KR20200108978A - Flame-retardant polyamide composition, method for preparing the same and method for preparing molding product containing the same - Google Patents

Abstract

The present invention relates to a flame-resistant polyamide resin composition, a method for preparing the same, and a molded product including the same. Particularly, the flame-resistant polyamide resin composition includes: 50-75 wt% of a polyamide resin; 5-30 wt% of glass fibers having a filament diameter of 10.6-11.9 micrometers; and 13-20 wt% of a phosphorus-based flame retardant, wherein the glass fibers are E-glass type chopped strands having a chopped length of 2-6 mm. According to the present invention, the flame-resistant polyamide resin composition shows significantly improved tensile strength and impact strength by using specific glass fibers, and provides a high-grade of flame resistance by using an eco-friendly flame retardant.

Description

Flame-retardant polyamide resin composition, a manufacturing method thereof, and a manufacturing method of a molded article comprising the same {FLAME-RETARDANT POLYAMIDE COMPOSITION, METHOD FOR PREPARING THE SAME AND METHOD FOR PREPARING MOLDING PRODUCT CONTAINING THE SAME}

The present invention relates to a flame-retardant polyamide resin composition, a method for manufacturing the same, and a method for manufacturing a molded article including the same, and in more detail, the tensile strength and impact strength are greatly improved by using a specific glass fiber, and high It relates to a flame-retardant polyamide resin composition and the like that provide an effect of providing a grade of flame retardancy.

Aliphatic polyamides represented by nylon 6 and nylon 66 have excellent properties such as heat resistance, chemical resistance, rigidity, abrasion resistance, and moldability, and are therefore used in many applications as engineering plastics. In the case of engineering plastics used in the electric and electronic field, in addition to the flame-retardant standard based on UL 94 standard, additional glow-resistant wire characteristics are newly required, and this can be seen as a plan to identify more practical flame-retardant behavior and prevent fire in advance. have. The flame retardant evaluation method of UL 94 standard is a method of simulating the flame retardant behavior based on the premise that a fire has already occurred by using a flame as a heat source, and the method for evaluating the characteristics of the glow wire according to the International Electrotechnical Commission (IEC) standard (Glow Wire) Flammability Index (GWFI) provides a heat source that can cause fire as a glow wire, and by understanding its behavior, it can be seen as an evolved flame retardant test method that considers safety in the event of a fire.

Halogen-based flame retardants introduced to impart flame retardancy to polyamides decompose due to low thermal stability due to high temperatures and pressures generated during processing, and as a result, corrosive toxic gases are generated, which adversely affects the working environment and human body. have. Accordingly, non-halogen-based flame retardants, especially melamine-based flame retardants, are being replaced, but melamine-based flame retardants have the advantage that they can achieve flame retardancy with a lower content than halogen-based flame retardants, but when applied to resins reinforced with inorganic fillers, flame retardant grade V- It is difficult to implement 0, and mechanical properties such as tensile properties are deteriorated.

Accordingly, the polyamide resin is given a high level of flame retardancy that passes GWFI measured at 960 ℃ according to the International Electrotechnical Commission (IEC) standard IEC 60695-2-12, and has excellent mechanical properties, especially high tensile properties. There is a need for research on a technology that can implement this.

Korean Patent Publication No. 2017-0023960

In order to solve the problems of the prior art as described above, the present invention is a flame-retardant polyamide resin that implements flame retardancy by using a phosphorus-based flame retardant, and the filament diameter is 10.6 to 11.9 μm, E-glass type ?h strands of glass. It is an object of the present invention to provide a flame-retardant polymide resin composition having very excellent mechanical properties such as tensile strength and impact strength by blending fibers, a method of manufacturing the same, and a molded article including the same.

