KR20200036621A - Polyamid resin composition and Molding produced from the same - Google Patents

Abstract

The present invention relates to a polyamide resin composition and a molded product produced therefrom and, more specifically, to a polyamide resin composition which is excellent in flame retardancy and glow wire properties, and to a molded product produced therefrom. The polyamide resin composition comprises: a polyamide resin; a halogen-based flame retardant; an antimony compound; reinforced fibers surface-treated with a silane coupling agent or a titanium coupling agent; and a zinc compound.

Description

Polyamide resin composition and molded produced from the same

The present invention relates to a polyamide resin composition and a molded article produced therefrom.

In modern society, the issue of environmental pollution is gradually increasing. In particular, regulations on fossil energy are getting stronger and interest in renewable energy is increasing. Accordingly, the use of electric energy is rapidly increasing in automobiles other than household appliances, and the use of higher voltages and currents is increasing to secure high energy efficiency. As a method of increasing energy efficiency, the importance of weight reduction of parts is gradually increasing, and thus, the use of plastic materials is increasing. The plastic material can increase the efficiency of energy with a light weight compared to the existing metal material, and also improve the productivity, and the special electric insulation properties are good, so the application range is widening. Nevertheless, since electric energy can cause serious injury to users when safety is not secured, the glow wire characteristics (IEC 60695-2-12, IEC 60695-2-12) 60695-2-13), and the trend is changing to require active flame retardant properties such as tracking tracking (Comparative Tracking Index).

Among various plastic materials, the application of engineering plastic is prominent in parts requiring performance such as mechanical strength, electrical properties, heat resistance, and chemical resistance, and it is required to apply halogen-free flame retardant materials due to environmental problems, but the flame retardant properties required by the industry Since it cannot satisfy, halogen-based flame retardants having better flame retardant properties are still applied. Halogen-based flame retardants are based on flame retardants containing halogen elements such as bromine, chlorine, and fluorine, and use antimony compounds as flame retardants to impart flame retardancy to plastic materials.

For example, in U.S. Patent No. EP1749052B1, Chinese Patent No. CN100564451C, flame retardancy and glow wire properties by applying a flame retardant comprising a metal phosphinate or diphosphonate salt or a condensation product of melamine and phosphoric acid to a polyamide resin This excellent polyamide resin composition is shown. However, in particular, in terms of the glow wire properties, the maximum 750 ° C properties at 1.0mm and 1.5mm are partially shown, indicating that they are not suitable for the glow wire properties 775 ° C at 0.8mm, which is required by the recent industry.

The present invention is to provide a polyamide resin composition excellent in flame retardancy and glow wire characteristics, and a molded article prepared therefrom.

One embodiment of the present invention is a polyamide resin; Halogen-based flame retardants; Antimony compounds; Reinforcing fibers surface-treated with a silane coupling agent; And a zinc compound, wherein the reinforcing fibers may be surface-treated with a content of 0.2 to 2.5 parts by weight based on 100 parts by weight of a polyamide resin with a silane coupling agent or a titanium coupling agent.

The polyamide resin may be characterized in that the relative viscosity is 2.0 to 3.5.

The polyamide resin may be selected from polyamide 6 or polyamide 66 resin.

The halogen-based flame retardant may be characterized by at least one selected from polydibromostyrene, polytribromostyrene, polypentabromostyrene, and polytribromomethylstyrene.

The halogen-based flame retardant and antimony compound may be characterized by being included in a weight ratio of 3: 1 to 2: 1.

The silane coupling agent may be selected from silane coupling agents having methoxy or ethoxy functional groups.

The surface-treated reinforcing fibers may be characterized in that the average length is 0.1 to 20 mm, and the aspect ratio representing L (average length of fibers) / D (average outer diameter of fibers) is 10 to 5,000.

The zinc compound may be selected from zinc compounds of 1 to 5 hydrate.

30 to 50 parts by weight of a halogen-based flame retardant relative to 100 parts by weight of the polyamide resin; 10 to 25 parts by weight of an antimony compound; 25 to 100 parts by weight of the surface-treated reinforcing fibers; And zinc compound 1.5 to 12.5 parts by weight.

Another embodiment of the present invention is to provide a molded article prepared from the above-described polyamide resin composition.

