KR20040088225A - Alloy Composition of Polyester-Styrene Copolymer - Google Patents

Abstract

PURPOSE: A fire-retardant polyester-styrene copolymer alloy composition is provided, which is friendly to environment and excellent in fire-retardance, heat-resistance, and physical properties and represents colors freely. CONSTITUTION: The fire-retardant polyester-styrene copolymer alloy composition contains 3-60wt% of polyester, 20-90wt% of styrene copolymer, 1-15wt% of phosphorus-based fire-retardant agent, and 0.05-5wt% of copper oxide. The polyester is a copolymer comprising 70-100wt% of a butylene terephthalate unit or a resin blend containing 70-100wt% of a polybutylene terephthalate. And the styrene copolymer is a mixture of a styrene-acrylonitrile copolymer(SAN) and an acrylonitrile-butadiene-styrene copolymer(ABS).

Description

Flame-retardant polyester-styrene copolymer alloy composition {Alloy Composition of Polyester-Styrene Copolymer}

The present invention relates to a flame retardant polyester-styrene based copolymer alloy composition. More specifically, the present invention relates to a flame-retardant polyester-styrene-based copolymer alloy composition which is environmentally friendly and has excellent heat resistance and physical properties by comprising a non-halogen-based flame retardant and a copper oxide.

Polyester has excellent mechanical and electrical properties and physical and chemical properties, and has been 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. In addition, the alloy between the polybutylene terephthalate and the styrene-based copolymer is expanding the application possibilities due to the advantages of balanced physical properties, dimensional stability, economical and the like.

Such polybutylene terephthalate and styrenic copolymer resins have been imparted flame retardancy by separately adding an organic halogen flame retardant and / or auxiliary flame retardant in a field requiring flame retardancy because of its ability to burn well. However, halogen-based flame retardants containing elemental chlorine or bromine have problems such as corrosion of the processing equipment and resin decomposition by hydrogen halide. In addition, toxic gases caused by a large amount of halogenated compounds generated in a fire cause personal and property damage. In addition, when the resin composition containing the organic halogen flame retardant and / or flame retardant aid is actually applied, the metal in contact with the molded article may be corroded to hinder the action of the part. For example, the contact metal of an electrical contact component is easily contaminated causing a change in electrical resistance. In addition, thermoplastic resins containing a halogen-based compound and / or an antimony compound-based flame retardant aid bring about a sharp decrease in tracking resistance, which is one of electrical properties.

Meanwhile, some European countries have proposed restrictions on the use of flame retardants such as polybrominated biphenyls (PBBs) and polybrominated biphenylethers (PBDEs) in response to dioxin generation during fire and incineration. In addition, there have been attempts to strictly limit the use of harmful heavy metals, bromine-based flame retardants, and antimony compounds in accordance with environmental stability evaluations in automotive and electrical and electronic components.

Therefore, there is an urgent need for the development of technology for non-halogen flame retardants.

Conventionally, as flame retardants of non-halogen flame retardant polybutylene terephthalate, U.S. Pat. Inorganic filler, Japanese Patent Application Laid-open No. Hei 8-259787 discloses a case where phosphoric acid ester and melamine cyanurate, and U.S. Patent No. 3,878,162 are used together with red phosphorus and phosphate ester. In addition, the alloy of the polyester resin and the styrene-based copolymer is generally a flame retardant containing a halogen compound.

However, such a technique requires a large amount of flame retardant in order to obtain a desirable degree of flame retardancy, which has the disadvantage of causing excessive cost increase, physical property deterioration, heat resistance decrease and electrical property deterioration. In particular, the flame retardant containing red generates phosphine gas even by a small amount of water contact during processing due to the high temperature stability deterioration, the flame retardant composition containing red is limited in the product color due to the red expression by the red itself.

