Polybutylene terephthalate resin composition, method for preparing same, and molded product comprising same

Abstract

The present invention relates to a polybutylene terephthalate resin composition, a method for preparing same, and a molded product comprising same, and has the effect of providing: a polybutylene terephthalate resin composition which has excellent mechanical properties, processability, flame retardancy, and elongation even with a high polybutylene terephthalate content, and thus is advantageous for use in electrical and electronic products or automobile parts; a method for preparing same; and a molded product comprising same.

Description

Polybutylene terephthalate resin composition, method for producing the same, and molded article comprising the same

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0132314, filed October 5, 2023, and Korean Patent Application No. 10-2024-0116556, filed August 29, 2024, which is hereby incorporated by reference in its entirety.

[0003] The present invention relates to a polybutylene terephthalate resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to a polybutylene terephthalate resin composition which contains a high content of polybutylene terephthalate and has excellent mechanical properties, processability, flame retardancy, and elongation, and is useful for use in electrical and electronic products or automobile parts, a method for producing the same, and a molded article comprising the same.

[0004] Recently, many studies have been conducted to resinify electrical and electronic products or automobile parts, and in particular, polybutylene terephthalate (PBT) is attracting attention as a material for metal replacement parts in terms of economic feasibility and physical properties.

[0005] The above polybutylene terephthalate (PBT) is a crystalline polymer that has advantages such as high heat resistance and fast manufacturing time, but has a problem in that it has poor compatibility with other resins or reinforcing agents such as glass fiber, and thus cannot exhibit additional physical properties such as flame retardancy and elongation.

[0006] In particular, electrical and electronic products or automobile parts must provide processability, impact stability, flame retardancy, and elongation even when exposed to harsh external environments, but it is difficult to satisfy these requirements with the non-reinforced polybutylene terephthalate (PBT).

[0007] [Prior Art Literature]

[0008] [Patent Document]

[0009] European Patent Publication No. 4101883

[0010] In order to solve the problems of the prior art as described above, the present invention aims to provide a polybutylene terephthalate resin composition having excellent mechanical properties, processability, and flame retardancy as well as excellent elongation, which is advantageous for use in electrical and electronic products or automobile parts, a method for producing the same, and a molded article comprising the same, despite containing a high content of polybutylene terephthalate.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below.

[0012] In order to achieve the above object, the present invention comprises: I) 100 parts by weight of polybutylene terephthalate; 1 to 30 parts by weight of an organometallic salt-based phosphinate flame retardant; 1 to 30 parts by weight of a phosphate-based flame retardant; and 1 to 30 parts by weight of a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer.

[0013] If the content of the above organometallic salt-based phosphinate flame retardant is a, the content of the phosphate-based flame retardant is b, and the content of the above polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer is c, then a>b>c is satisfied.

[0014] The above organometallic salt-based phosphinate flame retardant and phosphate-based flame retardant are in a weight ratio (a:b) of 7:2 to 7:4.

[0015] A polybutylene terephthalate resin composition is provided, characterized in that the phosphate-based flame retardant and the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer are included in a weight ratio (b:c) of 4:3 to 8:3.

[0016] II) In the above I), the polybutylene terephthalate may include polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5 and polybutylene terephthalate having an intrinsic viscosity (IV) of more than 0.8 and less than 1.1 in a weight ratio of 1:0 to 1:1.

[0017] III) In the above I) or II), the organometallic salt-based phosphinate flame retardant may have a structure represented by the following chemical formula 1.

[0018] [Chemical Formula 1]

[0019]

[0020] (Above, R1 and R2 are each an alkyl group or an aryl group having 1 to 6 carbon atoms, M is at least one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and a protonated nitrogen base, and n is 1 to 4.)

[0021] IV) In the above I) to III), the organometallic salt-based phosphinate flame retardant may have a structure represented by the following chemical formula 1-1, as a specific example.

[0022] [Chemical Formula 1-1]

[0023]

[0024] V) In the above I) to IV), the phosphate-based flame retardant may have a structure represented by the following chemical formula 2.

[0025] [Chemical Formula 2]

[0026]

[0027] (In the above chemical formula 2, R3, R4 and R5 are each independently hydrogen or a C1-C4 alkyl group, X is a C6-C20 aryl group or a C6-C20 arylene group substituted with a C1-C4 alkyl group, and n is an integer from 0 to 4.)

[0028] VI) In the above I) to V), the phosphate-based flame retardant may be resorcinolbis(2,6-dimethylphenyl) phosphate.

[0029] VII) In the above I) to VI), the polyester elastomer may be a compound composed of terephthalate as an aromatic dicarboxylic acid, 1,4-butanediol as an aliphatic diol, and polyoxytetramethylene glycol as an aliphatic polyether compound.

[0030] VIII) In the above I) to VII), the ethylene-glycidyl (meth)acrylate copolymer may be a polyethylene copolymer in which glycidyl (meth)acrylate is polymerized.

[0031] IX) In the above I) to VIII), the ethylene-glycidyl (meth)acrylate copolymer may be a copolymerization of an olefin monomer and a monomer containing an epoxy group.

[0032] X) In the above I) to IX), the ethylene-glycidyl (meth)acrylate copolymer may be polymerized by including ethylene, glycidyl (meth)acrylate and vinyl acetate.

[0033]

[0034] In addition, the present invention provides a composition comprising: XI) polybutylene terephthalate; organometallic salt-based phosphinate flame retardant; phosphate-based flame retardant; polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer; And a polybutylene terephthalate resin composition characterized in that, among a total of 100 wt% of additives, polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5 is included in an amount of 30 to 85 wt%, polybutylene terephthalate having an intrinsic viscosity (IV) of more than 0.8 and less than 1.1 is included in an amount of 0 to 40 wt%, the organometallic salt-based phosphinate flame retardant is included in an amount of 10 to 20 wt%, the phosphate-based flame retardant is included in an amount of 1 to 10 wt%, and the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer is included in an amount of 1 to 5 wt%.

[0035] XII) In the above XI), the additive may be at least one selected from the group consisting of a heat stabilizer, a flame retardant, a flame retardant auxiliary agent, an activator, a processing aid, a plasticizer, a coupling agent, a light stabilizer, a release agent, a dispersant, an anti-dripping agent, a weather stabilizer, an antioxidant, a compatibilizer, a pigment, a dye, an antistatic agent, an antiwear agent, a filler, and an antibacterial agent.

[0036] XIII) In the above XI) to XII), the polybutylene terephthalate resin composition may be a non-reinforced material.

[0037] XIV) In the above XI) to XIII), the polybutylene terephthalate resin composition may be a material used for electrical components.

[0038] XV) In the above XI) to XIV), the polybutylene terephthalate resin composition may have an elongation of 22% or more measured by ISO 527 at 50 mm / min.

[0039] XVI) In the above XI) to XV), the polybutylene terephthalate resin composition may have an Izod impact strength (23°C, Notched) of 4.7 kJ / m2 or more measured on a 4 mm thick specimen according to ISO 180.

[0040] XVII) In the above XI) to XVI), the polybutylene terephthalate resin composition may have a flame retardancy of V0 or higher measured for a specimen size of 0.8 mm according to the UL94 method.

[0041]

[0042] In addition, the present invention comprises XVIII) polybutylene terephthalate; organometallic salt-based phosphinate flame retardant; phosphate-based flame retardant; polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer; And a step of including 30 to 85 wt% of polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5, 0 to 40 wt% of polybutylene terephthalate having an intrinsic viscosity (IV) of more than 0.8 and less than 1.1, 10 to 20 wt% of the organometallic salt-based phosphinate flame retardant, 1 to 10 wt% of the phosphate-based flame retardant, and 1 to 5 wt% of the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer, and introducing the mixture into an extruder, melt kneading, and extruding,

[0043] If the content of the above organometallic salt-based phosphinate flame retardant is a, the content of the phosphate-based flame retardant is b, and the content of the above polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer is c, then a>b>c is satisfied.

