KR20210047256A - Thermoplastic resin composition, method for preparing the thermoplastic resin composition and molding products thereof - Google Patents

Abstract

The present invention is to provide a resin composition that can achieve flame retardancy while allowing laser transmission, wherein the resin composition comprises: 45 to 65 wt% of a polyamide-based resin; 20 to 35 wt% of glass fibers; 12 to 20 wt% of a phosphorus-based flame retardant; and 0.01 to 5 wt% of a colorant in which an organic dye and an inorganic pigment are combined, and the polyamide-based resin has a melting point of 200 to 240℃.

Description

Thermoplastic resin composition, manufacturing method thereof, and molded article including the same {THERMOPLASTIC RESIN COMPOSITION, METHOD FOR PREPARING THE THERMOPLASTIC RESIN COMPOSITION AND MOLDING PRODUCTS THEREOF}

The present invention relates to a thermoplastic resin composition, a manufacturing method thereof, and a molded article including the same, and more particularly, to a thermoplastic resin composition capable of implementing flame retardancy by laser transmission, a method of manufacturing the same, and a molded article including the same.

Methods of bonding synthetic resins include rotational fusion, vibration fusion, ultrasonic/harmonic fusion, and laser fusion. These methods are produced by generating heat (melting the surface of the bonding unit) and applying pressure directly through contact or radiation, or indirectly through internal/external friction or electrical effects.

Among them, laser fusion has the advantage of low cost and high efficiency, and it is a non-contact fusion method compared to the other fusion methods described above, so there is no external deformation of the product due to vibration, shock, or heat, and no burr or fluff is generated, so bonding quality. This is excellent. Above all, since it can be applied to 2D and 3D shaped products, it has the advantage of being independent of size and shape, but for laser fusion, the laser transmittance must be above the appropriate line.

In general, the thermoplastic resin composition used as a laser welding permeable material has mainly used NP color (natural pigment color) that does not contain any dyes or pigments. ) As the demand increases, various natural pigments have been used in combination to impart a color.

In general, in the case of materials that impart black color, dyes capable of laser transmission while expressing black have been developed because laser transmission is impossible, but all of them have a problem in that their structure is changed under high temperature conditions, causing discoloration and not implementing flame retardancy.

Therefore, development of a thermoplastic resin composition capable of laser transmission and securing flame retardancy while expressing black is required.

Korean Patent Publication No. 2010-0051745

In order to solve the problems of the prior art as described above, the present invention is to provide a resin composition capable of realizing flame retardancy while being capable of laser transmission. In addition, a colorant that exhibits black has excellent compatibility with a flame retardant, and even if it is mixed with a polyamide resin composition with a flame retardant, its discoloration inhibiting effect can be maintained, a method of manufacturing the same, and a molded article including the same. It aims to provide.

All of the above and other objects of the present description can be achieved by the present description described below.

In order to achieve the above object, the present invention is a polyamide-based resin 45 to 65% by weight; 20 to 35% by weight of glass fibers; 12 to 20% by weight of a phosphorus-based flame retardant; And 0.01 to 5% by weight of a colorant in which an organic dye and an inorganic pigment are combined, wherein the polyamide-based resin has a melting point of 200 to 240°C.

In addition, the present invention is a polyamide-based resin 45 to 65% by weight, glass fiber 20 to 35% by weight, phosphorus-based flame retardant 12 to 20% by weight, and 0.01 to 5% by weight of a colorant in which organic dyes and inorganic pigments are combined; mixing including And then producing a pellet using an extrusion kneader in a 10 to 100 pie standard under 200 to 330°C, wherein the polyamide-based resin has a melting point of 200 to 240°C. Provides.

In addition, the present invention provides a molded article comprising the thermoplastic resin composition.

According to the present invention, a thermoplastic resin composition that can be applied with high quality to automobile engine parts that are exposed to high temperatures for a long period of time, especially in the automotive field, due to its excellent flame retardancy while implementing a black color and allowing laser penetration to apply laser fusion, and a manufacturing method thereof And there is an effect of providing a molded article including the same.

In particular, the thermoplastic resin composition according to the present invention can minimize discoloration due to a high temperature applied in a molding process and/or an aging process while allowing a black color similar to that of a natural pigment to be expressed.

The discoloration inhibiting effect is also exhibited in a state where it is blended with a flame retardant in a polyamide-based resin composition, and such a resin composition is a product manufactured through a molding process and/or an aging process, as well as a product in which the product is exposed to high temperatures for a long period of time. It can also be expressed in the environment.

Hereinafter, the thermoplastic resin composition of the present disclosure, a method of manufacturing the same, and a molded article including the same will be described in detail.

The present inventors believe that when a polyamide resin having a predetermined melting point contains a colorant in which a glass fiber, a phosphorus-based flame retardant, and a predetermined organic dye and inorganic pigment are combined in a predetermined content range, laser fusion is possible and flame retardant. It was confirmed that this was secured, and based on this, the present invention was completed by further focusing on research.

A detailed look at the thermoplastic resin composition according to the present disclosure is as follows.

The thermoplastic resin composition of the present invention comprises 45 to 65% by weight of a polyamide-based resin; 20 to 35% by weight of glass fibers; 12 to 20% by weight of a phosphorus-based flame retardant; And 0.01 to 5% by weight of a colorant in which an organic dye and an inorganic pigment are combined, wherein the polyamide-based resin has a melting point of 200 to 240°C. In this case, as the black color is expressed, the laser transmittance is excellent, and the laser fusion property is expressed and the flame retardancy is excellent.