Therefore, the inventors of the present invention have achieved continuous flame retardants and phosphorus-based flame retardants and inorganic activators that do not include the phosphorus and inorganic activator as a result of continuous research to solve the above problems, and does not cost excessive costs, An alloy composition of an environmentally friendly flame-retardant polyester-styrene-based copolymer exhibiting balanced physical properties without deteriorating heat resistance and physical properties and free of color expression was completed.

The present invention is applied to an alloy composition of a thermoplastic polyester and a styrene-based copolymer, an effective flame-retardant uplift system including a copper oxide and a phosphorus-based flame retardant containing no halogens and phosphorus, so that physical balance is balanced without excessive cost increase, heat resistance, and physical property deterioration. It is an object to provide an alloy composition of an environmentally friendly flame retardant polyester-styrene-based copolymer exhibiting properties and free color expression.

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

In order to achieve the above object, the present invention comprises a flame retardant comprising 3 to 60% by weight of polyester, 20 to 90% by weight of styrenic copolymer, 1 to 15% by weight of flame retardant and 0.05 to 5% by weight of copper oxide. Polyester-styrene-based copolymer alloy composition is provided.

The flame-retardant polyester-styrene copolymer alloy composition is a silicone flame retardant, lubricant, antioxidant, light stabilizer, hydrolysis stabilizer, mold release agent, pigment, antistatic agent, conductivity imparting agent, EMI shielding agent, magnetic imparting agent, crosslinking agent, antibacterial agent, It may further comprise one or more additives selected from the group consisting of processing aids, metal deactivators, depressants, fluorine-based anti-dropping agents, friction-resistant anti-wear agents and coupling agents.

The polyester may be a copolymer composed of 70 to 100% by weight of butylene terephthalate units, or may be a resin blend including 70 to 100% by weight of polybutylene terephthalate.

The styrene-based copolymer may be composed of a mixture of styrene-acrylonitrile copolymer (SAN) and acrylonitrile-butadiene-styrene copolymer (ABS).

The copper oxide may be one or a mixture of two or more selected from the group consisting of copper oxide, copper sulfide compound, and organic copper acid salt as an oxidized copper-containing compound.

The present invention also provides an electrical component, an electronic component, an automotive component, and an industrial molded article including the flame-retardant polyester-styrene-based copolymer alloy composition as described above.

Hereinafter, the present invention will be described in detail.

In the flame-retardant polyester-styrene-based copolymer alloy composition, the present invention adopts a phosphorus-based flame retardant and an inorganic activator instead of a halogen-based flame retardant in order to impart environmentally friendly flame retardant and heat resistance, and in order to prevent degradation of physical properties of the resin. Characterized in that the composition.

That is, it consists of a composition of 3 to 60% by weight polyester, 20 to 90% by weight styrenic copolymer, 1 to 15% by weight flame retardant and 0.05 to 5% by weight copper oxide to achieve the object of the present invention.

The polyester of the present invention may be at least one selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and the like, but the polyester is made of 70 to 100% by weight of butylene terephthalate units It is more preferable for this invention to be a resin compound which is a coalescence or contains 70 weight% or more of polybutylene terephthalates. The polyester may be a polymer by esterification of butane-1,4-diol and terephthalic acid or transesterification of butane-1,4-diol and dimethyl terephthalate.

In addition, modified polybutylene terephthalate may be used to improve impact strength, and polytetramethylene glycol (PTMG), polypropylene glycol (PPG), and polyethylene glycol may be used during polymerization by chemical modification. Modified polybutylene terephthalate copolymerized with (polyethylene glycol, PEG), low molecular weight aliphatic polyester, low molecular weight aliphatic polyamide, etc., or modified polybutylene terephthalate blended with an impact modifier using physical modification For example.