[0044] The above organometallic salt-based phosphinate flame retardant and phosphate-based flame retardant are in a weight ratio (a:b) of 7:2 to 7:4.

[0045] A method for producing a polybutylene terephthalate resin composition is provided, characterized in that the phosphate flame retardant and the polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer are included in a weight ratio (b:c) of 4:3 to 8:3.

[0046]

[0047] In addition, the present invention provides a molded article characterized by including the polybutylene terephthalate resin composition described above XIX).

[0048] XX) In the above XIX), the molded product may be an automobile part or an electrical / electronic part.

[0049] XXI) In the above XIX) or XX), the molded product may be a component for electric vehicles.

[0050] XXII) In the above XIX) to XXI), the electric component may be a connector or a sensor component.

[0051] XXIII) In the above XIX) to XXII), the connector part may be a connector for a TV, etc.

[0052] According to the present invention, there is provided a polybutylene terephthalate resin composition having excellent mechanical properties, processability, flame retardancy, and elongation despite containing a high content of polybutylene terephthalate.

[0053] Therefore, the polybutylene terephthalate resin composition according to the present invention can be applied to various electrical material fields including connectors, sensors, and parking brake systems that particularly require its physical properties.

[0054]

[0055] Hereinafter, the polybutylene terephthalate resin composition of the present invention, its manufacturing method, and a molded article including the same are described in detail.

[0056]

[0057] As used herein, the term "comprising" may be defined as "comprising manufactured by polymerization," "polymerized by including," or "comprising as a derived unit," unless otherwise defined. As used herein, a polymer comprising a compound means a polymer polymerized by including the compound, wherein the units in the polymerized polymer are derived from the compound.

[0058] In this description, the composition ratio of the (co)polymer may mean the content of the unit constituting the (co)polymer, or may mean the content of the unit introduced during polymerization of the (co)polymer.

[0059] In this description, “content” means weight unless otherwise defined, and “%” means weight% unless otherwise defined.

[0060]

[0061] The present inventors have confirmed that when a polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5 is included in a high content, and an organometallic salt-based phosphinate flame retardant, a phosphate-based flame retardant, and a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer is included in a predetermined content, the mechanical properties, processability, and flame retardancy as well as elongation are particularly excellent, and based on this, they have devoted themselves to further research and completed the present invention.

[0062]

[0063] The polybutylene terephthalate resin composition of the present invention comprises, for example, 100 parts by weight of polybutylene terephthalate; 1 to 30 parts by weight of an organometallic salt-based phosphinate flame retardant; 1 to 30 parts by weight of a phosphate-based flame retardant; and 1 to 30 parts by weight of a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer; and is characterized in that it does not contain reinforcing fibers or polyethylene terephthalate, and in this case, while containing a high content of polybutylene terephthalate, it has the effect of providing excellent mechanical properties, processability, flame retardancy, and elongation, and a balance between properties.

[0064]

[0065] Hereinafter, each component constituting the polybutylene terephthalate resin composition of the present invention will be examined in detail.

[0066]

[0067] polybutylene terephthalate

[0068] The polybutylene terephthalate used in the present invention may be a non-reinforced material.

[0069] As a specific example, the polybutylene terephthalate may include a polybutylene terephthalate (first polybutylene terephthalate) having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5 and a polybutylene terephthalate (second polybutylene terephthalate) having an intrinsic viscosity (IV) of more than 0.8 and less than 1.1 in a weight ratio of 1:0 to 1:1. Within this range, there is an advantage of excellent mechanical strength and elongation.

[0070]

[0071] Polybutylene terephthalate

[0072] In the present description, the first polybutylene terephthalate may be a polybutylene terephthalate having an intrinsic viscosity (IV) of greater than 1.1 and less than or equal to 1.5.

[0073] The above first polybutylene terephthalate is not particularly limited as long as it follows the definition of the present invention, and for example, it may be polybutylene terephthalate that has not undergone a molding process such as injection molding after polymerization of monomers constituting polybutylene terephthalate, or an available polybutylene terephthalate corresponding thereto.

[0074] The above first polybutylene terephthalate may be referred to, for example, as first (virgin) polybutylene terephthalate, new polybutylene terephthalate, fresh polybutylene terephthalate, or non-recycled polybutylene terephthalate.

[0075] The first polybutylene terephthalate of the present invention can optimize elongation and flow index by having, for example, an intrinsic viscosity (IV) of greater than 1.1 and less than or equal to 1.5, preferably 1.15 to 1.5, and more preferably 1.15 to 1.3.

[0076] Unless otherwise specified, the above intrinsic viscosity is a value measured at 20°C using an Ubbelohde viscometer after completely dissolving the sample to be measured in a methylene chloride solvent at a concentration of 0.05 g / ml and filtering the filtrate using a filter.

[0077] The above first polybutylene terephthalate may have a polydispersity index of, for example, 2.75 or less, preferably 2.6 or less, more preferably 2.5 or less, and even more preferably 2.0 to 2.5, and within this range, it may satisfy an excellent physical property balance between elongation and flow index.

[0078] In this document, the polydispersity index (PI) refers to the distribution of molecular weight and is calculated by dividing the weight-average molecular weight by the number-average molecular weight. A high polydispersity index indicates a large standard deviation of the molecular weight distribution, implying that there are more molecules of higher or lower molecular weight than the weight-average molecular weight.

[0079] In this description, unless otherwise defined, the weight average molecular weight and number average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, can be measured as relative values ​​to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. At this time, as a specific measurement example, the solvent is THF, the column temperature is 40 ℃, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, the injection amount is 5 ㎕, the column model is 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B (250x4.6mm) + 1xPLgel 10㎛ MiniMix-B Guard (50x4.6mm), the measuring device is Agilent 1200 series system, the refractive index detector: Agilent G1362 RID, the RI temperature is 35 ℃, the data processing is Agilent ChemStation S / W, and the test method (Mn, Mw, and PDI) can be measured under OECD TG 118 conditions.

[0080] The above first polybutylene terephthalate may have a weight average molecular weight of, for example, 28,000 g / mol or more, preferably 29,000 g / mol or more, more preferably 30,000 g / mol or more, and even more preferably 30,000 to 37,000 g / mol, and within this range, it has excellent mechanical properties and property balance.

[0081] Polybutylene terephthalate (PBT) is not particularly limited and can be manufactured and used through a method known in the art, or a commercially available material can be used.

[0082] The polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5 may be included in an amount of, for example, 30 to 85 wt%, specifically 30 to 80 wt%, and preferably 35 to 80 wt%, of the total 100 wt% of the polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5, the metal salt of phosphinic acid, the non-halogen phosphate flame retardant, the polyester elastomer or the ethylene-glycidyl (meth)acrylate copolymer, and the additives, in which case an excellent physical property balance between elongation and flow index can be satisfied.

[0083] The first polybutylene terephthalate may be, for example, 25 to 75 wt%, preferably 25 to 70 wt%, and more preferably 30 to 70 wt% in the polybutylene terephthalate resin, and within this range, it has the advantage of excellent impact resistance and heat resistance.

[0084] The above first polybutylene terephthalate may be a polymerized resin including, for example, an aromatic diol compound and a carbonate precursor.

[0085] The above aromatic diol compounds include, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, It may be at least one selected from the group consisting of 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and α,ω-bis[3-(ο-hydroxyphenyl)propyl]polydimethylsiloxane, and preferably bisphenol A.

