KR20100118374A - Flame retarding polyester resin composition - Google Patents

Abstract

PURPOSE: An environment-friendly flame-retardant polyester resin composition is provided to secure the balanced physical and mechanical properties without decreasing the heat resistance. CONSTITUTION: An environment-friendly flame-retardant polyester resin composition contains 30~70wt% of polyester resin, 5~30wt% of phosphorous-based flame-retardant, 1~15wt% of nitrogen fire retardant synergist, 0.5~5wt% of layered silicate, 0.1~8wt% inorganic activation reagent, and 5~50wt% of filler. The polyester resin contains a compound selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate.

Description

Flame retarding polyester resin composition

The present invention relates to a flame retardant polyester resin composition, and more particularly to a flame-retardant polyester resin which is environmentally friendly and excellent in heat resistance and mechanical properties, including a phosphorus flame retardant, a nitrogen flame retardant, a layered silicate, an inorganic activator and a filler. It relates to a composition.

Polyester resins have excellent mechanical and electrical properties and physical and chemical properties, and are being applied to a wide range of fields such as automobiles, electrical and electronic devices, and office equipment. In particular, poly butylene terephthalate (Poly butylene terephthalate) is one of the five general purpose engineering plastics because of its excellent electrical properties and excellent moldability is increasing its use.

Polybutylene terephthalate resin is used in addition to the organic halogen-based flame retardant and / or flame retardant aid in the field that needs flame retardancy because of the burning property. However, halogen-based flame retardants containing chlorine, bromine, or the like have problems such as corrosion of the processing equipment and resin decomposition by hydrogen halide. In addition, a large amount of toxic gas is generated in the case of a fire due to the halogenated compound, which causes life and property damage. In the case where the resin composition containing the organic halogen flame retardant and / or flame retardant aid is actually applied, the metal in contact with the molded product may be corroded or contaminated to cause a change in the electrical resistance value, and may interfere with the action of the part.

In addition, thermoplastic resins comprising halogen-based flame retardants and / or antimony compound-based flame retardant aids bring about a sharp decrease in tracking resistance, which is one of electrical properties.

In recent years, some European countries have proposed restrictions on the use of flame retardants such as polybrominated biphenyls (PBBs) and polybrominated biphenylethers (PBDEs) due to concerns about the occurrence of dioxins during fire and incineration. Attempts have been made to strictly limit the use of hazardous heavy metals, some bromine-based flame retardants, and antimony compounds in accordance with environmental stability assessments in automotive and electrical and electronic components.

Therefore, the necessity of the technical development regarding the non-halogen-type flame retardant which can ensure the flame retardance of a polyester resin is calculated | required.

As non-halogen flame retardants of polybutylene terephthalate, U.S. Pat.Nos. 3,951,908 and 4,403,052 disclose an enemy, U.S. Patent 4,278,591 discloses a melamine pyrophosphate compound, and European Patent No.83,768Al Japanese Patent Laid-Open No. 8-259787 discloses phosphate esters and melamine cyanurates, and US Patent No. 3,878,162 discloses the use of phosphorus and phosphate esters together.

However, in order to obtain a desirable flame retardant effect with the above compounds, a large amount of flame retardant is required, which causes problems of excessive cost increase, physical property deterioration, heat resistance decrease, and electrical property deterioration. In addition, the flame retardant containing the red phosphine gas is generated even by a small amount of water contact during processing due to the low temperature stability, and due to the red color generated by the red product itself, there is a restriction in the product color implementation.

The present invention is to solve the problems of the prior art as described above, exhibits excellent flame retardancy, exhibits balanced physical and mechanical properties without excessive cost increase and heat resistance deterioration, and environmentally friendly flame retardant polyester free of color expression It is to provide a resin composition.

The present invention as a means for solving the above problems, a) 30 to 70% by weight of a polyester resin; b) 5 to 30% by weight phosphorus flame retardant; c) 1 to 15 weight percent of a nitrogen based flame retardant synergist; d) 0.5 to 5% by weight of layered silicates; e) 0.1 to 8% by weight of inorganic activator; And f) 5 to 50% by weight of a filler to provide a flame retardant polyester resin composition.