Examples of the impact modifier include m-acrylonitrile-butadiene-styrene (MBS) having a core of rubber and a shell of plastic, all acrylic rubber, and ethylene-propylene-diene. Ethylene-propylene-diene monomer copolymer (EPDM), styrene-butadien-styrene (SBS), styrene-isoprene-styrene SIS, styrene-butadiene -butadien, SB), Styrene-isoprene rubber, Ethylene-vinylacetate (EVA), Ethylene-ethyl acrylate (EEA), Ethylene-vinylalchol , EVOH) copolymer, polybutylene terephtalate (PBT) -based elastomer, polyethylene terephtalate PET-based elastomer and nylon (Nylon) elastomer selected from the group consisting of All. In addition to the above-mentioned resins, there is no particular limitation as long as the resin can improve the impact strength.

When the modified polybutylene terephthalate is prepared by adding the impact modifier, a compatibilizer or a dispersant may be further added. The compatibilizer or the dispersant may include maleic anhydride, oxazoline, and an epoxy group in the terminal group or the side chain. One or more types can be selected from the group which consists of an oligomer and a polymer.

In addition, polycarbonate, polyethylene terephthalate, phenol resin, etc. may be blended for the purpose of toughening polyester, improving the appearance, or improving the fluidity, and other resins for the purpose of increasing the amount. Can be blended with Also. Premodified polybutylene terephthalate may be used, or pure polybutylene terephthalate and other resins may be added together and mixed after melt kneading.

The content of the polyester is preferably 3 to 60% by weight, more preferably 5 to 50% by weight based on the total composition.

When the content of the polyester is used at 3% by weight or less with respect to the total composition, it is difficult to expect the physical properties of the heat resistance and strength properties of the polyester crystalline resin, and when used at 60% by weight or more, the dimensional stability of the amorphous resin alloy Deterioration occurs.

The styrene copolymer of the present invention is not particularly limited as long as it is a resin containing a styrene monomer. Thus, styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-ethylene-propylene-diene terpolymer-styrene (AES), acrylonitrile-butylacryl It may be a resin containing at least one member selected from the group consisting of late styrene (ASA), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) and the like. The resins may be combined in various ways with one or more selected from vinyl aromatic monomers including styrene-based monomers. In addition, the structure is not particularly limited, and may be a variety of structures such as a fine dispersion structure, core-shell structure, such as random, block and graft copolymer, and modified or modified forms are also possible.

The styrene monomer may be alpha-methylstyrene, meta-methylstyrene, or para-methylstyrene, alpha-methyl-para-methylstyrene, vinyl toluene, vinyl naphthalene, methoxy styrene, or vinyl benzene. One or more selected from the styrene monomers may be selected and copolymerized. As the vinyl monomers other than the styrene monomers, acrylonitrile, acrylate monomers, maleic anhydride, maleimide monomers, glycidyl group-containing monomers and the like which are vinyl cyan monomers can be used.

The styrene-based copolymer may be used alone or in combination of one or more according to the purpose of use. A typical example is the acrylonitrile-butadiene-styrene (ABS) copolymer containing a large amount of the rubber component and the same styrene-acrylonitrile (SAN) copolymer as the matrix component except the rubber component. To control the ingredients.

The content of the styrenic copolymer is preferably 20 to 90% by weight, more preferably 40 to 70% by weight based on the total composition.

When the styrene-based copolymer content is used at 20% by weight or less with respect to the total composition, it is difficult to expect properties such as dimensional stability of the amorphous resin alloy, and when used at 90% by weight or more, desired flame retardant properties cannot be obtained.

In the present invention, in order to impart environmentally friendly flame retardant, halogen-based flame retardant or non-phosphorous flame retardant is included, the phosphorus flame retardant is a liquid or powdered phosphate ester, phosphate, pyrophosphate, phosphate chemically similar to the phosphate ester At least one compound selected from the group consisting of nates and phosphonates. As the phosphate ester compound, triphenyl phosphate (TPP), trixylenyl phosphate (TXP), tricresyl phosphate (TCP), etc. may be mainly used as monomers having an aromatic group. Resorcinyl diphenyl phosphate (RDP), phenyl diresorcinyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate Xylenyl diphenyl phosphate), phenyl di (isopropylphenyl) phosphate, and the like may be used. Oligomers or polyphosphates more than dimers can be used. In the present invention, phosphorus-based flame retardants other than those mentioned above may be used alone or in combination of one or more thereof. In addition to the above-mentioned phosphate ester compounds, a phosphorus nitrogen composite flame retardant, a phosphazine compound, or the like can also be used. The compounds may be in liquid or solid form.