[0086] The above carbonate precursor may be, for example, at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformates, and from the viewpoint of manufacturing efficiency and physical properties, it may be preferable to use triphosgene, phosgene, or a mixture thereof.

[0087] As a specific example, polybutylene terephthalate formed by polymerization of the aromatic diol compound and carbonate precursor includes a repeating unit represented by the following chemical formula 3.

[0088] [Chemical Formula 3]

[0089]

[0090] In the above chemical formula 3, R'1 to R'4 are each independently hydrogen, C 1-10 Alkyl group, C 1-10 an alkoxy group, or a halogen, and Z' is unsubstituted or C 1-6 Alkyl group C 6-20 C substituted with an aryl group 1-10 Alkylene group, unsubstituted or C 1-10 C substituted with an alkyl group 3-15 Cycloalkylene group, O, S, SO, SO2, or CO.

[0091] Preferably, in the above chemical formula 3, R'1 to R'4 are each independently hydrogen or C 1-3 An alkyl group, and Z' is C which is unsubstituted or substituted with a methyl group or a phenyl group. 1-6 It may be an alkylene group.

[0092]

[0093] Secondary polybutylene terephthalate

[0094] In this description, the second polybutylene terephthalate has an intrinsic viscosity (IV) of greater than 0.8 and less than or equal to 1.1, preferably 0.85 to 1.1, more preferably 0.9 to 1.1, so that it can satisfy an excellent physical property balance between elongation and flow index.

[0095]

[0096] The above second polybutylene terephthalate may have a polydispersity index of, for example, greater than 2.75, preferably greater than 2.8, and more preferably from 2.8 to 3, and within this range, it has excellent mechanical properties and property balance.

[0097]

[0098] The above second polybutylene terephthalate may have a weight average molecular weight of, for example, 20,000 g / mol or more and less than 28,000 g / mol, preferably 22,000 to 27,000 g / mol, more preferably 23,000 to 27,000 g / mol, and within this range, it has excellent mechanical properties and property balance.

[0099]

[0100] The second polybutylene terephthalate is known to have been used in small amounts of less than 25 wt% in polybutylene terephthalate resin compositions in the past because all physical properties, such as impact resistance, heat resistance, heat resistance, and elongation, are lower than those of the first polybutylene terephthalate, but the polybutylene terephthalate resin composition according to the present invention has excellent mechanical properties, processability, flame retardancy, and elongation even when the second polybutylene terephthalate is included in an excessive amount of 20 wt% or more, preferably 23 wt% or more, in the polybutylene terephthalate-based resin.

[0101]

[0102] The monomer forming the second polybutylene terephthalate may preferably be selected within the same range as that mentioned for the first polybutylene terephthalate.

[0103] The above second polybutylene terephthalate may be a commercially available product, for example, as long as it follows the definition of the present invention.

[0104]

[0105] Organometallic salt phosphinate flame retardant

[0106] An organometallic salt-based phosphinate flame retardant is added to increase the flame retardancy of a resin composition, and can be represented by the structure of the following chemical formula 1.

[0107] [Chemical Formula 1]

[0108]

[0109] (Above, R1 and R2 are each an alkyl group or an aryl group having 1 to 6 carbon atoms, M is at least one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and a protonated nitrogen base, and n is 1 to 4.)

[0110] As a specific example, the above organometallic salt-based phosphinate flame retardant may have a structure represented by the following chemical formula 1-1.

[0111] [Chemical Formula 1-1]

[0112]

[0113] The above-mentioned organometallic salt-based phosphinate flame retardant may be, for example, 10 to 20 wt%, preferably 13 to 20 wt%, and more preferably 13 to 18 wt%, of the total amount of 100 wt% of all components constituting the polybutylene terephthalate resin composition (first polybutylene terephthalate, second polybutylene terephthalate, organometallic salt-based phosphinate flame retardant, phosphate-based flame retardant, polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer, and additives). If the amount is outside the above range, elongation and flame retardancy are reduced, and problems such as surface unevenness of the injection-molded product on the surface of the molded product manufactured using the polybutylene terephthalate resin composition including the same occur, which has the disadvantage of lowering the appearance quality.

[0114]

[0115] Phosphate flame retardants

[0116] A phosphate-based flame retardant is added to increase the flame retardancy of the resin composition by the first additive described above, and can be represented by the structure of the following chemical formula 2.

[0117] [Chemical Formula 2]

[0118]

[0119] (In the above chemical formula 2, R3, R4 and R5 are the same or different and are hydrogen or a C1-C4 alkyl group, X is a C6-C20 aryl group or a C6-C20 aryl group substituted with a C1-C4 alkyl group, and n is an integer from 0 to 4.)

[0120] X may preferably be derived from a dialcohol of resorcinol, hydroquinol or bisphenol A.

[0121] When n is 0, there are triphenyl phosphate, tricresyl phosphate, tricxilenyl phosphate, tri(2,6-dimethylphenyl) phosphate, tri(2,4,6-trimethylphenyl) phosphate, tri(2,4-ditertiary butylphenyl) phosphate, and tri(2,6-ditertiary butylphenyl) phosphate.

[0122] When n is 1, there are resorcinol bis(diphenyl)phosphate, resorcinol bis(2,6-dimethylphenyl)phosphate, resorcinol bis(2,4-ditertiarybutylphenyl)phosphate, hydroquinol bis(2,6-dimethylphenyl)phosphate, hydroquinol bis(2,4-ditertiarybutylphenyl)phosphate, etc.

[0123] The above phosphate flame retardants can be applied alone or as a mixture.

[0124] Preferably, the phosphate flame retardant may be resorcinol bis(2,6-dimethylphenyl)phosphate.

[0125] The above-mentioned organometallic salt-based phosphinate flame retardant: phosphate-based flame retardant can provide a synergistic flame retardancy effect without affecting other properties when used in a weight ratio of 1:0.2 to 1:0.9 or a weight ratio of 1:0.2 to 1:0.6.

[0126]

[0127] The above phosphate-based flame retardant may be present in an amount of, for example, 1 to 10 wt%, preferably 2 to 10 wt%, and more preferably 3 to 9 wt%, based on 100 wt% of the total weight of all components (first polybutylene terephthalate, second polybutylene terephthalate, organometallic salt-based phosphinate flame retardant, phosphate-based flame retardant, polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer, and additives) constituting the polybutylene terephthalate resin composition. If the amount is outside the above range, elongation and flame retardancy are reduced, and a problem of surface unevenness of the injection-molded product manufactured using the polybutylene terephthalate resin composition including the same occurs, which has the disadvantage of lowering the appearance quality.

[0128]

[0129] polyester elastomer

[0130] The polyester elastomer of the present invention can be used for impact reinforcement of a resin composition in combination with an ethylene-glycidyl (meth)acrylate copolymer described below.

[0131] The above polyester elastomer may include a unit derived from an aliphatic dicarboxylic acid or an ester-forming derivative thereof, a unit derived from an aliphatic diol, and a unit derived from a polyalkylene oxide.

[0132] The above aromatic dicarboxylic acid derived unit may be at least one selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 1,4-cyclohexane dicarboxylic acid.

[0133] The ester-forming derivative of the above aromatic dicarboxylic acid may be at least one derived unit selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethyl naphthalene dicarboxylate, and dimethyl 1,4-cyclohexane dicarboxylate, and among these, a derived unit from dimethyl terephthalate is preferable.

[0134] The above-mentioned unit derived from a dicarboxylic acid or an ester-forming derivative thereof may be included in an amount of 25 to 65 wt% or 30 to 60 wt% based on the total weight of the polyester-based elastomer, and of these, 30 to 60 wt% is preferred.

