above components, the polycarbonate resin composition having excellent transparency and flame retardancy of the present invention may include general additives such as lubricants, mold release agents, stabilizers, inorganic additives, pigments, or dyes according to their respective uses. It can be used within the range of 0 to 5 parts by weight, preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of component (A).

The resin composition of this invention can be manufactured by a well-known method. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.

The compositions of the present invention can be used for the molding of various products, and are particularly suitable for the manufacture of housings and components for electrical and electronic products, which require transparency and flame retardancy while being injected at high temperatures.

The invention can be better understood through the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specifications of (A) polycarbonate resin, (B) metal salt of aromatic sulfone compound, and (C) metal salt of perfluoroalkanesulfonic acid used in the following examples and comparative examples are as follows.

(A) polycarbonate resin

As the component (a ₁ ), a bisphenol-A polycarbonate having a weight average molecular weight (Mw) of 25,000 was used.

As the component (a ₂ ), a bisphenol-A polycarbonate having a weight average molecular weight (Mw) of 20,000 was used.

(B) metal salts of aromatic sulfone compounds

Potassium salt of diphenylsulfone-3-sulfonic acid (trade name: KSS) of SEALSAND, USA was used.

(C) metal salts of perfluoroalkanesulfonic acid

Potassium salt (trade name: FR-2025) of 3M perfluorobutanesulfonic acid was used.

Examples 1-2

Each component, antioxidant and heat stabilizer shown in Table 1 were added thereto, mixed in a conventional mixer, extruded using a twin screw extruder having L / D = 35 and φ = 45 mm, and then the extrudate was pelleted. The specimens for physical property measurement, flame retardancy, and transparency evaluation were prepared using a 10 OZ injection machine at an injection temperature of 300 ° C.

Comparative Example 1

Preparation was carried out in the same manner as in Example 1, except that both the metal salt of (B) aromatic sulfone compound and the metal salt of (C) perfluoroalkanesulfonic acid were used.

Comparative Example 2

It carried out similarly to Example 2 except using only 5 weight part of metal salts of (B) aromatic sulfone compound, and not using the metal salt of (C) perfluoro alkanesulfonic acid.

Comparative Example 3

The same procedure as in Example 1 was carried out except that (B) 0.5 parts by weight of the metal salt of perfluoroalkanesulfonic acid was used without using the metal salt of the aromatic sulfone compound.

Comparative Example 4

It carried out similarly to Example 1 except having used 10 weight part of metal salts of (B) aromatic sulfone compound, and 2 weight part of metal salts of (C) perfluoro alkanesulfonic acid.

The specimens molded in Examples and Comparative Examples were left at 23 ° C. and 50% relative humidity for 24 hours, and then measured in the following manner according to ASTM standards.

(1) Hazeness and transparency were measured on a 3 mm thick specimen using a Haze Meter (YDPO2-0D) manufactured by NIPPON DENSHOKU.

(2) Flame retardancy was evaluated using a 1/8 inch thick specimen in accordance with UL-94.

From the results in Table 1, it can be seen that in Examples 1 and 2, in which an appropriate amount of a polycarbonate resin mixed with a metal salt of an aromatic sulfone compound and a metal salt of perfluoroalkanesulfonic acid, the flame retardancy of the resin composition was excellent while maintaining transparency. have. On the other hand, in Comparative Examples 1 to 3 in which the metal salt of the aromatic sulfone compound and the metal salt of the perfluoroalkanesulfonic acid are not mixed or used alone, the flame retardancy of the metal salt of the aromatic sulfone compound or the metal salt of the perfluoroalkanesulfonic acid alone is used. It can be seen that is significantly reduced. In addition, in the case of Comparative Example 4 in which the amount of the metal salt of the aromatic sulfone compound and the metal salt of the perfluoroalkanesulfonic acid exceeded an appropriate level, Hazeness and transparency were remarkably decreased.

