KR20200058714A - Polycarbonate resin composition having chemical resistance and flame retardancy with transparency - Google Patents

Abstract

Disclosed is a flame-retardant resin composition which is excellent in transparency, thereby expressing a metallic color, is excellent in mechanical properties, thereby capable of being used as a housing material for electronic products, and has excellent chemical resistance to household chemicals (sunscreen, fragrance, and the like.) The present invention provides a chemical-resistant, flame-retardant polycarbonate resin composition, including: 60 to 80 wt% of polycarbonate resin; 10 to 30 wt% of polycyclohexylenedimethylene terephthalate resin; 5 to 15 wt% of phosphorus-based flame retardant; and 0.01 to 1 wt% of metal salt-based flame retardant.

Description

Flame retardant polycarbonate resin composition having excellent transparency {Polycarbonate resin composition having chemical resistance and flame retardancy with transparency}

The present invention relates to a polycarbonate resin composition, and more particularly, to a thermoplastic resin composition polycarbonate resin composition having excellent transparency, metal color expression can be improved, chemical resistance is improved, and flame retardancy is reinforced.

Polycarbonate resins are used for various purposes such as housing materials for electronic products due to their excellent characteristics such as impact resistance and heat resistance. However, there is a problem in that the appearance color is changed or cracks are generated and the product is deteriorated by female cosmetics, fragrances, and the like, which are commonly used on the market.

Polyester resins have excellent chemical resistance and mechanical strength, and thus, their use is increasing in the field of building interior materials or molded signage. However, the polyester resin has lower heat resistance than the polycarbonate-based material, and thus deterioration in physical properties and the like occurs due to changes in the surrounding environment, and thus, there is a problem in that it is not suitable for use alone in the housing material for electronic products.

Various attempts have been made to solve the problems of the polycarbonate resin or the polyester resin, and research on a method of blending the polycarbonate resin and the polyester resin has been continuously conducted.

In order to use for the housing application of electronic products, the resin composition must have flame retardancy, and both the polycarbonate resin and the polyester resin have a property of being easily burned. In addition, since the polycarbonate resin and the polyester resin have different melt viscosities and molecular structures, there are certain limitations in improving flame retardancy by simply blending them.

Accordingly, a flame retardant is used to impart flame retardancy to the resin composition. If a flame retardant is used in a high content to obtain high flame retardancy, dissolution of the flame retardant may occur and mechanical properties are remarkably deteriorated. In addition, when using an appropriate amount of a flame retardant, it is possible to realize flame retardancy, but the transparency of the composition is lowered, so there is a limitation in realizing metallic color.

Korean Patent Publication No. 2016-0075207 uses a polyester resin and a polycarbonate resin for the purpose of improving chemical resistance and mechanical properties for use as a housing material for electronic products, and additionally uses a phosphorus-based flame retardant to reinforce flame retardancy. Although it discloses a technology that secures flame retardancy of 0 (@ 3.0 mm), it exhibits insufficient flame retardancy for use in housing applications in actual electronic products, and does not mention metal color enhancement to improve transparency and appearance characteristics. There is a limit to its use.

Korean Patent Publication No. 2018-0067291 is a technology for a polymer resin composition having high flame retardant properties and insulation properties for use in electronics housing applications, and seeks to promote chemical resistance by blending polyester resins and polycarbonate resins. In order to reinforce the flame retardancy, a new bromine-based flame retardant (brominated polystyrene-based flame retardant) and antimony trioxide are used to achieve high flame retardancy of V-0 (@ 0.8 mm), but the use of bromine-based flame retardant and antimony trioxide is environmentally friendly. It does not accept the demand for it and does not mention improvement of transparency and appearance characteristics.

As such, there is a need for a technique for building an eco-friendly flame retardant system and improving appearance characteristics based on transparency.

The present invention provides a flame retardant resin composition excellent in transparency, capable of expressing a metallic color, excellent mechanical properties, and can be used as a housing material for electronic products, and excellent in chemical resistance to household chemicals (sun cream, fragrance, etc.) I want to.

In order to solve the above problems, the present invention, polycarbonate resin 60 to 80% by weight; 10 to 30% by weight of polycyclohexylenedimethylene terephthalate resin; Phosphorus flame retardant 5 to 15% by weight; And metal salt-based flame retardant 0.01 to 1% by weight; provides a chemical-resistant flame-retardant polycarbonate resin composition comprising a.