[0135] The above aliphatic diol-derived unit has a weight average molecular weight of 300 g / mol or less and may be a unit derived from an aliphatic diol.

[0136] The above aliphatic diol-derived unit may be at least one derived unit selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol, and among these, a 1,4-butanediol-derived unit is preferred.

[0137] The above aliphatic diol-derived unit may be included in an amount of 20 to 45 wt% or 25 to 40 wt% based on the total weight of the polyester-based elastomer, and of these, 25 to 40 wt% is preferred.

[0138] The above polyalkylene oxide-derived unit is an aliphatic polyether and can act as a soft segment in the polyester-based elastomer.

[0139] The above polyalkylene oxide derived unit may be at least one derived unit selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of polypropylene glycol, and a copolymer of ethylene oxide and tetrahydrofuran, and among these, a derived unit of polytetramethylene glycol or an ethylene oxide addition polymer of polypropylene glycol is preferable.

[0140] The polytetramethylene glycol may have a number average molecular weight of 600 to 3,000 g / mol, 1,000 to 2,500 g / mol, or 1,800 to 2,200 g / mol, of which 1,800 to 2,200 g / mol is preferable.

[0141] The ethylene oxide addition polymer of the above polypropylene glycol may be a polypropylene glycol whose terminals are capped with ethylene oxide, and may have a weight average molecular weight of 2,000 to 3,000 g / mol.

[0142] The above polyalkylene oxide-derived unit may be included in an amount of 10 to 50 wt% or 15 to 45 wt% based on the total weight of the thermoplastic polyester elastomer. When the above-described range is satisfied, the flexibility, heat resistance, and compatibility of the polyester elastomer may be improved.

[0143] Meanwhile, the polyester elastomer may have a weight average molecular weight of 2,000 to 3,000 g / mol.

[0144] The above polyester elastomer may have a Shore D hardness of 35 to 55D or 40 to 50D, and when the above-described range is satisfied, extrusion processing and molding of the polybutylene terephthalate resin composition can be facilitated, and chemical resistance can be improved.

[0145] When the weight of the above polyester elastomer is measured at a temperature of 230°C and a load of 2.16 kg for 10 minutes according to ASTM D1238, the melt index may be 0.1 to 10 g / min or 1 to 10 g / min. When the above-described range is satisfied, the extrusion processing and molding of the polybutylene terephthalate resin composition are easy, and the chemical resistance can be improved.

[0146]

[0147] Meanwhile, the polyester-based elastomer can be produced by a production method including: (a) a step of melt polymerizing an aromatic dicarboxylic acid or an ester-forming derivative thereof, an aliphatic diol, and a polyalkylene oxide to produce a polyester-based elastomer precursor; and (b) a step of solid-state polymerizing the polyester-based elastomer precursor to produce a polyester-based elastomer.

[0148]

[0149] Hereinafter, each step of the manufacturing method of the polyester elastomer is described in detail.

[0150] (a) Step for manufacturing a polyester elastomer precursor

[0151] First, an aromatic dicarboxylic acid or an ester-forming derivative thereof, an aliphatic diol, and a polyalkylene oxide can be prepared as starting materials.

[0152] The aromatic dicarboxylic acid or its ester-forming derivative may be added in an amount of 25 to 65 wt% or 30 to 60 wt% based on the total weight of the starting material, with 30 to 60 wt% being preferred. When the above-described range is satisfied, the reaction balance is excellent, allowing melt polymerization to be performed smoothly.

[0153] Specific examples of the aromatic dicarboxylic acid or its ester-forming derivatives are as described above.

[0154] The above aliphatic diol can be added in an amount of 20 to 45 wt% or 25 to 40 wt% based on the total weight of the starting material. When the above-described range is satisfied, the reaction balance is excellent, allowing melt polymerization to be performed smoothly.

[0155] Specific examples of the above aliphatic diols are as described above.

[0156] The polyalkylene oxide may be added in an amount of 10 to 50 wt% or 15 to 45 wt% based on the total weight of the starting material, and is preferably added in an amount of 15 to 45 wt%. When the above-described range is satisfied, the flexibility, heat resistance, and compatibility of the polyester elastomer can be improved.

[0157] Specific examples of the polyalkylene oxide are as described above.

[0158] Next, a catalyst is first added to the starting material, and melt polymerization can be initiated after the temperature is raised to 140 to 215°C.

[0159] The above catalyst may be titanium butoxide.

[0160] When the above melt polymerization is initiated, an ester exchange reaction can be performed between the starting materials, thereby producing an oligomer, preferably a bis(4-hydroxybutyl)terephthalate (BHBT) oligomer.

[0161] The above ester exchange reaction can be carried out for 1 to 3 hours or 1 hour 30 minutes to 2 hours 30 minutes.

[0162] Next, after a catalyst is secondarily added to the oligomer, the temperature is increased to 215 to 245°C, and then a polycondensation reaction can be performed while reducing the pressure from 760 torr to 0.3 torr, and a polyester elastomer precursor can be manufactured through the polycondensation reaction.

[0163] The above polycondensation reaction can be carried out for 1 to 3 hours or 1 hour 30 minutes to 2 hours 30 minutes.

[0164] When the above polyester elastomer precursor is weighed at a temperature of 230°C and a load of 2.16 kg for 10 minutes according to ASTM D1238, the melt index may be 15 to 25 g / min or 18 to 22 g / min.

[0165] Next, the polyester elastomer precursor can be extruded in the form of strands under nitrogen pressure and pelletized to produce a polyester elastomer precursor in the form of pellets.

[0166] Meanwhile, during the above melt polymerization, a branching agent may be further added to improve the melt viscosity and melt tension of the polyester elastomer.

[0167] The above branching agent may be at least one selected from the group consisting of glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylol propane, and neopentyl glycol, among which trimellitic anhydride is preferred.

[0168] The above branching agent may be included in an amount of 0.05 to 0.1 wt% based on 100 wt% of the starting material. When the above-described range is satisfied, the melt viscosity and degree of polymerization of the polyester elastomer are appropriate, making it easy to control the melt polymerization reaction and facilitating the discharge of the polyester elastomer precursor outside the reactor.

[0169] (A) Manufacturing steps of polyester elastomer

[0170] Next, the polyester elastomer precursor can be solid-phase polymerized to produce a polyester elastomer.

[0171] The above solid-state polymerization can be performed by introducing the polyester elastomer precursor into a solid-state polymerization reactor, and then gradually reducing the pressure to high vacuum under an inert atmosphere at 140 to 200°C for 10 to 24 hours.

[0172] The above solid-state polymerization reactor may be a vessel vacuum dryer connected to a rotatable high vacuum pump, and the inert atmosphere may be a nitrogen atmosphere.

[0173] Meanwhile, the polyester elastomer may be a commercially available material, and preferably, LG Chemical's KEYFLEX BT 1040D (DSC melting point 198°C, hardness Shore D 40) may be used.

[0174] The polyester elastomer may be present in an amount of, for example, 1 to 10 wt%, preferably 2 to 10 wt%, and more preferably 3 to 9 wt%, of the total amount of 100 wt% of all components (first polybutylene terephthalate, second polybutylene terephthalate, organometallic salt-based phosphinate flame retardant, phosphate-based flame retardant, polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer, and additives) constituting the polybutylene terephthalate resin composition. Within this range, there is an advantage in that impact resistance is greatly improved without deteriorating the original mechanical properties and compatibility of the resin.

[0175]

[0176] ethylene-glycidyl (meth)acrylate copolymer

[0177] The ethylene-glycidyl (meth)acrylate copolymer of the present invention can be used for impact reinforcement of a resin composition.

[0178] The above ethylene-glycidyl (meth)acrylate copolymer may be a polyethylene copolymer in which glycidyl (meth)acrylate is polymerized.