The content of the phosphorus flame retardant is preferably 1 to 15% by weight, more preferably 3 to 10% by weight based on the total composition.

When the content of the phosphorus-based flame retardant is used in less than 1% by weight based on the total composition, the flame retardancy is lowered, and when used in more than 15% by weight it is not possible to obtain a reduction in heat resistance and the desired product strength.

In the present invention, in addition to the non-halogen flame retardant as described above to include a copper oxide for the flame retardant activation, the copper oxide is copper oxide [CuO], copper oxide [Cu2O], copper sulfide [CuS], copper copper sulfide [Cu 2 S] compounds are preferred.

The content of the copper oxide is preferably 0.05 to 5% by weight based on the total composition, since the flame retardant activation effect is lowered at less than 0.05% by weight and the decomposition of the resin is promoted when it is more than 5% by weight. More preferably, it is 0.1-3 weight%.

Flame-retardant polyester-styrene copolymer alloy composition as described above is a silicone flame retardant, lubricant, antioxidant, light stabilizer, hydrolysis stabilizer, mold release agent, pigment, antistatic agent, conductivity imparting agent, EMI within the range that physical properties are not impaired It further comprises at least one additive selected from the group consisting of a shielding agent, a magnetic imparting agent, a crosslinking agent, an antibacterial agent, a processing aid, a metal inactivating agent, a depressant, a fluorine anti-dropping agent, an anti-wear antiwear agent, a coupling agent, and the like to impart other physical properties. can do.

The compositions of the present invention are first mixed with the above additives in a super mixer, and then a conventional twin-screw extruder, single-screw extruder, roll-mills, kneader After kneading by melt kneading using one of a variety of mixing processing equipment such as) or a banbury mixer, pellets were obtained by a pelletizer, and then sufficiently dried in a dehumidifying dryer or a hot air dryer, followed by injection molding to measure physical properties.

The present invention also provides an electrical component, an electronic component, an automotive component, and an industrial molded article including the flame-retardant polyester-styrene-based copolymer alloy composition as described above.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

Example 1

After mixing according to the ingredients and contents shown in Table 1, the mixture was mixed well by a super mixer, melt-kneaded in a twin-screw extruder, pelletized, dried, injection-molded, and sufficiently conditioned at room temperature. Physical properties of the specimens were measured in the following manners and the results are shown in Table 1.

◎ Tensile strength and elongation: It was measured by ASTM D638 method.

◎ Heat deflection temperature (HDT): measured by ASTM D648 method using a load of 18.6kgf / cm ² .

◎ Izod Impact was measured by ASTM D256 method.

◎ Flame retardancy: Measured by UL 94 test, a method defined by Underwriter's Laboratory Inc. of the United States, which remains after 10 seconds of flame infection of the burner on a vertically sized specimen. It is a method of evaluating flame retardancy from time or drip. 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 300mm below the lower end of the specimen. Determined by complexing with water, the flame retardancy grade is divided according to the table 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 5 Sample total flame time 250 seconds or less 250 seconds or less 50 seconds or less Ignition of cotton by drip has exist none none

◎ Tracking Resistance: Insulator may cause current on the surface between two electrodes due to contamination or corrosion, and to measure the resistance of the insulator against such electric current, and test the standard pollutants by ASTM D2863 method. The highest voltage (CTI) without tracking after dropping on was measured.

◎ Color Representation: Compared with natural colors.

◎ Phosphine gas generation amount: The generation amount of phosphine gas after heating at 150 ° C. for 1 hour was measured.