The polyamide resin composition according to the present invention and the molded article produced therefrom have excellent flame retardancy and glow wire properties, and thus can be usefully applied to electric and electronic parts.

According to an embodiment of the present invention, a polyamide resin; Halogen-based flame retardants; Antimony compounds; Reinforcing fibers surface-treated with a silane coupling agent; And a zinc compound, wherein the reinforcing fiber may provide a polyamide resin composition in which a silane coupling agent is surface-treated at a content of 0.2 to 2.5 parts by weight based on 100 parts by weight of the polyamide resin.

Hereinafter, the present invention will be described in detail.

(A) Polyamide resin

The polyamide resin (Polyamide, PA) used in the present invention can be used both polyamide 6 and polyamide 66. The polyamide resin has a relative viscosity of 2.0 to 3.5 (1 g solution of polyamide resin in 100 ml of 96% sulfuric acid at 20 ° C), and the number average molecular weight may be 2,000 to 50,000. At this time, if the relative viscosity of the polyamide resin is less than 2.0, mechanical strength and dimensional stability, etc. may decrease, resulting in problems in injection molding, and if it exceeds 3.5, excessive frictional heat between the screw and the resin in the molding machine may occur. In addition, the resin is decomposed or a high pressure is required for molding, which causes difficulty in the molding machine and the mold, making injection molding difficult. In addition, when the number average molecular weight is less than 2,000, it corresponds to a low viscosity, and there is a problem that the basic mechanical properties of the polyamide resin are not realized. If the molecular weight is more than 50,000, it corresponds to a high viscosity, and the fluidity of the polyamide resin is low, resulting in a precise structure. This can lead to problems of unmolding in injection and surface protrusion of the filler.

(B) Halogen flame retardant

The flame retardant used in the present invention may use a halogen group element selected from bromine, chlorine, and fluorine alone or in a mixed form for high glow wire properties. The halogen-based flame retardant may include a halogen-based polystyrene, at this time, the halogen-based polystyrene means a polystyrene containing a halogen element. That is, the halogen-based polystyrene may function as a flame retardant.

The halogen-based polystyrene is not particularly limited, and brominated polystyrene may be mentioned.

The brominated polystyrene may be selected from polydibromostyrene, polytribromostyrene, polypentabromostyrene, and polytribromoа-methylstyrene, and the brominated polystyrene may be brominated during polymerization of polystyrene or polyа-methylstyrene. It can be prepared by substitution reaction. Moreover, you may copolymerize a brominated styrene and an olefin which has an epoxy group, or graft copolymerize an unsaturated carboxylic acid or its derivative.

In addition, the bromine content in the brominated polystyrene may be 50 to 80% by weight compared to the total brominated polystyrene, and if the bromine content is less than 50% by weight, there is a problem that flame retardancy decreases, and if it exceeds 80% by weight, the benefit of exceeding the content There is no

The halogen-based flame retardant is preferably included in 30 to 50 parts by weight based on 100 parts by weight of the polyamide resin. If the content of the halogen-based flame retardant is less than 30 parts by weight, it is difficult to effectively impart flame retardancy at various thicknesses, and if it exceeds 50 parts by weight, it leads to a decrease in mechanical properties due to an increase in the flame retardant content, and also problems with processability in injection molding. Can cause

(C) Antimony compounds

The antimony compound used in the present invention includes an antimony oxide system to improve the flame retardant effect of halogen-based flame retardants.

The antimony compound may be used alone or in a mixed form of antimony trioxide and antimony pentoxide.

When used alone, the antimony compound cannot exhibit flame retardant properties, but when used together with a halogen-based flame retardant, it may exhibit a synergistic effect to exhibit better flame retardant properties than the natural flame retardant effect of the halogen-based flame retardant. When a halogen-based flame retardant is added in order to impart flame retardancy to the polyamide resin composition, when the amount of the halogen-based flame retardant added increases, the concentration of halogen increases and the mechanical properties of the resin may decrease, thereby further improving the flame retardant properties of the halogen-based flame retardant. The use of antimony trioxide can improve the flame retardant properties of halogen-based flame retardants without lowering the mechanical properties of the resin with increasing halogen concentration.