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

In order to achieve the above object, the present invention comprises 50 to 75% by weight of a polyamide resin, 5 to 30% by weight of glass fiber having a filament diameter of 10.6 to 11.9 μm, and 13 to 20% by weight of a phosphorus-based flame retardant, wherein the glass fiber is It provides a flame-retardant polyamide resin composition, characterized in that ?h strands of E-glass type, ?h chopped length is 2 to 6mm.

In addition, the present invention comprises a step of kneading and extruding, including 50 to 75% by weight of a polyamide resin, 5 to 30% by weight of glass fiber having a filament diameter of 10.5 to 12 μm, and 13 to 20% by weight of a phosphorus-based flame retardant, wherein the glass fiber Provides a method for producing a flame-retardant polyamide resin composition, characterized in that ?h strands of E-glass type, ?h length (chopped length) are 2 to 6mm.

In addition, the present invention provides a molded article comprising the flame-retardant polyamide resin composition.

According to the present invention, a flame-retardant polyamide resin that implements flame retardancy using a phosphorus-based flame retardant is blended with E-glass type ?h strands glass fibers having a filament diameter of 10.6 to 11.9 μm in a specific content ratio There is an effect of providing a flame-retardant polyamide resin composition having excellent mechanical properties, particularly tensile strength and impact strength, and a manufacturing method thereof, and a molded article including the same, securing a high level of flame retardancy of grade 1 or higher.

The flame-retardant polyamide resin composition of the present invention comprises 50 to 75% by weight of a polyamide resin, 5 to 30% by weight of glass fiber, and 13 to 20% by weight of a phosphorus-based flame retardant, wherein the glass fiber has a filament diameter of 10.6 to 11.9 μm. It features, and in this case, it is possible to secure a high level of flame retardancy passing through GWFI, and there is an effect of excellent mechanical strength.

Hereinafter, the flame-retardant polyamide resin composition of the present disclosure will be described in detail for each component.

Polyamide resin

For example, the polyamide may be included in 50 to 75% by weight or 56 to 65% by weight, preferably 56 to 61% by weight based on the flame retardant polyamide resin composition, and within this range, mechanical properties, extrusion processability, and appearance quality There is an advantage of excellent balance of physical properties such as.

The polyamide resin is a polymer having an amide bond (-NHCO-) in the main chain, and one obtained by condensation polymerization of two or more lactams or w-amino acids having a ring structure may be used.

The cyclic lactam may be, for example, ε-caprolactam or ω-laurolactam, and the w-amino acid is, for example, 6-aminocapronic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraamino. It may be one or more selected from the group consisting of methylbenzoic acid.

As another example, the polyamide resin may be a polyamide resin in which diacids and diamines are condensed.

The diacid is, for example, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3 -Diethylsuccinic acid, azelaic acid, sebacic acid, sveric acid, dodecanoic acid, eicodioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid , 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, diglycolic acid, etc., may be one or more selected from the group consisting of aliphatic, alicyclic or aromatic dicarboxylic acids, and the diamine is, for example, tetramethylenediamine, hexamethylene Diamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylene Diamine, paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane , Bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpipe It may be one or more selected from the group consisting of aliphatic, alicyclic, or aromatic diamines such as razine.

The polyamide resin may be one or more selected from the group consisting of nylon 6, nylon 66, nylon 610, nylon 1010, nylon 46, nylon 11, nylon 12, nylon MXD6 and polyphthalamide, for example, and preferably nylon 6 In this case, heat resistance, chemical resistance, and mechanical properties are excellent.

The polyamide resin may be, for example, a semi-crystalline or amorphous polyamide resin, and preferably may be semi-crystalline, and in this case, it has excellent effects such as chemical resistance.

In the present description, the semi-crystalline polyamide resin and the amorphous polyamide resin are not particularly limited in the case of a polyamide resin commonly recognized as a semi-crystalline polyamide resin and an amorphous polyamide resin in the technical field to which the present invention belongs.

The polyamide resin may have a melting temperature of 150 to 350°C, 200 to 300°C, or 220 to 280°C, for example, and has excellent heat resistance within this range.