In addition, the phosphorus-based flame retardant provides a chemical-resistant flame retardant polycarbonate resin composition characterized in that it is bisphenol-A bis (diphenylphosphate).

In addition, the metal salt-based flame retardant is N- (p-trisulfonyl) -p-toluenesulfonamide, N- (N'-benzylaminocarbonyl) sulfonylamide, N- (phenylcarboxyl) -sulfonylamide, Diphenylsulfone-3-sulfonic acid, diphenylsulfonic-3,3'-disulfonic acid, isophthalic acid dimethyl-5-sulfonic acid, 2,6-naphthalenedisulfonic acid, benzenesulfonic acid, o-benzenedisulfonic acid, 2,4,6 -Metal salts of dimethyl trichloro-5-sulfoisophthalate, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid and perfluoroalkanesulfonic acid; Potassium diphenylsulfone sulfonate, potassium perfluoro butane sulfonate, sodium trichlorobenzene sulfonate; And it provides a chemical resistant flame-retardant polycarbonate resin composition, characterized in that at least one selected from the group consisting of polystyrene sulfonic acid metal salts.

In addition, the polycarbonate resin composition is characterized in that the light transmittance (ASTM D1003, 3 mm thick specimens, based on no pigment) is 70% or more, and the flame retardancy (UL94, 1.5 mm thick specimens based) is V-0. Provided is a chemical resistant flame retardant polycarbonate resin composition.

According to the present invention, the polycarbonate resin and the polycyclohexylenedimethylene terephthalate resin contain a flame retardant having a specific composition, thereby maintaining excellent chemical resistance and excellent transparency, so that it is easy to express a metallic color and is particularly environmentally friendly. It is possible to provide a possible polycarbonate resin composition.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the description of the present invention, when it is determined that a detailed description of related known technologies may obscure the subject matter of the present invention, the detailed description will be omitted. Throughout the specification, when a part “includes” a certain component, this means that other components may be further included instead of excluding other components, unless specifically stated to the contrary.

The present inventors have established an eco-friendly flame retardant system and improved appearance characteristics based on transparency in using polyester resins and polycarbonate resins for the purpose of improving chemical resistance and mechanical properties for use as housing materials for electronic products in the related art. As a result of repeated research to develop a polycarbonate resin composition, it has been discovered that the polycarbonate resin and polycyclohexylenedimethylene terephthalate resin can be solved by containing a phosphorus-based flame retardant and a metal salt-based flame retardant of a specific composition, and has led to the present invention. .

Therefore, the present invention is a polycarbonate resin 60 to 80% by weight; 10 to 30% by weight of polycyclohexylenedimethylene terephthalate resin; Phosphorus flame retardant 5 to 15% by weight; And metal salt-based flame retardant 0.01 ~ 1% by weight; discloses a chemical resistant flame retardant polycarbonate resin composition comprising a.

The resin composition has a light transmittance (ASTM D1003, 3 mm thick injection specimen, based on no pigment added) of 70% or more, preferably 72% or more, and a flame retardance (UL94, based on a 1.5 mm thickness specimen) of V-0. It is easy to realize the metallic color by showing the characteristics, and it is possible to construct an eco-friendly flame retardant system with improved appearance characteristics.

Hereinafter, each component of the polycarbonate resin composition according to the present invention will be described in more detail.

(A) Polycarbonate resin

The polycarbonate (PC) resin used in the present invention is excellent in impact resistance, heat resistance, weather resistance, self-extinguishing property, flexibility, processability and transparency, and has excellent weather resistance to maintain high physical properties for a long time, excellent heat resistance and cold resistance, and severe temperature Maintains performance despite changes.

The polycarbonate resin is a bisphenol A polymer, and may have a weight average molecular weight (Mw) of 10,000 to 200,000, and preferably 20,000 to 50,000. In addition, branched chains may be used, preferably by adding 0.05 to 2 mol% of tri or more polyfunctional compounds, such as trivalent or higher phenolic groups, relative to the total amount of diphenol used for polymerization. The prepared polycarbonate thermoplastic resin can be used.

