TWI709609B - A production method of flame retardant thermoplastic nylon composite and application thereof - Google Patents

Abstract

Present invention relates to a production method of flame retardant thermoplastic nylon composite having a nylon polymer at least 30 wt%, a modified glass fiber 60~70 wt%, and a flame retardant at least 10wt%. By introducing modified glass fiber into thermoplastic polymer and accompanied with certain production method, the flame retardant thermoplastic nylon composite of the present invention has passed the regulation of CNS 14705-1 for proving with high quality of fire resistance and also has maintained with excellent process ability for injection or extruding. The modified glass fiber in the present invention can achieve high mechanical property which makes the present invention can be applied to all kinds of filed, such as construction, decoration or aviation. The present invention also can be formed in to any completed shape and various products with high quality and duration by injection and extruding process.

Description

Manufacturing method and application of flame-resistant thermoplastic nylon composite material

The invention relates to the field of fire-resistant and flame-resistant materials, in particular to a thermoplastic nylon composite material with high-level fire-resistant and flame-resistant grades and a manufacturing method thereof.

With the development of various composite materials, composite materials have excellent processing performance and mechanical performance advantages, making them widely used in various fields such as automobile industry, aerospace industry, architectural decoration and daily necessities, especially in the field of construction, composite materials It is one of the fairly common materials.

In addition to demanding mechanical strength such as shock resistance and high rigidity, construction and decoration materials can be resistant to high temperature, flame retardant or fire to a certain degree, and even higher levels of flame resistance and fire resistance are necessary considerations. Generally, the common building materials that can achieve the aforementioned high-level fire resistance such as flame resistance and fire protection are mainly inorganic building materials such as metal or stone. In plastic building materials, only thermosetting resin composite materials can achieve high-level performance such as flame resistance and fire protection, while thermoplastic resins Often only relatively low-level or basic flame retardant and fire retardant properties can be achieved.

However, although inorganic building materials such as metal or stone have high-level flame resistance and fire resistance, their high specific gravity and heavy weight make it difficult to be flexibly used in decoration materials; and thermosetting resin composite materials also have environmental protection problems such as unrecyclable. At present, there is a lack of a high-end flame-resistant and fire-resistant material made of thermoplastic composite materials, and at the same time, there is a material that has high processing characteristics such as injection and extrusion and good recyclability.

In order to solve the aforementioned problems of inorganic building materials such as metal or stone material having high-level fire resistance and fire resistance, but it is difficult to use flexibly, and thermosetting resin composite materials cannot be recycled, the present invention proposes a flame retardant after long-term and repeated research by the applicant. The thermoplastic nylon composite material comprises: a nylon resin of less than 30wt%; a glass fiber modified with a multiple coupling agent of 60~70wt%; and a flame retardant of less than 10wt%.

Wherein, the above-mentioned multiple coupling agent includes at least two coupling agents. The flame retardant contains magnesium hydroxide flame retardant or phosphorus nitrogen flame retardant.

Wherein, the at least two coupling agents comprise at least two silane coupling agents.

Wherein, the aforementioned silane coupling agent comprises n-aminopropyl trihexoxysilane, methacryloxypropyl trimethoxysilane or β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane .

Further, the present invention provides a method for manufacturing the aforementioned flame-resistant thermoplastic nylon composite material. The steps include: mixing 80% by weight of a nylon resin and 20% of a flame retardant into a nylon masterbatch; using a coupling agent to add a glass fiber Soaking and modifying for at least two times and drying; and kneading the nylon masterbatch with the modified glass fiber to obtain a thermoplastic nylon resin composite material.

Wherein, the aforementioned coupling agent uses at least two different coupling agents to modify the glass fiber in two immersion procedures.

Wherein, the thermoplastic nylon resin composite material is further injection molded.

Wherein, the nylon masterbatch and the modified glass fiber are kneaded using a counter-rotating twin screw machine.

Among them, when the nylon masterbatch is mixed with the modified glass fiber, the temperature in the first stage of mixing is set at 90°C, the temperature in the middle stage is raised to 180°C, the latter is mixed at a temperature of 280°C, and the screw speed of the whole stage is 450rpm.

Furthermore, the present invention provides a construction, decoration or aircraft material, which is made of the aforementioned flame-resistant thermoplastic nylon composite material.

