KR100877296B1 - Scratch-resistant flame retardant thermoplastic resin composition - Google Patents

Abstract

The present invention (A) 20 to 90% by weight of a polycarbonate resin; And (B) 10 to 80% by weight of methacrylate resin; 1 to 50 parts by weight of (C) flame retardant; And (D) 1 to 20 parts by weight of the aluminum silicate inorganic filler relates to a scratch-resistant flame retardant thermoplastic resin composition. The resin composition of the present invention may further include 1 to 30 parts by weight of the (E) impact modifier.

Description

Scratch-Resistant Flame Retardant Thermoplastic Resin Composition

Field of invention

The present invention relates to a scratch flame retardant thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition having excellent flame retardance without deterioration of scratch resistance including a polycarbonate resin, a methacrylate-based resin, and an aluminum silicate inorganic filler.

Background of the Invention

Electric and electronic products require various characteristics of resins according to the trend of larger size, specialization and light weight. In particular, since the appearance of the exterior material is more important, the scratch resistance of the resin itself is one of the important performances as high gloss materials are required. In addition, the demand for flame retardancy due to the stability of fire is increasing.

An approach that can be approached to achieve scratch resistance and flame retardancy simultaneously is to alloy polycarbonate (PC) resins and methacrylate-based resins, in particular polymethyl methacrylate (PMMA). Polycarbonate resin has excellent mechanical strength and is excellent in transparency, thermal stability, self-extinguishing and dimensional stability. It is widely used in electric and electronic products and automobile parts. It is easy to achieve flame retardancy with a small amount of flame retardant. However, the scratch resistance of the polycarbonate itself is not good in and around the pencil hardness B, there is a problem that can not achieve good scratch resistance with only polycarbonate resin. On the other hand, in the case of polymethyl methacrylate resin having excellent scratch resistance, the pencil hardness of the resin itself is very good, such as 3H, but has a disadvantage in that it is very difficult to achieve flame retardancy with a conventional flame retardant.

Therefore, the inventors of the present invention injected aluminum silicate inorganic filler (Halloysite) when blending the PC resin and PMMA resin, while ensuring excellent flame resistance and flame retardancy in the scratch resistance and flame retardant properties that are a mutual problem between PC resin and PMMA resin It was possible to have a level of scratch resistance.

An object of the present invention is to provide a flame retardant thermoplastic resin composition excellent in scratch resistance performance.

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

Summary of the Invention

Flame-retardant thermoplastic resin composition excellent in scratch resistance according to the present invention is based on 100 parts by weight of the base resin consisting of (A) 20 to 90% by weight of polycarbonate resin and (B) 10 to 80% by weight of methacrylate resin, (C) 1 to 50 parts by weight of a flame retardant; And (D) 1 to 20 parts by weight of the aluminum silicate inorganic filler.

In one embodiment of the present invention, the resin composition is characterized in that it further comprises 1 to 30 parts by weight of the impact modifier (E).

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

(A) polycarbonate resin

The aromatic polycarbonate resin (A) according to the present invention can be prepared by reacting diphenols represented by the following formula (1) with phosgene or carbonic acid diesters.

[Formula 1]

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

Specific examples of the diphenol of the general formula (1) include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, and 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 and the like. Among them, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 1,1-bis- (4- Bisphenols, such as hydroxyphenyl) -cyclohexane, are preferable, and 2, 2-bis- (4-hydroxyphenyl) propane also called bisphenol-A is especially preferable. The polycarbonate resin of the present invention has a weight average molecular weight (M _w ) of 10,000 to 200,000, preferably 15,000 to 80,000.

As the polycarbonate resin of the present invention, branched chains may be used, and preferably 0.05 to 2 mol% of tri- or more polyfunctional compounds, such as trivalent or higher, based on the total amount of diphenols used for polymerization. It can manufacture by adding the compound which has the above phenol group.

In the present invention, the polycarbonate resin (A) is used in the range of 20 to 90% by weight. Since the polycarbonate resin plays a role of facilitating flame retardancy, flame retardancy and mechanical strength decrease when applied at less than 20 wt%, and it is difficult to expect improvement in scratch resistance when applied at 90 wt% or more.

(B) methacrylate resin

The methacrylate resin in this invention consists of a mixture containing methyl methacrylate (MMA) as a main component and the monomer copolymerizable with this. At this time, it is preferable that the main component MMA maintains 50 parts by weight or more of the total monomers. When the MMA is less than 50 parts by weight, the transparency and mechanical strength of the polymerized methacrylic resin decreases.

There are no particular restrictions on the copolymerizable monofunctional unsaturated monomers, and methacrylates such as ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate, phenyl methacrylate and glycidyl methacrylate ; Acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; Acid anhydrides such as unsaturated carboxylic acids such as acrylic acid and methacrylic acid, maleic anhydride and the like; And monofunctional vinyl group-containing monomers such as styrene, acrylonitrile and methacrylonitrile, and mixtures thereof.