The polyamide resin may have a relative viscosity (RV) of 1.5 to 5.0, 2 to 4, or 2.0 to 3.5, preferably 2.1 to 2.5, and has excellent moldability and processability within this range.

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 noted.

The polyamide resin may have a number average molecular weight of 8,000 to 100,000 g/mol, 10,000 to 700,000 g/mol, 10,000 to 500,000 g/mol, or 10,000 to 50,000 g/mol, for example, and the appearance of the final molded product within this range Properties, mechanical strength, and the like are improved.

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 packing material. Can be measured.

Fiberglass

For example, the glass fiber may be included in an amount of 5 to 30% by weight or 15 to 30% by weight, preferably 20 to 25% by weight, based on the flame-retardant polyamide resin composition, and has excellent surface appearance and tensile properties within this range. It works.

The glass fiber may have, for example, a filament diameter of 10.6 to 11.9 μm or 10.6 to 11.5 μm, preferably 11.0 to 11.5 μm, and has a more excellent effect in tensile strength and impact strength within this range.

The glass fiber may be, for example, E-glass type ?h strands (chopped strands).

In the present description, the E-glass type is in accordance with ASTM D578-00, for example 52 to 62% by weight silicon dioxide, 12 to 16% by weight aluminum oxide, 16 to 25% by weight calcium oxide, 0 to 10% by weight borax, 0 to 5% by weight magnesium oxide, 0 to 2% by weight alkali metal oxide, 0 to 1.5% by weight titanium dioxide and 0 to 0.3% by weight iron oxide. In another example, the E-glass type is 52 to 62% by weight silicon dioxide, 12 to 16% by weight aluminum oxide, 16 to 25% by weight calcium oxide, 0.1 to 10% by weight borax, 0.1 to 5% by weight magnesium oxide, 0.01 to It is composed of 2% by weight of alkali metal oxide, 0.01 to 1.5% by weight of titanium dioxide and 0.001 to 0.3% by weight of iron oxide.

The glass fibers are, for example, ?h chopped strands having a chopped length of 2 to 6 mm or 3.0 to 4.5 mm, preferably 3.0 to 3.5 mm, and tensile strength within this range And there is an effect of more excellent impact strength.

The filament diameter and ?h length of the glass fiber were measured by a SEM (Scanning Electron Microscope) of 30 pieces, and an average value was calculated.

The glass fiber may be surface-treated with a silane-based compound as an example, and in this case, the glass fiber is evenly dispersed in the polyamide resin due to its excellent compatibility with the polyamide resin, and thus mechanical properties and thermal properties are excellent, It has an excellent effect on the surface properties of.

The silane-based compound is not particularly limited if it is an amino silane used as a coating agent for glass fibers, but examples include gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-gly Cydoxypropyl methyldiethoxy silane, gamma-glycidoxypropyl triethoxy silane, 3-mercaptopropyl trimethoxy silane, vinyl trimethoxysilane, vinyl triethoxy silane, gamma-methacryloxypropyl trimethoxy Silane, gamma-methacryloxy propyl triethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanato propyltriethoxy silane, gamma-acetoacetatepropyl trimethoxy It may be one or more selected from the group consisting of oxysilane, acetoacetatepropyl triethoxy silane, gamma-cyanoacetyl trimethoxy silane, gamma-cyanoacetyl triethoxy silane, and acetoxyaceto trimethoxy silane, In this case, the mechanical properties and thermal properties are excellent, and the surface properties of the injection product are excellent.

The glass fiber may be, for example, CPIC's ECS301HP-3-H (filament diameter 11 μm), and in this case, it is readily available, and the quality or composition is determined so that there is no change, excellent reproducibility. In particular, the tensile properties and Mechanical properties such as impact strength are more excellent.