In addition, the polycarbonate resin preferably has a melt index (220 ° C, 10 kg load) of 3 to 28 g / 10min, more preferably 5 to 20 g / 10min. When the melt index of the polycarbonate resin is less than 3 g / 10 min, the processing temperature may be high, which may cause difficulty in molding, and when it exceeds 28 g / 10 min, the strength may be weak.

On the other hand, the production of the polycarbonate resin used in the present invention can follow a commonly used manufacturing method, for example, in the presence of a molecular weight modifier and a catalyst, dihydroxyphenol (dihydroxy phenol) and phosgene (phosgen) are reacted. It can be prepared or prepared by using an ester interchange reaction of a precursor obtained by dihydroxy phenol and diphenyl carbonate.

In the present invention, the polycarbonate resin is included in an amount of 60 to 80% by weight in the total resin composition in consideration of specific amounts of the polycyclohexylenedimethylene terephthalate resin, phosphorus-based flame retardant, and metal salt-based flame retardant described below, preferably 65 to 75% by weight, more preferably 67 to 73% by weight may be included.

(B) Polycyclohexylenedimethylene terephthalate resin

The polycyclohexylenedimethylene terephthalate (PCT) resin used in the present invention is terephthalic acid (TPA) or dimethylterephthalate (DMT) and 1,4-cyclohexanedimethanol (1,4-cyclohexanedimethanol, CHDM) is a crystalline polyester produced by transesterification or transesterification and condensation polymerization, and has a very high melting point and a very fast crystallization rate.

The PCT resin has excellent heat resistance, chemical resistance, hygroscopicity, and flow resistance compared to general purpose polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and among them, the heat deflection temperature is 245 to 260 ° C. , The continuous use temperature is 130 ~ 150 ℃, which belongs to engineering plastics that can be replaced by metals. These PCT resins have excellent color stability when compared to other polymer resins, and have a very low water absorption, so they can be used for various purposes, such as housings for electrical and electronic products.

In the present invention, the PCT resin is included in an amount of 10 to 30% by weight in the total resin composition, preferably 15 to 25% by weight, and more preferably 17 to 23% by weight. When the PCT resin content is less than 10% by weight, the degree of chemical resistance improvement may be insufficient, and when it exceeds 30% by weight, even if an appropriate amount of a flame retardant component is included, flame retardancy is not satisfactory, and metallic color may be difficult to implement due to a decrease in transparency. have.

(C) phosphorus flame retardant

In the present invention, as the flame retardant of a specific composition in the polycarbonate resin and polycyclohexylenedimethylene terephthalate resin, by containing a phosphorus-based flame retardant together with a metal salt-based flame retardant to be described later, while maintaining excellent chemical resistance and easy to express the color of the metal, especially It is possible to construct an eco-friendly flame retardant system.

Examples of the phosphorus-based flame retardant include phosphate-based compounds, phosphonate-based compounds, phosphinate-based compounds, and metal salts thereof. Preferably, phosphate-based compounds can be used, and more preferably, they are a type of phosphate-based compounds. Aromatic phosphoric acid ester compounds can be used.

Examples of the aromatic phosphoric acid ester-based compound include bisphenol A diphosphate, bisphenol A bis (dialkylphosphate), and bisphenol A bis (diarylphosphate). Here, the alkyl group may be, for example, an alkyl group having 1 to 20 carbon atoms or 1 to 15 carbon atoms, and the aryl group may be, for example, an aryl group having 6 to 30 carbon atoms or 6 to 20 carbon atoms. Preferably bisphenol A bis (diphenylphosphate) (BDP) can be used.

In the present invention, the phosphorus-based flame retardant is used in an amount of 5 to 15% by weight in the total resin composition, preferably 7 to 13% by weight, and more preferably 9 to 11% by weight. In the phosphorus-based flame retardant content range, excellent flame retardancy, but excellent transparency, chemical resistance, mechanical properties such as mechanical properties can be achieved.

(D) Metal salt flame retardant

In the polycarbonate resin composition according to the present invention, a metal salt-based flame retardant is used in combination with the phosphorus-based flame retardant as a flame retardant. When the metal salt-based flame retardant or the phosphorus-based flame retardant is used alone, it is difficult to realize a physical property balance such as excellent flame retardancy, transparency, chemical resistance, mechanical properties, etc. as desired by the present invention.