Hereinafter, the thermoplastic resin composition of the present invention will be described in detail for each configuration.

Polyamide resin

The polyamide-based resin is, for example, 45 to 65% by weight, preferably 47.5 to 62.5% by weight, more preferably 50 to 60% by weight, even more preferably 52.5 to 57.5% by weight based on the total weight of the thermoplastic resin composition. Within this range, mechanical properties such as tensile strength and impact strength are secured, and both laser transmittance and flame retardancy are excellent.

The polyamide-based resin is not particularly limited if it is a polyamide-based resin having a melting point of 200 to 240°C, preferably 210 to 230°C, showing excellent mechanical properties by including a polyamide in its structure, in this case Injection molding has an excellent effect.

In the present description, the melting point of the polymer is measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, after heating the polymer to 300°C, maintaining the temperature for 5 minutes, cooling to 20°C and increasing the temperature again, at this time, the rate of increase and decrease of temperature were measured by adjusting each of 20°C. do.

The polyamide-based resin may preferably be a lactam-based polymer.

The lactam-based polymer is preferably one or more lactams selected from the group consisting of ε-caprolactam, ω-laurolactam, enanthlactam, piperidone and pilolidone as a monomer, and one polymer of the monomer, Or it may be a condensation polymer of two types of monomers, more preferably polyamide 6 (polycaprolactam) or polyamide 12 (polyaruyllactam), most preferably polyamide 6 (polycaprolactam) In this case, mechanical properties such as tensile strength and impact strength are secured, and both laser transmittance and flame retardancy are excellent.

The polyamide resin may have, for example, a relative viscosity measured in a 96% sulfuric acid solvent of 2.0 to 3.4, preferably 2.1 to 3.2, more preferably 2.2 to 3.2, and impact within this range. It has excellent mechanical properties such as strength, improves fluidity, and has excellent appearance characteristics.

In the present description, the relative viscosity can be measured at 20°C using a solution prepared by dissolving 1 g of polyamide in 100 ml of a 96% by weight sulfuric acid aqueous solution unless otherwise specified.

The number average molecular weight of this description is a relative value for a standard PS (Standard polystyrene) sample using tetrahydrofuran (THF) as a solvent at a temperature of 40°C through gel chromatography (GPC) filled with porous silica as a column-filling material. Can be measured.

Fiberglass

The glass fiber may be, for example, 20 to 35% by weight, preferably 22 to 33% by weight, and more preferably 25 to 33% by weight, based on the total weight of the thermoplastic resin composition, and mechanical stiffness and dimensions within this range It has excellent stability, good surface roughness, and excellent flame retardancy.

For example, the glass fiber may have a diameter of 5 to 30 µm, preferably 5 to 20 µm, more preferably 10 to 15 µm, and has excellent mechanical properties and property balance within this range.

The glass fiber may be, for example, chopped strands having a chop length of 2 to 15 mm, more preferably 3 to 10 mm, and even more preferably 3 to 5 mm, and resin within this range. There is an advantage in that the composition is excellent in strength and the surface roughness of the injection-molded product is good.

In the present invention, the diameter and length of the glass fibers are values measured with an electron microscope, unless otherwise specified, and an average value is calculated after measuring 30 pieces each.

It may be preferable to use the glass fiber surface-treated with a silane compound, and in this case, there is an effect of improving the moldability of the resin composition by improving compatibility with the polyamide resin.

The silane compound may be, for example, an epoxy silane compound or an amino silane compound, preferably gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl methyldie Toxic silane, gamma-glycidoxypropyl triethoxy silane, 3-mercaptopropyl trimethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-meth Acryloxy propyl triethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanato propyl triethoxy silane, gamma-acetoacetatepropyl trimethoxysilane, acetoacetate It may be one or more selected from the group consisting of propyl triethoxy silane, gamma-cyanoacetyl trimethoxy silane, gamma-cyanoacetyl triethoxy silane, and acetoxyaceto trimethoxy silane, in this case, mechanical properties and thermal properties. While having excellent properties, there is an effect that the surface properties of the injection product are excellent.

The silane compound may be used within the range of 0.1 to 0.5 parts by weight, for example, in a total of 100 parts by weight of the glass fiber that is not surface-treated, and compatibility is improved within this range.

Phosphorus flame retardant

The phosphorus-based flame retardant is for example 12 to 35% by weight, preferably 15 to 33% by weight, more preferably 17 to 30% by weight, even more preferably 20 to 30% by weight, based on the total weight of the thermoplastic resin composition, Most preferably, it may be 22 to 27% by weight, and within this range, there is an effect of securing flame retardancy while having excellent mechanical properties such as tensile strength and impact strength.

In the case of the phosphorus-based flame retardant, it is not particularly limited as long as it is a flame retardant containing phosphorus (P) in its molecular structure and has compatibility with a colorant.

The phosphorus-based flame retardant is, for example, a red-phosphorus (RP)-based flame retardant, a phosphate-based flame retardant, a phosphine-based flame retardant, a phosphite-based flame retardant, a phosphonate-based flame retardant, and a force. It may be one or more selected from the group consisting of a Phosphinate flame retardant, a phosphoric acid ester flame retardant, and a phosphoric acid ester and salts flame retardant. In this case, the laser transmittance is excellent and flame retardant is secured. Has the effect of being.