The glass fiber may be characterized by having a limiting oxygen index (LOI) of 0.45±0.1% by volume, for example, and in this case, the composition has excellent properties such as tensile strength and impact strength.

The limiting oxygen index of the glass fiber is a value measured according to ISO 1887.

The glass fiber may be characterized by having a water content of 0.05% by weight or less, for example, and in this case, the mechanical properties of the composition are excellent.

The moisture content of the glass fiber is a value measured according to ISO 3344.

The glass fiber may be characterized by having a bulk density of 0.7±0.1 g/cm ³ , for example, and in this case, the product molding of the composition and the balance of physical properties are excellent.

The bulk density of the glass fiber is a value measured according to ISO 15100.

The glass fiber may be, for example, a fiber having a circular cross section, and in this case, both the appearance quality and mechanical properties of the final product may be excellent.

Phosphorus flame retardant

For example, the phosphorus-based flame retardant may be included in an amount of 13 to 20% by weight, or 15 to 20% by weight, preferably 15 to 19% by weight, based on the flame-retardant polyamide resin composition, and within this range, the IEC 60695-2-12 standard It passes through the GWFI measured at 960 °C and has excellent flame retardancy and mechanical properties.

The phosphorus-based flame retardant may include, for example, at least one selected from the group consisting of phosphate ester, phosphonate, phosphinate, phosphine oxide, and phosphazene.

In the flame-retardant polyamide resin composition of the present disclosure, the weight ratio of the phosphorus-based flame retardant and the polyamide resin may be, for example, 1:3 to 1:5 or 1:3.5 to 1:4.5, and within this range, tensile strength and impact strength Etc. There are more excellent advantages.

Other additives

The flame-retardant polyamide resin composition of the present disclosure may further include a flame-retardant auxiliary agent if necessary, and the flame-retardant auxiliary agent may be, for example, magnesium hydroxide, aluminum hydroxide, or a mixture thereof, and in this case, flame retardancy is improved and the surface appearance is excellent. There is.

The magnesium hydroxide and/or aluminum hydroxide may be surface-treated with phosphorus, for example, and in this case, flame retardancy is improved and surface appearance is excellent.

The flame-retardant auxiliary agent may be included in an amount of less than 3% by weight, or 0.01 to 3% by weight, based on the flame-retardant polyamide resin composition as an example, and within this range, there is an advantage of having excellent flame retardancy and high surface appearance and mechanical properties.

In addition, the flame-retardant polyamide resin composition of the present disclosure may optionally be selected from the group consisting of lubricants, colorants, antistatic agents, plasticizers, thermal stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers (excluding glass fibers). It may include at least one selected.

Flame retardant polyamide resin composition

The flame-retardant polyamide resin composition of the present disclosure, for example, has a tensile strength (thickness of 40 mm, ASTM D638) of 148 MPa or more or 148 to 170 MPa, preferably 150 to 165 MPa, and a tensile elongation (thickness of 40 mm, ASTM D638) of 3.0% or more or 3.0 to 4.0%, the flexural strength (thickness 40 mm, ASTM D790) is 7800 MPa or more or 7800 to 8200 MPa, preferably 8000 to 8200 MPa, and the Charpy impact strength (thickness 40 mm, ASTM D256) is 12 kJ/m ² or more or 12 to It is 15kJ/m ² and its flame retardancy (UL 94 V TEST) is V-1 or higher, V-1 or VO, and it has the effect of providing a molded article with excellent flame retardancy and mechanical properties within this range.

The present description provides a method of manufacturing the flame-retardant polyamide resin composition, and in describing this, a description overlapping with the above will be omitted. It is obvious that the contents described above in the flame-retardant polyamide resin composition are equally included in the method for preparing the flame-retardant polyamide resin composition described later.