The polyester resin preferably includes at least one selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate.

The polyester resin is preferably a copolymer containing butylene terephthalate in a repeating unit of 70 to 100% by weight.

It is preferable that the said polyester resin is a resin mixture containing 70 weight% or more of polybutylene terephthalates.

The polyester resin is preferably modified polybutylene terephthalate by chemical or physical modification.

The phosphorus flame retardant is preferably a compound selected from the group consisting of liquid or powdered phosphate esters, phosphates chemically similar to the phosphate esters, pyrophosphates, phosphonates, metal-substituted phosphinates and phosphonates.

The phosphate esters include triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, resorcinyl diphenyl phosphate, phenyl diresorcinyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, and phenyl di ( It is preferably at least one selected from the group consisting of isopropylphenyl) phosphate.

The nitrogen-based flame retardant synergist consists of melamine, melamine cyanurate, triphenyl isocyanurate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkyl amine phosphate, and piperazine acid polyphosphate having a triazine structure. It is preferably at least one selected from the group.

The layered silicate is preferably at least one selected from the group consisting of smectite-based materials, vermiculite-based materials, layered illite-based materials and derivatives thereof.

The inorganic activator is at least one selected from the group consisting of hydrotalcite, aluminum hydrate, magnesium hydrate, calcium hydrate, zinc sulfide, zinc oxide, magnesium carbonate, calcium carbonate, zinc borate, zinc borate hydrate, and magnesium sulfate hydrate. desirable.

The fillers are carbon fibers, glass fibers, aramid fibers, mineral fibers, silicon carbide fibers, boron carbide fibers, potassium titanate whiskers, glass flakes, silica, calcium carbonate, carbon black, conductive carbon black, kaolin, wollastonite, talc, or mica It is preferably at least one selected from the group consisting of.

This invention provides the molded article manufactured from the flame-retardant polyester resin composition which concerns on this invention as another means for solving the said subject.

The flame retardant polyester resin composition according to the present invention is environmentally friendly, exhibits excellent flame retardancy, including phosphorus flame retardant, nitrogen flame retardant, layer silicate, inorganic activator and filler, and is balanced without excessive cost increase and deterioration of heat resistance. Physical and mechanical properties are shown, and color expression is free.

The present invention comprises a) 30 to 70% by weight of a polyester resin; b) 5 to 30% by weight phosphorus flame retardant; c) 1 to 15 weight percent of nitrogen based flame retardant synergists; d) 0.5 to 5% by weight of layered silicates; e) 0.1 to 8% by weight of inorganic activator; And f) 5 to 50% by weight of a filler.

The flame retardant polyester resin composition according to the present invention includes a nitrogen-based flame retardant, a layered silicate, an inorganic activator and a filler together with a phosphorus-based flame retardant which is a non-halogen-based flame retardant in order to impart environmentally friendly flame retardancy. It is characterized by exhibiting excellent flame retardancy, balanced physical properties and mechanical properties without the excessive cost.

Hereinafter, each component of the flame-retardant polyester resin composition according to the present invention will be described in detail.

a) polyester resin

The flame-retardant polyester resin composition of the present invention contains a polyester resin as a main resin, and the polyester resin preferably contains 30 to 70% by weight, more preferably 40 to 60% by weight.

It is preferable that the polyester resin used for this invention is polyalkylene terephthalate resin. More specifically, it may include one or more polyalkylene terephthalates selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and the like.

Preferably the polyester resin is a copolymer containing 70 to 100% by weight of butylene terephthalate in repeat units, or more than 70% by weight and less than 100% by weight of polybutylene terephthalate, other resin It can be mixed with and used.

The polyester resin may include polycarbonate, polyethylene terephthalate, or phenol resin for the purpose of toughening, improving the appearance, or improving the fluidity, and for the purpose of increasing the amount. Other resins may be included.

In addition, the polyester resin may be modified polybutylene terephthalate by chemical or physical modification. In the case of using such a modified resin, the impact strength can be further improved.