The phosphate-based flame retardant is, for example, aromatic polyphosphate (RDX), trialkyl phosphate, alkyldiaryl phosphate, triaryl phosphate, tris(2-chloro). Ethyl) phosphate (Tris (2-chloroethyl) Phosphate TCEP), TDCPP (tris (1,3-dichloro-2-propyl) phosphate)), TCPP (Tris 2-chloropropylphosphate), Resorcinol bisphenyl phosphate , RDP) and resorcinol disphenyl phosphate.

The phosphine-based flame retardant may be, for example, phosphine oxide, phosphine oxide diol, or a mixture thereof.

The phosphine oxide may be, for example, an organophosphine oxide having a compound represented by Formula 1 below.

[Formula 1]

In the above formula, R ¹ , R ² and R ³ are each independently C ₄ -C ₂₄ hydrocarbyl. C ₄ -C ₂₄ hydrocarbyl may be, for example, C ₄ -C ₂₄ alkyl, C ₆ -C ₂₄ aryl, C ₇ -C ₂₄ alkylaryl or C ₇ -C ₂₄ arylalkyl.

The organophosphine oxide is preferably triphenylphosphine oxide, tri-p-tolyl-phosphine oxide, tris(4-nonylphenyl)phosphine oxide, tricyclohexylphosphine oxide, tri-n -Butylphosphine oxide, tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, benzyl bis(cyclohexyl)phosphine oxide, benzyl bis(phenyl)phosphine oxide and phenyl bis It may be one or more selected from the group consisting of (n-hexyl)phosphine oxide.

The phosphite-based flame retardant may be, for example, a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R ³ is H, M is Mg, Ca, Al, Zn or Fe, and m is an integer of 1 to 4.

The phosphonate-based flame retardant may, for example, have a reactive crosslinked polyphosphonate structure by introducing a phosphate ester bond in the molecule, and specifically, a compound represented by the following formula (3) may have a repeating unit structure. It can be something to have.

[Formula 3]

In Formula 3, preferably, the phosphorus content may be 5 to 8% by weight, and the weight average molecular weight may be 45,000 to 50,000 g/mol.

In this description, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent ) Can be measured relative to the standard PS (standard polystyrene) sample.

The phosphinate is a kind of phosphorus compounds, for example, may be represented by the formula of OP(OR)R2, preferably a monophosphinate flame retardant represented by the following formula (4), It may be a diphosphinate flame retardant represented by the following Chemical Formula 5 or a mixture thereof.

[Formula 4]

[Formula 5]

In Formulas 4 and 5, R ¹ and R ² each independently represent a linear or branched C ₁ -C ₆ alkyl or phenyl, and R ³ is a linear or branched alkylene, arylene, alkyl-substituted aryl Represents ene or aryl-substituted alkylene, M is a metal such as calcium, magnesium, zinc or aluminum, m is an integer of 2 or 3, n is an integer of 1 to 3, and X is 1 or 2.

R ³ may preferably be C1-C10 alkylene, C6 arylene, C6 arylene substituted with one or more C1-C10 alkyl, or C1-C10 alkylene substituted with one or more C6 aryl.

More preferably, the phosphinate-based flame retardant may be an organic phosphinate and an organic-inorganic complex phosphinate, and specifically, aluminum diethylphosphinate, ammonium polyphosphate, APP), and mono ammonium phosphate (MonoAmonium Phosphate, MAP) may be used, and may include a metal salt.

The phosphoric acid ester flame retardant may be an aromatic phosphoric acid ester flame retardant represented by the following formula (6) as an example.

[Formula 6]

In Formula 6, R ₃ , R ₄ and R ₅ are each independently hydrogen or a C1-C4 alkyl group, X is a C6-C20 arylene group or a C6-C20 arylene group substituted with an alkyl group, resorcinol, It is derived from hydroquinol or a dialcohol of bisphenol-A. In addition, n is an integer of 0-4.

The phosphorus-based flame retardant may be preferably aluminum diethylphosphinate, and in this case, there are excellent effects in both black expression, laser transmittance and mechanical properties.

Colorants in combination with organic and inorganic pigments

The colorant in which the organic dye and inorganic pigment are combined is, for example, 0.01 to 5% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 3.5% by weight, most preferably 1.5% by weight, based on the total weight of the thermoplastic resin composition. To 3.2% by weight, and within this range, black expression, laser transmittance, laser fusion, heat resistance, and discoloration inhibiting properties are excellent.

The colorant may include, for example, one or more selected from the group consisting of polyamide 6 and polyolefin as a carrier resin, and in this case, there is an effect of excellent dispersibility.

As an example, the colorant may be used in the form of a master batch (M/B), based on one or more of polyamide 6 and polyolefin, that is, made of a carrier resin, and organic dyes and inorganic pigments are It may be a combination, and in this case, it is uniformly dispersed, so that color expression is excellent.

The colorant may include, for example, 35 to 95% by weight of at least one selected from the group consisting of polyamide 6 and polyolefin, and 5 to 35% by weight of organic dyes and inorganic pigments, and in this case, excellent black expression In addition, it has an excellent effect of laser fusion.

The polyamide 6 may be within the same range as the polyamide-based resin described above.