The present invention is prepared by mixing a polycarbonate resin, a metal salt of an aromatic sulfone compound and a metal salt of perfluoroalkanesulfonic acid, thereby maintaining transparency while maintaining balance of physical properties such as mechanical strength, heat resistance, impact resistance, thermal stability, workability and appearance characteristics. And an environmentally friendly polycarbonate resin composition having excellent flame retardancy.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

(A) 100 parts by weight of thermoplastic polycarbonate resin; (B) 0.01 to 5 parts by weight of a metal salt of an aromatic sulfone compound; And (C) 0.01 to 1 part by weight of a metal salt of perfluoroalkanesulfonic acid; Polycarbonate resin composition excellent in transparency and flame retardance, characterized in that consisting of. The metal salt of the aromatic sulfone compound (B) is a metal salt of an aromatic sulfonamide having a structure of formula (2) or (3) below, or a metal salt of aromatic sulfonic acid having a structure of formula (4). And polycarbonate resin compositions having excellent flame retardancy: [Formula 2]

Wherein Ar represents a phenyl group or an alkyl substituted phenyl group, M represents a metal cation; [Formula 3]

Wherein Ar represents a phenyl group or an alkyl-substituted phenyl group, R ₃ represents an organic group which may contain a sulfonyl group or a carbonyl group, or Ar may combine with R _3, and M represents a metal cation; [Formula 4]

Wherein R ₄ and R ₅ are the same or independently of each other represent a C ₁ to C ₆ aliphatic group, a phenyl group, a biphenyl group or an alkyl-substituted phenyl group, x is an integer of 0 or 1 to 6, y is 1 to 6 An integer with a value, M represents a metal cation. The polycarbonate resin composition having excellent transparency and flame retardancy according to claim 1, wherein the metal salt of (C) perfluoroalkanesulfonic acid has a structure represented by Formula 5 below: [Formula 5]

Wherein M is a metal cation and l represents an integer from 1 to 8. The metal salt of aromatic sulfonamide is a metal salt of saccharin, a metal salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide, N- (N'-benzylaminocarbonyl) sulfanyl. The metal salt of the mead and the metal salt of N- (phenylcarboxyl) -sulfanimide, wherein the metal salt of the aromatic sulfonic acid is a metal salt of diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3'- A polycarbonate resin composition excellent in transparency and flame retardancy, characterized in that it is selected from the group consisting of a metal salt of disulfonic acid and a metal salt of diphenylsulfone-3,4'-disulfonic acid. The metal salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide is a potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfoimide, and said N- ( The metal salt of N'-benzylaminocarbonyl) sulfanimide is the potassium salt of N- (N'-benzylaminocarbonyl) sulfanimide, and the metal salt of diphenylsulfone-3-sulfonic acid is diphenylsulfone- It is a potassium salt of 3-sulfonic acid, and the metal salt of diphenylsulfone-3,3'-disulfonic acid is a potassium salt of diphenylsulfone-3,3'-disulfonic acid. Carbonate resin composition. The metal salt of perfluoroalkanesulfonic acid according to claim 3, wherein the metal salt of perfluoromethanesulfonic acid, metal salt of perfluoroethanesulfonic acid, metal salt of perfluoropropanesulfonic acid, metal salt of perfluorobutanesulfonic acid, and perfluoro A polycarbonate resin composition having excellent transparency and flame retardancy, wherein the polycarbonate resin composition is selected from the group consisting of metal salts of pentansulfonic acid, metal salts of perfluorohexanesulfonic acid, metal salts of perfluoroheptanesulfonic acid, and metal salts of perfluorooctane sulfonic acid. The metal salt of perfluorobutanesulfonic acid is the potassium salt of perfluorobutanesulfonic acid, and the metal salt of perfluoropentanesulfonic acid is the potassium salt of perfluoropentanesulfonic acid. Polycarbonate resin composition. A pellet extruded with the polycarbonate resin composition according to any one of claims 1 to 7.