According to the above description, the present invention has the following advantages and advantages:

1. The present invention utilizes the combination of material formula and manufacturing process to successfully develop a high-end thermoplastic composite material that can reach the third-class flame resistance and fire protection performance specified by CNS 14705-1. It not only has the processing conditions for injection and extrusion molding, but also has high machinery. The characteristics of strength, especially suitable for but not limited to construction, decoration and other materials, as well as civilian products, industrial or aviation fields, such as aircraft (aircraft, drones) internal and external equipment materials, car or train interior decoration materials, floors or Floor tiles or ceilings, etc., and because of the characteristics of injection molding, can be processed into products of various shapes, with a wide range of applications and excellent quality and durability.

Further, the present invention is mainly a plastic component, which is used as an outer material of an aircraft, such as a casing or a wing, etc., to avoid the risk of lightning strikes caused by the use of metal materials. The excellent mechanical strength possessed by the present invention is also suitable for making structural parts of products, such as honeycomb panels.

2. The present invention can replace the existing calcium silicate board material used in ceiling decoration. Because the existing calcium silicate board absorbs moisture or leaking water in the air, it will cause the problem of material decay or damage for a long time. It needs to be replaced frequently, and it is more likely to cause problems such as bacteria growth due to full water absorption. The thermoplastic nylon composite material of the present invention has the characteristics of non-absorbent, and can be used to replace the existing calcium silicate board material of the ceiling when the product of the sheet is processed. It is especially suitable for the ceiling decoration of medical institutions, which can cause bacterial growth and cause environmental pollution. problem.

FIG. 1 is a schematic flow chart of a preferred embodiment of the process steps of the present invention.

In order to understand the technical features and practical effects of the present invention in detail, and implement it according to the content of the specification, the preferred embodiment shown in the figure is further described in detail as follows.

The invention is a thermoplastic nylon resin composite material, which not only has the high processing characteristics of thermoplastic resin, such as injection and extrusion, but also can achieve high-level fire and flame resistance. Several preferred examples of a flame-resistant thermoplastic nylon composite formulation are as follows:

"Formulation First Example"

Nylon resin 30wt% or less; glass fiber modified with multiple coupling agent 60~70wt%; and magnesium hydroxide flame retardant or phosphorus nitrogen flame retardant 10wt% or less.

The multiple coupling agent used in this embodiment or the present invention refers to at least two or more different coupling agents, preferably three different coupling agents to modify the glass fiber surface, these coupling agents are basically for increasing The mixing uniformity of the organic polymer nylon resin, the inorganic reinforcing material glass fiber and the flame retardant achieves the high dispersion and uniform mixing of the overall material, and the present invention can achieve high-level fire and flame resistance. In addition to the magnesium hydroxide flame retardant or phosphorus nitrogen flame retardant, this embodiment has the effect of making the nylon resin fire-resistant and flame-resistant. The glass fiber modified by the multi-coupling agent also has the effect of improving the fire-resistant and flame resistance of the present invention. .

"Formulation Second Example"

Nylon resin less than 30wt%; glass fiber modified with multiple silane coupling agent 60~70wt%; and Magnesium hydroxide flame retardant or phosphorus nitrogen flame retardant is less than 10wt%.

The multiple silane coupling agent of this embodiment mainly contains at least two or more different silane coupling agents, preferably three different silane coupling agents to modify the glass fiber surface. The silane coupling agent contains n-β-(aminoethyl Group)-γ-amino propyl trimethoxysilane (n-β-(amino ethyl)-γ-amino propyl trimethoxy silane, also known as UCC-A-1120, hereinafter referred to as 1120 silane coupling agent), methacrylic acid Γ-methacryloxy propyl trimethoxy silane (γ-methacryloxy propyl trimethoxy silane, also known as UCC-A-174, hereinafter referred to as 174 silane coupling agent), β-(3,4-epoxycyclohexyl)-ethyl trimethoxy silane Two or more arbitrary combinations of β-(3,4-epoxy cyclohexyl)ethyl tri methoxy silane (also known as UCC-A-186, hereinafter referred to as 186 silane coupling agent) can be used in the present invention The composite material provides good mixing uniformity and substantially improves the fire and flame resistance of the present invention.

Further, the present invention provides several methods for manufacturing the aforementioned nylon thermoplastic resin composite materials, and please refer to FIG. 1.

"The first embodiment of the process"

Step S1: Mix 80% by weight of a nylon resin and 20% of a flame retardant into a nylon masterbatch; Step S2: Use a coupling agent to soak and modify a glass fiber for at least two times and dry; Step S3: Combine The nylon masterbatch is mixed with the modified glass fiber to obtain a thermoplastic nylon resin composite material.