The polyolefin is, for example, _{a polymer prepared by polymerization from an olefin having the formula C n} H _2n , specifically polyethylene, polypropylene, polymethylene, polybutene-1, polyolefin elastomer, polyisobutylene, and ethylene propylene rubber. It may be one or more selected from the group consisting of.

The inorganic pigment may preferably be a heat-resistant inorganic pigment capable of suppressing destruction of the chromophore of the organic dye at high temperature, among generally known inorganic pigments.

The heat-resistant inorganic pigment is not particularly limited as long as it is commonly referred to as a heat-resistant inorganic pigment in the technical field to which the present invention belongs.

Among the generally known inorganic pigments, carbon black is a laser absorbing material, so if an inorganic pigment other than carbon black is combined with an organic dye to implement a black colorant, as described above, it can be used as a laser transmissive material by itself.

The inorganic pigment may be preferably at least one selected from the group consisting of ultramarine pigments, titanium dioxide, zinc sulfide, zinc tetracyclic, and iron oxide, preferably ultramarine pigments, more preferably ultramarine blue pigments. In this case, when black is expressed, laser transmittance is excellent, and thus laser adhesion is improved.

The organic dyes are, for example, perinone-based, anthraquinone-based, azo-based, quinoline-based, quinacridone-based, perylene-based, and phthalocyanine-based dyes. )-Based, and methane-based dye may be at least one selected from the group consisting of, in this case, excellent black expression and excellent laser transmittance, there is an effect of improving laser adhesion.

Preferably, the organic dye is 1 selected from the group consisting of perinone red dye, anthraquinone blue dye, anthraquinone violet dye, anthraquinone yellow dye, anthraquinone green dye, azo red dye, azo orange dye, and phthalocyanine blue dye. It may be more than a species, and in this case, there is an effect of improving laser adhesion due to excellent black expression and excellent laser transmittance.

The perinone red dye, for example, is not particularly limited as long as it is selected from perinone-based dyes having a good transmittance at 800 to 1200 nm, and is preferably C. I. Solvent Orange 60, 78, C. CI solvent Red 135,162,178,179, C. I. C.I solvent violet 29, C.I. It may be one or more selected from the group consisting of CI pigment Orange 43 and CI pigment Red, and in this case, the black expression is excellent and the laser transmittance is excellent, so that the laser adhesion is possible. There is an improvement effect.

The anthraquinone dye is not particularly limited as long as it is selected from among anthraquinone dyes having good transmittance at 800 to 1200 nm, and is preferably CI basic red dye 1,2,3. ,4,5,6,8,9,10,11,12,13,15,16,17,19,20,26,27,35,36,37,48,49,52,53,54, 66 ,68, Mr. I. CI basic blue dye 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,18,20,21,22,23,24 ,25,26,35,36,37,45,4 6,47,49,50,55,56,60,62,67,75,77,79,80,81,83,87,88,89, 90,94,95,96,97, C. I. CI basic violet dye 1,2,3,4,5,6,7,8,10,11,12,13,14,15,16,17,20,21,23,24,25 ,27,40, and C. I. It may be one or more selected from the group consisting of CI basic green dye 1,3,4,6,9,10, and in this case, the black expression is excellent and the laser transmittance is excellent, so that the laser adhesion is improved. It works.

In addition, the anthraquinone dye may more preferably include an amine capable of forming a salt in its dye, and specifically, an aliphatic amine, an alicyclic amine, an alkoxyalkyl amine, an amine having an alkanol, a diamine, or a guanidine derivative. It may include at least one selected from the group consisting of amines and aromatic amines, and in this case, there is an effect of improving laser adhesion due to excellent black expression and excellent laser transmittance.

The ratio (a2/a1) of the weight (a2) of the anthraquinone blue dye to the weight (a1) of the perinone red dye is, for example, 0.01 to 5, preferably 0.01 to 4, more preferably 0.01 to 3 , More preferably, it may be 0.01 to 2.5, most preferably 0.01 to 1.5, and within this range, a black color similar to that of a natural pigment is expressed, and the laser transmittance is excellent, thereby improving laser adhesion. .

In another example, the ratio (a3/a1) of the weight (a3) of the anthraquinone violet dye to the weight (a1) of the perinone red dye is 0.01 to 5, preferably 0.01 to 4, more preferably 0.01 To 3, more preferably 0.01 to 2.5, and most preferably 0.01 to 1.5, and within this range, a black color similar to that of a natural pigment is expressed, and the laser transmittance is excellent, thereby improving laser adhesion. have.

The organic dye blended as described above may have a color similar to that of a natural dye, and a resin composition including the same may have an excellent transmittance within the above-described range. However, this exemplifies an organic dye capable of exhibiting an improved effect, and one embodiment is not limited thereto.

In the colorant in which the organic dye and the inorganic pigment are combined, the inorganic pigment and the organic dye may have a weight ratio (inorganic: organic) of 0.01:1 to 0.5:1, for example, and have excellent black expression and laser transmittance within this range. Has an excellent effect.

The colorant combined to satisfy this, as supported by the experimental examples to be described later, expresses a level of black similar to that of the natural pigment based on the above-described organic dye properties, and the molded article of the thermoplastic resin composition including the same is in the above-described range. While to obtain an excellent transmittance of; By suppressing the structural change of the organic dye at high temperature based on the above-described inorganic pigment properties, it is possible to obtain a minimized color difference (ΔE*ab) value. However, this exemplifies a combination of an organic dye and an inorganic pigment that can exhibit an improved effect, and one embodiment is not limited thereto.