The chemically modified polybutylene terephthalate is polytetramethylene glycol (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG), low molecular weight aliphatic polyester, or low during polymerization. It is copolymerized including molecular weight aliphatic polyamide and the like.

The physically modified polybutylene terephthalate is a mixture of impact modifiers and polybutylene terephthalate.

The impact modifier that can be used for the physical modification is not particularly limited as long as it is a resin capable of improving the impact strength of the polybutylene terephthalate resin. For example, m-acrylonitrile-butadiene-styrene (MBS), ethylene-propylene-diene terpolymer (core) of rubber and shell of plastic structure Ethylene-propylene-diene copolymer (EPDM), Styrene-butadien-styrene (SBS), Styrene-isoprene-styrene (SIS), Styrene-butadien (SB), Styrene-isoprene rubber, ethylene-vinylacetate (EVA), ethylene-ethyl acrylate (EEA), ethylene-vinylalchol (EVOH) copolymer, One or more selected from the group consisting of polybutylene terephtalate (PBT) -based elastomers, polyethylene terephtalate PET-based elastomers and nylon-based elastomers may be used.

When the physically modified polybutylene terephthalate is prepared by mixing the impact modifier, a compatibilizer or a dispersant may be further added. The compatibilizer or dispersant may be selected from the group consisting of maleic anhydride, oxazoline, oligomers or polymers having an end group or side chain with an epoxy group.

Polybutylene terephthalate previously modified with a polyester resin as described above may be used, or pure polybutylene terephthalate and other resins may be mixed and mixed before melt kneading.

b) Phosphorus flame retardant

The flame retardant polyester resin composition of the present invention comprises 5 to 30% by weight of a phosphorus flame retardant to impart flame retardancy to the polyester resin.

The present invention does not contain halogen and does not include phosphorus-based flame retardants to impart environmentally friendly flame retardancy.

Phosphorus-based flame retardants usable in the present invention are liquid or powdered phosphate esters, phosphates chemically similar to the phosphate esters, pyrophosphates, phosphonates, metal-substituted phosphinates, phosphonates, nitrogen-based flame retardants, or phosphazines ( Phosphazine) compounds, and these may be used alone or in combination of two or more thereof.

The phosphate ester compound is not limited thereto, for example, triphenyl phosphate (TPP), trixylenyl phosphate (TXP), or tricresyl phosphate (Tricresyl phosphate) as a monomer having an aromatic group. TCP) and the like, and monomers having two or more aromatic groups include resorcinyl diphenyl phosphate (RDP), phenyl diresorcinyl phosphate, and cresyl diphenyl phosphate. , Xylenyl diphenyl phosphate, or phenyl di (isopropylphenyl) phosphate. In addition, oligomers or polyphosphates of a dimer or more than a monomer may be used.

The metal-substituted phosphinate is not limited thereto, and examples thereof include magnesium phosphinate, calcium phosphinate, aluminum phosphinate, and the like.

Preferably, as the phosphorus-based flame retardant, resorcinyl diphenyl phosphate, magnesium phosphinate, aluminum phosphinate is used.

The content of the phosphorus flame retardant is preferably 5 to 30% by weight, more preferably 7 to 20% by weight. If the content is less than 5% by weight, the flame retardant synergistic effect is lowered, and if it exceeds 30% by weight, heat resistance is lowered.

c) nitrogen-based flame retardants

The flame retardant polyester resin composition of the present invention contains 1 to 15% by weight of a nitrogen-based flame retardant increasing agent together with the phosphorus-based flame retardant to impart flame retardancy to the polyester resin.

Nitrogen-based flame retardant synergists usable in the present invention include nitrogen-containing flame retardants or nitrogen-phosphorus-containing flame retardants. Although not limited thereto, the nitrogen-containing flame retardant synergists include melamine, melamine cyanurate, or triphenyl isocyanurate having a triazine structure, and the like. The melamine phosphate (melamine phosphate), melamine pyrophosphate (melamine pyrophosphate), ammonium polyphosphate (ammonium polyphosphate), alkylamine phosphate (alkylamine phosphate), or piperazine acid polyphosphate (piperazine acid polyphosphate) and the like. In this invention, these can be used individually or in mixture of 2 or more types. In addition, various nitrogen-based flame retardants and / or intumescent additives (eg, polyhydric compounds such as dipentaerythritol, starch, dextrin, inorganic acids, etc.) may be mixed Can be used. Preferably melamine cyanurate, or melamine phosphate is used.