Among them, the types of the flame retardant and the coupling agent and the first embodiment and the second embodiment of the aforementioned formulation have been described in detail, and will not be repeated here. Steps 1 and 2 are basically steps that can be performed at the same time, and are not used to limit the order between the two steps. The method for modifying the glass fiber with the coupling agent in the present invention or this embodiment is preferably to use a soaking method. The glass fiber is completely immersed in the coupling agent liquid, and multiple and multiple soaking can be selected. The glass fiber surface has a surface close to nylon and the flame retardant, and it can be more uniform and dispersed when all subsequent materials are mixed.

The so-called multiple coupling agent types in this embodiment can refer to the second preferred embodiment of the aforementioned formula, and the multiple modification method of multiple coupling agents to the glass fiber is preferably to use oily silane coupling agent (ie 174 coupling agent and 1120 The glass fiber is soaked for the first time after the 10wt% acetic acid solution of each coupling agent is mixed. Through the soaking method, the coupling agent can penetrate into the glass fiber and contact the surface of each fiber, so that the glass fiber The active functional groups on the surface, such as oxygen-containing functional groups, open the bond. Then the glass fiber is soaked with an aqueous silane coupling agent (ie 186 silane coupling agent) for the second coupling and modification, so that the opened active functional groups The bonding can be grafted onto the polyamide functional group (Acrylate) that can react or bond with nylon, which is also used as the auxiliary modification process for the first modification. Finally, the modified glass fiber is cut and dried for backup. use.

"Second Embodiment of Manufacturing Process"

Step S1: Mix 80% by weight of a nylon resin and 20% of a flame retardant into a nylon masterbatch; Step S2: Use a coupling agent to soak and modify a glass fiber for at least two times and dry; Step S3: Combine The nylon masterbatch is mixed with the modified glass fiber to obtain a thermoplastic nylon resin composite material; step S4: the thermoplastic nylon resin composite material is injection-extruded into a finished nylon thermoplastic resin composite material.

Since the present invention uses thermoplastic nylon resin as the base material, the excellent processing characteristics of the thermoplastic material, especially the fluidity of the composite material of the present invention during processing, can be introduced into the injection extrusion molding process. Compared with the existing thermosetting resin composite material, the present invention It has excellent processability, and its fire and flame resistance effect is better than thermosetting resin composite material.

Wherein, when the nylon masterbatch of the present invention is mixed with the modified glass fiber, a counter-rotating twin-shaft screw machine can be used. During the process, it is better to adjust the screw mixing configuration of the mixing environment. The generated internal heat is increased to the extent that the polymer material is sintered, preferably before mixing The temperature is set within 90°C, the temperature in the middle section is raised to 180°C, and the last stage is mixed at a temperature of 280°C. The screw speed of the whole section is preferably 450rpm.

"Test results"

All the embodiments of the present invention have passed the test standards of CNS 14705-1 stipulated by CNS 14705-1. Please refer to the following table 1:

The foregoing descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of rights claimed by the present invention. All other equivalent changes or modifications completed without departing from the spirit disclosed by the present invention shall be included in the present invention. Within the scope of patent application.

Claims (4)

A method for manufacturing a flame-resistant thermoplastic nylon composite material. The steps include: mixing 80% by weight of a nylon resin and 20% of a flame retardant into a nylon masterbatch; using a coupling agent to soak and modify a glass fiber at least twice And dry, wherein: the coupling agent is the first soaking of the glass fiber with the oily silane coupling agent, and then the glass fiber is soaked with the water-based silane coupling agent for the second modification and dry cutting; A thermoplastic nylon resin composite material is obtained by mixing the pellets below 40wt% with the modified glass fiber 60~70wt%; and the thermoplastic nylon resin composite material is injection molded, and the molded thermoplastic nylon resin composite material conforms to CNS 14705- 1 Flame resistance grade is three grades. For example, in the method for manufacturing a flame-resistant thermoplastic nylon composite material in the scope of the patent application, the nylon masterbatch is mixed with the modified glass fiber using a counter-rotating twin screw machine. For example, the method for manufacturing the flame-resistant thermoplastic nylon composite material in the scope of patent application 1 or 2, when the nylon masterbatch is mixed with the modified glass fiber, the temperature before mixing is set at 90℃, and the temperature at the middle stage is increased to 180 ℃, the latter stage is mixed at 280℃, and the screw speed of the whole stage is 450rpm. A flame-resistant and fire-resistant construction, decoration or aircraft material, which is made by the method of manufacturing the flame-resistant thermoplastic nylon composite material of items 1 to 3 in the scope of patent application.

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