Thermoplastic resin composition

The thermoplastic resin composition may have a transmittance of 20% or more, preferably 20 to 30%, as measured by irradiating a specimen with a thickness of 2.5 mm at a wavelength of 980 nm using a transmittance meter (ETM-10 of Eurovison), for example. There is an effect of imparting laser fusion properties within the range.

The thermoplastic resin composition has a notched Izod impact strength of 8 J/m or more, preferably 9 J/m or more, more preferably 10 to 15, as measured at 23° C. with a specimen of 6.4 mm according to ASTM D256, for example. It may be J/m, and there is an effect that the physical property balance is excellent within this range.

The thermoplastic resin composition may have a tensile strength of 90 MPa or more, preferably 95 MPa or more, and more preferably 95 to 145 MPa, measured under 5 mm/min speed according to ASTM D638, for example, and physical properties within this range. There is a good balance effect.

The thermoplastic resin composition may have a heat deflection temperature of 183° C. or higher, preferably 185° C. or higher, and more preferably 185 to 205° C., measured under conditions of 1.8 MPa and 120° C./hr according to ASTM D648, Within this range, there is an effect of excellent physical property balance and heat resistance.

For example, the thermoplastic resin composition may have a flame retardancy of V0 as measured according to the UL 94 V test, and has an excellent balance of physical properties within this range.

The thermoplastic resin composition is, for example, injecting a specimen having a thickness of 2.5 mm at a molding temperature of 250° C. using an injection machine, cutting it into 60 mm x 60 mm x 2.5 mm, placing each 10 mm overlapping, and making the overlapped area 3 mm in diameter (Beam size 3mm) and welded with a CW laser with a wavelength of 1070nm to have weldability, and in this case, the physical property balance is excellent.

The thermoplastic resin composition has injection moldability at a molding temperature of 250° C. using an injection molding machine as an example, and in this case, there is an effect of excellent physical property balance and processability.

The thermoplastic resin composition, for example, may have a black color of the sample injected after being held in an injection machine at 300° C. for 40 minutes, and in this case, there is an effect of suppressing discoloration while having excellent physical property balance.

The thermoplastic resin composition is, for example, 0.1 to 3% by weight, preferably 0.5 to 2% by weight, based on the total weight of the thermoplastic resin composition at least one selected from the group consisting of antioxidants, lubricants, thermal stabilizers, light stabilizers, and flow modifiers. It can be included as, and in this case, there is an effect excellent in heat resistance, colorability and processability.

The lubricant may be, for example, 0.05 to 2% by weight, preferably 0.1 to 1.5% by weight, based on the total weight of the thermoplastic resin composition, and within this range, the inherent effect of the lubricant without deteriorating the mechanical properties and thermal stability of the resin There is an advantage that is well expressed.

The lubricant may be, for example, one or more selected from the group consisting of an ester-based lubricant, a metal salt-based lubricant, a carboxylic acid-based lubricant, a hydrocarbon-based lubricant, and an amide-based lubricant, and is preferably an amide-based lubricant, and more preferably, stera. It is a mid-based lubricant, more preferably alkylene bis (steramide) having 1 to 10 carbon atoms of the alkylene. In this case, the original effect of the lubricant is well expressed without deteriorating the mechanical properties and thermal stability of the resin. There is an advantage.

In the present disclosure, the steramid-based lubricant may include steramid and a steramid substituent in which at least one of its hydrogens is substituted with another substituent.

The ester-based lubricants, metal salt-based lubricants, carboxylic acid-based lubricants, hydrocarbon-based lubricants, and amide-based lubricants are not particularly limited as long as each is a material commonly used as a corresponding type of lubricant in the technical field to which the present invention belongs.

The heat stabilizer may be, for example, 0.05 to 2% by weight, preferably 0.1 to 1.5% by weight, based on the total weight of the thermoplastic resin composition, and has an effect of improving heat resistance within this range.

The thermal stabilizer may be one or more selected from the group consisting of a phenol-based thermal stabilizer, a phosphite-based thermal stabilizer, and a thioether-based thermal stabilizer, and preferably, a phenol-based thermal stabilizer and a phosphite-based thermal stabilizer.

The phenolic thermal stabilizer is, for example, tetrakis methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methane, 1,3,5-tris-(4-t-butyl- 3-hydroxy-2,6-dimethylbenzel)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and 1,3,5-tris-(3, 5-di-t-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)-trione may be one or more selected from the group consisting of.

The phosphite-based thermal stabilizer is, for example, trisnonylphenylphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol depot It may be a spite, or a mixture thereof.

The thioether-based thermal stabilizer is, for example, dilauryl thiodipropionate, dimyristyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodipropionate, dimethyl thiodipropionate. It may be one or more selected from the group consisting of nate, 2-mercaptobenzimidazole, phenothiazine, octadecyl thioglycolate, butyl thioglycolate, octyl thioglycolate, and thiocresol.

When the thermal stabilizer preferably includes a phenol-based thermal stabilizer and a phosphite-based thermal stabilizer, the heat resistance is more excellent due to the synergistic effect of these combinations.

The flow modifier may be, for example, 0.05 to 2% by weight, preferably 0.1 to 1.5% by weight, based on the total weight of the thermoplastic resin composition, and has an effect of improving processability within this range.