As the metal salt-based flame retardant, in particular, a sulfonate metal salt-based flame retardant may be included. In the present invention, the sulfonate-based flame retardant improves the flame retardancy of the polycarbonate resin and implements the desired physical properties balance of fluidity, mechanical properties, transparency, chemical resistance, and flame retardancy according to the combination use with a specific composition with the phosphorus-based flame retardant. .

Examples of the sulfonate metal salts include N- (p-trisulfonyl) -p-toluenesulfonamide, N- (N'-benzylaminocarbonyl) sulfonylamide, N- (phenylcarboxyl) -sulfonylamide , Diphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3'-disulfonic acid, isophthalic acid dimethyl-5-sulfonic acid, 2,6-naphthalenedisulfonic acid, benzenesulfonic acid, o-benzenedisulfonic acid, 2,4, Metal salt of 6-trichloro-5-sulfoisophthalate dimethyl, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid and perfluoroalkanesulfonic acid, potassium diphenylsulfone sulfonate, potassium perfluor Robutane sulfonate, sodium trichlorobenzene sulfonate, polystyrene sulfonic acid metal salt, and the like. These may be used alone or in combination of two or more, preferably potassium diphenylsulfone sulfonate or potassium purple Luo butane sulfonate can be used.

The sulfonate-based metal salt flame retardant may be used in an amount of 0.01 to 1% by weight in the total resin composition, preferably 0.05 to 0.5% by weight, and more preferably 0.12 to 0.2% by weight. If the content of the sulfonate metal salt flame retardant is less than 0.01% by weight, flame retardancy may be lowered, and when it exceeds 1% by weight, chemical resistance may be lowered.

The polycarbonate resin composition according to the present invention may further include an inorganic filler and a functional additive suitable for the intended use or effect, in addition to the main components described above. For example, carbon fibers, talc, light stabilizers, lubricants, colorants, lubricants, UV stabilizers, antioxidants, coupling enhancers, heat stabilizers, plasticizers, impact modifiers and the like can be added to be used for various purposes.

Hereinafter, a specific embodiment according to the present invention will be described.

First, the specifications of the components including the polycarbonate resin used in the Examples of the present invention are as follows.

(A) Polycarbonate (PC) resin

Bisphenol A type polycarbonate (PC-1100S, Lotte Chemical) having a weight average molecular weight of 33,000 and a melt index (300 ° C, 1.2 kgf) of 10 g / 10min was used.

(B) Polycyclohexylenedimethylene terephthalate (PCT) resin

PCT resin (SKYPURA 3402, SK Chemicals) having an intrinsic viscosity (IV) of 0.7 dl / g was used.

(C) phosphorus flame retardant

An aromatic phosphoric acid ester compound, bisphenol A bis (diphenylphosphate) (BDP, YOKE) was used.

(D) Metal salt flame retardant

Potassium diphenylsulfone sulfonate (KSS-FR, ARICHEM) was used.

Example 1

(A) 69.85% by weight of a polycarbonate resin, (B) 20% by weight of a PCT resin, (C) 10% by weight of a phosphorus-based flame retardant and (D) 0.15% by weight of a metal salt-based flame retardant, and mixed by mixing at a rate of 270 ° C to 300 ° C The thermoplastic resin composition was made into a chip state using a heated twin-screw extruder, and then dried at 110 ° C. for 4 hours using a hot air dryer, and then the specimen was injection molded using a mold for preparing a specimen.

Examples 2 to 8

In Example 1, the specimens were molded in the same manner as in Example 1, except that the components (A) to (D) were adjusted to the contents of Table 1 below.

Test example

The melt index, tensile strength, elongation, heat resistance, chemical resistance, light transmittance, and flame retardance of the specimens according to the examples were measured according to the following method, and the results are shown in Table 2 below.

[How to measure]

(1) Melt Index

It was measured according to ASTM D1238 under a load condition of 2.16 kg at 250 ° C.

(2) Tensile strength and elongation

Tensile strength and elongation were measured using a universal tester by making a test specimen according to ASTM D638.

(3) Heat resistance (heat deflection temperature, HDT)

A test specimen was prepared according to ASTM D648, and the heat resistance was measured using a heat resistance tester.

(4) Evaluation of chemical resistance

After injection of the manufactured pellets at the injection temperature of 260 ° C using the injection machine, the injected tensile strength specimen was adjusted for 24 hours under conditions of 23 ± 2 ° C and 50 ± 5% relative humidity, and the method was followed. Evaluation was carried out.