Therefore, the content of the antimony compound is preferably included 10 to 25 parts by weight based on 100 parts by weight of the polyamide resin of the present invention. When the content of the antimony compound is less than 10 parts by weight, the synergistic effect with the halogen-based flame retardant is small, so it is difficult to realize flame retardancy and glow-witer properties, and when it exceeds 25 parts by weight, mechanical properties are reduced, and injection and molding are also performed during injection. This can cause problems with processability.

The halogen-based flame retardant and the antimony-based compound are included in a mixed weight ratio of antimony oxide to a halogen element in the halogen-based flame retardant from 2: 1 to 3: 1.

(D) Reinforcing fiber

In the polyamide resin composition of the present invention, in order to improve mechanical properties such as tensile strength, flexural strength, flexural modulus, and heat resistance characteristics such as thermal deformation temperature, glass fibers may be included as a filler in the form of fibers.

In order to improve the glow wire properties, the glass fiber may be surface treated with a silane coupling agent or a tita coupling agent as an enhancer for interfacial adhesion between the reinforcing fibers and the resin, and more preferably treated with a silane coupling agent. Do.

The functional group of the silane coupling agent may be any of methoxy and ethoxy, and functional groups reactive with the organic material are amino, vinyl, epoxy, and methacryl. It may be any one of functional groups such as methacryloxy, acryloxy, ureido, chloropropyl, mercapto, sulfide, and isocyanato.

In addition, the glass fiber can be surface-treated with a solution of a silane coupling agent. The silane coupling agent solution is composed of a silane coupling agent and a solvent, and water and most organic solvents can be used as the solvent, but the treatment effect, Water is most effective when comprehensively considering the suitability and safety of the product.

The concentration of the silane coupling agent in the silane coupling agent solution may be 0.001 to 20 vol%, preferably 0.1 to 5 vol%. The concentration of the high silane coupling agent has problems such as cost effectiveness, overtreatment, adhesion between the objects to be treated, and difficulty in drying, and the concentration of the low silane coupling agent has a problem of a weak treatment effect. Vol% means silane coupling agent volume / solvent volume X100.

The silane coupling agent or titanium coupling agent used for surface treatment of the glass fiber may be included in an amount of 0.2 to 2.5 parts by weight based on 100 parts by weight of the polyamide resin.

The average length of the surface-treated glass fibers is usually in the range of 0.1 to 20 mm, preferably 0.3 to 6 mm, and the aspect ratio representing L (average length of fibers) / D (average outer diameter of fibers) is Glass fibers in the range of usually 10 to 5,000, preferably 2,000 to 3,000, can be used. The glass fiber may be 25 to 100 parts by weight based on 100 parts by weight of the polyamide resin.

(E) Zinc compound

In the polyamide resin composition of the present invention, a zinc compound containing zinc borate and zinc sulfide may be included, and in this case, zinc borate is in a stable form under processing conditions, that is, at a molding temperature, volatile substances are volatilized to a minimum. To satisfy the characteristics, it may be represented by the following formula (1).

[Formula 1]

(ZnO) _x (B ₂ O ₃ ) _y (H ₂ O) _z

In the above formula, x is an integer from 2 to 4, y is an integer from 1 to 3, and z is an integer from 0 to 5.

Specifically, the zinc borate may be selected from (ZnO) ₂ (B ₂ O ₃ ) ₃ (H ₂ O) ₁ , (ZnO) ₂ (B ₂ O ₃ ) ₃ (H ₂ O) ₅ and mixtures thereof. have.

In the present invention, the content of the zinc compound containing zinc borate and zinc sulfide may be 1.5 to 12.5 parts by weight with respect to 100 parts by weight of the polyamide resin, and if the content of the zinc compound is less than 1.5 parts by weight, flame retardancy and glow wire properties When it is lowered and exceeds 12.5 parts by weight, the mechanical properties are deteriorated, and the color stability of the final product is deteriorated due to the change in the color of the zinc compound, which causes color changes when the product is used for a long time.

In the present invention, in addition to the above-described components, an anti-drip agent may be further included. The anti-drip agent is a fluorinated polyolefin-based resin, which forms a fibrous net structure in the composition to suppress the flow of the resin during combustion and increase the shrinkage to prevent dripping of the composition.

To prevent such dripping, a fluorine-based drip inhibitor such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyhexafluoropropylene can be used.