The flow modifier may be, for example, a dendritic polymer, and the dendritic polymer has a reactive group at each end group, thereby preventing entanglement between polyamide chains and minimizing deterioration of mechanical properties of the thermoplastic resin composition.

The dendritic polymer may be, for example, a dendrimer, a hyperbranched polymer, or a mixture thereof.

The dendrimer refers to a polymer in which a chain of molecules regularly spreads in three dimensions from the center to the outside according to a certain rule.

In addition, the hyperbranched polymer refers to a multi-branched polymer having a branched structure in a repeating unit, and has a chemical structure similar to that of a dendrimer, but a highly regular branched structure of a dendrimer or a high degree of control of molecular weight is not achieved. In other words, there are some defects in the dendrimer structure, and branches are formed according to a probability distribution, and thus have a wide molecular weight distribution.

The dendrimer has a core unit located at the center of the entire spherical structure and a bridge unit, which is a unit structure that constantly repeats and extends around the core unit, increasing generation, and is located at the end connected to the bridge unit. It may include a dendron unit (which means "terminal functional group").

Preferably, the number of generations of the flow modifier may be 1 to 15, or 1 to 10, preferably 1 to 7, and in this case, mechanical properties, gloss and appearance characteristics of the resin composition are excellent.

For example, in the dendrimer, the terminal functional group may be selected from the group consisting of a hydroxyl group, a sulfhydryl group, an amino group, a carboxyl group, an aldehyde group, and an epoxy group, and in consideration of mechanical properties, gloss and appearance characteristics, it is preferable that the terminal functional group is an amino group. Do.

The dendrimer may be, for example, a compound represented by the following Chemical Formula 7. In this case, while having excellent mechanical properties such as impact strength, there is an effect of improving fluidity, gloss, and appearance characteristics.

[Formula 7]

In Formula 7, R is an alkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, m is an integer of 1 to 5, and n is an integer of 1 to 10.

As a specific example, the dendrimer may be a compound represented by the following Formula 8 or Formula 9, and in this case, it has an effect of improving fluidity, gloss, and appearance characteristics while having excellent mechanical properties such as impact strength.

[Formula 8]

[Formula 9]

In another example, in the hyperbranched polymer, the terminal functional group may be selected from the group consisting of a hydroxyl group, a sulfhydryl group, an amino group, a carboxyl group, an aldehyde group, and an epoxy group. In this case, the effect of improving fluidity, gloss and appearance characteristics There is.

The hyperbranched polymer may have a highly branched (branched) structure as a core part and have an acid group (e.g., carboxylic acid) and an acid decomposable group (e.g., carboxylic acid ester) at the molecular end. There is an effect that entanglement between molecules is small, and the degree of swelling by a solvent is small compared to a molecular structure that crosslinks the main chain.

Preferably, the hyperbranched polymer may be a hyperbranched polyester having a terminal functional group of a carboxyl group, and in this case, it has an effect of improving fluidity, gloss, and appearance characteristics while having excellent mechanical properties such as impact strength.

The thermoplastic resin composition may optionally contain at least one selected from the group consisting of an inorganic filler, an antistatic agent, a release agent and a sunscreen agent, as needed, from 0.01 to 5 parts by weight, preferably from 0.05 to 3 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. Parts, more preferably 0.1 to 2 parts by weight, and even more preferably 0.5 to 1 parts by weight, and within this range, the required physical properties without deteriorating the natural properties of the thermoplastic resin composition of the present disclosure There is an effect to be implemented.

Method for producing a thermoplastic resin composition

The method for preparing the thermoplastic resin composition of the present disclosure includes 45 to 65% by weight of a polyamide resin, 20 to 35% by weight of glass fiber, 12 to 20% by weight of a phosphorus-based flame retardant, and 0.01 to 5% by weight of a colorant in which an organic dye and an inorganic pigment are combined. After mixing including; comprising the step of preparing a pellet using an extrusion kneader in a 10 to 100 pie standard at 200 to 330 °C, wherein the colorant includes at least one of polyamide 6 and polyolefin, and the poly The amide resin has a melting point of 200 to 240°C. In this case, as the black color is expressed, the laser transmittance is excellent, and the laser welding property is excellent and the flame retardancy is excellent.

The manufacturing method of the thermoplastic resin composition shares all the technical characteristics of the above-described thermoplastic resin composition. Therefore, a description of the overlapping part will be omitted.

The step of preparing the pellets using the extrusion kneader may be carried out in a standard of 25 to 75 pies, preferably under 200 to 300°C, and more preferably performed in a standard of 20 to 80 pies under 220 to 300°C. In this range, stable extrusion is possible and the kneading effect is excellent. At this time, the temperature is the temperature set in the cylinder, and pi means the outer diameter (unit: mm).

The extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the technical field to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.

Molded article

The molded article of the present disclosure includes the thermoplastic resin composition, and in this case, the black color is exhibited, and the laser transmittance is excellent, and the laser fusion property is expressed and the flame retardance is excellent.

The molded article is formed by molding the thermoplastic resin composition by a method such as injection or extrusion, and may exhibit excellent transmittance. In addition, even when a high temperature is applied in the manufacturing (molding) process or when it is aged at a high temperature after molding, discoloration is suppressed and excellent black appearance quality can be maintained.