The method for preparing the flame-retardant polyamide resin composition of the present disclosure includes, for example, 50 to 75% by weight of a polyamide resin, 5 to 30% by weight of glass fibers having a filament diameter of 10.6 to 11.9 μm, and 13 to 20% by weight of a phosphorus-based flame retardant. Including the step of extruding, wherein the glass fibers are E-glass type ?h strands, ?h length (chopped length) of 2 to 6mm, the composition prepared in this way It has the advantage of excellent flame retardancy and excellent mechanical properties.

The kneading and extruding step is 200 to 280 ℃ and 200 to 400 rpm, for example; Alternatively 220 to 260° C. and 200 to 300 rpm; Although it may be performed under conditions, it is not limited thereto, and may be performed by appropriately selecting within the range commonly practiced in the art.

The kneading and extrusion step may be performed using a Banbari mixer, a single screw extruder, a twin screw extruder, a kneader reactor, etc., for example, and is not particularly limited.

In addition to the above-described components, for example, the extrusion step is one selected from the group consisting of flame retardant aids, lubricants, colorants, antistatic agents, plasticizers, heat stabilizers, antioxidants, light stabilizers, anti-drip agents, pigments and inorganic fillers (excluding glass fibers). It may include more than one.

The flame-retardant polyamide resin composition manufactured according to the above manufacturing method may be provided as a molded article through injection molding.

The molded article of the present disclosure is characterized in that it contains the flame-retardant polyamide resin composition.

The molded article may be, for example, a housing for an MCCB circuit breaker, a housing for an ACB circuit breaker, and a housing for an MCB circuit breaker.

Hereinafter, a preferred embodiment is presented to aid the understanding of 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 spirit of the present invention, It is natural that such modifications and modifications fall within the appended claims.

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

* Polyamide resin: Nylon 6 (melting temperature 250~270℃, relative viscosity 2.2~2.4, number average molecular weight 30,000g/mol)

* Phosphorus flame retardant: Clariant's OP1312 or Solvay's PA2

* Glass fiber 1: As a ?h strand glass fiber having a circular cross section, a filament diameter of 10 μm, and a length of 3 mm, CPIC ECS301HP-3 (filament diameter 10 μm) was used.

* Glass fiber 2: As a ?h strand glass fiber having a circular cross section, a filament diameter of 11 μm, and a length of 3 mm, CPIC ECS301HP-3-H (filament diameter 11 μm) was used.

* Glass fiber 3: As a ?h strand glass fiber having a circular cross section, a filament diameter of 13 μm, and a length of 3 mm, ECS301HP (filament diameter 13 μm) of CPIC was used.

[Example]

Examples 1 to 3 and Comparative Examples 1 to 4

After mixing with a mixer according to the components and contents shown in Table 1 below, a flame-retardant polyamide resin composition was prepared by melt-kneading and extruding in a temperature range of 220 to 290°C using a twin screw extruder. After extrusion, the pellets were pelletized using a pelletizer, dried at 120° C. for 4 hours or more, and then allowed to stand for 48 hours or more in a state where contact with air was blocked by injection molding, and then physical properties were measured.

[Test Example]

The properties of the specimens prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Table 1 below.

* Tensile strength (MPa) and tensile elongation (%)

Tensile strength and elongation at the breaking point were measured using a universal testing machine (UTM) according to ASTM D638. At this time, the thickness of the specimen was 40 mm, and the tensile speed was measured under the conditions of 5 mm/min.

* Flexural strength (MPa)

According to ASTM D790, a specimen with a thickness of 40 mm was used to measure the flexural strength under conditions of a span of 64 mm.

* Impact strength (kJ/m ² )

Charpy impact strength was measured using a 40 mm thick specimen according to ASTM D256.