[0179] The above glycidyl (meth)acrylate may be included in an amount of 3 wt% or more, 3 to 10 wt%, or 3 to 7 wt% of the total components constituting the ethylene-glycidyl (meth)acrylate copolymer, and in this case, it can sufficiently provide impact reinforcement and elongation increasing effects.

[0180] The above ethylene-glycidyl (meth)acrylate copolymer contains a compound represented by the following chemical formula 4, and in this case has the advantage of excellent impact resistance.

[0181] [Chemical Formula 4]

[0182]

[0183] The ethylene-glycidyl (meth)acrylate copolymer may be a copolymer of an olefin monomer and a monomer containing an epoxy group as in the above chemical formula 4.

[0184] As the above olefin monomer, ethylene can be used, and if necessary, an alkylene having 3 to 19 carbon atoms, such as propylene, isopropylene, butylene, isobutylene, octene, or a combination thereof, can be used.

[0185] As the monomer containing the above epoxy group, glycidyl (meth)acrylate or the like can be used. The glycidyl (meth)acrylate comonomer incorporated in this manner can be used in an amount of 0.01 wt% or more, 5 wt% or more, 5 to 40 wt%, 5 to 30 wt%, or 10 to 25 wt% of the total weight of all components constituting the copolymer.

[0186] Preferably, the glycidyl-modified olefin rubber polymer may be a polyethylene copolymer grafted with a compound represented by the chemical formula 4 and glycidyl (meth)acrylate, and in this case, excellent impact strength is achieved.

[0187] As a more preferred example, the glycidyl-modified olefin rubber polymer may be a copolymer polymerized including ethylene, glycidyl (meth)acrylate and vinyl acetate, in which case the impact strength is excellent.

[0188]

[0189] The above-mentioned glycidyl-modified olefin rubber polymer may be present in an amount of, for example, 1 to 10 wt%, preferably 2 to 10 wt%, and more preferably 3 to 9 wt%, of the total amount of 100 wt% of all components (first polybutylene terephthalate, second polybutylene terephthalate, organometallic salt-based phosphinate flame retardant, phosphate-based flame retardant, polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer, and additives) constituting the polybutylene terephthalate resin composition. Within this range, there is an advantage in that impact resistance is greatly improved without deteriorating the original mechanical properties and compatibility of the resin.

[0190]

[0191] polybutylene terephthalate resin composition

[0192] The above polybutylene terephthalate resin composition may preferably be a polybutylene terephthalate resin composition for injection molding, and has the advantage of being able to manufacture a product having a thin thickness or a complex structure during injection molding because it has excellent flame retardancy and elongation and thus does not cause phase separation.

[0193] For example, the polybutylene terephthalate resin composition of the present invention can satisfy a>b>c, where the content of the organometallic salt-based phosphinate flame retardant is a, the content of the phosphate-based flame retardant is b, and the content of the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer is c. In this case, compatibility, dispersibility, processability, etc. can be affected, and mechanical strength, processability, flame retardancy, and elongation can be significantly improved.

[0194] The above organometallic salt-based phosphinate flame retardant and the phosphate-based flame retardant may be in a weight ratio (a:b) of 7:2 to 7:4. In this case, compatibility, dispersibility, processability, etc. may be affected, and mechanical strength, processability, flame retardancy, and elongation may be significantly improved.

[0195] The above phosphate flame retardant and the polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer may have a weight ratio (b:c) of 4:3 to 8:3. In this case, compatibility, dispersibility, processability, etc. may be affected, and mechanical strength, processability, flame retardancy, and elongation may be significantly improved.

[0196]

[0197] The polybutylene terephthalate resin composition of the present invention may include, for example, at least one selected from the group consisting of a heat stabilizer, a flame retardant, a flame retardant auxiliary agent, a lubricant, a processing aid, a plasticizer, a coupling agent, a light stabilizer, a release agent, a dispersant, an anti-drip agent, a weather stabilizer, an antioxidant, a compatibilizer, a pigment, a dye, an antistatic agent, a wear-resistant agent, a filler, and an antibacterial agent, within a range that does not impair the physical properties of each component, depending on the purpose, and preferably may include at least one selected from the group consisting of an antioxidant, a colorant, a lubricant, a release agent, a heat stabilizer, and a plasticizer, and in this case, there is an advantage of excellent impact strength and processability without deteriorating mechanical properties.

[0198] The above additive is included in an amount of 7 wt% or less among a total of 100 wt% of polybutylene terephthalate; an organometallic salt-based phosphinate flame retardant; a phosphate-based flame retardant; a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer; and the additive, and may be included in an amount of 0.1 to 5 wt%, preferably 0.1 to 3 wt%, and more preferably 0.2 to 0.8 wt%.

[0199] As an example, the above antioxidant may be a known antioxidant that is incorporated into a polybutylene terephthalate resin composition.

[0200] Examples of the above antioxidants include phosphorus-based antioxidants and phenol-based antioxidants.

[0201] Examples of the above hindered phenol antioxidant include pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], thiodiethylene-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc.

[0202] The above-mentioned antioxidant may include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite or bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0203] According to the present invention, it may be desirable to use two different types of the aforementioned antioxidants in combination, and specifically, heat resistance can be further improved by using a combination of a hindered phenol antioxidant and a phosphorus antioxidant.

[0204] The above hindered phenol antioxidant and phosphorus antioxidant can be mixed and used in a weight ratio of, for example, 1:0.1 to 1:1, preferably 1:0.4 to 1:1, more preferably 1:0.6 to 1:1, and when mixed in the above mixing ratio, the heat resistance can be further improved without deterioration of the physical properties of the resin composition.

[0205] The antioxidant may be included in an amount of 0.01 to 5 wt%, preferably 0.01 to 3 wt%, of the total 100 wt% of polybutylene terephthalate; organometallic salt-based phosphinate flame retardant; phosphate-based flame retardant; polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer; and additives, and excellent heat resistance is achieved within this range.

[0206] As an example, the above anti-dropping agent may be a known anti-dropping agent that is incorporated into a polybutylene terephthalate resin composition.

[0207] As a specific example, it is preferable to use at least one of tetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / vinylidene fluoride copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and ethylene / tetrafluoroethylene copolymer because it can improve flame retardancy quality through an anti-dripping effect.

[0208] In one embodiment of the present invention, a commercially available product can be used as the anti-loading agent.

[0209] The above anti-drip agent may be included in at least one of polybutylene terephthalate, an organometallic salt-based phosphinate flame retardant, a phosphate-based flame retardant, a polyester-based elastomer, or an ethylene-glycidyl (meth)acrylate copolymer, in an amount of 0.01 to 5 wt%, 0.1 to 3 wt%, 0.1 to 2 wt%, 0.1 to 1 wt%, or 0.2 to 0.8 wt%, based on a total of 100 wt% of the lubricant, the antioxidant, and the anti-drip agent. If the content of the anti-drip agent is too high outside the above range, there is a disadvantage in that the moldability of a molded article manufactured using a polyester resin composition including the same is lowered, thereby lowering the quality, and if it is less than the range, the anti-drip effect cannot be sufficiently exhibited.

[0210] The above colorant may be included in a total of 100 wt% of polybutylene terephthalate; an organometallic salt-based phosphinate flame retardant; a phosphate-based flame retardant; a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer; and additives, for example, 0.01 to 5 wt%, preferably 0.01 to 3 wt%, and the processability is excellent within the above range.

[0211] The above-mentioned colorant masterbatch may be, for example, a carbon colorant masterbatch, in which case the composition has the effect of preventing layer separation and improving dispersibility.