① Tensile specimens were fixed with test fixtures by producing a chemical resistance test fixture with a critical strain of 1.0%.

② Sunscreen (SPF 50) and fragrance (general products sold for automobiles) were each applied to the tensile specimen for 1 minute and then left at 23 ± 2 ° C for 168 hours.

③ After 168 hours at 23 ± 2 ℃, the tensile specimen was removed from the test fixture, and then left at 23 ± 2 ℃ for about 1-2 hours.

④ After leaving for 1-2 hours as described above, the tensile properties of each specimen to which the sunscreen and fragrance were applied were evaluated.

⑤ When the properties of physical properties of 80% or more of the tensile properties and 50% or more of the elongation properties before the chemical resistance test were exhibited, the chemical resistance was evaluated as excellent.

(5) Light transmittance

Light transmittance was measured by making a test specimen (3 mm) according to ASTM D1003.

(6) Flame retardancy

The flame retardancy of the 1.5 mm thick specimen was measured according to UL94 flame retardant regulations.

Referring to Table 2, first, when the polycarbonate resin and the polycyclohexylenedimethylene terephthalate resin according to the present invention contain a phosphorus-based flame retardant and a metal salt-based flame retardant of a specific composition within a preferred content range (Example 1) It can be seen that it is possible to construct an eco-friendly flame retardant system by maintaining chemical properties and having high transparency, so that it is easy to express metallic colors and has excellent flame retardancy.

However, when the content of the metal salt-based flame retardant does not reach a certain level (Examples 2 and 5), it is difficult to implement satisfactory flame retardant properties, and on the contrary, when the content is excessive (Example 6), it is found that the chemical resistance decreases. Can be.

In addition, when the phosphorus-based flame retardant content does not reach a certain level (Example 3), it is also difficult to implement satisfactory flame retardant properties, and on the contrary, when the content is excessive (Example 4), it can be seen that transparency decreases.

On the other hand, when the polycyclohexylenedimethylene terephthalate resin content does not reach a certain level (Example 8), the chemical resistance decreases, whereas when the content is excessive (Example 7), the transparency decreases, optimal It can be seen that the flame retardancy is lowered even though the flame retardant composition is included.

The preferred embodiments of the present invention have been described above in detail. The description of the present invention is for illustrative purposes, and those skilled in the art to which the present invention pertains will appreciate that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention.

Therefore, the scope of the present invention is indicated by the claims, which will be described later, rather than by the detailed description, and all the changed or modified forms derived from the meaning, scope, and equivalent concepts of the claims are included in the scope of the present invention. Should be interpreted.

Claims (4)

60 to 80% by weight of polycarbonate resin; 10 to 30% by weight of polycyclohexylenedimethylene terephthalate resin; Phosphorus flame retardant 5 to 15% by weight; And metal salt-based flame retardant 0.01 ~ 1% by weight; Chemical-resistant flame-retardant polycarbonate resin composition comprising a. According to claim 1,
The phosphorus-based flame retardant is a bisphenol-A bis (diphenyl phosphate), chemical-resistant flame retardant polycarbonate resin composition. According to claim 1,
The metal salt-based flame retardant is N- (p-trisulfonyl) -p-toluenesulfonamide, N- (N'-benzylaminocarbonyl) sulfonylamide, N- (phenylcarboxyl) -sulfonylamide, diphenyl Sulfon-3-sulfonic acid, diphenylsulfonic-3,3'-disulfonic acid, dimethyl-5-sulfonic acid, 2,6-naphthalenedisulfonic acid, benzenesulfonic acid, o-benzenedisulfonic acid, 2,4,6-triclo Metal salts of chloro-5-sulfoisophthalate, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid and perfluoroalkanesulfonic acid; Potassium diphenylsulfone sulfonate, potassium perfluoro butane sulfonate, sodium trichlorobenzene sulfonate; And a polystyrene sulfonic acid metal salt, at least one selected from the group consisting of polystyrene sulfonic acid metal salts. The method according to any one of claims 1 to 3,
The polycarbonate resin composition has a light transmittance (ASTM D1003, 3 mm thick specimen, based on no pigment) of 70% or more, and flame retardance (UL94, 1.5 mm thick specimen based) is V-0. Flame-retardant polycarbonate resin composition.