In order to control the molecular weight and thermal stability of the methacrylate resin, a chain transfer agent and an antioxidant may be applied. Each amount used varies depending on the type, but 0.02 to 10 parts by weight is preferable. The polymerization method of the methacrylate resin is not limited, and is prepared according to methods known to those skilled in the art such as bulk polymerization, emulsion polymerization and suspension polymerization.

The methacrylate resin used in the present invention may be preferably 10 to 80% by weight of the base resin. When it is less than 10% by weight, it is difficult to impart scratch resistance, and when applied to 80% by weight or more, the flame retardancy is very low, and in particular, it is difficult to achieve flame retardancy with a phosphorus-containing flame retardant.

(C) flame retardant

The flame retardant used in the present invention mainly uses a phosphorus-containing flame retardant and contains 1 to 50 parts by weight based on 100 parts by weight of the base resin consisting of (A) + (B). It is preferable in flame retardancy and impact strength when it has the above content range.

Phosphorus-containing flame retardants that can be applied refer to conventional phosphorus-containing flame retardants. For example, red, phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene and metal salts thereof may be applied.

Depending on the use, halogen-based compounds may also be applied as flame retardants, and halogen-based compounds generally used may be used. Preferably, a halogen-based compound capable of melting at a normal processing temperature, more specifically, a compound having a melting point or a softening point at 250 ° C. or lower is preferable. Examples of such flame retardants include decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, octabromotrimethylphenylindan, ethylenebistetrabromophthalimide, tris Libromophenol) triazine, brominated polystyrene, etc. are mentioned.

(D) aluminum silicate inorganic filler

Aluminum silicate inorganic fillers used in the present invention include kaolinite, nacrite, decite, halosite, and the like. Of these, halosite is preferred. Haloysite is composed of aluminum, silicon, hydrogen, oxygen and its chemical formula is Al ₂ Si ₂ O ₅ (OH) ₄ . It is produced by the weathering of aluminum silicate minerals, such as feldspar, and has a fairly small hollow tube shape with a diameter of about 40 to 200 nanometers.

In the present invention, the aluminum silicate inorganic filler is applied 1 to 20 parts by weight based on 100 parts by weight of polycarbonate and methacrylate resin. More preferably, it is 3-15 weight part. When the inorganic filler is less than 1 part by weight, it does not help flame retardation during blending of polycarbonate and methacrylate, and when it is 20 parts by weight or more, mechanical properties and impact resistance are lowered.

(E) impact modifier

In the present invention, a graft copolymer or an olefin copolymer may be used as the impact modifier.

The graft copolymer may include styrene and alpha-methyl styrene capable of grafting copolymerization after polymerizing at least one rubber monomer selected from the group consisting of diene rubber, acrylate rubber, and silicone rubber monomer; Alkyl substituted styrenes; Acrylonitrile; Methacrylonitrile; Methyl methacrylate; Maleic anhydride; A monomeric monomer selected from the group consisting of alkyl or phenyl nucleosubstituted maleimide and the like is grafted onto a rubbery polymer, and the rubber content in the impact modifier is preferably 20 to 80% by weight.

As the diene rubber, butadiene is typically used as a monomer, and isoprene may be applied. As the acrylate rubber, monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate and 2-ethylhexyl methacrylate are used. do. Silicone rubbers can be prepared from cyclosiloxanes, for example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenyl Cyclotetrosiloxane, octaphenylcyclotetrasiloxane, and the like. Silicone rubber manufactured by selecting at least one type from the cyclosiloxane can be used.

In addition, polyolefin type rubbers, such as ethylene / propylene rubber and ethylene-propylene-diene terpolymer (EPDM), can be used.

Impact reinforcing agent used in the present invention can be selectively applied according to the use, it is preferable to apply 1 to 30 parts by weight based on 100 parts by weight of the base resin consisting of (A) + (B). When it has the said content range, it is preferable in a flame retardance and physical property balance.

The thermoplastic resin composition of the present invention may further include an additive. The additives include antidrip agents, flame retardants, antibacterial agents, mold release agents, thermal stabilizers, antioxidants, light stabilizers, compatibilizers, dyes, inorganic additives, surfactants, coupling agents, fillers, plasticizers, impact modifiers, admixtures, colorants, stabilizers, lubricants, Antistatic agents, pigments, flame retardants, weathering agents, sunscreens, nucleating agents, adhesion aids, pressure sensitive adhesives and mixtures thereof.

The additive may be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the base resin. If the content of the additive is less than 0.1 parts by weight, the additive may not have the effect of the original, if it exceeds 30 parts by weight may cause mechanical properties and surface defects.

The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. 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 composition of the present invention can be used for molding a variety of products, in particular for the production of electrical and electronic products, such as the housing of TVs and office automation equipment.

The invention can be better understood by the following examples. The following examples are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Preparation and specifications of the base resin, flame retardant, aluminum silicate inorganic filler, impact modifier, etc. used in the following Examples and Comparative Examples are as follows.

(A) Polycarbonate Resin (PC)

Panlite L-1225 Grade from Teijin, Japan, was used.