In the description of the thermoplastic resin composition of the present disclosure, its manufacturing method, and molded article, it is stated that other conditions or equipment that are not explicitly described can be appropriately selected within the range commonly practiced in the art, and are not particularly limited. do.

Hereinafter, preferred embodiments are presented to aid in the understanding of the present disclosure, but the following examples are only illustrative of the present disclosure, and that various changes and modifications are possible within the scope of the present disclosure and the scope of the technical idea will be apparent to those skilled in the art, It is natural that such modifications and modifications fall within the appended claims.

[Example]

Materials used in the following Examples and Comparative Examples are as follows.

* Polyamide resin A: Polyamide 6 (TK2451 from Taekwang Industrial Co., Ltd.) with a melting point of 220°C was used.

* Polyamide resin B: Polyamide 66 (INVISTA U3600) having a melting point of 260°C was used.

* Flame retardant A: Aluminum tris (diethylphosphinate) (Clariant's OP1230) was used.

* Flame retardant B: A flame retardant in which aluminum tris (diethylphosphinate), melamine polyphosphate, and zinc borate are mixed (OP1312 from Clariant) was used.

* Glass fiber: Owens corning's 123D was used.

* Colorant A: Carbon black master batch (K003 of Woosung Chemical) was used.

* Colorant B: A master batch based on polyamide 6 (EHL20 from MBSYS) containing Solvent Red 179, Solvent Blue 097 and Ultra Marine Blue was used.

* Colorant C: A polyolefin-based master batch (WHL140 manufactured by MBSYS) containing Solvent Red 179 and Solvent Blue 097 was used.

* Oxidation stabilizer: Phenol-based (IR1010), phosphite-based (PEP36) oxidation stabilizer was used.

* Lubricant: Ethylene bis stearamide (EBA) was used.

* PA flow modifier: CVD-7010 was used as a dendritic polymer.

Examples 1 to 4 and Comparative 1 to 11

The components shown in Tables 1 and 2 below are added to a super mixer in the contents described and kneaded, and then melt-kneaded at a barrel temperature of 220 to 300°C using a twin-screw extruder, and then extruded (using a pelletizer) to make pellets. It was prepared in a shape, dried at 100° C. for 4 hours or more, and then injected using an injection machine at an injection temperature of 230 to 300° C., and a resin composition specimen was left at room temperature for 48 hours or more.

In Tables 1 and 2 below, the additives were 1% by weight, including 0.1% by weight of IR1010, 0.1% by weight of PEP36, 0.4% by weight of EBA, 0.1% by weight of CVD-7010, and 0.3% by weight of other additives.

[Test Example]

The physical properties of the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 11 were measured by the following method, and the results are shown in Tables 1 and 2 below.

* Tensile strength (MPa): According to ASTM D638 standard, the tensile strength was measured at a rate of 5 mm/min.

* Impact strength (J/M): The notch impact strength of a 6.4 mm specimen was measured according to ASTM D256 standard.

* HDT (heat deflection temperature, ℃): was measured in accordance with the ASTM D648 standard 1.8 MPa, 120 ℃ / Hr conditions.

* Laser transmittance (%): A specimen of 2.5T thickness was injected, and the laser transmittance at a wavelength of 980 nm was measured with an ETM-10 device of Eurovison.

* Flame retardancy: Based on the UL94 V test (Vertical Burning Test), evaluation was conducted with a specimen of 2.5T thickness. Depending on the flame retardant grade, it was evaluated as V0, V1 or V2, and V0 was set as the target value.

* Injection molding: Using an injection molding machine (Engel, 80ton), it was judged whether or not injection molding was possible at a molding temperature of 250°C. If injection molding was possible, it was evaluated as ○, and if injection molding was not possible, it was evaluated as X.

* Injection retention evaluation: The color of the ejected specimen was observed after staying at 300°C for 40 minutes in the injection machine. Black was set as the target value.

* Laser Weldability: After ejecting a specimen of 2.5mm thickness at a molding temperature of 250℃, cut it into 60mm x 60mm x 2.5mm, arrange each 10mm to overlap, and make the overlapped area with a 3mm diameter (beam size 3mm) with a wavelength of 1070nm. The CW laser was welded to evaluate the presence or absence of weld formation. If weld formation was possible, it was evaluated as ○, and if weld formation was impossible, it was evaluated as X.

division Example Comparative example One 2 3 4 One 2 3 4 Polyamide resin A 55 45 61 56.9 55 61 64 53 Polyamide resin B - - - - - - - - Flame retardant A 17 18 13 17 - 20 21 21 Flame retardant B - - - - 13 - - - Fiberglass 25 33 30 25 25 20 20 20 Colorant A - - - - 2 - - Colorant B 2 3 5 0.1 - 5 5 5 Colorant C - - - - - - - additive One One One One One One One One Properties Tensile strength (MPa) 110 140 92 112 11 92 95 92 Impact strength (J/m) 10 12 8 10 10 8 8 7 HDT(℃) 195 185 201 195 195 201 204 194 Laser transmittance (%) 22 21 24 22 0 13 25 18 UL flame retardant V0 V0 V0 V0 V0 V0 V1 V0 Injection molding ○ ○ ○ ○ ○ ○ ○ ○ Injection stay evaluation black black black black black black black black Laser welding ○ ○ ○ ○ X ○ ○ ○