The content of the nitrogen-based flame retardant is preferably 1 to 15% by weight, more preferably 2 to 12% by weight. If the content is less than 1% by weight, the flame-retardant synergistic effect is lowered, and if the content exceeds 15% by weight, the rigidity may be lowered.

d) layered silicates

The flame retardant polyester resin composition of the present invention comprises 0.5 to 5% by weight of the layered silicate to improve the heat resistance of the polyester resin and to delay the combustion.

Layered silicates usable in the present invention include, but are not limited to, smectite-based materials such as montmorillonite, nontronite, batellite, vonconscote, hectorite, saponite or kenite; Vermiculite-based materials; Layered illite-based materials such as redicite; And these derivatives are mentioned, These can be used individually or in mixture of 2 or more types. Preferably, montmorillonite, nontronite, baydelite, vonconscote, hectorite, saponite or kenite are used.

The content of the layered silicate is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight. If the content is less than 0.5% by weight, the flame retardant synergistic effect is lowered, if it exceeds 5% by weight there is a fear that the rigidity is lowered.

e) inorganic activator

The flame retardant polyester resin composition of the present invention comprises 0.1 to 8% by weight of an inorganic activator together with the phosphorus-based flame retardant and the nitrogen-based flame retardant for the flame retardant activation of the polyester resin.

The inorganic activator which can be used in the present invention is not particularly limited, but for example, hydrotalcite, aluminum hydrate, magnesium hydrate, calcium hydrate, zinc sulfide Zinc oxide, Magnesium calcium carbonate, Magnesium carbonate, Calcium carbonate, Zinc borate, Zinc borate hydrate, and Magnesium sulfate Hydrate (Magnesium sulfate hydrate). Preferably hydrotalcite, zinc sulfide, or zinc borate is used.

The content of the inorganic activator is preferably 0.1 to 8% by weight, more preferably 0.3 to 5% by weight. This is because if the content is less than 0.1% by weight, the flame retardant activation effect is lowered, and if it exceeds 8% by weight, resin decomposition is promoted.

f) filling material

The flame retardant polyester resin composition of the present invention comprises 5 to 50% by weight of fillers for improving the mechanical properties of the polyester resin.

The present invention can use various organic and or inorganic fillers in fibrous, plate and particle form. More specifically, for example, carbon fiber, glass fiber, aramid fiber, mineral fiber, silicon carbide fiber, boron carbide fiber, potassium titanate whisker, glass flake, silica, calcium carbonate, carbon Black, conductive carbon black, kaolin, wollastonite, talc, mica, and the like, and these may be used alone or in combination of two or more thereof. It is preferable to use glass fibers, glass flakes, or talc.

The content of the filler is preferably 5 to 50% by weight, preferably 10 to 40% by weight. If the content is less than 5% by weight, the heat resistance may be lowered. If the content is more than 40% by weight, the moldability may be lowered.

Flame retardant polyester resin composition according to the invention is a silicone flame retardant, lubricant, antioxidant, light stabilizer, hydrolysis stabilizer, mold release agent, pigment, antistatic agent, conductivity imparting agent, EMI shielding agent, Magnetic properties, crosslinking agents, antibacterial agents, processing aids, metal deactivators, depressants, fluorine-based anti-dropping agents, anti-friction anti-wear agents, or coupling agents may be further included to impart desired physical properties.

The present invention also relates to a molded article prepared from the above flame retardant polyester resin composition. The molded article is not particularly limited, but includes, for example, industrial molded articles such as electric parts, electronic parts, and automotive parts.

The method for producing a molded article from the flame retardant polyester resin composition according to the present invention is not particularly limited, and a method commonly used in the art may be used.