(B) methacrylate resin

LG MMA's polymethyl methacrylate resin, IH830 Grade, was used.

(C) flame retardant

The flame retardant used in Examples and Comparative Examples of the present invention was CR-741 manufactured by Daihachi Chemical Co., Ltd. as bisphenol A diphosphate, an aromatic phosphate ester compound.

(D) aluminum silicate inorganic filler

Premium ultrafine halloysite manufactured by Imersys was used.

(E) Impact modifier (Methyl Methacrylate-Butadiene-Ethylacrylate Copolymer)

Metablen C223-A Grade, a methyl methacrylate-butadiene-ethylacrylate copolymer from MRC, was used.

(F) anti-drip agent (PTFE: Polytetrafluoroethylene)

Teflon (trade name) 7AJ of Dupont, USA was used.

Examples 1-3 and Comparative Examples 1-3

The material of (A) ~ (F) indicated above was added to the content as shown in the following [Table 1] to extrude at a temperature range of 220 ~ 260 ℃ in a conventional twin screw extruder to prepare a pellet. The prepared pellets were dried at 80 ° C. for 3 hours and then injected at 8 ° C. in a molding temperature of 250 ° C. and mold temperature of 60 ° C. to prepare impact, flame retardant, and pencil hardness specimens.

For the specimens prepared by the examples and comparative examples of Table 1, the flame retardancy was measured according to the UL 94 V flame retardant regulations, the Izod impact strength was measured according to the ASTM D-256 standard. In the case of measuring pencil hardness, the pencil hardness was measured in accordance with JIS K 5401 after leaving it for 48 hours at 50% of 23 ° C relative humidity for 10 × 10 cm 2 specimens. Scratch resistance was evaluated as 3B, 2B, B, HB, F, H, 2H, 3H and the like according to the pencil hardness results. The higher the H value, the better the scratch resistance. The higher the B value, the lower the scratch property.

As shown in Table 1, it can be seen that in Examples 1 to 3 using the halosite as the inorganic filler, the flame retardant performance was improved over Comparative Examples 1 to 3 without using the halosite. On the other hand, in the case of Comparative Examples 2 to 3 did not add the halosite, V2 flame retardancy and rejection was exceeded by dropping and burning time exceeding 30 seconds when evaluating flame retardancy, but in the case of Examples 2 to 3 added 5 parts by weight of halosite 1 / The 8 "Izod impact strength and scratch resistance have been improved without sacrificing the flame resistance of V0 and V2, respectively.

The present invention provides a thermoplastic resin composition having excellent flame retardancy without deterioration of scratch resistance.

 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 (9)

(A) 20 to 90% by weight of a polycarbonate resin; And (B) 10 to 80% by weight of methacrylate resin; Based on 100 parts by weight of basic resin (C) 1 to 50 parts by weight of a flame retardant; And (D) 1 to 20 parts by weight of halosite having a chemical formula of Al ₂ Si ₂ O ₅ (OH) ₄ ; Scratch-resistant flame retardant thermoplastic resin composition comprising a. The scratch-resistant flame retardant thermoplastic resin composition of claim 1, wherein the methacrylate-based resin (B) is a copolymer of 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of a monomer copolymerizable therewith. The method of claim 2, wherein the copolymerizable monomer is methacrylate including ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, phenyl methacrylate, glycidyl methacrylate; Acrylates including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; Unsaturated carboxylic acids including acrylic acid, methacrylic acid, and acid anhydrides including maleic anhydride; And a monofunctional vinyl group-containing monomer comprising styrene, acrylonitrile, methacrylonitrile, and mixtures thereof. The method of claim 1, wherein the flame retardant (C) is a phosphate (Phosphate), phosphonate (Phosphonate), phosphinate (Phosphinate), Phosphine Oxide (Phoshazine), phosphazene (Phosphazene), metal salts thereof And a flame-retardant thermoplastic resin composition selected from the group consisting of mixtures thereof. The flame retardant (C) according to claim 1, wherein the flame retardant (C) is decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, tetrabromobisphenol A-epoxy oligomer, octabromotrimethylphenylindan, ethylene bistetrabromorph A scratch-resistant thermoplastic resin composition, characterized in that it is a halogen flame retardant selected from the group consisting of deimide, tris (tribromophenol) triazine, brominated polystyrene and mixtures thereof. The scratch resistant thermoplastic resin composition of claim 1, wherein the halosite has a diameter of 40 to 200 nanometers. The scratch resistant thermoplastic resin composition according to claim 1, further comprising 1 to 30 parts by weight of the impact modifier (E). The anti-dripping agent, flame retardant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, dye, inorganic additive, surfactant, coupling agent, filler, plasticizer, impact modifier, admixture, colorant, stabilizer And a flame retardant thermoplastic resin composition further comprising an additive selected from the group consisting of lubricants, antistatic agents, pigments, flame retardants, weathering agents, sunscreen agents, nucleating agents, adhesion aids, pressure sensitive adhesives, or mixtures thereof. The molded article which shape | molded the scratch-resistant flame retardant thermoplastic resin composition of any one of Claims 1-8.