Preferably, the drip-preventing agent is contained in an amount of 1.0 to 2.5 parts by weight based on 100 parts by weight of the polyamide resin. When used in less than 1.0 part by weight, the drip-preventing effect may be deteriorated, and when used in excess of 2.5 parts by weight, extrusion processability may decrease due to an increase in viscosity.

The non-reinforced, halogen polyamide flame-retardant resin composition of the present invention has a flame retardancy measured by the UL-94 vertical flame retardancy evaluation method in the range of 0.4 mm to 3.0 mm, V0 grade, and glow wire properties measured according to the IEC 60695-2-13 standard It is characterized by having a CTI of at least 825 ° C and 400V or higher.

According to another embodiment of the present invention, to provide a molded article prepared from the above-described polyamide resin composition.

Due to the properties of the halogen polyamide flame retardant resin composition, the halogen polyamide flame retardant composition according to the present invention can be used for molding various products, and is particularly useful in housings for electrical and electronic connector parts that require excellent flame retardant and glow wire properties. Can be applied.

Hereinafter, the configuration and effects of the invention will be described in more detail through specific examples and comparative examples to help understanding of the present invention. However, the following examples are only for understanding the invention more clearly, and the invention is not limited to the following examples.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the scope of the present invention is not limited by these examples.

Examples 1 to 3 and Comparative Examples 1 to 14

Each component used in Examples and Comparative Examples is as follows.

(A) Polyamide resin: ASCEND Co. 50BW was used.

(B) Halogen-based flame retardant: A brominated polystyrene Albermarle BPS 7010 having a bromine content of 68% by weight and a melting point of 210 ° C was used.

(C) Antimony compound: IY-HW of ITC, which has an average particle diameter of 0.5 µm and an antimony trioxide content of 99.8% by weight or more, was used.

(D) Reinforcing fiber: As a reinforcing fiber surface-treated with a silane coupling agent, the silane coupling agent used Shinetsu's KBE-603 containing an amino system, and the reinforcing fiber used NEG 262H with an average diameter of 11 μm. Did.

(E) Compatibilizer: A homopolyolefin Dupont 493D product in which maleic anhydride was grafted 0.4 to 2 wt% was used.

(F) Zinc compound: ZB 245 manufactured by Firebrake, which has a zinc borate content of 98.8% or more, was used.

(G) Anti-drip agent: METABLEN A-3800 polytetrafluoroethylene manufactured by MITSUBISHI RAYON was used.

(H) Antioxidant / release agent: Antioxidant was used as a phenol, and Igarnox 1010 from BASF. As the release agent, L-C 102N product of Lion Chem, a polyethylene wax, was used.

According to the contents shown in Table 1 below, each component was melted and kneaded in a twin-screw extruder heated to 250 to 290 ° C to prepare a polyamide resin composition in a chip state, and dehumidified dryer at 120 ° C for 5 hours. And dried.

By manufacturing each specimen at the same temperature as when melting and kneading the polyamide resin composition prepared in Examples and Comparative Examples using a heated screw-type injection machine, ASTM standard specimens for measuring mechanical properties and UL for flame retardancy measurements Specimens of -94 and IEC 60695-2-13 were produced.

In the polyamide resins prepared in Examples and Comparative Examples, the rotational speed of the screw in the twin screw extruder was 350 rpm.

Property evaluation

(1) Tensile strength: According to ASTM D638, a 3.2 mm thick dumbbell-shaped test piece was measured at room temperature using a universal testing machine.

(2) Flexural strength: According to ASTM D790, a rectangular test piece having a thickness of 3.2 mm was measured at room temperature using a universal testing machine.

(3) UL-94 Vertical Flame Retardant: US Underwriter's Laboratory Inc. The thickness of 0.4mm, 0.8mm, 1.5mm, 3.0mm specimens was measured by UL94 test method. This evaluation method is a method of evaluating flame retardancy from the residual time or dripping property after the flame is immersed in a specimen of a certain size maintained vertically for 10 seconds. According to the above procedure, the material is classified as V-0, V-1, or V2 based on the test results, with V-0 showing the best flame retardancy and V-2 showing the lowest flame retardancy.

(4) Glow Wire Ignition Temperature (GWIT): Measured according to the International Electrotechnical Commission standard IEC-60695-2-12 using specimens having a thickness of 0.8 mm to 3.0 mm and a dimension of 60.0 Ⅹ 60.0 mm. The measured temperature corresponds to the maximum temperature at which the ignition does not ignite when the glow wire is brought into contact with the specimen for 30 seconds.