[0212] The above-mentioned active agent may be, for example, pentaerythritol tetrastearate, in which case it has the effect of improving the wettability of the composition of the present invention while also providing excellent heat resistance, processability, etc.

[0213] The above-mentioned active agent may be included in a total of 100 wt% of polybutylene terephthalate; an organometallic salt-based phosphinate flame retardant; a phosphate-based flame retardant; a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer; and additives, for example, 0.01 to 3 wt%, preferably 0.01 to 2 wt%, and within this range, the wettability of the polybutylene terephthalate composition is improved while at the same time exhibiting excellent mechanical properties.

[0214] The heat stabilizer may be, for example, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite (TBPP), 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite. It may be at least one selected from the group consisting of (2,4-di-t-butylphenyl) pentaerythritol diphosphite (PEP24), bis (2,4-dicumylphenyl)pentaerythritol diphosphite, and tetrakis(2,4-di-tertbutylphenyl)[1,1-biphenyl]-4,4'-diyl bisphosphonate.

[0215] The above heat stabilizer may be included in a total of 100 wt% of polybutylene terephthalate; an organometallic salt-based phosphinate flame retardant; a phosphate-based flame retardant; a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer; and additives, for example, 0.01 to 2 wt%, preferably 0.01 to 1 wt%, and within this range, heat resistance is excellent.

[0216] In this description, the release agent may be of a type used in the relevant technical field, as long as it does not affect impact strength, processability, flame retardancy, and high mold shrinkage.

[0217] The above release agent may be included in a total of 100 wt% of polybutylene terephthalate; an organometallic salt-based phosphinate flame retardant; a phosphate-based flame retardant; a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer; and additives, for example, 0.01 to 5 wt%, preferably 0.01 to 3 wt%, and excellent release properties are achieved within the above range.

[0218] In this description, the plasticizer may be of a type used in the relevant technical field, as long as it does not affect impact strength, processability, flame retardancy, and high molding shrinkage.

[0219] The plasticizer may be included in an amount of, for example, 0.01 to 5 wt%, preferably 0.01 to 3 wt%, of the total 100 wt% of polybutylene terephthalate; an organometallic salt-based phosphinate flame retardant; a phosphate-based flame retardant; a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer; and additives, and the flame retardancy is excellent within the above range.

[0220]

[0221] The polybutylene terephthalate resin composition of the present invention may have an elongation of 22% or more, or 22 to 50%, measured by ISO 527 at 50 mm / min, and has the effect of excellent elongation and improved durability within this range.

[0222] The polybutylene terephthalate resin composition of the present invention may have an Izod impact strength (23°C, Notched) of 4.7 kJ / m2 or more, or 4.8 to 5.1 kJ / m2, measured on a 4 mm thick specimen according to ISO 180, and has the effect of improving the physical property balance within this range.

[0223] The polybutylene terephthalate resin composition of the present invention may have a flame retardancy of V0 or higher measured for a specimen size of 0.8 mm according to the UL94 method.

[0224] The polybutylene terephthalate resin composition of the present invention may have a fluidity measured according to ISO1133 of 9.2 g / 10 min or more, or 9.2 to 30 g / 10 min.

[0225]

[0226] Hereinafter, a method for producing a polybutylene terephthalate resin composition of the present invention will be described.

[0227]

[0228] Method for producing polybutylene terephthalate resin composition

[0229] When describing a method for manufacturing a polybutylene terephthalate resin composition of the present invention, all of the contents of the polybutylene terephthalate resin composition described above are included.

[0230] The method for producing a polybutylene terephthalate resin composition of the present invention is characterized by including a step of introducing polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5, a metal salt of diethylphosphinic acid, a resorcinol-based phosphate ester, and a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer into an extruder, melt-kneading, and extruding the mixture. In this case, the composition satisfies a balance between physical properties, thereby providing excellent mechanical strength, processability, flame retardancy, and elongation to electrical and electronic products or automotive parts having a thin thickness or complex structure, and has the advantage of realizing excellent injection molding characteristics.

[0231] The method for producing the above polybutylene terephthalate resin composition may include the above-described additive.

[0232] In the method for producing the above polybutylene terephthalate resin composition, mixing and extrusion can be performed through a single-screw extruder, a twin-screw extruder, or a Banbury mixer, and is preferably performed through a twin-screw extruder. In this case, the composition is uniformly dispersed, and there is an effect of excellent compatibility.

[0233] The step of manufacturing pellets using the above extrusion mixer can be performed, for example, at a barrel temperature in a range of 210 to 290°C, 230 to 270°C, or 240 to 260°C, in which case sufficient melt mixing can be achieved while the processing amount per unit time is appropriate, and there is an effect of not causing problems such as thermal decomposition of resin components.

[0234] The step of manufacturing pellets using the above extrusion mixer can be performed under conditions where the screw rotation speed is, for example, 100 to 300 rpm / min, specifically 150 to 300 rpm / min, and preferably 200 to 300 rpm / min. In this case, the processing amount per unit time is appropriate, so the process efficiency is excellent, while there is an effect of suppressing excessive cutting.

[0235] The above polybutylene terephthalate resin composition pellets can be used as is or after being dehumidified and dried under hot air.

[0236] The above dehumidifying drying can be performed, for example, in a hot air dryer at a temperature range of 80 to 100°C for 3 hours or more.

[0237] The above pellets can be manufactured into an injection molded product using, for example, an injection molding machine at an injection barrel temperature of 210 to 300°C, 220 to 290°C, or 240 to 270°C.

[0238] The above extruder may have, for example, 6 or more, preferably 7 or more, more preferably 8 or more, preferably 8 to 15, and more preferably 9 to 12 kneading blocks. At this time, it may be effective to use the kneading blocks in combination in the order of forward, orthogonal, and reverse with respect to the resin flow direction, and a continuous or separated block combination may be used depending on the mixing method. In this case, the dispersibility of the components, the compatibility of the composition, etc. are further improved, thereby providing a kneaded product of higher quality.

[0239] The type of the above extruder is not particularly limited, and considering uniform mixing and dispersion, ease of processing, and economy, it may be preferable to use a twin-screw extruder with two screws.

[0240] The extruder is composed of a feeder for supplying materials into a barrel, a screw for transporting and mixing the materials supplied into the barrel, and a die for extruding the mixed materials, and the screw is composed of a plurality of screw elements to provide various functions.

[0241] The above raw material feeder may be one or more, and optionally, two or more may be provided as needed. For example, a main feeder and optionally, an auxiliary feeder may be provided, and two or more auxiliary feeders may be provided as needed.

[0242] For example, all components except the polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer may be injected into the main inlet, and the polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer may be injected into the auxiliary inlet 1.

[0243] As another example, it is also possible to input all components except the polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer and the flame retardant into the main input port, input the polyester elastomer or ethylene-glycidyl (meth)acrylate copolymer into the auxiliary input port, and input the flame retardant into the auxiliary input port 2.

[0244]

[0245] Hereinafter, a molded article comprising the polybutylene terephthalate resin composition of the present invention will be described. When describing the molded article of the present invention, all of the contents of the polybutylene terephthalate resin composition described above are included.

[0246]

[0247] molded products

[0248] The molded article of the present invention can be formed by including the polybutylene terephthalate resin composition. That is, the molded article of the present invention can be manufactured by extrusion molding or injection molding the polybutylene terephthalate resin composition described above, without limitation, using any method used in the art.

[0249] For example, the above-mentioned molded product may be formed by mixing and extruding the above-mentioned polybutylene terephthalate resin composition. The mixing and extrusion may be performed using a conventional extruder, and preferred examples include a single-screw extruder, a twin-screw extruder, etc.