* Flame retardant (UL 94 V TEST)

UL 94 manufactures a specimen of a predetermined thickness by injection molding, the specimen is placed vertically, and the specimen is lit with a burner, so that the fire on the specimen should be extinguished by itself within a certain period of time. It was divided into grades of -2, V-1, and V-0. The V-0 grade has the best flame retardancy.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 PA 56 61 61 56 70 57 56 Flame retardant 19 15 19 19 10 23 19 Glass fiber 1 (diameter 10㎛) - - - 25 - - - Glass fiber 2 (diameter 11㎛) 25 25 20 - 20 25 - Glass fiber 3 (diameter 13㎛) - - - - - - 25 Physical property measurement result The tensile strength 163 165 150 140 145 145 145 Tensile elongation 3.3 3.0 3.5 2.8 3.0 2.8 3.0 Flexural strength 8080 8200 7800 7700 7800 7600 7700 Impact strength 12 14 14 10 12 12 10 Flame retardant V-0 V-1 V-0 V-0 V-1 V-0 V-0

As shown in Table 1, it was confirmed that the flame-retardant polyamide resin compositions of Examples 1 to 3 according to the present invention were excellent in flame retardancy of V-1 or higher, and excellent in tensile strength, tensile elongation, flexural strength, and impact strength. In particular, it can be seen that the tensile strength and impact strength are significantly improved compared to Comparative Examples 1 and 4 using different types of glass fibers from the examples.

On the other hand, when a phosphorus-based flame retardant is applied in a small amount or in an excessive amount, and the weight ratio of the phosphorus-based flame retardant and the polyamide resin is out of the scope of the present application by 1:7 (Comparative Example 2) and when out of the scope of the present application by 1:2.5 (Comparative Example 3), It can be seen that the tensile strength is significantly lowered compared to the Example, and the remaining physical properties are also lower than the same.

Claims (11)

Including 50 to 75% by weight of a polyamide resin, 5 to 30% by weight of glass fibers having a filament diameter of 10.6 to 11.9 μm, and 13 to 20% by weight of a phosphorus-based flame retardant,
The glass fiber is an E-glass type of ?h strands, characterized in that the ?h chopped length is 2 to 6mm.
Flame-retardant polyamide resin composition. The method of claim 1,
The phosphorus-based flame retardant and the polyamide resin are characterized in that included in a weight ratio of 1:3 to 1:5
Flame-retardant polyamide resin composition. The method of claim 1,
The glass fiber is characterized in that the limiting oxygen index (LOI) is 0.45±0.1% by volume.
Flame-retardant polyamide resin composition. The method of claim 1,
The glass fiber is characterized in that the moisture content is less than 0.05% by weight
Flame-retardant polyamide resin composition. The method of claim 1,
The glass fiber is characterized in that the bulk density is 0.7 ± 0.1g / cm ³
Flame-retardant polyamide resin composition. The method of claim 1,
The glass fiber is characterized in that the cross section is circular
Flame-retardant polyamide resin composition. The method of claim 1,
The polyamide resin is characterized in that at least one selected from the group consisting of nylon 6, nylon 66, nylon 610, nylon 1010, nylon 46, nylon 11, nylon 12, nylon MXD6, and polyphthalamide.
Flame-retardant polyamide resin composition. The method of claim 1,
The flame-retardant polyamide resin composition has a tensile strength (thickness of 40 mm, ASTM D638) of 148 MPa or more, and a flame retardancy (UL 94 V TEST) of V-1 or more.
Flame-retardant polyamide resin composition. Including the step of kneading and extruding, including 50 to 75% by weight of a polyamide resin, 5 to 30% by weight of glass fibers having a filament diameter of 10.6 to 11.9 μm, and 13 to 20% by weight of a phosphorus-based flame retardant,
The glass fiber is an E-glass type of ?h strands, characterized in that the ?h chopped length is 2 to 6mm.
Method for producing a flame-retardant polyamide resin composition. It comprises a flame-retardant polyamide resin composition according to any one of claims 1 to 8, characterized in that
Molded products. The method of claim 10,
The molded product is a housing for an MCCB circuit breaker, a housing for an ACB circuit breaker, and a housing for an MCB circuit breaker.
Molded products.