division Comparative example 5 6 7 8 9 10 11 Polyamide resin A 63 40 38 66 - 56 55 Polyamide resin B - - - - 55 - - Flame retardant A 13 10 12 8 17 13 17 Flame retardant B - - - - - - - Fiberglass 18 46 46 20 25 20 25 Colorant A - - - - - - - Colorant B 5 3 3 5 2 10 - Colorant C - - - - - - 2 additive One One One One One One One Properties Tensile strength (MPa) 89 200 200 92 120 87 110 Impact strength (J/m) 7 16 16 8 9 8 10 HDT(℃) 203 180 178 206 225 201 195 Laser transmittance (%) 24 21 20 26 24 24 22 UL flame retardant V0 V1 V0 V1 V0 V0 V0 Injection molding ○ ○ ○ ○ X ○ ○ Injection stay evaluation black black black black black black Red Laser welding ○ ○ ○ ○ ○ ○ ○

As shown in Table 1, Examples 1 to 4 according to the present invention have superior tensile strength and impact strength compared to Comparative Examples 1 to 11, and have high laser transmittance, enabling laser welding, and flame retardancy, injection molding, and injection retention evaluation. It was also confirmed that it is excellent.

In addition, Comparative Example 1 not including the colorant according to the present invention and Comparative Example 2 including other types of flame retardants other than the phosphorus-based flame retardant had no or low laser transmittance, and thus laser welding was not possible.

In addition, Comparative Example 3 containing phosphorus-based flame retardants below the scope of the present invention did not reach the V0 grade, and Comparative Example 4 containing phosphorus-based flame retardants beyond the scope of the present invention was unable to laser welding due to low laser transmittance. .

In addition, Comparative Example 5 containing glass fibers below the scope of the present invention had lower tensile strength and impact strength, and Comparative Example 6 containing glass fibers beyond the scope of the present invention had lower heat deflection temperature.

In addition, Comparative Example 7 containing polyamide 6 resin below the range of the present invention had a lower heat deflection temperature, and Comparative Example 8 containing polyamide resin beyond the scope of the present invention had lower flame retardancy and injection retention evaluation.

In addition, Comparative Example 9 including a polyamide 66 resin having a melting point of 260° C. was not injection-molded at 250° C., and Comparative Example 10 including a colorant beyond the scope of the present invention had a lower tensile strength, according to the present invention. In Comparative Example 11, which included other colorants in addition to the colorant, the specimen was discolored to red after the injection was held.

Claims (13)

45 to 65% by weight of a polyamide resin;
20 to 35% by weight of glass fibers;
12 to 20% by weight of a phosphorus-based flame retardant; And
Including; 0.01 to 5% by weight of a colorant in which an organic dye and an inorganic pigment are combined,
The polyamide-based resin, characterized in that the melting point is 200 to 240 ℃
Thermoplastic resin composition.
The method of claim 1,
The phosphorus (P)-based flame retardant, red-phosphorus (RP)-based flame retardant, phosphate (Phosphate)-based flame retardant, phosphine-based flame retardant, phosphite (Phosphite)-based flame retardant, phosphonate-based It is characterized in that at least one selected from the group consisting of flame retardants, phosphinate-based flame retardants, phosphoric acid ester flame retardants, and phosphoric acid ester and salts flame retardants.
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that it contains 0.1 to 3% by weight of additives
Thermoplastic resin composition.
The method of claim 3,
The additive is characterized in that at least one selected from the group consisting of antioxidants, lubricants, thermal stabilizers, light stabilizers and flow modifiers.
Thermoplastic resin composition.
The method of claim 1,
The glass fiber is characterized in that the diameter is 5 to 30 ㎛, chop (chop) length is 2 to 15 ㎜
Thermoplastic resin composition.
The method of claim 1,
The polyamide-based resin is characterized in that the lactam-based polymer
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that the transmittance measured by irradiating a specimen with a thickness of 2.5 mm at a wavelength of 980 nm using a transmittance meter (ETM-10 of Eurovison) is 20% or more.
Thermoplastic resin composition.
The method of claim 1,
The colorant is characterized in that it comprises at least one selected from the group consisting of polyamide 6 and polyolefin as a carrier resin.
Thermoplastic resin composition.
The method of claim 1,
The colorant, characterized in that in the form of a master batch
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition injects a specimen with a thickness of 2.5 mm at a molding temperature of 250° C. using an injection machine, and then cuts it into 60 mm x 60 mm x 2.5 mm, arranged so that each 10 mm overlaps, and the overlapped area is 3 mm in diameter (beam size 3 mm). ) By welding with a CW laser with a wavelength of 1070 nm to have weldability.
Thermoplastic resin composition.
The method of claim 1,
The thermoplastic resin composition is characterized in that the flame retardancy measured according to the UL94 V test is rated V0
Thermoplastic resin composition.
Polyamide resin 45 to 65% by weight, glass fiber 20 to 35% by weight, phosphorus flame retardant 12 to 20% by weight, and 0.01 to 5% by weight of a colorant in which an organic dye and an inorganic pigment are combined; 200 to 330 after mixing Including the step of producing a pellet using an extrusion kneader in a 10 to 100 pie standard under ℃,
The polyamide-based resin, characterized in that the melting point is 200 to 240 ℃
Method for producing a thermoplastic resin composition.
It comprises the thermoplastic resin composition of any one of claims 1 to 11, characterized in that
Molded products.