[Examples 2 to 5 and Comparative Examples 1 to 3]

Except that the specimen was prepared according to the composition of Table 1, after the specimen was prepared in the same manner as in Example 1, the physical properties were measured and shown in Table 1.

division Example Comparative example One 2 3 4 5 One 2 3 Composition (% by weight) Polyester PBT 30 30 50 20 10 50 20 31 PET - 10 - - - - - - Styrene Copolymer ABS 60 50 30 70 82 30 - 60 MBS - - 11 - - - 70 - Flame retardant TPP 9 - 7 9.8 - - - 9 RDP - 9 - - 7 - - - Of - - - - - - 8 - Brominated Flame Retardants (DECA) - - - - - 15 - - Antimony trioxide - - - - - 5 - - Copper oxide Copper oxide One One 2 0.2 One - 2 - Properties Tensile Strength (Kgf / cm ² ) 450 430 460 410 400 450 420 430 % Elongation 32 25 40 20 15 25 17 30 Heat deflection temperature (℃) 82 85 82 80 84 82 87 80 Impact Strength (Kgfcm / cm) 20 24 45 25 18 25 18 20 Flame Retardant (1.6mm Thickness) V2 V1 V2 V2 V2 V1 V1 HB Tracking (CTI, volts) 400 400 400 500 450 170 350 400 Color expression possible possible possible possible possible possible Impossible possible Halogen Free radish radish radish radish radish U radish radish Phosphine Gas Generation (ppm) 0 0 0 0 0 0 50 0

As shown in Table 1 above, Examples including a non-halogen flame retardant and a copper oxide include Comparative Example 1 including a halogen flame retardant, Comparative Example 2 including red and copper oxides, and a non-halogen flame retardant, but a copper oxide Compared with Comparative Example 3, which does not contain phosphine gas, it exhibits effective flame retardancy without generating phosphine gas, and its physical properties such as tensile strength, elongation, heat deformation temperature, impact strength and tracking resistance are not deteriorated as compared with Comparative Examples. It can be seen that the expression is also free.

As described above, the flame-retardant polyester-styrene-based polymer alloy composition according to the present invention includes a phosphorus-based flame retardant and a copper oxide that does not contain halogen and phosphorus, and is environmentally friendly, exhibits effective flame retardancy, and is free of color expression. It is a useful invention having the effect of providing the ester-styrene-based polymer alloy composition without the heat resistance, physical property degradation and excessive cost.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (6)

3 to 60% by weight of polyester, 20 to 90% by weight of styrenic copolymer, 1 to 15% by weight of phosphorus flame retardant, and 0.05 to 5% by weight of copper oxide Roy composition. The method of claim 1, The flame-retardant polyester-styrene copolymer alloy composition is a silicone flame retardant, lubricant, antioxidant, light stabilizer, hydrolysis stabilizer, mold release agent, pigment, antistatic agent, conductivity imparting agent, EMI shielding agent, magnetic imparting agent, crosslinking agent, antibacterial agent, Flame retardant polyester-styrene copolymers comprising at least one additive selected from the group consisting of processing aids, metal deactivators, depressants, fluorine anti-dropping agents, frictional anti-wear agents, and coupling agents Roy composition. The method of claim 1, Flame-retardant polyester-styrene copolymer characterized in that the polyester is a copolymer consisting of 70 to 100% by weight of butylene terephthalate units, or a resin blend comprising 70 to 100% by weight of polybutylene terephthalate Alloy composition. The method of claim 1, Flame retardant polyester-styrene copolymer alloy composition, characterized in that the styrene copolymer is made of a mixture of styrene-acrylonitrile copolymer (SAN) and acrylonitrile-butadiene-styrene copolymer (ABS). The method of claim 1, A flame retardant polyester-styrene copolymer alloy composition, wherein said copper oxide is cuprous oxide [CuO], cuprous oxide [Cu2O], cuprous sulfide [CuS], or cuprous sulfide [Cu2S] compound. An electrical component, an electronic component, an automotive component, and an industrial molded article comprising the composition of any one of claims 1 to 5.