 (5) Glow Wire Flammability Temperature (GWFI): was measured according to the International Electrotechnical Commission standard IEC-60695-2-13 using specimens having a thickness of 0.8mm to 3.0mm and dimensions of 60.0 0.0 60.0mm. The measured temperature corresponds to the maximum temperature at which the flame extinguishes within 30 seconds after the glow wire is retracted when the glow wire is brought into contact with the specimen for 30 seconds.

division Tensile strength (kg / cm ² ) Flexural modulus (kg / cm ² ) Flame retardant (0.8mm PLC thickness) GWIT (Thickness 0.8mm, ℃) Example 1 1,530 97,300 V-0 825 Example 2 1,590 99,420 V-0 850 Example 3 1,620 99,850 V-0 850 Comparative Example 1 1,475 91,230 V-0 775 Comparative Example 2 1,530 91,100 V-0 775 Comparative Example 3 1,590 90,420 V-0 775 Comparative Example 4 1,620 90,850 V-0 750 Comparative Example 5 1,690 87,320 V-0 775 Comparative Example 6 1,610 86,570 V-0 750 Comparative Example 7 1,680 84,440 V-2 750 Comparative Example 8 1,720 82,330 Flame retardant X 725

As shown in Table 2, it can be seen that the specimens prepared with the compositions of Examples 1 to 3 are excellent in flame retardancy, glow wire properties, and mechanical properties, and are suitable for electrical and electronic connector parts.

On the other hand, when the silane coupling agent is not used or is replaced with other compatibilizers (Comparative Examples 1 to 4), the flexural modulus is lowered and the glow wire properties (GWIT) are low, and no zinc compound is added (Comparative Example) 5,6) also shows that GWIT is falling.

In addition, when the antimony compound is used alone or when the halogen-based flame retardant is used in a ratio of less than 3: 1 or greater than 2: 1, it shows that the flame retardance is not shown at all and the GWIT properties are also lowered.

From this, in the case of a halogen-based polyamide resin composition comprising a glass fiber and a zinc compound surface-treated with a silane coupling agent according to the present invention, it is possible to obtain a high glow wire property while having a higher flexural modulus value than a general polyamide flame retardant material. , It can be applied to electrical and electronic connector parts.

Claims (10)

Polyamide resins;
Halogen-based flame retardants;
Antimony compounds;
Reinforcing fibers surface-treated with a silane coupling agent or titanium coupling agent; And
Zinc compounds,
The reinforcing fiber is a polyamide resin composition in which a silane coupling agent or a titanium coupling agent is surface-treated in an amount of 0.2 to 2.5 parts by weight based on 100 parts by weight of the polyamide resin.
The polyamide resin composition according to claim 1, wherein the polyamide resin has a relative viscosity of 2.0 to 3.5.
The polyamide resin composition according to claim 1, wherein the polyamide resin is selected from polyamide 6 or polyamide 66 resin.
The polyamide resin composition according to claim 1, wherein the halogen-based flame retardant is at least one selected from polydibromostyrene, polytribromostyrene, polypentabromostyrene, and polytribromomethylstyrene.
The polyamide resin composition according to claim 1, wherein the halogen-based flame retardant and the antimony compound are contained in a weight ratio of 3: 1 to 2: 1.
The polyamide resin composition according to claim 1, wherein the silane coupling agent is selected from silane coupling agents having methoxy or ethoxy functional groups.
The method of claim 1, wherein the surface-treated reinforcing fiber has an average length of 0.1 to 20 mm, and an aspect ratio of L (average length of fibers) / D (average outer diameter of fibers) is 10 to 5,000. Polyamide resin composition.
The polyamide resin composition according to claim 1, wherein the zinc compound is selected from zinc compounds of 1 to 5 hydrate.
According to claim 1, 30 to 50 parts by weight of halogen-based flame retardant relative to 100 parts by weight of the polyamide resin; 10 to 25 parts by weight of an antimony compound; 25 to 100 parts by weight of the surface-treated reinforcing fibers; And zinc compound 1.5 to 12.5 parts by weight of a polyamide resin composition comprising a.
A molded article made from the polyamide resin composition according to claim 1.