[0250] The above-mentioned molded product may be, for example, an electrical / electronic product capable of injection molding or an automobile interior material, and in this case, the polybutylene terephthalate resin composition of the present invention has the advantage of being able to provide a high-quality molded product by satisfying all of the heat resistance, processability, electrical properties, flame retardancy properties, and high injection molding properties required by the market.

[0251] The above-mentioned molded article can be manufactured by extrusion molding the above-mentioned polybutylene terephthalate resin composition in various forms, for example, by molding it into the shape of various deformed extrusion molded articles, sheets, films, etc. by extrusion molding. The various extrusion molding methods include, but are not limited to, cold runner method, hot runner method, injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including cases by injection of supercritical fluid), insert molding, in-mold coating molding, insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding.

[0252] Therefore, the polybutylene terephthalate resin composition according to the present invention can be applied to various electrical material fields including connectors, sensors, and parking brake systems that particularly require its physical properties.

[0253]

[0254] In describing the polybutylene terephthalate resin composition, its manufacturing method and molded article of the present invention, it is stated that other conditions or equipment, etc. that are not explicitly described can be appropriately selected within the range commonly practiced in the art and are not particularly limited.

[0255]

[0256] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0257]

[0258] [Example]

[0259] Examples 1 to 5 and Comparative Examples 1 to 10

[0260] The raw materials used in the examples and comparative examples are as follows.

[0261] (A) Polybutylene terephthalate

[0262] (A-1) Intrinsic viscosity (IV) 1.2, Jangchunsa product name PBT 1100-211S

[0263] (A-2) Intrinsic viscosity (IV) 1.0, Tunhe product name TH6098A

[0264] (A-3) Intrinsic viscosity (IV) 0.8, Tunhe product name TH6082A

[0265] (B) Organometallic salt-based phosphinate flame retardant: Clariant, Exolit® OP 1240 (substance represented by the following chemical formula 1-1)

[0266] [Chemical Formula 1-1]

[0267]

[0268] (C) Phosphate flame retardant: Resorcinol bis(2,6-dimethylphenyl)phosphate (PX200, Daihachi, Japan) phosphorus content 8.7 wt%

[0269] (D-1) Polyester elastomer: keyflex BT 1040D (LG Chemical Co., Ltd.) with a hardness of 40D, composed of terephthalate as an aromatic dicarboxylic acid, 1,4-butanediol as an aliphatic diol, and polyoxytetramethylene glycol as an aliphatic polyether compound.

[0270] (D-2) Ethylene-glycidyl (meth)acrylate copolymer: DuPont product name Elvaloy PTW (GMA content 5 wt%)

[0271] (D-3) Melamine cyanurate

[0272] (D-4) Melamine polyphosphate

[0273] (E) Additives

[0274] E-1) Active agent: Lione Chemtec LC102N (PE-based)

[0275] E-2) Antioxidant: Songnox 6260

[0276] E-3) Anti-dropping agent: Teflon JF-4A

[0277]

[0278] The raw materials of the polybutylene terephthalate resin composition described in Tables 1 and 2 below were mixed, and then a polybutylene terephthalate resin composition having a uniform dispersion was manufactured in the form of pellets through extrusion. Then, a specimen was manufactured through an injection process in which the pellets were heated, injected into a mold, and then cooled.

[0279] Specifically, each component shown in Tables 1 and 2 below was mixed with a mixer, and then fed into the main inlet at a feed rate of 50 kg / h at 250 rpm using a twin-screw extruder (φ40, L / D: 42, SM Platek equipment) set to 250°C, and extruded to produce pellets of a polybutylene terephthalate resin composition. At this time, glass fiber was fed into the auxiliary inlet, and nine mixing blocks of the extruder were used.

[0280] The above pellets were dried in a convection oven at 120°C for more than 4 hours, and then injection molded using an injection molding machine (ENGEL, 80 tons) at an injection temperature of 250°C, a mold temperature of 60°C, and an injection speed of 30 mm / sec to produce a specimen.

[0281] Classification Example 1 Example 2 Example 3 Example 4 Example 5 A-173.375.377.751.451.4A-2---25.925.9B1414141414C86444D-13333-D-2----3

[0282] (The raw materials used in Table 1 above are each added in units of weight % for 100 wt %, which is the total of 0.8 wt % of the E-1) activator, 0.4 wt % of the E-2) antioxidant, and 0.5 wt % of the E-3) anti-dropping agent mentioned above in A-1 to D-2.)

[0283] ClassificationComparison Example 1Comparison Example 2Comparison Example 3Comparison Example 4Comparison Example 5Comparison Example 6Comparison Example 7Comparison Example 8Comparison Example 9Comparison Example 10A-176.376.376.376.351.471.377.369.379.377.8A-2----------A-3----25.9-----B14141414142010141414C--484481224D-1----333333D-2----------D-38---------D-4-84-------

[0284] (The raw materials used in Table 2 above were each added in units of weight % relative to 100 wt %, which is the total of 0.8 wt % of the E-1) lubricant, 0.4 wt % of the E-2) antioxidant, and 0.5 wt % of the E-3) anti-dropping agent, as described above in A-1 to D-4, and the raw materials used in Comparative Example 10 were each added in units of weight % relative to 100 wt %, which is the total of 0.8 wt % of the E-1) lubricant, and 0.4 wt % of the E-2) antioxidant, as described above in A-1 to D-4.)

[0285] Test Example 1: Evaluation of physical properties of molded product specimens

[0286] The physical properties of the molded product specimens manufactured in Examples 1 to 5 and Comparative Examples 1 to 10 were evaluated. The evaluation criteria are as follows.

[0287] -Tensile strength (MPa): Measured according to ISO 527 at 50 mm / min.

[0288] - Elongation (%): Measured according to ISO 527 at 50 mm / min.

[0289] -Flexural strength (MPa): Measured according to ISO 178 at 2 mm / min.

[0290] -Impact strength (IZOD): Measured on 4 mm thick specimens according to ISO 180 (Notched, 23 ℃).

[0291] -Flame retardancy: Measured using a specimen size of 0.8 mm according to UL94.

[0292]

[0293] The results measured using the above evaluation criteria are shown in Tables 3 and 4 below.

[0294] ClassificationExample 1Example 2Example 3Example 4Example 5Tensile strength (MPa)3337393839Elongation (%)42.526.729.427.525.7Flexural strength (MPa)5364646765Impact strength (kJ / m) 2 )4.85.15.15.14.8 Flame retardancyV0V0V0V0V0

[0295] ClassificationComparative Example 1Comparative Example 2Comparative Example 3Comparative Example 4Comparative Example 5Comparative Example 6Comparative Example 7Comparative Example 8Comparative Example 9Comparative Example 10Tensile strength (MPa)47494841404543304439Elongation (%)1.72.55.21919.72.22342.121.128.1Flexural strength (MPa)77797868687271487264Impact strength (kJ / m 2 )2.62.72.73.24.92.65.24.25.44.9Flame retardancyV0V1V1V0V0V0V1V0V0Not measurable

[0296] Referring to Tables 3 and 4 above, it can be confirmed that the polybutylene terephthalate resin compositions of Examples 1 to 5 according to the present invention contain an organometallic salt-based phosphinate flame retardant, a phosphate-based flame retardant, and a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer in a predetermined mixing ratio in polybutylene terephthalate, thereby maintaining or improving mechanical strength, processability, and flame retardancy while significantly improving elongation, thereby providing product reliability as an electrical component. On the other hand, it was confirmed that Comparative Example 1, which did not contain a phosphate-based flame retardant and used melamine cyanurate, showed significantly lower elongation and impact strength compared to Example 1, and thus failed to provide product reliability as an electrical component.