Although not limited thereto, for example, pellets may be prepared after melt kneading the flame retardant polyester resin composition, and a molded article may be manufactured by compression molding and injection molding. The melt kneading may be performed after first mixing the flame retardant polyester resin composition in a super mixer, followed by twin-screw extruder, single-screw extruder, roll mills, kneader or balm It can be performed using a variety of compound processing equipment, such as a banbury mixer.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which are intended to help a specific understanding of the present invention, and the scope of the present invention is not limited by the Examples.

<Examples 1-5 and Comparative Examples 1-5>

According to the components and contents shown in Table 2 below, the components of each composition were first mixed and then secondly mixed with a super mixer. Thereafter, melt-kneaded in a twin-screw extruder to make pellets, followed by drying and injection molding to prepare a specimen.

[Test Example]

The specimens prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were sufficiently conditioned at room temperature, measured in the following manner, and the results are shown in Table 2 below.

1. Tensile strength and elongation

It was measured by ASTM D638 method.

2. Heat Deflection Temperature (HDT)

It was measured by ASTM D648 method using a load of 18.6 kgf / cm ² .

3. Izod Impact

It was measured by ASTM D256 method.

4. Flame retardant

Measured by UL 94 test, a method specified by Underwriter's Laboratory Inc. of the United States, which indicates the afterglow time or drip after 10 seconds of flame burner on a vertically sized specimen. A method of evaluating flame retardancy from sex. Afterflaming time is the length of time that the specimen continues flame-burning after the ignition source is far away, and the surface of the drip is dripping from the specimen about 300 mm below the bottom of the specimen. Determined by complexing with water, the flame retardancy grade is divided according to Table 1 below.

division V2 V1 V0 HB Residual flame time of each sample 30 seconds or less 30 seconds or less 10 seconds or less Flame retardant Total residue time of 5 samples 250 seconds or less 250 seconds or less 50 seconds or less Ignition of cotton by drip has exist none none

5. Tracking Resistance

Insulators may cause currents on the surface between the two electrodes due to contamination or corrosion.This is to measure the resistance of the insulator to such currents.It is best not to track after dropping the standard contaminants on the specimen by ASTM D3638 method. Voltage CTI was measured.

6. Color Representation

The natural color expression was compared.

7. Phosphine Gas Generation Amount

The amount of phosphine gas generated after heating at 150 ° C. for 1 hour was measured.

Example Comparative example One 2 3 4 5 One 2 3 4 5 (a) PBT 39 34 44 41 32 46 50 42 43 52 PET - 10 - - 10 - - 10 - - (b) RDP 20 - 20 10 10 15 - - 20 20 Aluminum
Phosphinates - 13 - 10 5 - - - - - Of - - - - - - - 8 - - Brominated Flame Retardants - - - - - - 20 - - - (c) Melamine
Cyanurate 8 8 10 7 8 7 - 10 7 - (d) Cloisite® 93A 2 3 3 2 3 2 - - - 8 (e) CLC120 One 2 3 2 2 - - 2 3 2 (f) Fiberglass 30 30 20 30 30 30 30 30 30 20 Halogen content radish radish radish radish radish radish U radish radish radish Phosphine Gas Generation (ppm) 0 0 0 0 0 0 0 50 0 0 Tensile Strength (Kgf / cm ² ) 1000 1050 900 1080 1100 950 1200 1150 1000 800 % Elongation 3 3 4 3 3 3 3 3 3 4 Heat deflection temperature (℃) 200 205 190 200 200 200 206 200 195 180 Impact Strength (Kgfcm / cm) 5.5 5.7 5.0 5.8 6.0 5.0 7.0 6.5 6.0 5.0 Flame Retardant (1.6mm Thickness) V0 V0 V0 V0 V0 V1 V1 V0 V1 V2 Tracking resistance (CTI, volts) 600 600 500 600 600 600 150 500 600 600 Color expression possible possible possible possible possible possible possible Impossible possible possible * PBT: Polybutylene terephthalate [GP-2000 (LG Chemical)]
* PET: polyethylene terephthalate [BB-8055 (SK product)]
* RDP: Resorcinyl diphenyl phosphate
* Layered Silicate: Cloisite 93A (SCP)
Glass fiber: 183F (Owens corning)
Inorganic activator: CLC-120 (DOOBON Hydrotalcite)