[0297] In addition, Comparative Examples 2 and 3, which did not include a phosphate-based flame retardant and used melamine polyphosphate, showed significantly lower elongation and impact strength compared to Example 1, and thus failed to provide product reliability as a component for electrical equipment.

[0298] Meanwhile, Comparative Example 4, which did not include either a polyester elastomer or an ethylene-glycidyl (meth)acrylate copolymer, showed significantly lower elongation and impact strength and poor processability compared to Example 1, and thus failed to provide product reliability as a component for electrical equipment.

[0299] In addition, Comparative Example 5, in which the inherent viscosity of unreinforced polybutylene terephthalate was inadequate, showed excellent processability compared to Example 1, but the elongation was reduced, resulting in poor results as a part.

[0300] In addition, Comparative Example 6, which used an excessive amount of the organometallic salt-based phosphinate flame retardant beyond the appropriate range, showed poor results with significantly reduced elongation and impact strength compared to Example 1.

[0301] In addition, Comparative Example 7, which used a small amount of an organometallic salt-based phosphinate flame retardant outside the appropriate range, showed poor flame retardancy compared to Example 1, making it unsuitable for application to parts.

[0302] In addition, Comparative Example 8, which used an excessive amount of phosphate-based flame retardant beyond the appropriate range, was confirmed to have lower tensile strength and flexural strength and poor processability compared to Example 1.

[0303] In addition, Comparative Example 9, which used a small amount of phosphate-based flame retardant outside of the appropriate range, showed a decrease in elongation compared to Example 1, resulting in a failure to provide product reliability.

[0304] In addition, Comparative Example 10, which did not include an anti-flammability agent, showed poor flame retardancy compared to Example 3.

[0305]

[0306] That is, the polybutylene terephthalate resin composition according to one embodiment of the present invention contains a high content of polybutylene terephthalate and includes one component selected from the group consisting of an organometallic salt-based phosphinate flame retardant, a phosphate-based flame retardant, a polyester-based elastomer, and an ethylene-glycidyl (meth)acrylate copolymer, thereby improving the mechanical properties, processability, flame retardancy, and elongation of a molded article manufactured therefrom, making it suitable for use in electrical components, etc.

Claims

1. Contains 100 parts by weight of polybutylene terephthalate; 1 to 30 parts by weight of an organometallic salt-based phosphinate flame retardant; 1 to 30 parts by weight of a phosphate-based flame retardant; and 1 to 30 parts by weight of a polyester-based elastomer or an ethylene-glycidyl (meth)acrylate copolymer. If the content of the above organometallic salt-based phosphinate flame retardant is a, the content of the phosphate-based flame retardant is b, and the content of the above polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer is c, then a>b>c is satisfied. The above organometallic salt-based phosphinate flame retardant and phosphate-based flame retardant are in a weight ratio (a:b) of 7:2 to 7:

4. A polybutylene terephthalate resin composition characterized in that the phosphate-based flame retardant and the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer are included in a weight ratio (b:c) of 4:3 to 8:

3.

2. In paragraph 1, A polybutylene terephthalate resin composition characterized in that the polybutylene terephthalate comprises polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5 and polybutylene terephthalate having an intrinsic viscosity (IV) of more than 0.8 and less than 1.1 in a weight ratio of 1:0 to 1:

1.

3. In paragraph 1, A polybutylene terephthalate resin composition characterized in that the above organometallic salt-based phosphinate flame retardant has a structure represented by the following chemical formula 1. [Chemical Formula 1] (Above, R1 and R2 are each an alkyl group or an aryl group having 1 to 6 carbon atoms, M is at least one selected from the group consisting of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and a protonated nitrogen base, and n is 1 to 4.) 4. In paragraph 1, A polybutylene terephthalate resin composition characterized in that the above phosphate-based flame retardant has a structure represented by the following chemical formula 2. [Chemical Formula 2] (In the above chemical formula 2, R3, R4 and R5 are each independently hydrogen or a C1-C4 alkyl group, X is a C6-C20 aryl group or a C6-C20 arylene group substituted with a C1-C4 alkyl group, and n is an integer from 0 to 4.) 5. In paragraph 1, A polybutylene terephthalate resin composition characterized in that the polyester elastomer is a compound composed of terephthalate as an aromatic dicarboxylic acid, 1,4-butanediol as an aliphatic diol, and polyoxytetramethylene glycol as an aliphatic polyether compound.

6. In paragraph 1, The above ethylene-glycidyl (meth)acrylate copolymer is a polybutylene terephthalate resin composition characterized in that an olefin monomer and a monomer containing an epoxy group are copolymerized.

7. Among the total 100 wt% of polybutylene terephthalate; organometallic salt-based phosphinate flame retardant; phosphate-based flame retardant; polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer; and additives, Containing 30 to 85 wt% of polybutylene terephthalate having an intrinsic viscosity (IV) of greater than 1.1 and less than or equal to 1.5, Contains 0 to 40 wt% of polybutylene terephthalate having an intrinsic viscosity (IV) of greater than 0.8 and less than 1.1, The above organometallic salt-based phosphinate flame retardant is contained in an amount of 10 to 20 wt%, The above phosphate flame retardant is contained in an amount of 1 to 10 wt%, A polybutylene terephthalate resin composition characterized in that the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer is contained in an amount of 1 to 5 wt%.

8. In paragraph 7, A polybutylene terephthalate resin composition characterized in that the additive is at least one selected from the group consisting of a heat stabilizer, a flame retardant, a flame retardant auxiliary agent, a lubricant, a processing aid, a plasticizer, a coupling agent, a light stabilizer, a release agent, a dispersant, an anti-dripping agent, a weather stabilizer, an antioxidant, a compatibilizer, a pigment, a dye, an antistatic agent, an abrasion agent, a filler, and an antibacterial agent.

9. In paragraph 1 or paragraph 7, A polybutylene terephthalate resin composition characterized in that the above polybutylene terephthalate resin composition is a material used in electrical components.

10. In paragraph 1, The above polybutylene terephthalate resin composition has an elongation of 22% or more as measured by ISO 527 at 50 mm / min, The Izod impact strength (23℃, Notched) measured on a 4 mm thick specimen according to ISO 180 is 4.7 kJ / m2 or more. A polybutylene terephthalate resin composition characterized in that the flame retardancy measured for a specimen size of 0.8 mm according to the UL94 method is V0 or higher.

11. Polybutylene terephthalate; organometallic salt-based phosphinate flame retardant; phosphate-based flame retardant; polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer; And a step of including 30 to 85 wt% of polybutylene terephthalate having an intrinsic viscosity (IV) of more than 1.1 and less than 1.5, 0 to 40 wt% of polybutylene terephthalate having an intrinsic viscosity (IV) of more than 0.8 and less than 1.1, 10 to 20 wt% of the organometallic salt-based phosphinate flame retardant, 1 to 10 wt% of the phosphate-based flame retardant, and 1 to 5 wt% of the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer, and introducing the mixture into an extruder, melt kneading, and extruding, If the content of the above organometallic salt-based phosphinate flame retardant is a, the content of the phosphate-based flame retardant is b, and the content of the above polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer is c, then a>b>c is satisfied. The above organometallic salt-based phosphinate flame retardant and phosphate-based flame retardant are in a weight ratio (a:b) of 7:2 to 7:

4. A method for producing a polybutylene terephthalate resin composition, characterized in that the phosphate-based flame retardant and the polyester-based elastomer or ethylene-glycidyl (meth)acrylate copolymer are included in a weight ratio (b:c) of 4:3 to 8:

3.

12. A molded product characterized by comprising a polybutylene terephthalate resin composition according to any one of claims 1 to 10.

13. In paragraph 12, A molded product characterized in that the above molded product is a component for a battlefield.

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