Referring to Table 2, Examples 1 to 5 including the flame retardant polyester resin composition according to the present invention exhibited effective flame retardancy without generating phosphine gas, tensile strength, elongation, heat deformation temperature, impact strength And physical properties such as tracking resistance were not lowered as compared with the comparative example, and color expression was also free.

In contrast, Comparative Example 1, which does not include a filler, has a low flame retardancy, and Comparative Example 2, which includes a halogen flame retardant as a flame retardant, and does not include a nitrogen-based flame retardant, an inorganic activator, and a layered silicate, is flame retardant and tracking resistant. The castle was degraded. In Comparative Example 3, which contained red as a flame retardant but did not include layered silicate, phosphine gas was generated and color expression was not free. The comparative example 4 which does not contain layered silicate fell in flame retardance. In Comparative Example 5, which did not contain the nitrogen-based flame retardant, the tensile strength and the flame retardancy were lowered.

Claims (12)

a) 30 to 70% by weight of polyester resin; b) 5 to 30% by weight phosphorus flame retardant; c) 1 to 15 weight percent of a nitrogen based flame retardant synergist; d) 0.5 to 5% by weight of layered silicates; e) 0.1 to 8% by weight of inorganic activator; And f) 5 to 50% by weight of a filler. The method of claim 1, The polyester resin is flame retardant polyester resin composition, characterized in that it comprises at least one selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. The method of claim 1, The polyester resin is a flame-retardant polyester resin composition, characterized in that the copolymer containing butylene terephthalate 70 to 100% by weight in repeat units. The method of claim 1, The polyester resin is a flame-retardant polyester resin composition, characterized in that the resin mixture containing polybutylene terephthalate in more than 70% by weight and less than 100% by weight. The method of claim 1, The polyester resin is a flame-retardant polyester resin composition characterized in that the modified polybutylene terephthalate by chemical or physical modification. The method of claim 1, The flame retardant flame retardant polyester resin composition, characterized in that the compound selected from the group consisting of liquid or powdered phosphate ester, pyro phosphate, phosphonate, metal substituted phosphinate and phosphonate. The method of claim 6, The phosphate esters include triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, resorcinyl diphenyl phosphate, phenyl diresorcinyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, and phenyl di ( Flame retardant polyester resin composition, characterized in that at least one selected from the group consisting of isopropylphenyl) phosphate. The method of claim 1, The nitrogen-based flame retardant synergist consists of melamine having a triazine structure, melamine cyanurate, triphenyl isocyanurate, melamine phosphate, melamine pyrophosphate, ammonium polyphosphate, alkyl amine phosphate, and piperazine acid polyphosphate Flame retardant polyester resin composition, characterized in that at least one selected from the group. The method of claim 1, The layered silicate is flame retardant polyester resin composition, characterized in that at least one selected from the group consisting of smectite-based materials, vermiculite-based materials, layered illite-based materials and derivatives thereof. The method of claim 1, The inorganic activator may be at least one selected from the group consisting of hydrotalcite, aluminum hydrate, magnesium hydrate, calcium hydrate, zinc sulfide, zinc oxide, magnesium carbonate, calcium carbonate, zinc borate, zinc borate hydrate, and magnesium sulfate hydrate. A flame retardant polyester resin composition characterized by the above. The method of claim 1, The fillers are carbon fibers, glass fibers, aramid fibers, mineral fibers, silicon carbide fibers, boron carbide fibers, potassium titanate whiskers, glass flakes, silica, calcium carbonate, carbon black, conductive carbon black, kaolin, wollastonite, talc, or mica Flame retardant polyester resin composition, characterized in that at least one selected from the group consisting of. The molded article manufactured from the flame-retardant polyester resin composition of any one of Claims 1-11.